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Union Chem Report FLUOR DANIEL GTI
To Dave Egan Project Manager Reviewed by Tim Pac Copy Rick Lewis Paul Farrington file
From Michael Doherty Project Engineer Subject Potassium Permanganate Field TesfReport Date January 13 1998 Attachments Field Implementation Plan
Field Test Work Plan Potassium Permanganate Jar Test Report
10 INTRODUCTION The report summarizes the activities performed and the results obtained during the Potassium Permanganate Field Test performed from October 20 to November 111997 at the Union Chemical site in South Hope Maine
20 BACKGROUND
Inorganic compounds dissolved in the groundwater at the Union Chemical site result in significant maintenance costs and potential discharge compliance issues at the Union Chemical groundwater treatment system A reduction in the concentration of inorganics in the extracted groundwater would provide a considerable cost savings and result in a more effective pump and treat system with less potential for permit discharge exceedences In addition dissolved organic compounds at the Union Chemical site are currently addressed via a groundwater pump and treat system While pump and treat technology provides hydraulic containment and control it is not an aggressive approach to removing contaminant mass from the saturated zone
Fluor Daniel GTI believes that introducing a strong oxidant specifically potassium permanganate into the groundwater could significantly reduce the concentrations of inorganic and organic compounds dissolved in the groundwater at the Union Chemical site As mentioned above this would result in more efficient operation of the groundwater extraction and treatment operations decreased potential for exceeding the discharge requirements and a more aggressive treatment approach for the dissolved organic contaminant mass in the groundwater at the Union Chemical site
30 TEST OBJECTIVES
The primary objective of the field test was to measure the effects of adding a solution of potassium permanganate KMnO4l into the groundwater beneath the Union Chemical site Specifically the reactions between the potassium permanganate and the inorganic and organic compounds dissolved in the groundwater were evaluated
Inorganic Compounds KMnO4 is well known in the waste water treatment industry for its ability to react with dissolved metals It also has been used as part of the metals removal system in the Union Chemical treatment plant KMnO4
will readily oxidize the dissolved inorganic compounds into their respective inorganic oxides (or particulate) states By applying this reaction in-situ the soil formation at the site should filter out these particulate inorganics within the soil matrix thereby resulting in lower inorganic concentrations in the extracted groundwater
Organic Compounds In addition KMnO4 will react with a wide range of organic compounds relatively quickly and completely Specifically KMnO4 reacts preferentially with chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE and PCE (as shown in the attached Potassium Permanganate Jar Test Report) The ability to control and perform this reaction in-situ at the Union Chemical site was evaluated
In addition the following test objectives were also evaluated
hydraulic control of the oxidant solution bull potential fouling or scaling in the soil matrix and well screen around the addition well bull field applicability of adding oxidant solution into a wells bull health and safety considerations in dealing with a oxidant
site specific geologic andor hydrogeologic conditions that may limit application
40 TEST METHODOLOGY AND RATIONALE
The test addition well (P-21) is located in the middle of the site surrounded by active pumping wells the potassium permanganate solution once added to the groundwater is drawn out to the surrounding active extraction wells (P-16 P-16a P-20 P-22 P-25) In this way the cylindrical volume of groundwater and saturated soil surrounding the addition well comes in contact with the permanganate solution A site map showing the test well locations is included as Figure 1 Measurements of oxidationreduction potential and visual appearance were periodically monitored in groundwater in the extraction wells surrounding P-21 to estimate the flow paths and the reaction time of the potassium permanganate solution
The following deliverables and events summarize the activities performed to plan and document the permanganate field Test activities
Potassium Permanganate Jar Test and Report July 221997 Field Test Work Plan July 29 1997 (submitted to Agencies) Verbal Work Plan Approval by Agencies September 18 1997 (during meeting) Field Implementation Plan October 21997 Field Test Performed October 201997 - November 141997
The daily test procedure was as follows
1 Daily preparation of a predetermined concentration of KMnO4 solution in a temporary tank next to the addition well (P-21)
2 Addition of the KMnO4 solution at a constant rate for six to eight hours per day 3 Periodic monitoring of surrounding pumping wells (P-16 P-16a P-20 P-22 and P-25) for
oxidationreduction potential and visual observations
The test procedures and methodologies are detailed in the Field Test Work Plan dated July 291997 and the Field Test Implementation Plan dated October 21997 these plans are attached to this report and summarized below The potassium permanganate solution concentration was based on the results of the bench-top permanganate test performed during the spring of 1997 (a copy of the report is attached)
41 Pre-Test Activities
On October 191997 the following baseline (pre-test) conditions were measured in the addition well (Pshy21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
In addition the extraction pump at P-21 was turned off and removed from the well All other groundwater extraction pumps remained active
42 Testing Activities
bull The Potassium Permanganate Field Test was performed from October 201997 through November 111997 for a total of 22 days Potassium permanganate was added during 14 of the 22 days the other days being weekends and days the field technician was unavailable
bull A total of 6500 gallons of 350 mgl KMnO4 solution (approximately 20 Ibs of KMnOJ was added to the groundwater over the course of the test
bull An average of 460 gallons per day of potassium permanganate solution was added to P-21 during the test addition days (Monday through Friday)
bull The KMnO4 solution was added to P-21 at approximately 100 to 125 gallons per minute (gpm) this rate was determined to be the maximum addition rate at P-21
43 Post Test On November 141997 two days after stopping the addition of KMnO4 the following post-test conditions were measured in the addition well (P-21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
These parameters were also measured two weeks later on December 2 1997
44 Test Quality Control
The following activities were performed periodically throughout the test to ensure that relative and accurate data was being documented during the testing activities
weekly calibration of the ORP probe bull daily mixing of the permanganate solution
50 TEST RESULTS
The test data is attached in the following summary tables and summarized below
