DISCLAIMER

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsi- bility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Refer- ence herein to any specific commercial product, process. or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recom- mendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

PNL- 10595 UC-606

WASTE TANK VAPOR PROGRAM

Vapor Space Characterization of Waste Tank 241-T-107: Results from Samples Collected on 1/18/95

K. H. Pool R. B. Lucke B. D. McVeety G. S. Klinger 'T. W. Clauss M. W. Ligotke K. B. Olsen 0. P. Bredt J. S. Fruchter S. C. Goheen

June 1995

Prepared for Westinghouse Hanford Company under a Related Services Agreement with the U.S. Department of Energy Contract DE-ACO6-76RLO 1830

Pacific Northwest Laboratory Richland, Washington 99352

DISTRIBUTION OF, THIS DOCUMENT- IS UNLIMITED . LJ

MASTER

DISCLAIMER

Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

Summary

This report describes inorganic and organic analyses results from samples obtained from the headspace of the Hanford waste storage Tank 241-T-107 (referred to as Tank T-107). The results described here were obtained to support safety and toxicological evaluations. A summary of the results for inorganic and organic analytes is listed in Table 1. Detailed descriptions of the results appear in the text.

Quantitative results were obtained for the inorganic compounds ammonia (NH,), nitrogen dioxide (NOJ, nitric oxide (NO), and water (H20). Sampling for hydrogen cyanide (HCN) and sulfur oxides (SO3 was not requested. In addition, quantitative results were obtained for the 39 TO-14 compounds plus an additional 14 analytes. Of these, 1 was observed above the 5-ppbv reporting cutoff. Six organic tentatively identified compounds (TICS) were observed above &e reporting cutoff of (ca.) 10 ppbv and are reported with concentrations that are semiquantitative estimates based on internal-standard response factors. The estimated concentration of all 7 organic analytes observed in the tank headspace are listed in Table 1 and account for approximately 100% of the total organic components in Tank T-107. Two permanent gases, carbon dioxide (COJ and nitrous oxide (N,O), were also detected in the tank-headspace samples.

Table 1. Summary Results of Inorganic and Organic Samples Collected from the Headspace of Tank T-107 on 1/18/95

Category

Inorganic

Organic

Permanent Gas

Analvte

N H 3 NO2 NO H20

Acetone Methyl Alcohol Propane

1-Butanone Acetonitrile Ethanol

I-Butano!

Vapor"' Concentration

125 f 2 I 0 . 0 3 5 0.05

13.4 f 0.2

2.41 1.11 0.A 0.09 0.20 0.20 0.12

80.7 41.5

Units

PPmv PPmv PPmv m a

mg/m3 mg/m3 mg/m3 mg/m3 mg/m3 mg/m3 mg/m3

(a) Vapor concentrations were determined using sample-volume data provided by Westinghouse Hanford Company and are based on averaged data.

iii

Acknowledgments

The authors gratefully acknowledge the support of other project staff at Pacific Northwest Laboratory who contributed to the successful completion of this sampling and analysis activity. Jeff Edwards served as the PNL single-point-of-contact and coordinated sample handling and comunications with Westinghouse Hanford Company. Sally Slate, May-Lin Thomas, and Karen Schielke analyzed inorganic samples, and Gary Dennis prepared the solid-sorbent sample trains. Brenda M. Thornton provided word processing support.

V

Abbreviations

CAS COC

DIW emf EPA GCIMS GC/TCD HP IC IL IS MDL NIST OSHA PFA PNL PPbV PPmv QA REL RPD SCIC SIE SRM STP TEA TIC vss WHC

C"

Chemical Abstracts Service chain of custody concentration by volume deionized water electromotive force U.S. Environmental Protection Agency gas chromatography/mass spectrometry gas chromatography/thermal conductivity detection Hewlett Packard ion chromatography impact level internal standard minimum detection limit National Institute for Standards and Technology Occupational Safety and Health Administration perfluoroalkoxy Pacific Northwest Laboratory part per billion by volume part per million by volume quality assurance recommended exposure limit relative percent difference suppressed-conductivity ion chromatography selective ion electrode standard reference material standard temperature and pressure triethanolamine tentatively identified compound vapor sampling system Westinghouse Hanford Company

vii

.......... ... >-& . ~- . ... . . . . . . . . . . . . -~.iiiij. _ _ ..-. . . . . . ..,. . . -~

Contents

Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments v

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Abbreviations vii

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . 0 Introduction 1

2.0Inorganic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 2.1 Standard Sampling Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2 Analytical Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.3 Quality Assurance/Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Inorganic Sample Results 9

3.OOrganic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 SUMMAm Canister Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Sample Analysis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Quality Assurance/Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Analysis Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.0 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.OReferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.OFurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13 13 13 14 16

19

19

21

Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dist . 1

ix

Tables

2.1

2.2

2.3

3.1

3.2

3.3

3.4

3.5

3.6

Analysis Procedures and Typical Detection Limits of Target Inorganic Analytes . . . . . . . . 8

List of PNL Inorganic Samples, Controls, and Gravimetric Results Obtained from a Heated Tube Inserted into the Headspace of Tank T-107 on 1/18/95 . . . . . . . . . 10

Inorganic Vapor Sample Results Obtained from a Heated Tube Inserted into the Headspace of Tank T-107 on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Positively Identified and Quanitated Target Analytes of Samples Collected from the Headspace of Tank T-107 in SUMMA" Canisters on 1/18/95 . . . . . . . . . . . . 22

Tentatively Identified Compounds and Estimated Concentrations of Samples from the Headspace of Tank T-107 in SUhfMAm Canisters Collected on 1/18/95 . . . . . . 24

Positively Identified and Quantitated Target Analytes of Replicate Analyses of a Single SUMMA" Canister Collected from the Headspace of Tank T-107 on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

Tentatively Identified Compounds and Estimated Concentrations of Replicate Analyses of a Single SUMMAM Canister Collected from the Headspace of Tank T-107 on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

Tentatively Identified Compounds and Estimated. Concentrations for Ambient Air and Ambient Air Sampled Through VSS Collected Near Tank T-107 in SUMMA" Canisters on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

Permanent Gas Analysis Results for Samples Collected from the Headspace of Tank T-107 and for Ambient Air and Air Through the VSS Collected near Tank T-107 in SUMMA" Canisters on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

Figures

1.1 Chain-of-Custody for Tank T-107 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3.1 Total Ion Chromatogram for Hanford Waste Tank T-107 SUMMAM Canister Sample S5-001-AO8.012 Collected on 1/18/95 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

X

1.0 Introduction This report describes results of the analyses of tank-headspace samples taken from the

Hanford waste Tank 241-T-107 (referred to as Tank T-107). Pacific Northwest Laboratory (pNL)(a) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and to analyze inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The organic analytes for TO-14 compounds were extended to include 14 analytes identified by the Toxicological Review Panel for Tank C-103 and reported by Mahlum et al. (1994). Program management included these analytes for future tank analyses as identified in the fiscal year work plan. This plan is attached to a letter dated 9/30/94 and addressed to Mr. T. J. Kelly of WHC. The plan also requires PNL to analyze for selected permanent gases. The sample job was designated S5001, and samples were collected by WHC on Janu-ary 18, 1995, using the vapor sampling system ( V S S ) .

Sampling devices, including six sorbent trains (for inorganic analyses), and six SUMMA" canisters (for organic analyses) were supplied to the WHC sampling staff on January 12. Samples were taken (by WHC) from the tank headspace on January 18 and were returned to PNL from the field on February 15. Inorganic (sorbent trap) samples were delivered to PNL on chain of custody (COC) 008093 (see Figure 1.la). The SUMMAm canisters were delivered on COC 008092 (see Figure 1.lb).

The samples were inspected upon delivery to the 326/23B laboratory and logged into PNL record book 55408 as described in PNL Technical Procedure PNL-Tvp-07'b). Custody of the sorbent traps was transferred to PNL personnel performing the inorganic analysis and stored at refrigerated (I 10°C) temperature until the time of analysis. The canister was stored in the 326/23B laboratory at ambient (25°C) temperature until time of analysis. Access to the 326/23B laboratory is limited to PNL personnel working on the waste-tank safety program. Analyses described in this report were performed at PNL in the 300 area of the Hanford Reservation. Analytical methods that were used are described in the text. In summary, sorbent traps for inorganic analyses containing sample materials were either weighed (for water analysis) or weighed and desorbed with the appropriate aqueous solutions (for ammonia, nitrogen dioxide, and nitric oxide analyses). The aqueous extracts were analyzed by either selective electrode or ion chromatography (IC). Organic analyses were performed using cryogenic preconcentration followed by gas chromatography/mass spectrometry (GCMS). . Permanent gas analysis was performed using gas chromatography/thermal conductivity detection (GC/TCD).

