WASTEWATER PHARMACEUTICALS AND PERSONAL CARE PRODUCTSREMOVAL AND DEGRADATION USING BIOBRIMSTONE™ TECHNOLOGY

Kelly M. Polk, deceasedDistrict ManagerMontalvo Municipal Improvement District3555 Ventura RoadVentura, California 93003

Stan RuskChief Plant Operator3555 Ventura RoadVentura, CA 93003stanruskmmid@aol.com

Marcus G. Theodore, CEOEarth Renaissance Technologies, LLC466 South 500 EastSalt Lake City, Utah 84102theodore@xmission.com

Terry R. Gong, Managing PartnerEarth Renaissance Technologies, LLC1217 Larch AvenueMoraga, California 94556Westernso2@aol.com

Abstract

Pharmaceuticals, hormones, and other organic and chemical wastewater contaminants entering wastewater are becoming an environmental concern. The wide variety of chemicals, their ever changing composition and occurrence in minute amounts constantly entering wastewater streams, makes their removal difficult. Most traditional municipal wastewater treatment plants produce secondary treated recycled effluent, which does little to degrade, but removes some of these chemicals. Tertiary treatments have some effect on removal and degradation of these pharmaceuticals and chemical contaminants, but generally address only certain pharmaceuticals and chemical types, which are often expensive to implement and monitor. This article will outline the manner in which proprietary patented hybrid chemical/biological dewatering and disinfection wastewater treatment technology owned by Earth Renaissance Technologies, LLC (ERT)1 may be

1 Earth Renaissance Technologies, LLC (ERT) is owned by Stewardship Water & Gas Company’s (SWAGCO) and Harmon Systems International (HSI), which was formed to blend SWAGCO’s wastewater treatment technology with HSI’s extensive irrigation water and soil conditioning technology to recover and condition wastewater for an end

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employed for inactivating, degrading, and removing a number of pharmaceutical and chemical components. This ERT wastewater treatment technology entails an oxidation/reduction, acidification/alkalinization cycle to condition recovered wastewater to grow aquatic photo biomass to further inactive, degrade, and remove those susceptible pharmaceuticals and chemicals. The Biobrimstone™ method was employed as a retrofit at the Montalvo Municipal Improvement District’s wastewater treatment facility in Ventura, California to pre-treat influent to remove pharmaceuticals and personal care products (PPCP) and suspended solids before entering the plant’s sequential batch reactors. The Biobrimstone™ technology provides an economical wastewater pre-treatment retrofit disinfection option removing suspended solids without polymers and activated waste digestion to inactivate, degrade, and remove a number of different pharmaceuticals and chemicals as part of a multi-step treatment process to provide recovered wastewater suitable for land application.

Introduction

Pharmaceuticals in wastewater streams have become a cause for concern as pharmaceuticals and their metabolites have been established as nearly ubiquitous environmental pollutants in ground and surface waters. Chemicals used everyday in homes, industry and agriculture can enter the environment in wastewater. Unfortunately there are thousands of different chemicals entering a wastewater treatment system, the composition of which constantly changes. These chemicals include human and veterinary drugs (including antibiotics), hormones, detergents, disinfectants, plasticizers, fire retardants, insecticides, and antioxidants.2 The shear number of the different types of chemicals, their low concentrations3, and continually changing makeup makes the design of wastewater treatment systems to remove the same, impractical. For example, if a wastewater treatment system is designed for removal of a particular chemical, manufacturers may cease producing the product, or alter its composition to accelerate decomposition, rendering the design useless. Or waste disposal plans for a particular pharmaceutical may be adopted by a municipality for gathering the same for disposal

user’s agricultural and soil needs. ERT holds key patents on its technology and has accumulated additional related water treatment technology, all of which are the subject of pending patent applications.2 USCG Fact Sheet FS-027-092, Pharmaceuticals, Hormones, and Other Organic Wastewater Contaminants in U.S. Streams, June 2002, Background.3 For example, steroid estrogens have the potential to exert estrogenic effects in the low ng/L (1 part/trillion) level, whereas alkylphenolic compounds are estrogenic at µg/L (1 part/billion). Natural and synthetic hormones are frequently detected in sewage treatment work effluents and receiving surface waters with concentrations ranging from pg/L (1 part/quadrillion) to ng/L (1 part/trillion); see page 4 “Municipal Wastewater Concentrations of Pharmaceutical and Zeno-Estrogens: Wildlife and Human Health Implications” by Maxine Wright Walters and Conrad Voltz; www.chec.pitt.edu?Exposure_concentration_of_Xenoestrogen_in_pharmaceutical_and_Municipal_Wastewster_Final8-28-07%5B1%5D.pdf.

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preventing the pharmaceutical from entering the wastewater gathering system4. Further, it is very difficult to test the effectiveness of a wastewater treatment system to remove all of these chemicals and pharmaceuticals. Most small wastewater treatment facilities do not have the necessary laboratory testing equipment or the skilled personnel to operate the same so testing is problematic. Consequently, most wastewater treatment plants are limited to providing primary and secondary treatment.

“Traditional [wastewater treatment plants] WWTPs treat influent by adding chemicals (alum, ferric chloride and/or synthetic polymers) to encourage coagulation (neutralizing suspended sediments) and flocculation (aggregating particles). The resulting bigger particles (flocs) are then able to be filtered out, as sewage sludge. The residual liquid is then disinfected, often with chlorine in the United States and ozonation in Europe. This system is optimized to remove pathogens, and other biological material, and dissolved organic carbon (Ellis 2006), not pharmaceuticals or other chemicals; consequently, these conventional treatment processes appear to be insufficient in removing pharmaceutical compounds (Ellis 2006; Brun et al. 2006; Snyder et al. 2003). Considering the ineffectiveness of water treatment processes, WWTPs should be considered an important and continuous source of pharmaceuticals to the environment (Brun et al. 2006).”5

Primary treatment allows influent to partition based on density; solids that float or settle to the bottom are filtered out6, while liquids and smaller particles pass through. A common secondary treatment process utilizes bacteria to break down organic material in an aerated tank7; then, the material is allowed to settle and the water is filtered again.8 At first blush, secondary treatment utilizing bacteria to break down organic material resulting in large carbon emissions appears to be cost effective. However, pending legislation requiring the purchase of carbon off-sets may make this alternative cost prohibitive.

4See Page 27, Disposal programs, “Pharmaceuticals in Wastewater Streams: Disposal Practices and Policy Options in Santa Barbara”, a Master’s Project for the Donald Bren School of Environmental Science and Management dated May 2007 by James Kallaos, Kaleena Wheeler, Crispin Wong, and Margaret Zahller, Faculty Advisor, Matthew Kotchen.5 Page 10, “Pharmaceuticals in Wastewater Streams: Disposal Practices and Policy Options in Santa Barbara”, supra.6 Some pharmaceuticals may be removed by sorption to particles filtered out; see “Factors Affecting the Concentrations of Pharmaceuticals Released to the Aquatic Environment” by David L. Sedlak, and Karen E. Pinkston, University of California; see Page 56, Introduction, www.ucowr.siu.edu/updates/pdfn??V120_A7.pdf.7 Some pharmaceuticals are removed by biotransformation in this break down process; see Page 56, Introduction, supra.8 “Pharmaceuticals in Wastewater Streams: Disposal Practices and Policy Options in Santa Barbara”, supra, page 28, Potential contamination from WWTPs, landfills, and septic tanks.