Table 1 Daily addition volumes and ORP measurements in the test wells Table 2 Inorganic concentrations in groundwater (preduringpost -test) Table 3 Organic concentrations in groundwater (preduring post -test)
60 OBSERVATIONS
Inorganic Compounds 1 Total iron concentrations in the five pumping wells surrounding the addition well decreased an
average of 54 from pre-test levels
2 Total manganese concentrations in the five pumping wells surrounding the addition well decreased an average of 16 from pre-test levels
3 Total copper concentrations in the five pumping wells surrounding the addition well decreased an average of 69 from pre-test levels
4 A comparison of the immediate post-test and two week after post-test results show no significant rebound in inorganic concentrations in the groundwater
Organic Compounds 5 TCE average pre-test concentration 1674 ugl
largest concentration reduction P-16a (55)
TCE concentrations in the five pumping wells surrounding the addition well decreased an average of 39 immediately after the test completion this dropped to 33 reduction when compared with the two week post-test samples
6 PCE average pre-test concentration 75 ugl largest concentration reduction P-25 (81)
PCE concentrations in the five pumping wells surrounding the addition well decreased an average of 41 immediately after the test completion this dropped to 30 reduction when compared with the two week post-test samples
7 Total DCEs average pre-test concentration 2566 ugl largest concentration reduction P-20 (28)
Total DCEs averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well although two wells (P-16a and P-20) did show approximately 20 decrease in concentrations
8 11 -DCA average pre-test concentration 2798 ugl largest concentration reduction P-16a (19)
11-DCA averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
9 Total xylenes average pre-test concentration 4297 largest concentration reduction P-22 (8)
Total xylenes averaged no significant reductions in the pre- and post-test levels in the five
pumping wells surrounding the addition well
10 Toluene average pre-test concentration 665 largest concentration reduction P-22 (31)
Toluene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
11 Ethyl-benzene average pre-test concentration 650 largest concentration reduction P-20 (0)
Ethyl-benzene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
12 Chlorinated non-conjugated (non-aromatic) double bonded compounds (specifically TCE and PCE) were reduced to a much greater extent than single bonded chlorinated compounds (DCAs) and non-halogenated aromatics (toluene xylenes)
Other observations 13 The rebound in organic concentrations between the immediately post-test and two week after
post-test results indicate that a stronger solution of potassium permanganate may be beneficial for future testing potentially resulting in greater contaminant mass reduction
14 No evidence of inorganic fouling or scaling in the test addition well or surrounding soil matrix were observed The addition rate at P-21 remained constant at 100 to 125 gpm throughout the testing activities
15 Besides the precautionary aspects of handling a strong oxidant no other potential Health and Safety concerns arose during the testing activities Further no Health and Safety concerns are anticipated in future testing activities (with the exception of bulk material handling)
16 Although sufficient the potassium permanganate delivery system utilized during the field test activities was labor intensive future activities would benefit from a more automated KMnO4
delivery system
70 CONCLUSION
The results from the permanganate addition field test show that potassium permanganate does signficantly reduce the concentrations of inorganic and specific organic compounds dissolved in the groundwater beneath the Union Chemical site The field test results support the opinion that a larger application of potassium permanganate addition into the groundwater at the Union Chemical site would be appropriate to better evaluate long term effects and other parameters not evaluated during this field test
From the desk of
MICHAEL E DOHERTY PE Project Engineer
Fluor Daniel GTI Inc 100 River Ridge Drive
Norwood MA 02062
(617)769-7602 Fax(617)769-7785
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
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Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
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Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
Inorganic Compounds KMnO4 is well known in the waste water treatment industry for its ability to react with dissolved metals It also has been used as part of the metals removal system in the Union Chemical treatment plant KMnO4
will readily oxidize the dissolved inorganic compounds into their respective inorganic oxides (or particulate) states By applying this reaction in-situ the soil formation at the site should filter out these particulate inorganics within the soil matrix thereby resulting in lower inorganic concentrations in the extracted groundwater
Organic Compounds In addition KMnO4 will react with a wide range of organic compounds relatively quickly and completely Specifically KMnO4 reacts preferentially with chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE and PCE (as shown in the attached Potassium Permanganate Jar Test Report) The ability to control and perform this reaction in-situ at the Union Chemical site was evaluated
In addition the following test objectives were also evaluated
hydraulic control of the oxidant solution bull potential fouling or scaling in the soil matrix and well screen around the addition well bull field applicability of adding oxidant solution into a wells bull health and safety considerations in dealing with a oxidant
site specific geologic andor hydrogeologic conditions that may limit application
40 TEST METHODOLOGY AND RATIONALE
The test addition well (P-21) is located in the middle of the site surrounded by active pumping wells the potassium permanganate solution once added to the groundwater is drawn out to the surrounding active extraction wells (P-16 P-16a P-20 P-22 P-25) In this way the cylindrical volume of groundwater and saturated soil surrounding the addition well comes in contact with the permanganate solution A site map showing the test well locations is included as Figure 1 Measurements of oxidationreduction potential and visual appearance were periodically monitored in groundwater in the extraction wells surrounding P-21 to estimate the flow paths and the reaction time of the potassium permanganate solution
The following deliverables and events summarize the activities performed to plan and document the permanganate field Test activities
Potassium Permanganate Jar Test and Report July 221997 Field Test Work Plan July 29 1997 (submitted to Agencies) Verbal Work Plan Approval by Agencies September 18 1997 (during meeting) Field Implementation Plan October 21997 Field Test Performed October 201997 - November 141997
The daily test procedure was as follows
1 Daily preparation of a predetermined concentration of KMnO4 solution in a temporary tank next to the addition well (P-21)
2 Addition of the KMnO4 solution at a constant rate for six to eight hours per day 3 Periodic monitoring of surrounding pumping wells (P-16 P-16a P-20 P-22 and P-25) for