.

(a)

(b)

Pacific Northwest Laboratory is operated for the U. S. Deparqnent of Energy by Battelle Memorial Institute under Contract DE-AC06-76RLO 1830. PNLTVP-07, Rev. 0, October 1994, Sample Shipping and Receiving Procedure for PNL Waste Tank Samples, PNL Technical Procedure, Tank Vapor Project, Richland, Washington.

1

. .

Westing h o us e Hanford Company

Ccstody Form Initiator J. A. EdwardS-PNL

CHAIN OF CUSTODY JVHC OOS093

C o n ~ z n y Contact R. D. Mahon-WHC

Project DesignationlSamplin,o Locations 241-T-107 Tank . Vapor Sample SAF SS-001

Ice Chest No.

200 West Tank Farm

(VSS Truck)

Bill of LzidingIAi~bill No. N I A

Method of Shipment Government Truck

Telephone (509) 373-0141 Page E53009 / FAX 376-0418 .

Telephone (509) 373-7437 Page 85-9656 I FAX 373-7076

Collection date 01 -g- 95 Preparation d3te 0: - 10 - 95 Field Logbook No. WHC- &7- L/

Offsite P:openy No. N/A .

Shipped to PNL

Possible Sample HazardslRemarks Unknown 3t time of sampling

Samole Identificztion

S5-001 - A26 . V45' S5-001 - A27 . V 4 6 ~ S5-001 - A28 . V47. S5-001 - A29 . V48' S5-001 - A30 . V49b S5-001 - AS1 . V50;

S5-001 - A32 . V51 S5-001 - A33 . V 5 2 ~ S5-001 - A34 . V53-.

NH3/NOx/H20 (Trap $ 1) Line :: 9 NH3/NOx/H20 (Trap $ 2) Line $10 NH3/NOx/H20 (Trap % 3) Line :: 8 NH3/NOx/H20 (Trap :: 4) Line 210 NH3/NOx/H20 (Trap rr" 5) Line +? 9 . NH3/NOx/H20 (Trap g 6) Line $10

NH3/NOx/H20 & (Trap Trip Blanke 1) NH3/NOx/Hi0 4 (Trap Trip Bankg 2) NHg/NOx/H2O&(Trap Trip Blank5 3)

ia-SS

I

Final Sample Disposition Comments:

. . .. . .. * ~ . . -;:::: , ..: I-, !%;

Figure l . la Chain-of-Custody for Inorganic Samples

2

Westinghouse Hanford Company

Cusiody Form Inilialor J. A. Edwards-PNL

CIIAIN OF CUSTODY . WIIC 008092

Company Contact R. D. Mahon-WHC

Project DesignationlSampling Locations 200 West Tank Farm 241-T-107 Tank

Ice chest Nn.

Vapor Sample SAF S5-001 (VSS Truck)

Tclcphonc (509) 373-0141 Page 85-3009 I FAX 376-0418

Telephone (509) 373-7437 Page 85-9656 I FAX 373-7076

Collection date 01 -,& 95 Preparation date 01 - 10 - 95

Field Logbook No. WHC-&-dB-L/

Dill of LadingIAirbill No. N I A OlTsitc Property No. N I A

Mcthod of Sliipmcnt Government Truck

Ship@ to PNL

Possible Sample 1lazard.dRernarks Unknown at time, of sampling

Samplc Jdcntification

S5-001 - A01 .002” Ambient Air SUMMA #I Upwind T-107

S5-001 - A04 .OO& SUMMA #3 Port 1 1 (store for OGI) S5-001- A05 ,005 SUMMA #4 Port 13 (storc for OGI)

(PNL) . S5-001- A02.006 Ambient Air SUMMA #2 Through Port 15 (PNL)

S5-001 - AOG. OloL SUMMA #5 Port I5 (store for OGI)

S5-001 - A07.011’ SUMMA tG Port 12 (PNL) S5-001 - A08 .012 ’ SUMMA#7 Port 14 (PNL) S5-001 - A09 .021\ SUMMA #8 Port 16 (PNL)

Finn1 Saniple Disposition . Cnmmcnts:

J‘NL fonlv) Chccklisl s2xlmms Mcdia lnhelcd and checked? Lctlcr of instruction? Mcdin in gnod condition? COC infdsignnturcs coiaplcte? I N ImN Sorhents shipped on ice7 -wt) I -m-Pf i Rod rclci~.sc stickers nn simples? I @N Aciivity r c p n from U Z S ? COC copy fnr L R ~ . RIDS filed? COC copy for torhcnl follow-on?

(Rcviscd 1(Yl7/94 PNL)

Figure l . lb Chain-of-Custody for Organic Samples

3

2.0 Inorganic

Solid sorbent traps, prepared in multi-trap sampling trains, were supplied to WHC for sampling the tank headspace using the VSS. Blanks, spiked blanks (when requested), and exposed samples were returned to PNL for analysis. Analyses were performed to provide information on the tank-headspace concentration of the following analytes: ammonia (NH,), nitrogen dioxide (NOJ, nitric oxide (NO), and water (H,O). Procedures were similar to those developed previously during sample jobs performed with the VSS connected to the headspace of Tank C-103 (Ligotke et al. 1994). During those sample jobs, control samples provided validation that samples were effectively trapping NH3 and mass, Sample preparation, handling, and disassembly were performed as described in Technical Procedure PNL-TVP-09(a). Analytical accuracy was estimated based on procedures used. Sample preparation and analyses were performed following PNL quality assurance (QA) impact level (IL) II requirements.

2.1 Standard Sampling Methodology

Standard glass tubes containing sorbent materials to trap vapors of selected analytes of NH,, NO, NO,, and H,O (SKC Inc., Eighty Four, Pennsylvania) were obtained, prepared, and submitted for use by WHC. The sorbent traps were selected based on their use by the Occupational Safety and Health Administration (OSHA) to perform workplace monitoring, and because of available procedures and verification results associated with that particular application. The typical sorbent traps used consisted of a glass tube containing a sorbent material specific to the compound of interest. In general, the tubes contained two sorbent layers, or sections; the first layer was the primary trap, and the second layer provided an indication of breakthrough. In the tubes, sorbent layers are generally held in packed layers separated by glass wool. The sorbent traps, having glass-sealed ends, were received from the vendor.

The type and nominal quantity of sorbent material varied by application. Sorbent traps were selected for the tank sample job and included the following products. The NH3 sorbent traps contained carbon beads impregnated with sulfuric acid; nominally, 500 mg were contained in the primary and 250 mg in the breakthrough sections. The NH3 was chemisorbed as ammonium sulfate {(Ni&)zso4}. The NOz traps contained a zeolite impregnated with triethanolamine (TEA), with 400 mg in the primary and 200 mg in the breakthrough sections. The NO, was absorbed and disproportionated to equi-molar quantities of nitrite ions (NO;) and nitrate ions (NO,-). Glass tubes containing 800 mg of an oxidant such as chromate were used to convert NO to NO,. The converted NO was then collected as nitrite and nitrate in an NO, trap. The water traps contained 300 mg of silica gel in the primary and 150 mg in the breakthrough sections.

Samples provided by PNL to trap horganic compounds include all or some of the following: samples, spiked samples, spares, single trap blanks, and spiked blanks. The samples of each were prepared from same-lot batches, with the oxidizer sections 'of the NO, sorbent trains having been stored previously in a freezer. After sample preparation, all samples, spiked samples, blanks, and spiked blanks were stored in a freezer, primariiy because of handling recommendations for the oxidizer tubes attached to some samples. After receipt of exposed and radiologically cleared saniples

(a) Pacific Northwest Laboratory. 10194. Sorbent Trap Preparation for sampling and Anaiysis: Waste Tank Inorganic Vapor Samples, PNL-TVP-09 (Rev.O), PNL Technical Procedure, Richland, Washington.

5

from WHC and disassembly of the sorbent trains, samples were provided to the analytical laboratory at ambient temperature, aqd selected oxidizer sections were returned to a freezer until completion of analyses.

The sorbent traps were prepared in multi-trap sorbent trains configured so sample flow passed in order through the traps, targeting specific analytes, and then through a desiccant trap. The specific order of traps within the various sorbent trains is described in Section 2.4. The ends of the glass-tube traps were broken, and the traps were weighed and then connected to each other using uniform lengths of 3/8-in. perfluoroalkoxy (PFA)-grade Teflon@ tubing. The tubing was heated in hot air and forced over the open ends of the traps to form a tight seal. The inlets of the sorbent trains each consist of a short section of tubing having a 3/8-in. stainless steel Swagelok@ nut, sealed using a Swagelok@ cap. The trailing ends of the sorbent trains (the downstream end of the traps containing silica gel) were each sealed with red-plastic end caps provided by the manufacturer. The sorbent-tube trains remained sealed other than during the actual sampling periods. C-Flex@ tubing was provided by WHC to connect the downstream ends of the sorbent trains to the sampling exhaust manifold connections.