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Several types of tertiary treatment wastewater treatment systems have been designed to further clean secondary treated wastewaters. The following tertiary systems may also inactivate or capture pharmaceuticals: 1) reverse osmosis systems, 2) ozonation disinfection systems, and 3) light inactivation systems. Each has its advantages and disadvantages. For example, reverse osmosis systems often require the removal of suspended solids first9 and take a lot of energy to remove a wide variety of pharmaceuticals from the wastewater streams, which are concentrated in separated brines creating brine disposal problems. Ozonation systems10 do not inactivate those chemical species not subject to oxidation. Light inactivation systems also use a lot of energy, and are not as effective as ozone treatment of certain species11. Nor do they inactivate those chemical species resistant to photo degradation. Consequently, it is difficult to compare each system’s effectiveness relative to one another where they operate on different chemical species in different manners.12 This article will therefore not evaluate the effectiveness of various wastewater treatment systems to inactivate chemical and pharmaceuticals, but will address the mechanisms inherent in the Biobrimstone™ wastewater treatment process developed by Earth Renaissance Technologies, LLC to inactivate, degrade, and remove some pharmaceuticals and chemicals.

The Biobrimstone™ hybrid chemical/biological dewatering and disinfection

9 EPA 625/R-00/008 Onside Wastewater Treatment Systems Technology Fact Sheet 9, page 3, “Reverse osmosis”.10 To reduce the release of pharmaceuticals and endocrine disruptors into the aquatic environment or to remove them from wastewater, municipal wastewater effluents may be treated with ozone; see “Oxidation of Pharmaceuticals during Ozonation of Municipal Wastewater Effluents: A Pilot Study”, by Marc M. Huber, Anke Gobel, Adrino Joss, Nadine Hermann, Dirk Loffler, Christa S. McArdel, Achim Ried, Hansruedi Siegrist, Thomas A. Ternes, and Urs von Gunten, published in Environ. Sci. Technol., 2005, 39 (11), pp 4290-4299.11 See article entitled “Degradation of Selected Acidic and Neutral Pharmaceutical Products in Primary-Treated Wastewater by Disinfection Processes” by Christian Gagnon, Andre Lajeunesse, Patrick Cezka, Francous Gagne, and Robert Hausler, Ozone: Science & Engineering, Volume 30, Issue 5 September 2008, pages 387-391 where ozone treatment was compared with UV-radiation disinfection processes carried out at the Montreal wastewater treatment plant to determine their effects on pharmaceutical products like salicylic acid, clofibric acid, ibuprofen, naproxen, triclosan, carbamezepine, diclofenac, and 2-hydroxy-ibuprofen. For ozone doses of 20 mg/L were used removal rates as high as 70% were observed. Conversely, the removal rates for UV radiation were often below 10% among the substances studied. Irradiation used for bacterial treatment (25 mJ/cm2) was too low to cause significant breakdown of many of these pharmaceutical substances.12 Testing costs are also burdensome where the nature of these chemicals and pharmaceuticals and their extremely low concentration levels in wastewater makes sampling analysis difficult, and often requires sophisticated laboratory techniques, such as reversed-phase high-performance liquid chromatography–electro spray tandem mass spectrometry following solid phase extraction to determine the presence of targeted pharmaceuticals selected from a priority list.

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wastewater treatment technology was employed at the Montalvo Municipal Improvement District’s wastewater treatment facility in Ventura, California where aeration is employed providing oxidation degradation of some protein pharmaceuticals.13 Montalvo Municipal Improvement District owns the Montalvo Water Pollution Control Plant (Plant), located at 3555 Ventura Road, Montalvo, California. Treated domestic and commercial wastewaters are discharged under Waste Discharge Requirements contained in Order No. 87-092, adopted by the Regional Board on June 22, 1987.

An overview of the Montalvo wastewater treatment processing sequence provides bar screening, comminuting, influent holding tank, two independent sequencing aerobic and denitrification batch reactors, with discharge into percolation ponds. The waste activated wastewater liquids between the floating and settling solids in the sequencing batch reactors is extracted and discharged to the subsurface through four evaporation/percolation ponds with a combined capacity of two million gallons. The aerobic and denitrification treated solids and liquids have polymers added to aid in separation and are sent to a digester to reduce solids volume before draining in woven polypropylene bags on drying beds to collect the solids. The liquids from the woven polypropylene bags in the drying beds are collected and recirculated back through the sequencing batch reactors for nitrification/denitrification. No off-site transfer or usage of treated wastewater is presently employed. As there is no off-site disposal of the treated liquids, effluent limitations are not exceeded. The drawing below outlines a general overview of a processing sequence.

The actual equipment layout of the Montalvo wastewater treatment system comprises an influent wet well, muffin monster grinder, flow screen bar rake, equalization tank, three influent variable speed influent pumps, two sequencing batch reactors (SBRs), and effluent decanted to four percolation ponds. The SBRs utilize various aerobic and anaerobic bacteria to sequentially undergo nitrification and denitrification by adjusting

13 Abstract, “Chemical instability of protein pharmaceuticals: mechanism of oxidation and strategies for stabilization” Biotechnology and bioengineering Journal, 1995 vol. 48, note 5 (129 p.) by Shihong Li; Schoneich C.; Borchardt, R.T.; University of Kansas Department Pharmaceutical Chemistry, Lawrence, KS 66045, 1994, Wiley, New York, New York discussing oxidation chemical degradation of methionine, cysteine, histidine, tryptophan, and tyrosine, which are most susceptible to oxidation due to their high reactivity with various reactive oxygen species

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oxic or aerobic conditions, and anoxic anaerobic/ fermentive anaerobic conditions via the addition and withholding of oxygen14. The biological removal of nitrogen is a two-part reaction called nitrification and denitrification. Nitrification takes place under aerated conditions, where nitrifying bacteria known as nitrosomonas convert the influent ammonium to nitrite, and then another group of nitrifying bacteria known as nitrobacter convert the nitrite to nitrate. These bacteria require free oxygen (at least 3 ppm), as well as alkalinity, correct pH, temperature and time. Efficient nitrification requires ammonia and nitrite as sources of nitrogen in addition to carbon, phosphorous and trace element nutrients.15 The carbon must be inorganic measured as carbonate alkalinity (carbonates and bicarbonates). Sodium bicarbonate or Calcium carbonate is commonly used to increase alkalinity, which should always be at least eight times the level of ammonia. Wastewaters with more than 100 mg CaCO3/L is normally adequate for low levels of ammonia. The lack of carbonate alkalinity will stop nitrification as values outside of 6.0 to 8.5 pH can be expected to reduce nitrification efficiency. As Nitrosomonas bacteria produce acid during growth, the pH must be monitored and adjusted.To finally remove the nitrogen, facultative bacteria consume organic matter (raw wastewater) under anoxic (no free dissolved oxygen) conditions. Facultative bacteria can use free dissolved oxygen, nitrate, sulfate and carbon dioxide as a sort of oxygen source. They prefer free DO, since it’s not combined with anything like nitrate or sulfate.If free DO is not available, they break apart the chemical bond holding the nitrogen and oxygen together in a nitrate molecule (NO3) and utilize the oxygen, freeing the nitrogen to become nitrogen gas. This process of reducing the nitrate to nitrogen gas is called denitrification and requires an electron donor. The two part nitrogen removal and phosphorous removal from wastewater can be tracked using an oxidation reduction potential meter in combination with a dissolved oxygen meter to monitor biological removal. The SBR processes are shown in the diagram below taken from the TPO article:

14 See “It’s Not Black Magic” by Ron Trygar, CET, November 2011 issue of TPO Magazine.15 Efficient Nitrification/Denitrification in Wastewater Treatment, by Karl F. Ehrilich, Ph.D, IET-Aquaresearch, Ltd., Feb. 21, 2012.