oxidationreduction potential and visual observations
The test procedures and methodologies are detailed in the Field Test Work Plan dated July 291997 and the Field Test Implementation Plan dated October 21997 these plans are attached to this report and summarized below The potassium permanganate solution concentration was based on the results of the bench-top permanganate test performed during the spring of 1997 (a copy of the report is attached)
41 Pre-Test Activities
On October 191997 the following baseline (pre-test) conditions were measured in the addition well (Pshy21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
In addition the extraction pump at P-21 was turned off and removed from the well All other groundwater extraction pumps remained active
42 Testing Activities
bull The Potassium Permanganate Field Test was performed from October 201997 through November 111997 for a total of 22 days Potassium permanganate was added during 14 of the 22 days the other days being weekends and days the field technician was unavailable
bull A total of 6500 gallons of 350 mgl KMnO4 solution (approximately 20 Ibs of KMnOJ was added to the groundwater over the course of the test
bull An average of 460 gallons per day of potassium permanganate solution was added to P-21 during the test addition days (Monday through Friday)
bull The KMnO4 solution was added to P-21 at approximately 100 to 125 gallons per minute (gpm) this rate was determined to be the maximum addition rate at P-21
43 Post Test On November 141997 two days after stopping the addition of KMnO4 the following post-test conditions were measured in the addition well (P-21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
These parameters were also measured two weeks later on December 2 1997
44 Test Quality Control
The following activities were performed periodically throughout the test to ensure that relative and accurate data was being documented during the testing activities
weekly calibration of the ORP probe bull daily mixing of the permanganate solution
50 TEST RESULTS
The test data is attached in the following summary tables and summarized below
Table 1 Daily addition volumes and ORP measurements in the test wells Table 2 Inorganic concentrations in groundwater (preduringpost -test) Table 3 Organic concentrations in groundwater (preduring post -test)
60 OBSERVATIONS
Inorganic Compounds 1 Total iron concentrations in the five pumping wells surrounding the addition well decreased an
average of 54 from pre-test levels
2 Total manganese concentrations in the five pumping wells surrounding the addition well decreased an average of 16 from pre-test levels
3 Total copper concentrations in the five pumping wells surrounding the addition well decreased an average of 69 from pre-test levels
4 A comparison of the immediate post-test and two week after post-test results show no significant rebound in inorganic concentrations in the groundwater
Organic Compounds 5 TCE average pre-test concentration 1674 ugl
largest concentration reduction P-16a (55)
TCE concentrations in the five pumping wells surrounding the addition well decreased an average of 39 immediately after the test completion this dropped to 33 reduction when compared with the two week post-test samples
6 PCE average pre-test concentration 75 ugl largest concentration reduction P-25 (81)
PCE concentrations in the five pumping wells surrounding the addition well decreased an average of 41 immediately after the test completion this dropped to 30 reduction when compared with the two week post-test samples
7 Total DCEs average pre-test concentration 2566 ugl largest concentration reduction P-20 (28)
Total DCEs averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well although two wells (P-16a and P-20) did show approximately 20 decrease in concentrations
8 11 -DCA average pre-test concentration 2798 ugl largest concentration reduction P-16a (19)
11-DCA averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
9 Total xylenes average pre-test concentration 4297 largest concentration reduction P-22 (8)
Total xylenes averaged no significant reductions in the pre- and post-test levels in the five
pumping wells surrounding the addition well
10 Toluene average pre-test concentration 665 largest concentration reduction P-22 (31)
Toluene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
11 Ethyl-benzene average pre-test concentration 650 largest concentration reduction P-20 (0)
Ethyl-benzene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
12 Chlorinated non-conjugated (non-aromatic) double bonded compounds (specifically TCE and PCE) were reduced to a much greater extent than single bonded chlorinated compounds (DCAs) and non-halogenated aromatics (toluene xylenes)
Other observations 13 The rebound in organic concentrations between the immediately post-test and two week after
post-test results indicate that a stronger solution of potassium permanganate may be beneficial for future testing potentially resulting in greater contaminant mass reduction
14 No evidence of inorganic fouling or scaling in the test addition well or surrounding soil matrix were observed The addition rate at P-21 remained constant at 100 to 125 gpm throughout the testing activities
15 Besides the precautionary aspects of handling a strong oxidant no other potential Health and Safety concerns arose during the testing activities Further no Health and Safety concerns are anticipated in future testing activities (with the exception of bulk material handling)
16 Although sufficient the potassium permanganate delivery system utilized during the field test activities was labor intensive future activities would benefit from a more automated KMnO4
delivery system
70 CONCLUSION
The results from the permanganate addition field test show that potassium permanganate does signficantly reduce the concentrations of inorganic and specific organic compounds dissolved in the groundwater beneath the Union Chemical site The field test results support the opinion that a larger application of potassium permanganate addition into the groundwater at the Union Chemical site would be appropriate to better evaluate long term effects and other parameters not evaluated during this field test
From the desk of
MICHAEL E DOHERTY PE Project Engineer
Fluor Daniel GTI Inc 100 River Ridge Drive
Norwood MA 02062
(617)769-7602 Fax(617)769-7785
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
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Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
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Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
41 Pre-Test Activities
On October 191997 the following baseline (pre-test) conditions were measured in the addition well (Pshy21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
In addition the extraction pump at P-21 was turned off and removed from the well All other groundwater extraction pumps remained active
42 Testing Activities
bull The Potassium Permanganate Field Test was performed from October 201997 through November 111997 for a total of 22 days Potassium permanganate was added during 14 of the 22 days the other days being weekends and days the field technician was unavailable