2.1.1 Concentration Calculations. The concentrations of target compounds in the tank headspace were determined from sample results, assuming effective sample transport to the sorbent traps. Concentration, in parts per million by volume (ppmv), was determined by dividing the mass of the compound, in pmol, by the volume of the dried tank air sampled in mol. The micromolar sample mass was determined by dividing the compound mass, in pg, by the molecular weight of the compound, in g/mol. The molar sample volume was determined, excluding water vapor, by dividing the standard sample volume (at 0°C and 760 torr), in L, by 22.4 Llmol. For example, the concentration (C,) of a 3.00-L sample containing 75.0 pg of NH, equals

c, = 75.0 pg ( 3.00 L )-I = 32.9 ppmv 17 glmol 22.4 L/mol

This calculational method produces concentration results that are slightly conservative (greater than actual) because the volume of water vapor in the sample stream is neglected. The volume of water vapor is not included in the measured sampled volume because of its removal in desiccant traps upstream of the mass flowmeter. However, the bias is generally expected to be small. For a tank- headspace temperature of 35"C, the magnitude of the bias would be about 1 to 6%, assuming tank- headspace relative humidities of 20 to 100 %, respectively. The concentration of mass (determined gravimetrically) was also per dry-gas volume at standard conditions.

2.2 Analytical Procedures

The compounds of interest were trapped using solid sorbents and chemisorption (adsorption of water vapor). Analytical results were based on extraction and analysis of selected ions. Analytical procedures used are specified in the text. All were compiled in PNL-MA-599.

2.2.1 Ammonia Analysis. The sorbent material from the NH3-selective sorbent traps was placed into labeled 20-mL glass scintillation vials. Vials ,containing front-, or primary-, section sorbent material were treated with 10.0 mL of deionized water (DIW), and vials containing back-up-section

6

sorbent material were treated with 5.0 mL of DIW. After extraction, the MI3 sorbent traps were analyzed using the selective ion electrode (SIE) procedure PNL-ALO-226(a). Briefly, this method includes 1) preparing a lOOO-pg/mL (pprn) NH3 stock standard solution from dried reagent-grade NH,Cl and DIW on the day analyses are performed; 2) preparing 0.1-, OS- , 1.0-, 10-, and 100-ppm NH3 working calibration standards by serial dilution of the freshly made stock standard; 3) generating an initial calibration curve from the measured electromotive force (emf) signal versus NH3 concentration data obtained for the set of working standards; 4) performing a calibration-verification check, using one of the midrange standards, after analyzing every four or five samples; 5) continuing this sequence until all samples of the batch have been measured, including duplicates and spiked samples; and 6) remeasuring the complete set of calibration standards (at the end of the session). Emf signal measurements obtained for samples are compared to those for standards, either graphically or algebraically (using linear regression) to determine NH3 concentration in the samples.

2.2.2 Nitrite Analysis. The sorbent traps for NO, and NO were desorbed m an aqueous TEA and n-butanol solution and analyzed by suppressed-conductivity ion chromatography (SCIC) for nitrite according to PNGALO-212, Rev. 1" modified to obviate interferences by concentrations of non- target analytes. Specifically, the modifications used were 1) eluent 1.44 mM N%CO, + 1.8 mM NaHCO, at 2.0 mL/min, 2) one guard column (AG4A) and two separator columns (AS4A) in series instead of just one separator column, and 3) all standards, samples, and blanks injected into the IC sample loop through 0.45-pm syringe filters.

For the analysis, the sorbent materials were placed into labeled 20-mL glass scintillation vials. To each vial, 3.0 mL of desorbing solution (15 g TEA + 1 mL n-butanol in 1.0 L DW) was added. Primary sorbent-tube sample materials and back-up (breakthrough) sorbent-trap materials were analyzed separately using identical procedures. Each analytical session was conducted as follows. Working nitrite standards (0, 0.1, 0.25, and 0.5 ppm) were prepared by diluting a stock nitrite standard with desorbing solution. An initial calibration curve was prepared from the instrument response (chromatographic peak height) versus nitrite standard concentration data for the set of working standards. A calibration verification check using one of the midrange standards was performed after the analysis of every six samples. If the instrument response indicated that sample nitrite concentration was outside the calibration range (> 0.5 ppm nitrite), the sample was diluted with desorbing solution and reanalyzed. After all samples of a batch were analyzed, the complete set of calibration standards was remeasured to verify consistent instrument response, and the analytital .

session was terminated.

Instrument responses (peak height) observed for samples were compared to those for standards to determine the nitrite concentration of the samples. Because NO, and NO converted to NO, were collected on the sorbent as equal quantities of nitrite and nitrate, and the analysis was specific for nitrite, the molar masses of NO, and NO were determined by doubling the 'analytically determined molar mass of nitrite.

(a) Procedure entitled "Ammonia (Nitrogen) in Aqueous Samples," PNL--226, in the AnaIyticaI Chemistry Moratory (ACL) Procedure Compendium, Vol. 3: Inorganic Instrumental Methods. Pacific Northwest Laboratory, Richland, Washington. Procedure entitled "Determination of Inorganic Anions by Ion Chromatography," PNGALO-212, in the Analytical Chemistry Laboratory (ACL) Procedure Compendium, Vol. 3: Inorganic Instrumental Methods. Pacific Northwest Laboratory, Richland, Washington.

(b)

7

2.2.3 Mass (Water) Analysis. Sorbent traps used to make each sample train were weighed using a semi-micro mass balance, after labeling and breaking the glass tube ends, without plastic end caps. After receipt of exposed samples, the sorbent traps were again weighed to determine the change in mass. Records of the measurements were documented on sample-preparation data sheets. The mass concentration, generally roughly equal to the concentration of water, was determined by dividing the combined change in mass from all traps in a sorbent train by the actual volume of gas sampled. Blanks and spiked blanks were included to provide information on uncertainty.

2.3 Qualily Assurance/Quality Control

Analytical work was performed according to quality levels identified in the project QA plan and several PNL documents. The samples were analyzed following PNL IL II. The PNL documents include PNL-MA-70 (Part 2), PNL-ALO-212, PNL-ALO-226, and MCS-046. A su~ l l fnary of the analysis procedures and limits for the target inorganic compounds is provided in Table 2.1. From the table, it can be seen that the minimum detection limit (MDL) required to resolve the analyte at one- tenth of the recommended exposure limit (REL) for each of the target analytes is achieved using current procedures and with a vapor-sample volume of 3 L and a desorption-solution volume of 3 mL (10 mL for NH,).

Table 2.1 Analysis Procedures and Typical Detection Limits of Target Inorganic Analytes

EL‘”) 0.1 x MDL@) Analvte Formula Procedure 0 i€z!!EQ 0

Nitrogen Dioxide NO, PNL-ALO-212 1 0.1 0.02

Nitric oxide NO PNL-ALO-212 25 2.5 0.02

Mass (water)@) n/a n/a n/a n/a n/a

Ammonia N H 3 PNL-ALO-226 25 2.5 0.5

(a) (b)

Target analytical limits are equal to one-tenth of the REL. MDL is defined as the vapor concentration that can be detected with an uncertainty equal to about the magnitude of the measurement. The uncertainty is expected to reduce to abbut onequarter of the magnitude of the measurement at a concentration of four times the MDL. The MDLs were based on the assumption that 3 L of vapor are sampled; if greater volumes of vapor are sampled, correspondingly smaller MDLs can be achieved. The MDLs were also based on desorbing-solution volumes of 10 mL for NH3 and 3 mL for the other analytes. The vapor-mass concentration, thought to be largely water vapor, is determined gravimetrically. (c)

The accuracy of concentration measurements depends on errors associated with both sampling and analysis (see Section 2.4). Sampling information, including sample volumes, was provided by WHC; sample volume uncertainty was not provided. The accuracy of analytical results depends on the method used. For NH, analyses, the accuracy of laboratory measurements by SIE was estimated to be k 5% relative, independent of concentration at 1 pg/mL or greater levels. The uncertainty includes preparation of standards, purity of the ammonium salt used to prepare standards, potential operator bias, ambient temperature variations, etc. Unfortunately, no known National Institute for Standards and Technology (NIST)-traceable standard reference material (SRM) is available against which to compare working standards. Similarly, no known NIST SRM is available for nitrite analysis (for NO, and NO). Based on experience in comparing nitrite working standards prepared from

8

several different sources and factors mentioned for NH, above, the estimated maximum bias for samples derived from sampling for NO, is f lo%, and for samples derived from sampling for NO, it is f 5% relative. The accuracy of measurements of sample mass is f 0.05 mg, or much less than 1 % of the mass changes of most samples. The analytical accuracy of measurements of the change in mass of sorbent trains is typically about f 2 mg per 5-trap sorbent train.