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ORP meters were installed in both SBRs at MMID to track the changes in electrical potentials during a typical mix/fill 15 minute aeration cycle, the 70 minute react fill anaerobic cycle, the 50 minute settling cycle, and the 30 minute decant cycle as shown below for SBR #2:

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As noted, the nitrification (3) cycle oxidation reduction potential did not occur, yet the amount of nitrogen in the treated effluent remains low most likely because of the low amount of nitrogen in the influent. It is expected that the SBR nitrogen/phosphate removal cycles can be shortened by Biobrimstone™ pre-treatment removing the suspended solids and reducing the nitrogen and phosphate levels in half so that settlement is not necessary and less dwell time is required for removal. This shortening of the treatment cycles should provide more capacity to treat additional wastewater—future monitoring will evaluate possible expanded treatment capacity from reducing the loading on the sequential batch reactors.

Also, the sulfites from the sulfurous acid treatment provide electron donors should promote denitrification. Presently, the waste activated sludge from the sequencing batch reactors is then pumped to a first Ennix Digester, and then to a second Ennix Digester. The sludge from the second Ennix Digester is mixed with additional polymers and pumped into Geotubes

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placed on a sludge basin for solids separation. To maintain a level and sludge retention time, decant from the second Ennix Digester is pumped back into the sequencing batchreactors. The decant from the Geotubes is pumped back to the sequential batch reactors or the second Ennix Digester. The dried sludge from the Geotubes is periodically hauled to a disposal site.The wet weather plant has a design capacity of 750,000 gallons per day (gpd). An average daily dry weather flow of up to 366,000 gpd was discharged during 1995. Waste sludge is treated onsite by aerobic digestion, and then discharged into lined sludge drying beds with woven polyethylene bags to collect the solids. Treated separated sludge is hauled offsite and disposed of at a legal disposal facility.During high flows and/or maintenance of the sequential batch reactor process, a 1,000,000 gallon concrete lined emergency is used to hold influent for later return to the sequencing batch reactors. A standby emergency power generator is at the ready for any power interruption. The drawing below outlines the actual plant layout processing sequence.

The plant utilizes four sequential evaporation/percolation ponds located in Section 20, Township 2N, Range 22W, San Bernardino Base & Meridian. The plant's latitude is 34°14'17"; its longitude 119°11'34". The evaporation/percolation ponds take up over three quarters of the wastewater treatment facility footprint as can be seen from the pond locations shown below. These ponds are 8 to 9 feet in depth, with their bottoms approximately 5 feet above the aquifer, whose ground water level seasonally varies from approximately 180 inches during the summer to approximately 170 inches during the

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rainy season in February. The ideal would be to reduce the number of evaporation/percolation ponds required for soil aquifer infiltration of treated wastewater decants.

Percolation Pond #1 (Pond 1) is L shaped approximately 135’ x 120’ with sloping sides and a depth of approximately 9 feet having a capacity of approximately 1,090,584 gallons, which equals 121,176 gallons/foot depth, or for every inch in increased depth 10,098 gallons is added to the percolation pond. Percolation Pond #2 (Pond 2) is approximately 150’ x 240’ with sloping sides and a depth of approximately 7 feet having a capacity of approximately 1,429,428 gallons, which equals 204,204 gallons/foot depth, or for every inch in increased depth 17,017 gallons were added to the percolation pond. Percolation Pond 3 (Pond 3) is approximately 174’ x 135’ with sloping sides and a depth of approximately 7 feet having a capacity of approximately 1,229,936 gallons, which equals 175,705 gallons/foot depth, or for every inch in increased depth 14,642 gallons is added to the percolation pond. Pond 3 is located on very porous soil, which rapidly drains any wastewater added thereto at greater infiltration rates than the other three ponds. Percolation Pond #4 is approximately 120’ x 120’ with a depth of approximately

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8 feet giving it a capacity of approximately 598,400 gallons when filled, or 74,800 gallons/foot, which equals 6,234 gallons for every inch in increased depth. To determine if the Biobrimstone processing sequence would improve the current MMID processing plant’s ability to remove PPCP’s and its costs, approximately one half of the influent was diverted and pre-treated with sulfurous acid to disinfect, precipitate and remove the suspended solids with sorbed PPCP’s from the treated effluent, which will then be lime adjusted to remove heavy metals before entering the MMID SBRs as shown below.

Acidification was accomplished with three tanks. The first mixed sulfurous acid with the influent to acid leach the heavy metals into solution. This acidified influent was sent to a settling tank to disinfect and agglomerate the suspended solids for filtration through a first geotextile tube. The disinfected filtered effluent was then sent to a third tank for admixing with lime to elevate the pH to precipitate out phosphorous and heavy metals, which were filtered by a second geotextile tube as shown below:.

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The resultant pre-treated influent was then tested for pharmaceuticals removal against the baseline readings. Below is the site layout showing how the diverted influent is pre-treated before entering the existing MMID SBR treatment system.

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The testing protocol first established baselines for coliforms, heavy metals, and the pharmaceuticals in the MMID influent and SBR treated effluent. Against this baseline, the impacts on PPCPs and costs of the Biobrimstone™ pre-treatment was then determined. A final bioreactor post-treatment test will be conducted using a Biodome™ testing module provided by Wastewater Compliance Systems, Inc. of Salt Lake City, Utah.

Coliforms BaselineColiform and heavy metals samples were sent to FGL on September 15, 2010. The FGL lab analysis showed both the influent and treated effluent had total and fecal coliforms >1600 MPN as a baseline.

Heavy Metals BaselineThe FGL lab analysis showed low levels of heavy metals in the influent. The following influent heavy metals concentrations establish a baseline:

Barium 0.095 mg/lCopper 0.34 mg/lLead 0.005 mg/lMercury 0.0007 mg/lMolybdenum 0.02 mg/lNickel 0.01 mg/lZinc 0.2 mg/l

The treated effluent removed all but the following:Barium 0.049 mg/lMolybdenum 0.01 mg/l

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The existing MMID treatment process thus removed most of the heavy metals normally encountered. The ERT sulfurous acid/liming cycle should remove the remaining Barium as Barium Sulfite (BaSO3), and Barium Sulfate (BaSO4) precipitates. Calcium in the liming process should remove molybdenum as calcium molybdinate (CaMoO) precipitates. If other influent heavy metals become an issue, the Biobrimstone process should remove them via the liming pH adjustment process:Copper as Copper (I) hydroxide (Cu2O), and Copper (II) hydroxide [Cu(OH)2].