bull A total of 6500 gallons of 350 mgl KMnO4 solution (approximately 20 Ibs of KMnOJ was added to the groundwater over the course of the test
bull An average of 460 gallons per day of potassium permanganate solution was added to P-21 during the test addition days (Monday through Friday)
bull The KMnO4 solution was added to P-21 at approximately 100 to 125 gallons per minute (gpm) this rate was determined to be the maximum addition rate at P-21
43 Post Test On November 141997 two days after stopping the addition of KMnO4 the following post-test conditions were measured in the addition well (P-21) and the surrounding active pumping wells (P-16 P-16a p-20 P-22 P-25)
ORP values in the groundwater bull physical appearance of groundwater bull organic compounds by EPA 8240 bull total metals concentrations in the groundwater
These parameters were also measured two weeks later on December 2 1997
44 Test Quality Control
The following activities were performed periodically throughout the test to ensure that relative and accurate data was being documented during the testing activities
weekly calibration of the ORP probe bull daily mixing of the permanganate solution
50 TEST RESULTS
The test data is attached in the following summary tables and summarized below
Table 1 Daily addition volumes and ORP measurements in the test wells Table 2 Inorganic concentrations in groundwater (preduringpost -test) Table 3 Organic concentrations in groundwater (preduring post -test)
60 OBSERVATIONS
Inorganic Compounds 1 Total iron concentrations in the five pumping wells surrounding the addition well decreased an
average of 54 from pre-test levels
2 Total manganese concentrations in the five pumping wells surrounding the addition well decreased an average of 16 from pre-test levels
3 Total copper concentrations in the five pumping wells surrounding the addition well decreased an average of 69 from pre-test levels
4 A comparison of the immediate post-test and two week after post-test results show no significant rebound in inorganic concentrations in the groundwater
Organic Compounds 5 TCE average pre-test concentration 1674 ugl
largest concentration reduction P-16a (55)
TCE concentrations in the five pumping wells surrounding the addition well decreased an average of 39 immediately after the test completion this dropped to 33 reduction when compared with the two week post-test samples
6 PCE average pre-test concentration 75 ugl largest concentration reduction P-25 (81)
PCE concentrations in the five pumping wells surrounding the addition well decreased an average of 41 immediately after the test completion this dropped to 30 reduction when compared with the two week post-test samples
7 Total DCEs average pre-test concentration 2566 ugl largest concentration reduction P-20 (28)
Total DCEs averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well although two wells (P-16a and P-20) did show approximately 20 decrease in concentrations
8 11 -DCA average pre-test concentration 2798 ugl largest concentration reduction P-16a (19)
11-DCA averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
9 Total xylenes average pre-test concentration 4297 largest concentration reduction P-22 (8)
Total xylenes averaged no significant reductions in the pre- and post-test levels in the five
pumping wells surrounding the addition well
10 Toluene average pre-test concentration 665 largest concentration reduction P-22 (31)
Toluene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
11 Ethyl-benzene average pre-test concentration 650 largest concentration reduction P-20 (0)
Ethyl-benzene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
12 Chlorinated non-conjugated (non-aromatic) double bonded compounds (specifically TCE and PCE) were reduced to a much greater extent than single bonded chlorinated compounds (DCAs) and non-halogenated aromatics (toluene xylenes)
Other observations 13 The rebound in organic concentrations between the immediately post-test and two week after
post-test results indicate that a stronger solution of potassium permanganate may be beneficial for future testing potentially resulting in greater contaminant mass reduction
14 No evidence of inorganic fouling or scaling in the test addition well or surrounding soil matrix were observed The addition rate at P-21 remained constant at 100 to 125 gpm throughout the testing activities
15 Besides the precautionary aspects of handling a strong oxidant no other potential Health and Safety concerns arose during the testing activities Further no Health and Safety concerns are anticipated in future testing activities (with the exception of bulk material handling)
16 Although sufficient the potassium permanganate delivery system utilized during the field test activities was labor intensive future activities would benefit from a more automated KMnO4
delivery system
70 CONCLUSION
The results from the permanganate addition field test show that potassium permanganate does signficantly reduce the concentrations of inorganic and specific organic compounds dissolved in the groundwater beneath the Union Chemical site The field test results support the opinion that a larger application of potassium permanganate addition into the groundwater at the Union Chemical site would be appropriate to better evaluate long term effects and other parameters not evaluated during this field test
From the desk of
MICHAEL E DOHERTY PE Project Engineer
Fluor Daniel GTI Inc 100 River Ridge Drive
Norwood MA 02062
(617)769-7602 Fax(617)769-7785
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
50 TEST RESULTS
The test data is attached in the following summary tables and summarized below
Table 1 Daily addition volumes and ORP measurements in the test wells Table 2 Inorganic concentrations in groundwater (preduringpost -test) Table 3 Organic concentrations in groundwater (preduring post -test)
60 OBSERVATIONS
Inorganic Compounds 1 Total iron concentrations in the five pumping wells surrounding the addition well decreased an
average of 54 from pre-test levels
2 Total manganese concentrations in the five pumping wells surrounding the addition well decreased an average of 16 from pre-test levels
3 Total copper concentrations in the five pumping wells surrounding the addition well decreased an average of 69 from pre-test levels
4 A comparison of the immediate post-test and two week after post-test results show no significant rebound in inorganic concentrations in the groundwater
Organic Compounds 5 TCE average pre-test concentration 1674 ugl
largest concentration reduction P-16a (55)
TCE concentrations in the five pumping wells surrounding the addition well decreased an average of 39 immediately after the test completion this dropped to 33 reduction when compared with the two week post-test samples
6 PCE average pre-test concentration 75 ugl largest concentration reduction P-25 (81)
PCE concentrations in the five pumping wells surrounding the addition well decreased an average of 41 immediately after the test completion this dropped to 30 reduction when compared with the two week post-test samples
7 Total DCEs average pre-test concentration 2566 ugl largest concentration reduction P-20 (28)