2.4 Inorganic Sample Results

Samples were obtained by WHC from the headspace of Tank T-107 on 1/18/95 using the VSS. The sample job designation number was S5001. Samples were prepared, submitted to WHC, returned to PNL, and then analyzed to provide information on the concentrations of NH3, NO,, NO, and mass (largely H,O). Sampling and analysis for hydrogen cyanide (HCN) and sulfur oxides (SO3 was not requested. The inorganic samples were received from WHC on 2/15/95; the sample-volume information was received on 2/15/95.

A list of samples, sampling information, sample volumes, and gravimetric results is shown in Table 2.2. The types of sample trains used and the order of sorbent traps within each train are also shown in the table. For example, the sorbent train NH3/NOxM20 contained an NH3 trap at the inlet end, an NO, series in the middle (Section 2.4.2), and a desiccant trap at the outlet end. Analytical mass and concentration results are shown in Table 2.3.. Sample volumes were provided by WHC; sample-volume uncertainty was not provided. Tank-headspace concentration results (Table 2.3) are based on this information, and the listed uncertainties equal plus-or-minus one standard deviation of the individual results from each set of samples. Where analytical results from samples were nearly indistinguishable from those of blanks, indicating very low vapor concentrations of the analyte, the concentration results (Table 2.3) are listed as "less than or equal to" a probable maximum value determined by subtracting the average of the blanks less one standard deviation from the average of the samples plus one standard deviation. Results of control samples, 'such as spiked blanks, are discussed in this section. Spiked blanks, when used, were transported to the field but not opened. Spiked samples, when used, were opened in the field and used to collect tank vapors. Sample results were not corrected for the percentage recoveries of spiked blanks.

2.4.1 Ammonia Results. The concentration of NH3 was 125 f 2 ppmv, based on all six samples. The NH3 quantities in the sorbent traps ranged from 16.4 to 17.1 pmol'in the front and about 0.04 pmol in back sorbent sections. Blank corrections, I 0.09 pmol in front and back sections, were less than 0.6% of collected quantities and were neglected. Although spiked blanks were not tested, the percentage recoveries of three sets of blanks spiked with 12.2, 22.3, and 46.4 pmol of NH3 were 101 f 4%, 109 f 2%, and 104 f 1%, respectively, during related sample jobs (Clauss et al. 1994; Ligotke et al. 1994). The analysis of one sample was duplicated and yielded a repeatability of f 1 % . One sample leachate was spiked after initial analysis with roughly the quantity of NH, in the sample and yielded a percentage recovery of 102%. A 5-point calibration was performed over an NH3 range of 0.1 to 1000 pg/mL.

2.4.2 Nitrogen Oxides Results. Measurements of NO, and NO were made using six 5-segment NH3/N0,/H,0 sorbent-trap trains (the NO, trains consisted of NO, trap, oxidizer, and NO, trap). Related sample jobs, performed using the VSS in Tanks BY-104, -105, and -106 both with and without NO, trains protected by a leading NH3 trap (e.g., Clauss et al. 1994), indicated that the

9

Table 2.2

Sample Number

Samples:

s5001-A26-v45 S5001-A21-V46 S500 1-A28-V47 S5001-A29-V48 S5001-A30-V49 S500 1-A3 1-V50

Controls:

List of PNL Inorganic Samples, Controls, and Gravimetric Results Obtained from a Heated Tube Inserted into the Headspace of Tank T-107 on 1/18/95

Sorbent Twe

Sample Port and Volume Information (a)

Sample Flow Rate Duration Volume - Port (mL/min) (min) 0

NH3/N0,/H,0 Train 9 NH3/NO,/H2O Train 10 IG13/N0,/H20 Train 8 NH3/N0,/H20 Train .lo NH3/N0,/H20 Train 9 NH3/N0,/H20 Train 10

200 200 200 200 200 200

d a d a d a

15.0 15.0 15.0 15.0 15.0 15.0

d a d a d a

3.01 3.01 3.01 3.01 3101 3.01

S5OOLA3 1-V51 NH3/N02/H20 Blank dab) 0.0020 S5001-A32-V52 NHJNOJHZO Blank d a 0.0025 S5001-A33-V53 N H J N 0 2 M 2 0 Blank n/a 0.0023

(a)

(b) n/a = not applicable.

Sampling information and dry-gas sample volumes, corrected to 0°C and 760 torr, were provided by WHC. Uncertainty values were not provided with sample-volume results.

d a d a d a

Mass Gain (9)

0.0420 0.0430 0.0424 0.0418 0.0428 0.0430

presence of the upstream NH, traps resulted in NO concentrations that were about 1.3- to 1.6-fold less than those from unprotected NO, traps. The NO, concentrations were also potentially less following an NH, trap.

The concentrations of NO, and NO were I 0.03 and I 0.05 ppmv, respectively, based on all six (NOJ and five of six (NO) samples. Blank-corrected NO; quantities in the sorbent traps averaged 5 0.0020 pmol (NO, samples) and S 0.0034 pmol (NO samples). Nitrite blank levels used to correct data were 0.0134 f 0.0009 pmol in front (three of six blanks analyzed) and 0.0074 f 0.0001 pmol in back (two of six blanks analyzed) sorbent sections. One NO sample (S5001-A31-V50) was apparently contaminated and was excluded from the results because it varied significantly from the other five samples. Although spiked blanks were not tested, blanks spiked with 0.0064, 0.047, 0.11, and 0.74 pmol of NO; during related sample jobs yielded percentage recoveries of 153 f 14%, 103 f 4%, 106 f 8%, and 111 f 7%, respectively (Clauss et al. 1994; Ligotke et al. 1994). The analysis of two samples was duplicated and yielded repeatabilities of f 0 and f 2%. Two sample leachates were spiked with 0.25 ppm NO; and yielded percentage recoveries of 90 and 100%. A'Ppoint calibration was performed over a concentration range of 0 to 0.5 pg NO; per mL in the desorbing matrix.

2.4.3 Gravimetric Results. The. mass concentration of material collected in the 5-trap sorbent trains, believed to be primarily water vapor, was 13:4 f 0.2 mg/L. The result was based on an average mass gain of 40.2 mg from all six NH,/NO,/H,O sample trains. The blank correction applied to the results was -2.3 f 0.3 mg per sample train, based on a minor gain in the blank sorbent trains. Although no spiked blanks were tested, the percentage recovery of mass from three blank

10

H,O traps spiked with 51 mg of water was 103 f 2% during a related sample job (Clams et ai. 1994).

11

~ . . . .. .

Table 2.3 Inorganic Vapor Sample Results Obtained from a Heated Tube inserted into the Headspace of Tank T-107 on 1/18/95

Analytical Results (@mol)

Sample Volume 2 - 3.01'')

VapoP) Concentration

(uumv) Front Back Total@)

Section Section Blank-Corrected Sample

NH? Samples: - 16.7" 125 + 2'')

SSOOI-A26-V45 S500 1-A27-V46 S500 1-A28-V47 S500 1-A29-V48 S5001-A30-V49 S500 I-A3 1-V50

16.8 16.8 17.1 16.8 16.5 16.4

0.03 0.06 NA" NA 0.04 NA

16.8 16.8 17.1 16.8 16.5 16.4

3.01 3.01 3.01 3.01 3.01 3.01

125 125 127 125 123 122

3.01 - NO, Samples: < 0.03 50.0020

0.0138 0.0071 0.0144 0.0073 0.0142 NA 0.0138 NA 0.0140 NA 0.0125 NA

n/aCd) d a d a d a d a n/a

S500 1-A26-V45 S5001-A27-V46 S500 l-A28-V47 S5001-A29-V48 S500 1 -A30-V49 S500 1 -A3 1 -V50

3.01 3.01 3.01 3.01 3.01 3.01

n/a d a d a d a d a n/a

- 3.01 10.0034 0.05 NO Samples:

S5001-A26-V45 S5001-A27-V46 S500 1 -A28-V47 S5001-A29-V48 S5001 -A30-V49 SSOOl-A3 1-V50

0.0144 NA 0.0149 NA 0.0149 NA 0.0160 NA 0.0159 0.0077 0.0298~ 0.0077

d a d a n/a n/a n/a

0.0164x

3.01 3.01 3.01 3.01 3.01 3.01

d a d a d a n/a d a

0.24x

40.2 mg - 3.01 Gravimetric Samples (mg.m,dL): 13.4 t 0.2 m d L

S500 1-A26-V45 S500I-A27-V46 S5001-A28-V47 S5001-A29-V48 S500 1-A30-V49 S5001-A3 1-V50

nla n/a d a n/a nla n/a

n/a n/a n/a d a nla d a

39.7 40.7 40.1 39.5 40.5 40.7

3.01 3.01 3.01 3.01 3.01 3.01

13.2 13.5 13.3 13.1 13.5 13.5

( 4 Blankarr@id vapor concentrations were calculated using WHC-reported dry-air sample volumes (corrected to 0°C and 760 torr). In the calculation for concentration, the nitrite values (listed) were doubled to account for unanalyzed nitrate. Sample results were not corrected for percentage recovery of spiked samples or spiked blanks. Total blankarrected analyte masses (nitrite for NO2 and NO) were determined, when significant, by subtracting the quantity of analyte found in blanks from that found in samples. The level of analytes found in blanks is described in the subsections of Section 2.4. Underlined values represent the average of the set samples. Concentration uncertainty equals f 1 standard deviation (absolute) for each set of samples. The use of LL C is defined in Section 2.4. NA = not analyzed; d a = not applicable; x=not included in determination of average concentration. Only selected back sorbent sections were analyzed. Past results have shown back sections of NH, samples to contain insignificant quantities of the analyte.