Lead (II) as Lead (II) hydroxide (Pb(OH)2)Mercury (I) as Mercury (I) chloride (Hg2Cl2) in saline influent, Mercury (I) sulfate (Hg2SO4) in sulfurous acid treatment, or Mercury (II) hydroxide (HgO) in the liming adjustment processNickel as Nickel (II) hydroxide (Ni(OH)2)

Zinc as Zinc hydroxide (Zn(OH)2)

PPCP BaselineTo establish a PPCP baseline, PPCP samples of the Montalvo influent and treated effluent were sent to AmeriTest’s Sacramento Laboratory on September 20, 2010 as this was the closest EPA certified laboratory with PPCP testing capabilities. Testing was based on 1694 Anti-Bacterial (LCMS/MS), 1694 Pharmaceuticals (LCMS/MS), 1698 Steroids/Hormones (LCMS/MS), and Organochlorine Pesticides by HRGC/HRMS tests to measure CEC’s and PPCPs.The TestAmerica Final Report dated November 10, 2010 surveyed samples of the Montalvo influent and treated effluent taken September 20, 2010 for pesticides, pharmaceuticals, and steroids and hormones. The TestAmerica Final report showed that the influent and effluent contained none of the following Water,8081A, Pesticides: alpha-BHC, gamma-BHC (Lindane), Heptachlor, Aldrin, beta-BHC, delta-BHC, Heptachlor epoxide, Endosulfan I, gamm-Chlordane, alpha-Chlordane, 4,4’-DDE, Dieldrin, Endrin, 4,4’-DDD, Endosulfan II, 4,4’-DDT, Endrin aldehyde, Mehodxychlor, Endosulfan sulfate, Endrin keton, and Toxaphen. Also, the influent and treated effluent contained none of the following Water, Steroids/Hormones: Equilenin, 17a-Estradiol, 17b-Estradio, Estriol, Estrone, 17a-Ethynyl Estradio, Progesterone, and Testosterone. However, the Montalvo influent and effluent contained the following Water, 1694 Pharmaceuticals above the reporting limit: Caffeine 1500 ng/L (3 times reporting limit), Cotinine (1.2 times reporting limit), Ibuprofen 450 ng/L (2 times reporting limit), Naproxen 620 ng/L (1.2 times reporting limit), Sulfamethoxazol 6000 ng/L (25 times reporting limit), Trimethoprim 920 ng/L (9 times reporting limit), Diltiazem 410 ng/L (8 times reporting limit), and Gemfibrozil 1800 ng/L (3.6 times reporting limit). Acetaminophen, Iobromide, Fluoxetine, Lincomycin, and Tylosin were not detected and Carbamazepine Triclosan, and Triclocarban were below the reporting limits. Also note the pharmaceutical concentrations of the influent and treated effluent were approximately the same:Pharmaceuticals Reporting Limit Date 9/20/2010 Influent EffluentAcetaminophen 500 ng/L ND NDCaffeine 500 ng/L 1500 ng/L 1600 ng/LCarbamazepine 100 ng/L 19 J 20 J

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Cotinine 100 ng/L 120 B 150 BIbuprofen 250 ng/L 450 ng/L 440 ng/LIopromide 500 ng/L ND NDLincomycin 100 ng/L ND NDNaproxen 500 ng/L 620 ng/L 660 ng/LSulfamethoxazole 250 ng/L 6000 ng/L 6300 ng/LTrimethoprim 100 ng/L 920 ng/L 880 ng/LDiltiazem 50 ng/L 410 ng/L 390 ng/LFluoxetine 250 ng/L ND NDGemfibrozil 500 ng/L 1800 ng/L 1800 ng/LTriclosan 500 ng/L 380 J 430 JTriclocarban 100 ng/L 32J 31 JTylosin 100 ng/L ND ND

Baseline Testing SummaryIn comparing the concentrations of PPCPs in the influent and the treated effluent, the existing Montalvo SBR treatment had little effect on the removal of pharmaceuticals and coliforms, but there was some removal of heavy metals. Consequently future Montalvo testing was focused on tracking: 1) disinfection and heavy metals (using FGL), and 2) pharmaceuticals (using TestAmerica). As so much disinfection data has been taken over the last 4 years at Montalvo, only a couple of samples were taken to check coliform reduction from >1600 MPN to <2 MPN to make sure the retrofit system is working. Heavy metals and irrigation suitability of the treated effluent was also tested by the FGL Laboratory. Consequently, pharmaceutical samples were separately sent to TestAmerica West Sacramento Lab for a more focused analysis based on 1694 Anti-Bacterial (LCMS/MS), 1694 Pharmaceuticals (LCMS/MS), 1698 Steroids/Hormones (LCMS/MS), and Organochlorine Pesticides by HRGC/HRMS to measure CEC’s and PPCPs).

Green House GasesWaste activated digesters are used at Montalvo to reduce approximately 40 tons

of the 240 tons/year of sludge generated after separation using an essentially anaerobic digestion process, which emits hydrogen sulfide, carbon dioxide, methane, and other green house gases. One of the testing objectives was to evaluate if solids separation and reduction could be achieved without polymers and anaerobic digestion avoiding the production of these green house gases.

Hanging Bag TestsAs the heavy metals precipitates are suspended in the liquid phase or sorbed onto

the suspended solids, it was necessary to effectively remove them with filtration using minimal electrical costs. For filtration, geotextile tubes were selected as they had been successfully employed at the MMID facility in the past, utilized no energy costs for separation, added oxygen during filtration for disinfection, and contained odors from the solids. On October 29, 2010, nine different geotextile hanging bags were tested at the MMID facility to determine drainage time for sizing the geotextile bags to handle the treated effluent vs. clarity of the filtrate. These hanging bag tests showed the following:

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Hanging Bag Test October 29, 2010

Geotextile material Color Acid drain time Clarity Basic drain time Clarity(minutes) (minutes)

*A. CSI 1853 w/4 oz nonwoven Tan/black liner 1 min 30 sec Best -3 25 sec. Best-5*B. CSI 1853 w/8 ox nonwoven Tan/black liner 1 min 30 sec Best -2 30 sec. Best-3*C. CSI 4x6 w/4 oz nonwoven Black/black liner 1 min 10 sec Best 1 28 sec. Best-2*D. CSI 4x6 w/ 8 oz nonwoven Black/black liner 30 sec. Best-5 36 sec. Best-6*E. CSI 4x6 w/4 oz nonwoven Black/black liner 32 sec. Best-6 30 sec. Best-1*F. CSI 1853 Tan 60 sec. Best-9 40 sec. Best-4*G. CSI 4x6 Black 20 sec Best-8 22 sec. Best-7**H. Thrase-Ling WIK (CSI) White 25 sec. Best-4 20 sec. Best-8**I. Huesker 1000 (CSI) White 40 sec. Best-7 1 min 35 sec. Best-9

*All A-G out hanging bag fabrics are polypropylene with nonwoveninside liner fabrics extruded andneedle punched polypropylene classified by weight/square yard

**H and I are woven polyesters

Based on these hanging bag tests, standard 30 ft C/30 ft/L 30 ft tubes were ordered to provide 15,000 gallon/hr filtration of the 90,000 gallons/six hour shift as the limiting factor was the 4x6 pp fabric which drains at 25 gpm/sf. Fabric C, the GSI 4x6 w/4 oz nonwoven lined geotextile tube was selected for acid filtration and the Fabric H, the Thrase-Ling WIK (GSI) (Triton TT1712 PET) geotextile tube was selected for basic filtration.

PPCP TESTING APPROVALSApproval of the testing protocol to install the pre-treatment retrofit equipment was submitted on August 22, 2010 to the SDHS-Recycled Water Unit, 1180 Eugenia Place, Ste. 200, Carpinteria, CA 93013 Health Department to reduce the pharmaceutical/personal care products at MMID WWTP.