Total DCEs averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well although two wells (P-16a and P-20) did show approximately 20 decrease in concentrations
8 11 -DCA average pre-test concentration 2798 ugl largest concentration reduction P-16a (19)
11-DCA averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
9 Total xylenes average pre-test concentration 4297 largest concentration reduction P-22 (8)
Total xylenes averaged no significant reductions in the pre- and post-test levels in the five
pumping wells surrounding the addition well
10 Toluene average pre-test concentration 665 largest concentration reduction P-22 (31)
Toluene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
11 Ethyl-benzene average pre-test concentration 650 largest concentration reduction P-20 (0)
Ethyl-benzene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
12 Chlorinated non-conjugated (non-aromatic) double bonded compounds (specifically TCE and PCE) were reduced to a much greater extent than single bonded chlorinated compounds (DCAs) and non-halogenated aromatics (toluene xylenes)
Other observations 13 The rebound in organic concentrations between the immediately post-test and two week after
post-test results indicate that a stronger solution of potassium permanganate may be beneficial for future testing potentially resulting in greater contaminant mass reduction
14 No evidence of inorganic fouling or scaling in the test addition well or surrounding soil matrix were observed The addition rate at P-21 remained constant at 100 to 125 gpm throughout the testing activities
15 Besides the precautionary aspects of handling a strong oxidant no other potential Health and Safety concerns arose during the testing activities Further no Health and Safety concerns are anticipated in future testing activities (with the exception of bulk material handling)
16 Although sufficient the potassium permanganate delivery system utilized during the field test activities was labor intensive future activities would benefit from a more automated KMnO4
delivery system
70 CONCLUSION
The results from the permanganate addition field test show that potassium permanganate does signficantly reduce the concentrations of inorganic and specific organic compounds dissolved in the groundwater beneath the Union Chemical site The field test results support the opinion that a larger application of potassium permanganate addition into the groundwater at the Union Chemical site would be appropriate to better evaluate long term effects and other parameters not evaluated during this field test
From the desk of
MICHAEL E DOHERTY PE Project Engineer
Fluor Daniel GTI Inc 100 River Ridge Drive
Norwood MA 02062
(617)769-7602 Fax(617)769-7785
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
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Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
pumping wells surrounding the addition well
10 Toluene average pre-test concentration 665 largest concentration reduction P-22 (31)
Toluene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
11 Ethyl-benzene average pre-test concentration 650 largest concentration reduction P-20 (0)
Ethyl-benzene averaged no significant reductions in the pre- and post-test levels in the five pumping wells surrounding the addition well
12 Chlorinated non-conjugated (non-aromatic) double bonded compounds (specifically TCE and PCE) were reduced to a much greater extent than single bonded chlorinated compounds (DCAs) and non-halogenated aromatics (toluene xylenes)
Other observations 13 The rebound in organic concentrations between the immediately post-test and two week after
post-test results indicate that a stronger solution of potassium permanganate may be beneficial for future testing potentially resulting in greater contaminant mass reduction
14 No evidence of inorganic fouling or scaling in the test addition well or surrounding soil matrix were observed The addition rate at P-21 remained constant at 100 to 125 gpm throughout the testing activities
15 Besides the precautionary aspects of handling a strong oxidant no other potential Health and Safety concerns arose during the testing activities Further no Health and Safety concerns are anticipated in future testing activities (with the exception of bulk material handling)
16 Although sufficient the potassium permanganate delivery system utilized during the field test activities was labor intensive future activities would benefit from a more automated KMnO4
delivery system
70 CONCLUSION
The results from the permanganate addition field test show that potassium permanganate does signficantly reduce the concentrations of inorganic and specific organic compounds dissolved in the groundwater beneath the Union Chemical site The field test results support the opinion that a larger application of potassium permanganate addition into the groundwater at the Union Chemical site would be appropriate to better evaluate long term effects and other parameters not evaluated during this field test
From the desk of
MICHAEL E DOHERTY PE Project Engineer
Fluor Daniel GTI Inc 100 River Ridge Drive
Norwood MA 02062
(617)769-7602 Fax(617)769-7785
Original includes coW coding
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
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Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
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TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
TABLE 2
POTASSIUM PERMANGANATE ADDITION FIELD TEST SUMMARY OF TOTAL INORGANIC CONCENTRATION DATA UNION CHEMICAL SITE
120897 CONCENTRATION (mgl)
P-21 P-16a P-20 P-22 P-25
IRON 102097 (pre-test)-A 102 616 42 242 62 278 111497 (post-test)-B 403 315 28 169 162 101
mdash120297 (post-test)-C 0727 32 0964 527 0407 Reduction - AB mdash 49 33 30 97 64 Reduction - AC mdash 24 60 92 85 mdash
- MANGANESE 102097 (pre-test)-A 0295 137 0422 0198 0298 0097 111497 (post-test)-B 216 0873 069 0178 0164 0092 120297 (post-test)-C 8 mdash 052 0126 0251 0063 Reduction -AB mdash 36 -64 10 45 5 Reduction - AC mdash -23 36 16 35 mdash
COPPER 102097 (pre-test)-A 00308 00354 0454 00356 0161 0236 111497 (post-test)-B 044 00162 00188 00145 00031 00105
mdash120297 (post-test) -C 0166 0177 0031 00216 00777 Reduction -AB 54 96 59 98 96 mdash
Reduction -AC mdash 61 13 87 67 mdash
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
TABLE 3
POTASSIUM PERMANGANATE ADDITION FIELD TEST ANALYTICAL LABORATORY DATA SUMMARY UNION CHEMICAL SITE
120897 ANALYTICAL LAB DATA - (ugl)
ADDITION TEST MONITORING WELLS WELL
P-21 tlfi P-16a P=2Q
TCE 102097 (pre-test)-A 16 1100 1700 370 111497 (post-test)- 319 549 547 300 120397 (post-test)- 3500 620 770 290 Reduction - AB mdash 50 68 19 Reduction -AC mdash 44 55 22
PCE 102097 (pre-test) -A BDL 84 70 8 111497 (post-test)-B 44 64 31 3 120397 (post-test) - 430 44 63 8 Reduction bull AB mdash 24 56 63 _ Reduction -AC 48 10 0
TOLUENE 102097 (pre-test)-A 10 470 1100 7 111497 (post-test)-B TBD 403 600 4 120397 (post-test) - 1800 670 870 10 Reduction - AB mdash 14 45 43 Reduction - AC mdash -43 21 -43
E-BENZENE 102097 (pre-test) -A BDL 170 1400 17 111497 (post-test)-B 167 383 264 4 120397 (post-test) - 1400 310 1500 17 Reduction - AB bull125 81 76 mdash Reduction - AC mdash -82 -7 0