(b)

( 4

(d)

12

3.0 Organic

3.1 SUMMA" Canister Preparation

Before sending SUMMA" canisters out to the field for sampling, the canisters are cleaned and verified contaminant free according to PNL Technical Procedure PNL-TVP-02(a). The cleaning procedure uses an EnTech 3000 cleaning system that controls 1) filling the canisters with purified humid air and 2) evacuating, for several cycles with applied heat, before allowing the canister to evacuate overnight. The canister is filled a final time with purified humid air for analysis by PNL Technical Procedure PNL-Tvp-O1@), which is a modification of U.S. Environmental Protection Agency (EPA) compendium Method TO-14. If the canister is verified as clean, free of TO44 and unknown contaminants to a level of 5 parts per billion by volume (ppbv), the canister is evacuated to 5 mtorr Hg, tagged, and stored for use in the field. Before sending the canisters out to the field for sampling, the canister vacuum is measured to determine if any leakage has occurred. If the vacuum has remained constant during storage, the canisters are prehumidified with 100 pL of distilled water and labeled with a field-sampling identification. Canisters stored more than 30 but less than 60 days are re-evacuated and rehumidified before use. If stored more than 60 days, the canisters are recleaned and validated before use.

3.2 Sample Analysis Methods

The SUMMA" canister sample was analyzed according to PNL Technical Procedure PNL- TW-03(c) which is a modified version of EPA compendium Method TO-14. The method uses an EnTech cryoconcentration system interfaced with either a 5971 or a 5972 Hewlett Packard (HP) benchtop GC/MS. The EnTech concentrator is used to pull a metered volume of sample air from the SUMMA" canister, cryogenically concentrate the air volume, then transfer the volume to the GC/MS for analysis. A 100-mL volume of sample is measured and analyzed from the tank headspace. The organic components in the sampled air are separated on an analytical column, J&W Scientific DB-1 phase, 60-m by 0.32-mm internal diameter with 3-pm film thickness. The GC oven is programmed to run a temperature gradient beginning at 40°C, holding for 5 min, and ramping at 4°C per min to a final temperature of 260°C, with a 5-min hold. Twenty-four hours before the analysis, the SUMMA" canister samples were pressurized with purified air (Aadco Instruments, Inc., 1920 Sherwood St., Clearwater, Florida 34625). The starting pressure was first measured using a calibrated diaphragm gauge (Cole Parmer) then pressurized to a level exactly twice the original pressure. For example, if the canister had a starting pressure of 740 torr, it was pressurized to 1480 torr. This dilution was an effort to improve the precision of the analysis. The sample dilution was taken into account when calculating the analysis results.

(a) Pacific Northwest Laboratory. 8/94. Cleaning SUMMA" Canisters and the Validarion 4th Clem*ng Process,

@) . PNtTvp-02 (Rev. 0). PNL Technical Procedure, Richland, Washington. Pacific Northwest Laboratory. 8/94. Determination of TO-14 Volatile Organic Gmpowtdr in Ambient Air Using SUMMA" Passivated W t e r Sampling and Gar Chromogrqhic-Mass Spectromemk Analysis, PNLTVp-01 (Rev. 0). PNL Technical Procedure, Richland, Washington. Pacific Northwest Laboratory. 8/94. Determination of TO-14 Volatile Orgmk Compounds in Hajord Tank Headspace Samples Using SUMMA " Passivated Canister Sampling and Gar Chromatographic-Mass Spectromemk Analysis, PNL-TW43 (Rev. 0). PNL Technical Procedure, Richland. Washington.

( 4

13

The instrument calibration mixture for the TO-14 analysis consists of the standard 39 organic analytes with an additional 14 tank-related compounds. Together, these 53 compounds that are directly quantified in this analysis make up the target analyle list (these 53 compounds will be referred to as target analytes). The calibration mixture was prepared by blending a commercially prepared 39-compound TO-14 calibration mixture with a 14-compound mixture created using a Kin-TeP penneation-tube standard generation system. The operation of the permeation tube system follows the method detailed in PNL Technical Procedure PNL-TVP-06("). The standard calibration mix was analyzed using six aliquot sizes ranging from 5 mL to 300 mL. Depending on the concentration of each analyte in the mixture, either five or six points were used to construct the calibration curve. Butonoic acid was added to the mixture, but was not detected in the analysis. Butanal was recovered very poorly, producing a much lower than expected response. This results in a much higher measured amount reported in the sample analysis. While this problem is under investigation, butanal will continue to be measured as a tentatively identified compound (TIC). This results in a much higher measured amount reported in the sample analysis. This problem is currently under investigation. Perfonnance-based detection limits for the target analytes will be developed as a pool of calibration data becomes available. Currently, the nominal detection limit of 5 ppbv is met.

The SUMMA" canister samples were analyzed for permanent gases according to PNL Technical Procedure PNL-TVP-05@) with the exceptions listed in the following text and in the Quality Assurance/Quality Control section of this report. This method was developed in-house for the analysis of permanent gases defined as hydrogen (Hd, carbon dioxide (COJ, carbon monoxide (CO), methane (CH,), and nitrous oxide (N,O) by GC/TCD and is not validated in any other laboratory. No previous work up of the sample canister is necessary before permanent gas analysis. Aliquots of sampled air are manually drawn from each canister into a 5-mL gas-tight syringe and directly injected into a GClTCD fitted with a 1.0-mL injection loop. An aliquot of 5 mL is used so that the injection loop is flushed and filled with sample air, ensuring that no dilution of the sample takes place within the injection loop. One set of GC conditions is used to analyze for CO, CO,, N,O, and CH, using Helium (He) as the carrier gas. A second GC analysis is performed for H, (using nitrogen as the carrier gas) to enhance the signal sensitivity and lower the detection limit for this analyte. A total of 30 to 60 mL, depending upon the number of repeat analyses performed, may be drawn from each 6-L canister.

3.3 Quality Assurance/Quality ControI

Before the tank sample was analyzed, a diagnostic check was performed on the GCMS instrument by running an instrument "high-sensitivity tune," as described in PNL-TVP-03. Upon satisfactory completion of the instrument diagnostic check, a blank volume of purified nitrogen was analyzed to check the cleanliness of the system. The instrument was then calibrated over 5 to 7 data points ranging from 5 ppbv to 300 ppbv, using a standard gas mixture conraining 39 volatile organic compounds listed in EPA compendium Method TO-14 and an additional 14 tank-related compounds. A gas mixture containing bromochloromethane, 1 ,Mifiuorobenzene, and chlorobenzene-d, was used as an internal standard (IS) for all blank, calibration standard, and sample analyses. Analyte

(a)

@I

Pacific Northwest Laboratory. 8/94. Preparation of TO-14 Volatile Organic Compounak GaF Standarak, PNL-Tvp-06 (Rev. 0). PNL Technical Procedure, Richland, Washington. Pacific Northwest Laboratory. 8/94. Anniysis Method for the Determination of P e m n t Guses in Hanford Waste Tmrk Vapor SMlples Collected in SUMMX Passivated Stainless Steel Canisters, PNGTW-05 (Rev. 0). PNL Technical Procedure, Richland, Washington.

14

responses from sample components, ISs, and standards were obtained from the extracted ion plot from their selected mass ion. The calibration curve was generated by calculating the relative response ratios of the IS to calibration standard responses and plotting the ratios against the ratio of the calibration-standard concentration (in ppbv) to the IS concentration. A least-squares linear-regression routine was applied to the data set to generate the best-fit line for each compound. The equation for that line was then used to quantify the target analytes found in the tank samples.