The reduction mechanisms to be evaluated to improve pharmaceutical removal and decomposition are as follows:

1. Sorption onto suspended solids—removal of steroid hormones from water is largely the result of sorption (see page 4 “Anaerobic degradation of steroid hormones by novel denitrifying bacteria” by Michael Fahrbach, Tag der mundlichen Prufung: 12.Dezember 2006.)

Sulfurous acid addition at around pH 3 self-agglomerates suspended solids according to the Montalvo SAT tests; leaving clear treated effluent.

2. Acid solids suspension--Coagulation/Flocculation is improved by adding acid prior to coagulant additions such as aluminum chloride, ferric sulfate, ferric chloride,

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(see page 19 “Anaerobic degradation of steroid hormones by novel denitrifying bacteria” by Michael Fahrbach, Tag der mundlichen Prufung: 12.Dezember 2006; “Micropollutants—New Challenge in Wastewater Disposal?”, page 8 EAWAG news 57)

The sulfurous acid addition disinfects and acid leaches heavy metals and other chemicals off the suspended solids for subsequent pH adjustment removal.

3. Lime Flocculation—organic compounds potentially removed through coagulation/flocculation are hydrophobic, low molecular weight acidic function groups (e.g., carbonyl and carboxyl function groups), or high molecular weight compounds (USEPA, 1989). Raising the pH after acidification and filtration, therefore may remove pharmaceuticals and chemicals via flocculation.

Raising the pH of the filtered acidified treated effluent with subsequent lime addition at around a pH of 7 to 9 precipitates metal hydroxides and other Ca+2 salts, which are easily filtered.

4. Chemical precipitation—hard water containing Ca+2 ions from lime binds with pesticide molecules to form insoluble salts and precipitate out of solution, such as 2,4-D, dicamba, glyphosate and clopyralid (page 2, “Carrier Water Quality Influences Pesticide Stability” by Dara Park et al, Clemson Cooperative Extension; http://www.clemson.edu/extension/horticulture/turf/pest_guidelines/wa...) Excess sulfates and phosphates also precipitate out as harmless calcium salts. In addition, heavy metal hydroxides precipitate out as the pH is raised; see Hoffland Environmental Inc., Wastewater Treatment Systems, “Hydroxide Precipitation.”; http://www.hoffland.net/src/tks/3.xml. Some, such as Ferric hydroxide, often contain various chemicals, such as arsenic sorbed onto them, and can be removed via filtration.

5. Photodegradation—several pharmaceutical compounds have been shown to degrade due to the action of sunlight (Boreen, A.L., Arnold, W.A., and McNeill, K. Photodegradation of pharmaceuticals in the aquatic environment: A review, Aquat. Sci 65, 320-341, 2003; Poiger, T., Buser, H.R. and Muller, M.D. Photodegradation of the pharmaceutical drug diclofenac in a lake: Pathway, field measurements, and mathematical modeling, Environ. Toxicol. Chem. 20 256-263, 2001). The clear double filtered treated effluent is thus amenable to ultraviolet photodegradation of certain pharmaceuticals.

The double filtered clear filtrate is susceptible to photodegradation in open ponds.

6. Acid hydrolysis—sulfonylurea herbicides are more susceptible to acid hydrolysis at pH less than 6.0 (see page 1, “Carrier Water Quality Influences Pesticide Stability” by Dara Park et al, Clemson Cooperative Extension; http://www.clemson.edu/extension/horticulture/turf/pest_guidelines/wa...)

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Lowering the pH to around 2 to 3.5 for disinfection also effectuates some pharmaceuticals acid hydrolysis reduction.

7. Basic hydrolysis—organophosphorous pesticides are primarily susceptible to alkaline hydrolysis with less acidic catalysis (Abstract, “Abiotic hydrolysis of pesticides in the aquatic environment.” Rev. Environ Contam Toxicol. 2002; 175:79-261 by Katagi T.; http://www.ncbi.nlm.nih.gov/pubmed/12206055.

Raising the pH from 7 to 9 to precipitate heavy metals and calcium salts, also effectuates some pharmaceuticals basic hydrolysis reduction.

8. Chemical reduction—free sulfur dioxide in solution is a powerful reducing agent used to reduce chlorine and other hypochlorites before open stream discharge (Tchobanoglous, George. Wastewater Engineering. 3rd Ed. New York: McGraw Hill, 1979)

Free SO2 used for disinfection also reduces certain oxidizing chemicals, such as perchlorates, chlorine, and other hyperchlorites, which may have entered the influent.

9. Biodegradation—the transformation or biological decomposition of drug substances can take place under aerobic and/or anaerobic conditions. For example, steroid estrogens in both wastewater and sewage sludge showed that estradiol and estrone were mainly degraded in the denitrification step during wastewater treatment (removal > 90%), (see page 67 “Anaerobic degradation of steroid hormones by novel denitrifying bacteria” by Michael Fahrbach, Tag der mundlichen Prufung: 12.Dezember 2006; “Micropollutants—New Challenge in Wastewater Disposal?”, page 8 EAWAG news 57). “The removal rate of endocrine disrupting compounds (EDCs, measured as estrogen, anti-estrogen, androgen, and anti-androgen with yeast essay screen) was also conducted. On a typical day (November 11, 2010), at an HRT of 8 days, and an average water temperature of 5° C, the bio-film in the Poo-Gloos removed 64% of carbonaceous organic material (measured as COD), 96% of TSS, 89% of ammonia/ammonium, and 13% of total Phosphorous. 90% of EDCs were also removed. “ (see WEFTEC abstract for the Oct, 2011 conf in LA submitted by Wastewater Compliance Systems, Inc.)

The twice filtered acidified/alkalinized treated wastewater is then passed through the bacterial digesters for further pharmaceuticals degradation.

10. As wastewater influent is a complex system of various components, full scale field tests are required to determine the suitability of Biobrimstone™ pre-treatment as an alternative to more expensive reverse osmosis pharmaceutical removal systems.

On September 30, 2010, Kurt Sousa of the SDHS-Recycled Water Unit discussed and approved the proposed testing protocol for the field tests at the Montalvo Municipal Improvement District (MMID) of a pre-treatment retrofit of the MMID wastewater treatment facility to determine operational costs and improvement of the existing treated

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effluent and any additional benefits by disinfecting and removing upfront suspended solids and heavy metals from the influent before it enters the MMID plant’s SBR treatment system. As the filtered, disinfected, pre-treated influent was passed through the MMID existing SBR treatment system no further action was required by the Health Department where the discharge permit conditions wouldn’t change or deteriorate with Biobrimstone™ pre-treatment process. In addition to aeration by the existing MMID SBR treatment system, ERT geotextile bag filtration further exposed the filtrate to additional aeration for virus inactivation.

He also indicated that the Health Department had not yet promulgated regulations regarding PPCP removal and therefore his office was not able to provide input or assistance as to this aspect of the testing protocol.

With respect to possible use of the disinfected, demetalized pre-treated influent for landscaping on-site at the facility, he indicated that there is an exemption for wastewater treatment operators using their own treated effluent on site for landscaping under Title 22.