XYLENE 102097 (pre-test)-A BDL 500 8100 55 111497 (post-test)-B 1042 1160 984 12 120397 (post-test)- 14000 1130 9100 153 Reduction - AB mdash bull132 88 78 Reduction -AC mdash -126 -12 -178
11DCA 102097 (pre-test)-A BDL 1500 4200 190 111497 (post-test)-B 620 1500 2300 190 120397 (post-test)- 5700 1900 3400 200 Reduction - AB mdash 0 45 0 Reduction -AC mdash -27 19 -5
DCEs 102097 (pre-test)-A 6 500 5290 2131 111497 (post-test)-B 325 1160 2390 1792 120397 (post-test) - 1330 1780 4440 1526 Reduction - AB mdash -132 55 f6 Reduction -AC mdash -256 16 28
P-22
3900 3300 4000 15 -3
180 170 160 6
11
1600 1600 1100
0 31
1300 1200 1500
8 -15
8000 9200 7400 -15
8
6300 6600 5800 -5 8
2430 2460 2500 -1 -3
P-25
1300 742 680
43 48
32 13 6
59 81
150 BDL 190
-27
360 500 480
-39 -33
2030 2570 2660 -27 -31
1800 2000 1900 -11 -6
2480 2360 2060
5 17
notes test was performed from 102097 -111297 BDL = below detection limit
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
FIELD IMPLEMENTATION PLAN FOR THE POTASSIUM PERMANGANATE TEST UNION CHEMICAL SITE
October 21997
Note this plan describes how things should actually be done in the field for the bigger picture ff bull the formal Kmno4 work plan should be used to support this document
1 INTRODUCTION
11 Overview The pilot test will add KMnO4 to a central extraction (pumping) well P21 and determine the oxidation and fixation effects on metals in the groundwater at that well and the surrounding extraction wells P16 P16A PP20 P22 and P25 Pre- and post-test groundwater samples will be taken from the wells and analyzed for metals concentrations KMnO4 solution will be added to the central well until it is detected by observation in the surrounding P wells Water samples will be taken from the surrounding P wells at set frequencies
When KMnO4 is visually detected at the surrounding wells water will be added to the central well to flush the KMnO4 through the soil
12 Equipment List
PPE - Level D equipment plus face shield goggles chem resist gloves apron and boots 55 gallon drum drum mixer glass sample jars and graduated cylinders Reid filtering equipment -bull Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe Solinst water level tape Chemical pump and hose for use with KMnO4 solution Tarp Hose for clean non-potable water
13 Staffing
Pilot test set up pre-test pumping pump removal and initial KMnO4 addition will be performed by
Mark Courtenay Jason Coxall Tim Pac
Initial sampling monitoring during the pilot test and post test sampling will be performed by
Mark Courtenay Carolyn McMahon
KMnO4 level maintenance in the well and water level maintenance for flushing will be performed by
Mark Courtenay Carolyn McMahon
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
2 PRE-TEST
21 Pre-Test Sampling - Measurement of baseline subsurface conditions
Determine which surrounding monitoring wells are suitable for collecting groundwater samples during the pilot test with all P wells pumping Measure total and dissolved iron and manganese in all test P wells and selected monitoring wells Collect groundwater samples from each surrounding P well P21 P16 P16A PP20 P22 and P25 and selected monitoring wells
Document initial colorings of each wells water Measure oxidationreduction potential with ORP probe Determine preliminary concentration determinations with Hach kits Submit to the lab for standard metals analysis (full suite) Document all data on standardized data forms
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe glass sample jars and graduated cylinders
22 Well Preparation
Pump all water from P21 by manually operating the pump Shut off air to the pump and close all valves on the air and discharge piping Remove the pump and all hoses from the well Remove all pump related hose accessories and pipe possible from the well box Setup 55 gallon drum on secure base adjacent to well box with drum mixer chemical pump water hose tarp for coverage and chemical hazard signage Install warning tape around P21 and the pilot test chemical storage area Install hose from chemical drum pump to near bottom of well
23 Preparation of the 360 mgl KmnO4 solution at the well head
Take 114 liters of saturated Kmno4 solution (from WTP) Add to and mix thoroughly with approximately 50 gallons of treated water to make a 360 mgl KmnO4 solution
Equipment needed 55 gallon drum drum mixer collection of 1 liter graduated cylinders and other lab bottles
3 INITIATE TEST
31 Charge Test Well with KmnO4 Solution
Slowly pump or drain KmnO4 solution into test well periodically stopping to gauge solution level in the well CAUTION Be aware that KMnO4 solution may react with slimes in the well casing causing foaming or other reaction Continue until the solution level in the well is approximately 5 feet from top of casing Monitor well level every 15 -30 minutes to evaluate drop rate of the solution in the well until the rate stabilizes and the well will not go dry overnight
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
32 Maintain the KmnO4 solution level in the test well
Based on the initial drop rate determine appropriate operating levels for the solution level (ie 5 - 10 ft from TOC or 5 - 20 feet from TOG) depending on the rate of refill Rule of thumb = refill every 2 -3 days gets you through weekends without refilling the well Maintain well full with KMnO4 until ij reaches a surrounding P well
Equipment needed 50 gallon drum drum mixer Chemical pump and hose for use with KMnO4 solution Solinst water level tape
40 Monitor Surrounding Monitoring and Extraction (P) Wells
41 Grab samples from all surrounding P wells P21 P16 P16A PP20 P22 and P25 Sample at discharge piping sample port Document color andor visible turbidity Measure oxidationreduction potential Do not retain samples Document all data on standardized data forms
Equipment needed collection of 1 liter graduated cylinders Hach Iron and Manganese testing kits and solutions Water Quality meter - ORP probe
42 Monitoring Schedule
The above monitoring should follow the below schedule (or maybe you could use the one in the formal work plan)
First day of test set up and initiate test sample at least 2 times 2nd day sample once 3rd day no sampling 4th day sample once 5th day no sampling 6th day sample once remainder of test at least once per day until color shows at an extraction P well
Note this sampling schedule should be reviewed after the first few days of testing and based upon the initial results modified accordingly
50 Measurement of post test subsurface conditions
51 Initial post-test monitoring
Following determination that KMnO4 has reached an extraction P well remove KMnO4 and related equipment necessary to keep P21 full of KMnO4 solution and fill well with water Maintain well full of water by dripping or refills at the same interval as KMnO4 addition
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
1 Grab a sample from all Test P wells P16 P16A PP20 P22 and P25 and document initial colorings of each wells water
2 Measure oxidationreduction potential in all test wells 3 Continue to measure oxidationreduction potential and observe color in all test wells until it is determined that all KMnO4 has been used
Equipment needed collection of 1 liter graduated cylinders Water Quality meter - ORP probe
52 Final post-test monitoring