Standards for the permanent gas analysis were blended from commercially prepared and certified standards for each of the analytes reported in Table 3.5. The instrument was calibrated over three data points for CO, C02, N20, and CH4 using He as a carrier gas, and then the samples were analyzed. The carrier was changed to N2, the calibration was performed for H2 only, and the samples were reanalyzed. A least-squares linear-regression routine was applied to the data set to generate the best fit for each compound. The quantitation for each analyte was performed by direct comparison of sample analyte peaks to the plot generated for the compound. The lowest calibration standard for each analyte is reported as the method detection limit. An h4DL for the instrument has not been determined. An N2 reagent blank, ambient air sample collected - 10 m upwind of T-107, and the ambient air collected through the VSS were used as method blanks and used to determine the potential for analyte interferences in the samples. Continuing calibration standards for this sample set fell within f 25% of the expected concentrations for the analytes reported.

3.3.1 Quantifation Results of Target Analytes. The quantitative-analysis results for the target analytes were calculated directly from the calibration curve generated using the IS method described above and in PNL-TVP-03. The conversion from ppbv to mg/m3 assumes standard temperature and pressure (STP) conditions of 760 torr and 273K and was calculated directly from the following equation:

- (ppbv/iOOO) x g mol wt of compound mg/m - 22.4 L/mol

(3.1)

3.3.2 Identification aqd Quantitation of Tentatively Identified Compounds. The TICS are determined by mass-spectral interpretation and comparison of the spectra with the EPA/NIST/WILEY Library, which is a part of the HP 59716972 instrument operating system. Chromatographic peaks with an area count greater than, or equal to, one tenth of the total area count of the nearest eluting IS are tentatively identified and quantitatively estimated. The quality of the mass-spectral searches was then reviewed by the principal investigators before the identification was assigned to each chromatographic peak.

The concentration of each TIC was estimated using a relative response factor calculated using the total peak area for the nearest eluting IS. The IS peak area was used to calculate a response factor using the 1s concentration in mg/m3:

IS conc. (mg/m3) IS peak area

Response Factor, = (3.2)

The calculated response factor was then multiplied by the TIC peak area to give an estimated concentration for that compound.

15

The ppbv concentrations are calculated from mg/m3 and the molecular weight of the analyte.

TIC (mg/m3) x 22.4 L/mol x 1000 TIC g mol wt

TIC in ppbv = (3.3)

The IS level added to all blank, standard, and sample injections was 104 ppbv for bromochloromethane, 101 ppbv for 1,4difluorobenzene, and 98.5 ppbv for chlorobenzene4. The IS concentrations were converted from ppbv to mg/m3 at STP using a molecular weight of 129.39 (g/mol) for bromochloromethane, 114.09 for 1,4-difluorobenzene, and 117.6 for chlorobenzene-d,. All sample concentrations were multiplied by a factor of two to account for the dilution step described in Section 3.2.

3.4 Analysis Results

The results from the GCNS analysis of the tank-headspace samples are presented in Tables 3.1 and 3.2. The results of replicate analyses on a single SUMMA" canister are presented in Tables 3.3 and 3.4. The results of GC/MS analysis of ambient air sample collected upwind of Tank T-107 and through the VSS near Tank T-107 are presented in Table 3.5. The GC/TCD analysis results for permanent gases for both the ambient samples and the tank headspace are presented in Table 3.6. A representative total ion chromatogram showing the identity of major constituents is given in Figure 3.1.

Table 3.1 lists the quantitative results for compounds listed as target analytes. Acetone was the only target analyte above the 5-ppbv MDL detected in the tank-headspace samples. Acetone at 2.4 mg/m3 accounted for 58% of the total compounds identified by both the target and TIC analyses.

Table 3.2 lists the semi-quantitative results for the TICs. Six TICs were identified in the analyses. The predominant species observed in this sample were methyl alcohol, propane, and acetonitrile. The total concentration of the TIC compounds was found to.be 1.94 mg/m3.

SUMMA" canister PNL 12 was analyzed in replicate for target analytes and TICs to determine analytical precision. The relative percent difference (RPD) results are presented in Tables 3.3 and 3.4. The FWD was calculated for analytes detected above the detection limit and found in both replicates. Acetone, the only taiget analyte, had an RPD of 0.9%. All three TICs detected had RPDs less than 10%.

Table 3.5 lists the compounds identified in the ambient air collected upwind of Tank T-107 and ambient air collected though the VSS. No target analytes were identified in the analysis. Two compounds, 2-pentanone and 2-butanone, were identified in the upwind sample. Four compounds, acetaldehyde, 2-pentanone, 2-butanone, and tridecane, were identified in the ambient air collected through the VSS. None of these compounds were identified in the tank-headspace samples.

Table 3.6 lists results of permanent gas analysis from samples collected from the headspace of Tank T-107, ambient air collected - 10 m upwind of the tank, and ambient air collected through the VSS. Permanent gases observed in the headspace were CO, and N,O. Carbon dioxide in the headspace was at a lower concentration than in ambient air. Nitrous oxide was not detected either in the ambient air collected - 10 m upwind of the Tank T-107 or ambient air collected through the VSS.

16

A replicate analysis was performed on one of the samples collected from this tank (see footnote c, Table 3.6); however, only the results from the first analysis are reported.

17

4.0 Conclusions

The concentrations of selected inorganic and organic compounds were determined from samples of the headspace of Tank T-107 on 1/18/95. Sampling and analysis methods followed those described by Ligotke et al. (1994) and C law et al. (1994) for samples obtained from C-103, a tank containing a relatively complex headspace composition. Method-validation measurements during that study did appear to validate the trapping and analysis of NH,, but did not eliminate the possibility of interferences that could affect NO, results. It is recommended that additional control samples be obtained if a tank is discovered in the future to contain significant quantities of NO,. In the current sample job, NO, samples were obtained after first passing the sample flow through an NH3 trap. The average and standard deviation of the concentration results from inorganic sorbent trains were 125 f 2 ppmv (NH3), 10.03 ppmv (NOJ, 50.05 ppmv (NO), and 13.4 f 0.2 m g L (vapor-mass concentration). The vapor-mass concentration is expected to consist largely of water vapor.

Organic analysis of the tank-headspace samples from Tank T-107 identified one target analyte above the 5-ppbv MDL and six TICs above the 10-ppbv MDL. Only five of the six TICs were identified in two or more of the SUMMA" samples. Acetone, the only target analyte identified, accounted for 58% of the total compounds identified by both the target analyte and TIC analyses. The TICs accounted for 42% of the total compounds identified by both analyses. Methyl alcohol, propane, and acetonitrile were the highest concentration TICs measured. These analytes accounted for 88 % of the TIC concentration and 37 % of the total compounds concentration identified by both the target analyte and TIC analyses. All results of replicate analysis on a single SUMMA"' canister had WDs of less than 10%. Two compounds, 2-pentanone and 2-butanone7 were identified in the upwind sample. Four compounds, acetaldehyde, 2-pentanone, 2-butanone, and tridecane were identified in the ambient air collected through the VSS. None of these compounds were identified in the tank-headspace samples. Two permanent gases, C02 and N20, were also detected in the tank- headspace samples.

5.0 References

Clauss, T. W., M. W. Ligotke, B. D. McVeety, K. H. Pool, R. B. Lucke, J. S. Fruchter, and S. C. Goheen. 1994. Vapor Space Characterization of Waste Tank 241-BY-I 04: Resultsfrom Samples Collected on 6/24/94. PNL-10208. Pacific Northwest Laboratory, Richland, Washington.

Ligotke, M. W., K. H. Pool, and B. D. Lerner. 1994. Vapor Space characterization of Waste Tank 241-C-103: Inorganic Resultsfrom Sample Job 7B (5/12/94 - 5/25/94). PNL-10172, Pacific Northwest Laboratory, Richland, Washington.

Mahlum, D. 1994. Toxicological Evaluation of Analytesfram Tank 241-C-103. PNL-10189, Pacific Northwest Laboratory, Richland, Washington.

19

6.0 Further Reading

Pacific Northwest Laboratory. Analytical Laboratory Procedure Compendium. Procedures PNL- ALO-212, -226, -271. PNL-MA-599, Richland, Washington.

Pacific Northwest Laboratory. Quality Assurance Manual, Part 2: Good Practices Standard. PNL- MA-70, Part 2, Richland, Washington.

Pacific Northwest Laboratory. PNL TWRS Tank Vapor Program. MCS-046, Richland, Washington.

Pacific Northwest Laboratory. 1994. Determination of TO-14 Volatile Organic Compounds in Hanford Waste Tank Headspace Samples Using SUMMA Passivated CQnister Sampling and Gas Chromatographic-Mass Spectrometry Analysis, PNL-TVP-03 (Rev. 0), PNL Technical Procedure, Richland, Washington.