Coliforms, Heavy Metals, and PPCP Baseline Tests

Coliforms, Heavy MetalsOn September 15, 2010 background coliform and heavy metals samples of the

influent and treated effluent were sent to FGL for testing. These samples showed the following:

MMID PPCP Baseline Test Summary Coliforms/Heavy MetalsParameters/Date Reporting Limit Baseline Date Influent Treated EffluentColiforms >10 MPN 9/14/2010 >1600 MPN >1600 MPN

Heavy Metals 9/14/2010Antimony ND NDArsenic ND NDBarium 0.095 mg/L 0.049 mg/LBerylium ND NDCadmium ND NDChromium ND NDCobalt ND NDCopper 0.34 mg/L NDLead 0.005 mg/L NDMercury 0.00007 mg/L NDMolybdenum 0.02 mg/L 0.01 mg/LNickel 0.01 mg/L NDSelenium ND NDSilver ND NDThallium ND NDVanadium ND NDZinc 0.2 mg/L ND

PPCPs

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On September 21, 2010, background samples of the influent and treated effluent were sent to TestAmerica Labs for testing. The TestAmerica lab reports of the Montalvo WWTP raw influent and treated effluent showed the following PPCPs in the influent:

MMID PPCP Baseline Test Summary Pesticides, Pharmaceuticals, (9/21/2010)Steroids/Hormones

PesticidesReporting Limit

Baseline Date Influent

Treated Effluent

Pesticides >10 MPN 9/21/2010 alpha-BHC 0.24 ug/L ND NDgamma-BHC (Lindane) 0.24 ug/L ND NDHeptachlor 0.24 ug/L ND NDAldrin 0.24 ug/L ND NDbeta-BHC 0.24 ug/L ND NDdelta-BHC 0.24 ug/L ND NDHeptachlor epoxide 0.24 ug/L ND NDEndosulfan I 0.24 ug/L ND NDgamma-Chlordane 0.24 ug/L ND NDalpha-Chlordane 0.24 ug/L 0.048 J,PG ND4,4'-DDE 0.49 ug/L ND NDDieldrin 0.49 ug/L ND NDEndrin 0.49 ug/L ND ND4,4'-DDD 0.49 ug/L ND NDEndosulfan II 0.49 ug/L ND ND4,4'-DDT 0.49 ug/L ND NDEndrin aldehyde 0.49 ug/L ND NDMethoxychlor 9.8 ug/L ND NDEndosulfan sulfate 0.49 ug/L ND NDEndrin ketone 0.49 ug/L ND NDToxaphene 9.8 ug/L ND ND

Steroids/Hormones 9/20/2010Equilenin 50 ng/L ND ND17a-Estradiol 100 ng/L ND ND17b-Esradiol 100 ng/L ND NDEstriol 500 ng/L ND NDEstrone 100 ng/L ND ND17a-Ethynyl Estradiol 500 ng/L ND NDProgesterone 50 ng/L ND NDTestosterone 200 ng/L ND ND

Pharmaceuticals 9/20/2010Acetaminophen 500 ng/L ND NDCaffeine 500 ng/L 1500 ng/L 1600 ng/LCarbamazepine 100 ng/L 19 J 20 JCotinine 100 ng/L 120 B 150 BIbuprofen 250 ng/L 450 ng/L 440 ng/LIopromide 500 ng/L ND ND

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Lincomycin 100 ng/L ND NDNaproxen 500 ng/L 620 ng/L 660 ng/LSulfamethoxazole 250 ng/L 6000 ng/L 6300 ng/LTrimethoprim 100 ng/L 920 ng/L 880 ng/LDiltiazem 50 ng/L 410 ng/L 390 ng/LFluoxetine 250 ng/L ND NDGemfibrozil 500 ng/L 1800 ng/L 1800 ng/LTriclosan 500 ng/L 380 J 430 JTriclocarban 100 ng/L 32J 31 JTylosin 100 ng/L ND ND

The tests thus established that only barium and molybdenum were present in the treated effluent, and that coliforms were not disinfected as part of the MMID WWTP operations. Further, only some pharmaceuticals were present in the influent and treated effluent.

California Regional Water Quality Control Board

On October 20, 2010, MMID requested permission to conduct the PPCP tests from the California Regional Water Quality Control Board. A meeting was held on December 8, 2010 with staff Senior Water Resources Control Engineer Ph.D. P.E. Rebecca Chou and water resource control engineer David Koo to discuss the request and provide additional information regarding the project. At that time, MMID permit renewal was discussed, along with testing requirements for the project. The staff was favorably disposed to the pre-treatment project at the meeting, and later requested the resubmission of the project overview and data. In April of 2011, having not heard further from the California Regional Water Quality Control Board, MMID notified the Board that it was proceeding with the construction of the retrofit as it assumed that the California Regional Water Quality Board had taken the same position as the Health Department that no further action is required where the discharge permit conditions don’t change or deteriorate with this pre-treatment process.

On November 23, 2011, the California Regional Water Quality Control Board was notified that basic construction was completed November 23, 2011, and that PPCP testing would commence.

Construction

In January, 2011, Kelly Polk, Stan Rusk, and Enrique Perez, independent contractors for MMID and Terry Gong and John Harmon of ERT began the design of automated equipment for continuous flow treatment of 70 g/min of the MMID influent as shown below:

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The design utilized three treatment tanks and two geotextile bags with different weaves to not only add oxygen for disinfection, but filter and contain the suspended solids. The lime adjusted second geotextile drain bag also acted as temporary storage of the filtrate to defer entry into the SBRs until the evening hours to take advantage of the extra treatment capacity when inflows were the least. Thus, the geotextile bags more evenly spread the influent load into the SBRs so that they were at optimal capacity.

The retrofit minimally impacted the layout of the present MMID plant and utilized enclosed tanks for odor control.

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The sulfur generator generated SO2 as needed eliminating the need for gas storage.

The engineering and design of a fully automated Biobrimstone wastewater pre-treatment system was completed in December, 2011.

On December 8, 2011, the system was run to test the geotextile bags filtration and odor containment capabilities. The suspended solids were removed from the filtrate without H2S production, and the odors were contained.

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The filtrate was slightly turbid, and could be clarified with 90 micron filtration for

open stream discharge. However, turbid filtrates are sufficient for SBR treatment, so no further filtration was incorporated in the final design.

On January 5 and 6, 2012, the new Biobrimstone™ pre-treatment system was run to collect laboratory samples to confirm disinfection, heavy metals removal, and PPCP removal. The 30 mesh self cleaning screen worked well to prevent plugging of the sulfur burner, but a single geotextile black bag was too small for continual 24 hour operation. This suggested that a second or larger bag should be employed to defer and continue

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dewatering into the evening hours when nighttime influent flows entering the SBRs were less than half the daytime flows.

Coliform samples were taken from Bag 1 acid filtrate, and Bag 2 lime filtrate and sent to FGL Environmental. These tests showed good initial disinfection (<2 MPN) through two-thirds of the system through Bag 1, but since Tank 3 and Bag 2 were not disinfected from prior runs they had the same level of disinfection as the influent (>1600 MPN). Thus, a start-up protocol was designed to first disinfect the entire system running ~pH 3 acid for about an hour before the liming system was turned on to adjust the pH of the pre-treated influent before entering into the SBRs.