Following determination that KMnO4 has been used sample at extraction P wells P16 P16A PP20 P21 P22 and P25 for EPA Method 8240 metals analysis for manganese and iron in particular
Equipment needed Field filtering equipment Hach Iron and Manganese testing kits and solutions glass sample jars
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
__t
r r
July 291997
DRAFT Mr Randy Smith American Environmental Consultants PO Box 310 Mont Vernon New Hampshire 03057
RE Union Chemical Site Pilot Test Proposal Metals Fixation in the Subsurface
Dear Randy
This is written as a follow up to our discussion of Thursday July 241997 regarding a method for reducing the influent concentrations of manganese from the groundwater at the Union Chemical groundwater treatment facilfty by fixing it in the soil Recent data reported by Fluor Daniel GTl Inc (Fluor Daniel GTl) on the groundwater treatment process and additional operator testing within the process train indicates that manganese in the discharge to Quiggle Brook has on occasion exceeded the surface water discharge criteria set by MEDEP This is information ascertained subsequent to several months of successful manganese management which followed installation of the metals removal system and greensand filters
Fluor Daniel GTl proposes to perform a pilot test to evaluate the potential of metal ion fixation in the aquifer This pilot test would involve treatment of the groundwater insitu to evaluate of metal ion concentrations can be reduced to levels that can be further reduced effectively by the treatment plant The insitu reduction would be done on a limited pilot test basis using a standard water treatment chemical potassium permanganate (KMNOJ We feel that if iron and manganses can be reduced in the groundwater being pumped the metals removal portion of the treatment plan systems may operate more reliably
We request that the Agencies evaluate this proposal and provide comments or acceptance as soon as possible
Background
Ruor Daniel GTl has been involved in the development of insitu treatment process for the treatment of groundwater In recent years we have conducted numerous projects involving the fixation of metal ions in soil This fixation process leaves the metal ions in an insoluble form within the soil matrix In this way the
groundwater is substantially improved and the presence of the target metal ions are eliminated or greatly reduced This is very similar to the metal ion removal processes that are used in water treatment plants for removal of manganses and other metal ions
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
Mr Randy Smith American Environmental Consultant Mont Vcmon NH 03057 Page 2 Union Chemical Site Pflot Test Proposal Metals Fixation in the Subsurface July 291997
In this proposal pilot test KMNO4 would be used to precipitate the manganese iron Potassium permanganate as an oxidizer is essentially completely used up by the metals with which it comes in contact in solution After addition of a controlled permanganate solution into the groundwater it would be essentially totally removed through the oxidation process The pilot test would allow us to test this process in a small area of the site to obtain information as to the effectiveness of applying this process to the areas of high metal concentrations The proposed pilot test is relatively simple and could be performed in a manner to assure that the permanganate would be isolated to a small area within the treatment area of the site
Pilot Test Procedure
There are 28 groundwater extraction (P) wells operating on the site Groundwater extraction wells in the central portion of the site are surrounded by other groundwater extraction wells Small concentrations of potassium permanganate in water give the water a distinctive purple coloration making possible determination of permanganate in through a visual test The pilot test would use a single central P well as an insertion point The surrounding groundwater extraction wells which are at known distances would be monitored to determine when the permanganate solution reaches them This would indicate the time required for the permanganate cross the known distances The surrounding pumping wells would also prevent the flow of permanganate beyond the test area
Pre-test and post-test metate analyses would allow Ruor Daniel GTI to determine the potential level of metals oxidation taking place in the subsurface Metals analysis of the groundwater in the central well in particular would indicate the potential reduction in manganese that could be seen by the groundwater treatment process from site-wide permanganate treatment
The proposed pilot test would include well selection pre-test metals analyses addition of permanganate in a central P well mentoring the discharge of the surrounding P wells to determine when permanganate reaches the wells post test metals analyses and preparation of a report It would proceed as follows upon acceptance by the Agencies
1 Selection of the central P well and surrounding P wells to be used We anticipate the use of P-21 as the central well as it is in dose proximity to the surrounding P wells
2 Verification of the known distances between the wells
3 Verification of the pump operation in the surrounding wells to reduce the possibility of a pump failure Note pump operation since QEDs on-site testing and replacement has almost eliminated this concern
4 Label the wells for monitoring
p_iinicflemvhmixgt4pilar
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
bullM-~
Mr Randy Smith American Environmental Consultant Mont Vemon NH 03057 Page 3 Union Chemical Site PBot Test Proposal Metals Fixation In the Subsurface July 29 1997
5 Sample groundwater from each of the selected P wells for metals analysis
6 Remove the pump and hoses from the central P well
7 Addition of an predetermined (approx 80 mgI) permanganate solution into the central P well Sufficient volume will be placed in the well to bring the solution surface to grade and provide a fluid surface gradient between the central and surrounding wells
8 Monitor and maintain the permanganate solution level in the central P well until breakthrough (purple permanganate shows up in pumping well water samples) is achieved in at least half of the surrounding P wells
9 Visually monitor the groundwater pumped from the selected surrounding P wells twice per day after the first 24 hours until breakthrough is achieved in the first of the surrounding P wells
10 Continue monitoring and estimate permanganate concentration using colorimetric testing
11 After breakthrough fill the central P well with treated groundwater maintain water level in the well and continue monitoring the surrounding P wells until permanganate levels exhibit a downward trend in the surrounding P wells
12 Re-install pumping equipment in central P well and pump from all wells daily with permanganate monitoring until colorimeteric test indicate all permanganate has been removed or used
13 Sample all P wells involved in the pilot test and perform metals analysts for manganese
14 Waft two weeks and repeat sampling and analyses
15 Prepare written report on the pflot test
Summary
The pilot test as proposed would
1 allow us to evaluate if manganese fixation is a viable process addition which would allow us to meet the MEDEP surface water discharge criteria