Pacific Northwest Laboratory. 1994. Sample Shipping and Receiving Procedure - DRQFT for PhE Waste Tank Samples. PNL-TVP-07 (Rev. 0), PNL Technical Procedure, Richland, Washington.

21

Table 3.1 Positively Identified and Quantitated Target Analytes(') of Samples Collected from the Headspace of Tank T-107 in SUMMATM Canisters on 1/18/95

Analvte Dichlorodifluoromethane Chloromethane 1 ,ZDichloro- 1,1,2,2-tetrafluoroethane Vinyl Chloride Bromomethane Chloroethane Trichlorofluoromethane 1,l-Dichloroethene Methylene Chloride 1,1,2-Trichloro-l,2,2-trifluoroethane 1,l -Dichloroethane cis-1,2-Dichloroethene Chlorofonn 1 ,2-Dichloroethane 1 , 1 , 1-Trichloroethane Benzene Carbon Tetrachloride 1,2-Dichloropropane Trichloroethene cis-l,3-Dichloropropene trans- 1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethylene Chlorobenzene Ethylbenzene p-Xylene(d) m-Xylene(4

Styrene 1,1,2,2-Tetrachloroethane

i2ASkh 75-71-8 74-87-3 76- 1 4-2 75-0 1-4 74-83-9 75-00-3 75-69-4 75-35-4 75-09-2 76-13-1 75-34-3 156-59-2 67-66-3 107-06-2 71-55-6 71-43-2 56-23-5 78-87-5 79-0 1-6

1006 1-0 1-5 10061-02-6

79-00-5 108-88-3 106-93-4 127-18-4 108-90-7 1 00-4 1-4 106-42-3

M!UA 120.9 50.5 170.9 62.5 94.9 64.5 137.4 96.9 84.9 187.4 99.0 96.9 119.4 99.0 133.4 78.1 153.8 113.0 131.4 11 1.0 1 11.0 133.4 92.1 187.9 165.8 112.6 106.2 106.2

100-42-5 104.2 79-34-5 167.9

S5-001-A07.011@) PNL 1 I(') ~mg!m3) (&)

<0.03 < 5 <0.01 < 5 <0.04 < 5 <0.01 < 5 <0.02 < 5 <0.01 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5 X0.04 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 c0.02 < 5 < 0.03 < 5 <0.02 < 5 <0.03 < 5 <0.03 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 <0.02 < 5 c0.04 < 5 <0.04 < 5 <0.03 < 5 <0.02 < 5 <0.02 <5

<0.02 < 5 <0.04 < 5

S5-001-A08.0 12@) PNL 12'" (D.Eh3) (ppby)

<0.03 < 5 <0.01 < 5 <0.04 < 5 <0.01 < 5 <0.02 < 5 <0.01 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5 <0.04 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 <0.02 < 5 <0.03 < 5 <0.02 < 5 <0.03 < 5 <0.03 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 <0.02 < 5 <0.04 < 5 <0.04 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5

<0.02 < 5 <0.04 < 5

S5-00 1-A09.02 1@' PNL 2 1 (') (b3) (PP!D!)

<0.03 < 5 <0.01 < 5 <0.04 < 5 <0.01 < 5 <0.02 < 5 <0.01 < 5 <0.01 < 5 <0.02 < 5 <0.02 < 5 <0.04 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 <0.02 <5 <0.03 < 5 <0.02 < 5 <0.03 < 5 <0.03 < 5 <0.03 < 5 <0.02 < 5 <0.02 < 5 <0.03 < 5 X0.02 < 5 CO.04 < 5 <0.04 < 5 <0.03 < 5 K0.02 < 5 c0.02 < 5

<0.02 < 5 <0.04 < 5

Table 3.1 (Coiitd)

h a l i d e 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene

. 1,2,4-Drichlorobenzene Hexachloro-l,3-butadiene 2-Butanone Acetone Acetonitrile Heptane Tetrahydrofuran Pyridine Butanenitrile Cyclohexane Decane Hexane 4-Methyl-2-pentanone Propanenitrile Cyclohexanone Propanol

CASNo, MolWt 95-63-6 120.2

541-73-1 147.0 10646-7 147.0 95-50-1 147.0

120-82-1 181.5 87-68-3 260.8 78-93-3 72.1 67-64-1 '. 58.1 75-05-8 41.1

142-82-5 100.2 109-99-9 72.1 110-86-1 79.1 109-74-0 69.1 110-82-7 84.2 124-18-5 142.3 110-54-3 86.2 108-10-1 100.2 107-12-0 55.1 108-94-1 98.1 71-23-8 150.1

S5-00 I-A07.011@) S5-00 1-A08.012@xc) S5-00 1 -A09.02 1 @)

PNL ll(Q (m

<0.03 < 5 c0.03 < 5 c0.03 < 5 <0.03 < 5 CO.04 < 5 <0.60 < 5 -4.02 < 5

2.38 918 <0.01 < 5 c0.02 < s <0.02 < 5 <0.02 < 5 c0.02 < 5 <0.02 < 5 c0.03 e5 <0.02 < 5 c0.02 < 5 <O.Ol < 5 <0.02 < 5 co.01 < s

PNL 12(Q !I)DbV)

c0.03 < 5 c0.03 e5 c0.03 < 5 C0.03 < 5 co.04 < 5 c0.60 < 5 4 . 0 2 4

2.26 872 co.01 < 5 c0.02 < 5 c0.02 < 5 <0.02 < 5 c0.02 < 5 co.02 < 5 c0.03 < 5 <0.02 < 5 <0.02 < 5 <0.01 < 5 C0.02 < 5 <0.01 < 5

TO-I4 plus 14 additonal target molytes. WHC sample identification number. PNL canister number. Replicates of tliis sample are found in Table 3.3 Average andor standard deviation are not meaningful for this analyte. m-Xylene and pXylene coelute; the reported concentration is the sum of tliese hvo compounds.

~-

PNL 2l(Q (d3) cw

<0.03 < S

<0.03 < 5 c0.03 e5 <0.04 < 5 c0.60 < 5 a . 0 2 4

2.58 995 co.01 < 5 <0.02 < 5 <0.02 < 5 <0.02 < s <0.02 < 5 C0.02 < 5 ~ 0 . 0 3 < 5 c0.02 < 5 <0.02 < 5 co.01 e5 c0.02 < 5 <0.01 < 5

K0.03 < 5

Means and Standard Deviations

(b3) StDev StDev

Table 3.2 Tentatively Identified Compounds and Estimated Concentrations(') of Snmples from the Headspace of Tnnk T-107 in SUMMAm Canisters Collected on 1/18/95

Tentatively Identified Compound(') Propane Methyl Alcohol Ethanol Acetonitrile 2-Butnnone I-B~tnnol

Mol CAS No.(') Wt

74-98-6 44 67-56-1 32 64-17-5 46 75-05-8 41 78-93-3 72 7 1-36-3 74

- -

S5-00 1 -A07.0 1 10) S5-001-AO8.0 1 2@xc) S5-00 1-AO9.02 I@) Ret PNL 1 PNL 12(4 PNL 21(Q Time !&9 CDDbv) !mn/m3) Ceabv) !!!I&!?) !I?&!)

3.8 4 . 0 2 c 10.0 0.22 110 0.23 116 5.1 1.07 748 1 .OS 755 1.19 832 7.1 4 . 0 2 c 10.0 <0.02 c 10.0 0.12 58 7.6 0.20 110 0.19 103 0.20 109

13.3 0.15 45 0.19 58 0.20 63 0.09 27 0.09 27 17.3 0.09 28 .

(a) (b) WHC sample identification number. (c) (d) PNL SUMMAn' canister number. (e) (0

Semiquantitative estimate calculated using concentration of closest eluting IS.

Replicates of this sample are found in Table 3.4.

Obtained by mass spectral interpretation,amd compnrison with the EPNNIST/WILEY Library. Mean and/or standard deviation are not meaningful for this analyte.