In addition, five samples of the influent, and the pre-treated: Bag 1 filtrate, Bag 1 90μ filtrate, Bag 2 filtrate, and Bag 2 90μ filtrate were sent to FGL Environmental for general minerals, CAM 17 metals, TSS, NH3-N, Phosphorous TKN, Total N, PO4, BOD, and LTB analysis. These tests showed that pre-treatment reduced total nitrogen from 52 mg/L to 35 mg/L (20 mg/L if 90μ filtered), and that phosphorous was reduced from 9.2 mg/L to 5.9 mg/L (3.7 mg/L if 90μ filtered). BOD was slightly lowered by pre-treatment (from 282 mg/L to 206 mg/L). The SAR was lowered from 8.3 to 3.6 and chlorides were reduced from 710 mg/L to 150 mg/L so the pre-treated influent was suitable for land application. An FGL follow-up irrigation suitability test, and phosphate and nitrogen tests will be taken on the Bag 2 filtrate to verify the initial results.

Heavy metals were minimally present in the influent, and were reduced somewhat by the addition of lime and subsequent filtration. The lab results did not show significantly increased metal removal by 90μ filtration, so future metals tests will only be re-run for the influent vs. the Bag 1 acid and Bag 2 base filtrates.

Next five samples of the influent, and the pre-treated: Bag 1 filtrate, Bag 1 90μ filtrate, Bag 2 filtrate, and Bag 2 90μ filtrate were sent January 6, 2012 to TESTAMERICA for PPCP analysis of pharmaceuticals present in the MMID influent. Based on the previous baseline results, only Acetaminopen, Bisphenol-A, Caffeine, Ibuprofen, Naproxen, Sulfamethoxazole, Trimethoprim, Gemfibrozil, and Triclosan were tested. The results showed that Bisphenoll-A was completely removed by Bag 1 acid treatment. Caffeine was reduced 33% by Bag 2 lime treatment. Ibuprofen was reduced 60% by acid treatment. Naproxen was reduced 33% by lime reduction. Triclosan was reduced 50% by lime reduction. The other post treatment pharmaceuticals showed higher concentrations than the influent and were thought to be the result of testing samples taken later in the day, which may have had higher concentrations of pharmaceuticals than in the influent, since there was some pH rising drift during the day.16 Evidence for this change in concentrations was further evident when an additional sample of Bag 2 filtrate was required for completion of the 90μ filtration test and the lab results showed higher pharmaceutical concentrations than was present in the initial Bag 2 filtrate sample as shown in Table 2. Consequently, further tests are required to confirm the preliminary results comparing the Pharmaceutical reductions between the influent and unfiltered pre-treated effluent from Bag 2 shown below:

16 See page 7 footnote 3 of “Pharmaceuticals in Wastewater Streams: Disposal Practices and Policy Options in Santa Barbara”, May 2007 by James Kallaos et al, Donald Bren School of Environmental Science & Management, University of Santa Barbara wherein it was found that effluent samples not timed to coincide with influent samples result in some effluent concentrations being larger than the influent concentrations.

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Pharmaceuticals 01/05/2012 Influent* Effluent*Acetaminophen NR 87000E

Bisphenol-A 100% reduction 2500 NDCaffeine 33% reduction 180000 ng/L 100000 ng/L

CarbamazepineCotinineIbuprofen 60% reduction 35000 ng/L 15000 ng/LIopromide

LincomycinNaproxen 33% reduction 18000 ng/L 12000 ng/L

Sulfamethoxazole ** 860 ng/L 1500 ng/LTrimethoprim ** 310 ng/L 780 ng/L

DiltiazemFluoxetine

Gemfibrozil ** 990 ng/L 3200 ng/LTriclosan ~50% reduction 28000E ng/L 15000 ng/L

TriclocarbanTylosin

As the initial tests failed to show significant PPCP removal differences by 90μ filtration, future tests were re-run only for the influent vs. Bag 1 and Bag 2 filtrate samples.

The flows through the pre-treatment system remained constant during the runs based on the early morning adjustments. The pH of Tank 1 drifted upward during the day starting at about 1:30 p.m. It is therefore believed that the concentrations of the various water components became more concentrated during the day, which would account for some of the later readings having higher pharmaceutical concentrations than the influent taken almost two hours earlier. Consequently, further PPCP testing was conducted to confirm that these ratio reductions continue to occur.

A new woven white bag similar to that used for liming precipitation removal without a liner was ordered for new runs on January 18, 2012 to determine if faster dewatering would be possible. This new woven white bag was part of a stress test of the Yardley filter by dropping a chopper pump further into the equalization tank to test filter and bag performance with coarser solids. The chopper pump was then placed at the same level to test if fine particles would be produced possibly impacting the 30 mesh filter. The 30 mesh filter continued to perform well even with the courser solids.

These runs established:1. Additional or larger bags with 24 hour run capacity need to be employed, with one on standby while the other drained.2. 90μ filtration was not required unless the effluent was for discharge in an open stream, or if total nitrogen and phosphorous had to be reduced.3. A new Phase II sulfur burner equipment design is required, which doesn’t balance flow streams into Tank 1 to increase acidification faster in response to pH drift. 4. Some PPCP removal occurred.5. The pre-treated wastewater provided irrigation quality water suitable for re-sale.

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6. The pre-treated wastewater reduced nitrogen and phosphorous concentrations expanding the capacity of the SBRs to remove the same. 7. More operator options were available by using acid, lime, delayed SBR deliveries, etc. providing more flexible operations—particularly with respect to accelerating SAT treatment using mild acid and adjusting time of deliveries.

Follow-Up Lab Test ResultsFollow-up pharmaceutical and personal care product (PPCP) tests were conducted

at the Montalvo facility on February 9, 2012 after the system was disinfected by running 2 hours of pH 3 sulfurous acid through the entire system. FGL Laboratories coliform tests confirmed that both Bag 1 Acid and Bag 2 Basic samples had <2 MPN so that the entire system held disinfection. Additional samples of the influent, Bag 1 Acid and Bag 2 Basic were then sent to FGL Laboratories for irrigation suitability and nitrogen/phosphorous testing. These FGL Laboratories showed:

MMID Irrigation SuitabilityTest Matrix

Table 2-5*

Potential Problem* units Degree of Restriction on UseAcid Pre-Treated WW

Basic Pre-Treated WW

None Slight to Moderate Severe

2.4 3 pH Normal Range 6.5-8.4Salinity

3.23 3.02 ECw dS/m <0.7 0.7 - 3.0 >3.01530 2670 TDS mg/L <450 450 - 2000 >2,000

Infiltration4.4 3.9 SAR**

SAR = 0-3 & ECw = >0.7 0.7 - 0.2 <0.24.4 & 3.23 3.9 & 3.02 SAR = 3-6 & ECw = >1.2 1.2 - 0.3 <0.3

SAR = 6-12 & ECw = >1.9 1.9-0.5 <0.5SAR = 12-20 & ECw= >2.9 2.9-1.3 <1.3SAR = 20-40 & ECw = >5 5.0-2.9 <2.9Specific Ion Effects

252 259 Sodium mg/L3.23 3.02 Surface irrigation SAR <3 3 to 9 >90.011 0.011 Sprinkler irrigation meq/L <3 >3180 200 Chloride mg/L0.005 0.005 Surface irrigation meq/L <4 4 to 10 >10

Sprinkler irrigation meq/L <3 >30.8 0.9 Boron mg/L <0.7 0.7-3.0 >3.0

Bicarbonate meq/LND ND overhead sprinkling <1.5 1.5 to 8.5 >8.5

*Table 2-5 Guidelines for Interpretation of Water Quality for Irrigation, Page 40 Western Fertilizer Handbook, Ninth Edition, Interstate Publishers Inc, Danville, Ill. 2002.