2 be a controlled and easily observable process
3 leave nothing in the ground or groundwater but inert materials and
4 have no impact on the surrounding area
SL
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
Mr Randy Smith American Environmental Consultant Mont Vetnon NH 03057 Page 4 Union Chemical Sfte Pilot Test Proposal Metals Fixation in the Subsurface July 291997
We believe this could be a valuable test and provide the data necessary to develop a means to meet the MEDEP discharge criteria for this site If you or the Agencies have any questions on the proposed pilot test we would be glad to provide answers We would like to move forward with the pilot test as soon as possible and would appreciate any efforts that would yield a timely and favorable response from the Agencies
Sincerely Fluor Daniel GT1 Inc
Paul Farrington PJL Project Manager
cc R Lewis T Pac M Doherty T Nunno T Connelly EPA R Hewett MEDEP
p_unictieintoiiio4pijr
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
Union Chem Memo FLUOR DANIEL GTI
To Paul Farrington cc Rick Lewis Tim Pac file
From Michael Doherty Pages 3 Date July 221997
Subject Potassium Permanganate Jar Test
Paul
This memo summarizes the procedures results and observations from the Potassium Permanganate (KMnO4) jar test performed at the Union Chemical site this past spring The testing was performed on 41897 with follow up work on 5897 A site map and laboratory analysis reports are attached to this memo
OBJECTIVE
The objective of the test was to provide a preliminary evaluation of the effectiveness of using potassium permanganate to oxidize dissolved organics in the groundwater at the Union Chemical site
PROCEDURES
Preparation of the KMnO4 solution
All KMnO4 jar test solutions were prepared from the stock potassium permanganate solution used in the metals removal treatment process at the Union Chem WTP The stock permanganate solution is prepared to approximately a 20000 mgl concentration (saturated solution) All of the jar test KMnO4 solutions were diluted using
Cone x Volume = Cone 2 x Volume 2
where Cone = known concentration of solution 1 - Volume = known volume of solution 1^^ Conc2 = target concentration of solution 2 Volume 2 = unknown volume of concentration 2
Preparation of the Jar Test solutions
1 A sample of groundwater was grabbed from P-27 located immediately off of and east of the cap (refer to attached map)
2 The groundwater samples were divided into separate glass beakers and prepared as outlined
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
a control solution no KMnO4 solution was added to this sample designated as P-27-0
b residual permanganate solution 05 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 05 mgl KMnO4 solution designated as P-27-12
c moderate permanganate solution 5 mis of a 200 mgl KMnO4 solution was added to 200 mis of groundwater to make a 5 mgl KMnO4 solution designated as P-27-5
d strong permanganate solution 2 mis of a 20000 mgl KMnO4 solution was added to 500 mis of groundwater to make a 80 mgl KMnO4 solution designated as P-27-60
Please note A b and c above were sampled and prepared on 4189 Upon reviewing these results it was not dear if the oxidization reactions had gone to completion or were limited by the amount of KMnO4 added to the samples Therefore it was decided to sample P-27-80 which was done on 5897 and analyze for manganese and potassium as well to better evaluate if the oxidation reactions had been complete
3 All samples were mixed well and let stand open to atmosphere for hour prior to being packaged and sent to the lab for analysis Although loss of VOCs during mixingpreparing the samples probably occurred the loss should of been consistent across all samples since the procedures were identical
RESULTS
Concentrations and Percent Reduction Summary Table
Compound P-27-0 P-27-05 bullbull
s
127-5 P-27-80 ~ Cone (mgl Cone
(mgl) x j Reduction Cone rogJ Reduction (mgI) ^ ^Reduction j -shy bullbulllaquomdashlaquo
11 DCE 1200 860 283 910 242 lt130 100
11 DCA 5200 4600 115 4400 154 5000 38
cis12DCE 8700 7500 138 7100 184 lt1300 100
111 TCA 1900 1700 105 1600 158 880 537
TCE 2500 2100 160 2000 200 lt130 100
Toluene 1900 1600 158 15000 211 1600 158
ethylbenzene 4100 3400 171 3100 244 4100 00
tot xylenes 20100 20500 00 17200 144 18600 75
Notes P-27-0 = unaltered groundwater sample used as control P-27-05 = 05 mgl KMnO4 solution light rose in color P-27-5 = 5 mgl KMnO4 solution purple color P-27-80 = 80 mgl KMnO4 solution dark purple color 1 = reduction calculated as (P-27-0) - (P-27-V(P-27-0) 2 = estimated values comparing 5897 and 41897 data actual reduction is probably +- 25 of value shown
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond
P-27-12 and P-27-5 showed average reductions oft
20 for the chlorinated non-conjugated double bonds (11 DCE C12DCE TCE) 10-15 for single bonded chlorinated compounds (DCA TCA) 15-20 for toluene and ethylbenzene
bull 0-15forxylenes
P-27-80 showed average reductions of bull gt90 reduction in chlorinated non-conjugated double bonds (11 DCE c-12 DCE and TCE)
50 reduction in 111 TCA bull app 15 reduction in toluene
app 10-20 reduction in xylenes
approximately 20 mgl of excess KMnO4 remained in the P-27-80 sample Suggesting that the oxidation reactions had not been limited by KMnO4 concentration (as was more likely the case for the P-27-05 and P-27-5 samples) and that the oxidation reactions had probably advanced as far as would be of benefit
bull the P-27-80 was also analyzed for DMF and MEK DMF concentrations were measured at 85 mgl and MEK concentrations were measured at 1300 mgl (the other samples were not analyzed for these compounds)
OBSERVATIONS
bull chlorinated non-conjugated (non-aromatic) double bonded compounds such as TCE 11 DCE and cis 12 DCE were reduced to a much greater extent than the single bonded chlorinated (11 DCA and 111TCA) and the aromatic compounds (TEX)
The lower percent reductions in samples P-27-05 and P-27-5 for TCE and DCE were probably the result of insufficient concentrations of potassium permanganate in the groundwater sample
Removal of TCE and DCE to below the detection limit in P-27-80 and the presence of potassium permanganate in the sample at the time of analysis suggests that the more readily oxidized compounds (chlorinated non-conjugated double bonds) oxidize completely when not limited by KMnO4 levels (as was probably the case for P-27-05 and P-27-5)
RECOMMENDATIONS FOR FUTURE WORK
bull The results from this test should be compared against the groundwater closure plan to ensure that compounds which be reduced the most by the addition of KMnO4 would also be the more critical target compounds in reaching the site closure requirements
if practical an in-situ pushpull or other type of permanganate injection test should be performed at the site to measure the oxidation results during in-situ application to better evaluate the effects of organics in the soil matrix mobility reaction times etc
review the feasibilitycost benefit of this technology against other conventional and non conventional approaches A paper discussing one non-conventional (using poplar trees to reduce dissolved TCE concentrations) is attached
mdashjnwno ond