Means and Standard Deviations (p~&~) StDev (&) StDev

0.22 (0 113 (0 1.11 0.07 779 46.6 0.12 (0 58 (0 0.20 0.01 107.3 4 .O 0.18 0.03 56 9.4 0.09 0.00 27 0.5

I

Table 3.3 Positively Identified and Quantitnted Target Annlytes(') of Replicate Analyses of a Single SUh&fAm Canister Collected from Uie Headspace of Tank T-107 on 1/18/95

Relative S5-001-A08.012@' S5-001-A08.012@) Percent

balvte Dichlorodi fluoromelhae Chloromethane 1,2-Dichloro-l ,I ,2,2-tetrafluoroetliane Vinyl Chloride Bromomethane Cliloroethane Trichlorofluoromelhane 1,l-Dicldoroethene Methylene Chloride 1,1,2-Trichloro-l,2,2-trifluoroetl1ane 1 ,I-DichloroeUiane cis-l,2-Dichloroethene Chloroform 1,2-Dichloroethae 1 ,I ,I-Trichloroethane Benzene Carbon Tetrachloride 1,2-Dichloropropnne TrichloroeLhene cis-l,3-Dichloropropene trnns-l,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoetliae Tetrachloroethylene Chlorobenzene EUiy lbenzene p-XyIene(Q m-XyIene(Q

Styrene 1, I ,2,2-TetracllloroeUiane o-Xylene

P I C 12(c) PNL 12(4 Difference CASNo, WolWt (mp/m3) (m (mn/m3) (ppbvJ - % . ~~ . . - _ _ 75-71-8 120.9 c0.03 < 5 co.03 CS 74-87-3 76-14-2 75-014 74-83-9 75-00-3 75-694 75-354 75-09-2 76-13-1 75-34-3

156-59-2 67-66-3

107-06-2 71-55-6 7143-2 56-23-5 78-87-5 79-01-6

61-02-6 61-01-5

79-00-5 108-88-3 106-934 127-184 108-90-7 100414 10642-3

50.5 170.9 62.5 94.9 64.5

137.4 96.9 84.9

187.4 99.0 96.9

119.4 99.0

133.4 78.1

153.8 113.0 131.4 111.0 111.0 133.4 92.1

187.9 165.8 112.6 106.2 106.2

c 0.01 < 0.04 c 0.01 c 0.02 co.01 c 0.03 c 0.02 c 0.02 < 0.04 c 0.02 c 0.02 ,*

C 0.03 c 0.02 c 0.03 c 0.02 c 0.03 C 0.03 < 0.03 < 0.02 c 0.02 C 0.03 c 0.02 C 0.04 C 0.04 C 0.03 c 0.02 c 0.02

c 0.01 c 0.04 c 0.01 c 0.02 c 0.01 < 0.03 c 0.02 c 0.02 c 0.04 c 0.02 < 0.02 < 0.03 c 0.02 C 0.03 c 0.02 C 0.03 C 0.03

0.03 c 0.02 c 0.02 C 0.03 c 0.02 C 0.04 c 0.04 < 0.03 c 0.02 c 0.02

100-42-5 104.2 c 0.02 < 5 c0.02 c5 79-34-5 167.9 C 0.04 C 5 c0.02 c5 9547-6 106.2 c 0.02 < 5 c0.02 c5

Table 3.3 (Contd)

Mnlvte lY3,5-Trimethylbenzene 1,2,4-Trimetliylbenzene 1,3-Dichlorobenzene Iy4-Dichlorobenzene 1 ,2-Dichlorobenzene 1,2,4-Drichlorobenzene Hexachloro-l,3-butadiene 2-Butanone Acetone Acetonitrile Heptane Tetrahydrofiuan Pyridine Butanenitrile C yclohexane Decane Hexane 4-Methyl-2-pentanone Propmenitrile Cyclohexanone Propanol

Relative Percent S5-OOl-AO8.012@) S5-OOl-AO8.012@)

PNL 12@) CASNo. Mol Wt (p~&) (d) -- 108-67-8 95434

54 1-73-1 10646-7 95-50-1

120-82-1 87-68-3 78-93-3 67-64-1 75-05-8

142-82-5 109-99-9 110-86-1 109-74-0 110-82-7 124-18-5 110-54-3 108-10-1 107-12-0 108-94-1 71-23-8

120.2 120.2 147.0 147.0 147.0 181.5 260.8 72.1 58.1 41.1

100.2 72.1 79.1 69.1 84.2

142.3 86.2

100.2 55.1 98.1 60.1

< 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.04 < 0.60 < 0.02

2.26 e 0.01 < 0.02 < 0.02 e 0.02

0.02 e 0.02 e 0.03 e 0.02 < 0.02 e 0.01 < 0.02 < 0.01

PNL 12(') Difference - YO

< 0.03 < 0.03 < 0.03 < 0.03 < 0.03

0.03 0.04

< 0.02 2.28

< 0.01 < 0.02 < 0.02 < 0.02 < 0.02 < 0.02

0.02 < 0.02 < 0.03 < 0.02 < 0.02 < 0.01

(a) TO-I4 plus 14 additonal target analytes. (b) WHC sample identification number. (c) PNL canister number. (d) m-Xylene and pXylene coelute; the reported concentration is the sum of these two compounds.

Table 3.4 Tentatively Identified Compounds and Estimated Concentrations(’) of Replicate Analyses of a Single SUMMAm Canister Collected from the Headspnce of Tank T-107 on 1/18/95

Tenh tivel y Jdentified Comr)oimd(d)

S5-001 -A08.0 1 2@) Mol Ret PNL 12(‘) PNL 12CC)

CASNO.(~ Wt Time (mp/ln3) (m) (&’) (p$wJ Propane 74-98-6 44 3.8 0.22 110 Methyl Alcohol 67-56-1 32 5.1 1.08 755 Etlianol 64-17-5 46 7.1 4 . 0 2 <10.0 Acetonitrile 75-05-8 41 7.6 0.19 103 2-Butanone . 78-93-3 72 13.3 0.19 58 1 -Butanol 71 -36-3 74 17.3 0.09 27

(a) Semiquantitative estimnte calculated using concentration of closest eluting IS. (b) WI1C sample identification number. (c) PNL SUMMA^' canister number. (d) Obtained by mass spectral interpretation amd comparison with the EPNNISTNilLEY Library.

4 .02 1.09 0.08 0.19 0.18 0.09

< 10.0 762

38 104 54 27

Relative Percent Difference

- %

0.9

1.1 6.6 1.1

N U

Table 3.5 Tentatively Identified Compounds and Estimated Concentrations(') for Ambient Air and Ambient Air Sampled Through VSS Collected Near Tank T-107 in SUMMAm Canisters on 1/18/95

Upwind Tlrougb vss S5-00 1-A0 1.002@' S5-001-A01.006@)

Tentatively Mol Ret PNL2(') PNL 6(') Identified Comoound(d) CASNO.'~) - Wt ~ i m e (mdrn7 (~nbv) (mdrn') (DD~V) Acetaldehyde 2-Pentanone 2-Butanone Tridecane

75-07-0 44 4.9 <0.02 40.0 0.10 50 107-87-9 86 12.7 0.11 29 0.08 21 78-93-3 72 13.3 0.08 25 0.06 18 629-50-5 184 47.7 <0.08 40.0 0.06 6.9

(a) Semiquantitative estimate calculatcd using conccntration of closest eluting IS. (b) WHC sample identification number. (c) PNL canister number. (d) Obtained by mass spectral interpretation amd comparison with the EPA/NIST/WILEY Library.

i

Table 3.6 Permanent Gas Analysis Results for Samples Collected from the Headspace of Tank T-I07 and for Ambient Air and Ambient Air Through the VSS Collected near Tank T-107 in SUMMArw Canisters on 1/18/95

Ambient Air Ambient Air Tank Samples Upwind Through VSS

PNL 2" PNL 6" PNL ll@' PNL 12" PNL 21 Concentration Permanent Gas Concentration Concentration Concentration Concentration Concentration Tank Samples

S5-OOl-AO 1.002"' S5-001-AO2.006"' S5-001-AO7.0 1 1"' S5-001-A08 .O 12"' S5-001-A09.021" Average '

Analyte (ppmv) (ppmv) (ppmv) (ppmv) (ppmv) (ppmv) Hydrogen < 94 c 94 < 94 < 94 < 94 <94 Methane < 61 < 61 < 61 < 61 < 61 < 61 Carbon Dioxide 362 368 63.8 80.8 80.1 74.9 Carbon Monoxide < 12 < 12 < 12 c 12 < 12 < 12 Nitrous Oxide C 12.6 C 12.6 48.0 35.6 41 .O 41.5

(a) WHC sample identification number. (b) PNL canister number. (c) Replicate analysis for PNL 21 resulted in a concentration of 86.6 ppmv for carbon dioxide

and 33.3 ppmv for nitrous oxide.

1.1-

1.0-

0.9-

0.e-

0.7-

Os€-

O S -

0.4-

0.2-

0.2-

0.1-

Figure 3.la Total Ion Chromatogram (2 - 30 min) for Hanford Waste Tank T-107 SUMMA" Canister Sample S5-001-AO8.012 Collected on 1/18/95

30

1.1-

1.0-

0 . e

0.8-

0.7-

0.6-

0 . 5

0.4-

0 . 3

0.2-

.0.1-

Figure 3.lb Total Ion Chromatogram (30 - 58 min) for Hanford Waste Tank T-107 SUMh4Am Canister Sample S5-001-AO8.012 Collected on 1/18/95

31

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