**SAR = Na/√(Ca + Mg)/2

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The TDS and Electrical Conductivity when taken separately are higher than normal for irrigation water. However, when combined with the SAR readings reflecting the elevated sulfate and calcium levels in the pre-treated recovered wastewater, which offset the sodium chlorides, the Biobrimstone pre-treatment provides quality irrigation water as shown in the green and blue readings in the matrix applying the Western Fertilizer Handbook Table 2-5 criteria. These MMID Biobrimstone treated reclaimed wastewaters were also similar in composition to those tested at Saticoy, where the reclaimed conditioned wastewaters were proved suitable for raising salt sensitive avocados and other crops.Conditioned treated effluent at Montalvo contained 33 mg/L total Nitrogen and 6.6 mg/L total Phosphorous, 240 mg/L Calcium, 57 mg/L Magnesium, 20 mg/L Potassium, and 259 mg/L Sodium, 1890 mg/L Sulfate, 200 mg/L Chloride, and 1.5 mg/L Nitrate, where 1 mg/L = 2.72 lbs/AF. Assuming current prices for Nitrogen at $.532/lb, Phosphate at $.599/lb, Calcium at $.08/lb, and Potash at $.437/lb, the conservative values of the main fertilizer components contained in the treated effluent would have a fertilizer value of $134/AF.

Constituent LBS/AF*CURRENT $

Value/AFTotal

Nitrogen89.76 47.75

Phosphorus 17.82 10.67Calcium 652.8 52.22Magnesium 155 Potassium 54.4 23.77Sodium 704.5 Sulfate 5140Chloride 544

TOTAL Fertilizer

value$134/AF

Lastly, pharmaceutical samples of the influent, Bag 1 Acid and Bag 2 Basic were sent to TestaAmerica’s Sacramento Laboratory for testing. Detection limits for Bisphenol-A were raised to 3000 ng/L, well beyond its influent concentration, for more accurate testing of caffeine, ibuprofen, and naproxen, which had thousands order of magnitude concentration than Bisphenol-A. These tests more accurately confirmed the reductions of caffeine, ibuprofen, and naproxen as shown below:

Pharmaceuticals 02/09/2012 reduction Influent Bag 1/Bag 2

Acetaminophen 17%/9% red. 120,000 100000/110000Bisphenol-A ND* ND*Caffeine 33%/22% red. 140000 ng/L 94000/110000Carbamazepine

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Cotinine Ibuprofen 44%/18% red. 23000 ng/L 13000/19000**Iopromide Lincomycin Naproxen 8%/16% red. 13000 ng/L 12000/11000Sulfamethoxazole 35%/** 1200 ng/L 790/1500Trimethoprim 25%/** 510 ng/L 380/750**Diltiazem Fluoxetine Gemfibrozil ** 1100 ng/L 1800**/1600**Triclosan ~62%/61% red. 1500 ng/L 580/590JTriclocarban Tylosin

*The detection limits for Bisphenol-A were raised beyond the influent concentrations to better measure Caffeine, Ibuprofen, Naproxen and Sulfamethoxazole percentage removal, so Bisphenol-A reduction calculations were not be made.**these measurements showed higher concentrations in the effluent than in the influent, so the samples may not have been timed to coincide for comparison.

It is interesting to note that the acidified filtrate from Bag 1 showed greater PPCP reductions for some pharmaceuticals than those shown for the neutralized filtrate from Bag 2. Further, daily influent concentrations relative to the treated filtrates from Bags 1 and 2 at MMID are exacerbated as MMID is a smaller plant where the evening influent flows are roughly half those of daytime influent flows. The one month testing delays in receiving PPCP results are of limited value for field operations. Where these low concentration PPCP components are not visible or directly responsive to other easily measured factors such as pH, rapid operational adjustments are not possible. Thus, until new field testing protocols and testing techniques are designed to better match the tested influent concentrations relative to the treated filtrates in real time, it is difficult to firmly quantify PPCP reductions because of: 1) different orders of magnitude of the concentrations of the PPCPs; 2) the time of the day in which PPCPs enter the influent; and 3) whether sorbed PPCPs on the solids re-enter the basic filtrates upon neutralization. In addition, composite sampling to measure PPCP influent vs. treated effluent is not possible using the Biobrimstone™ method as this requires longer sample collection dwell times where acid hydrolysis or basic hydrolysis of the PPCPs would distort measurements relative to an actual WWTP plant’s one hour treatment time. The new protocol would therefore require daily hourly tracking comparisons using hydraulic analysis of the tanks and geotextile bag dwell time hydraulics to match when the treated influent is actually acted upon by the chemicals at any given time. Without a better tracking protocol, the present testing protocol only provided estimates of the actual percentages of PPCP reduction and elimination relative to that contained in the influent.

New Filtration Design

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Now that the chemistry has been established, testing of different handling equipment continues to provide operators with more flexibility and control to respond to day to day changing inflows. For example, to eliminate pH drift, the influent filtration design was modified to send more water through the sulfur burner by diverting suspended solids through a modified Fresno Filter separator. The separated solids were diverted around the sulfur burner and pumped by a chopper pump into Tank 1 where the majority of the filtered influent was passed through the burner at an increased burn rate for better pH control. This new design was installed the week of 3/26/12 and testing confirmed that the sulfur generator did not clog allowing the system to operate 24/7. Other tests continue to determine the best types of geotextile bags to better contain foaming and greases

Conclusion

It was found that the Biobrimstone™ retrofit at the Montalvo Municipal Improvement District’s wastewater treatment facility in Ventura, California removed some pharmaceuticals and personal care products (PPCP) from the influent. By removing suspended solids before entering the plant’s sequential batch reactors via pre-treatment entailing an oxidation/reduction, acidification/alkalinization cycle, a disinfected, demetalized, conditioned recovered wastewater was produced suitable for either the sequential batch reactors or land application. Removal of the suspended solids without polymers for chemical dewatering further obviated the need for the waste activated digesters and their associated odors and green house gas emissions. The Biobrimstone™ technology thus provided an economical wastewater pre-treatment retrofit disinfection option removing suspended solids without polymers and activated waste digestion to inactivate, degrade, and remove a number of different pharmaceuticals and chemicals as part of a multi-step treatment process to provide recovered wastewater suitable for land application.

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Table 1

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BASELINE MMID 2012 PPCP Test Summary PharmaceuticalsPharmaceuticals Reporting Limit Baseline Date Influent Treated Effluent

9/20/2010Acetaminophen 500 ng/L ND NDBisphenol-ACaffeine 500 ng/L 1500 ng/L 1600 ng/LCarbamazepine 100 ng/L 19 J 20 JCotinine 100 ng/L 120 B 150 BIbuprofen 250 ng/L 450 ng/L 440 ng/LIopromide 500 ng/L ND NDLincomycin 100 ng/L ND NDNaproxen 500 ng/L 620 ng/L 660 ng/LSulfamethoxazole 250 ng/L 6000 ng/L 6300 ng/LTrimethoprim 100 ng/L 920 ng/L 880 ng/LDiltiazem 50 ng/L 410 ng/L 390 ng/LFluoxetine 250 ng/L ND NDGemfibrozil 500 ng/L 1800 ng/L 1800 ng/LTriclosan 500 ng/L 380 J 430 JTriclocarban 100 ng/L 32J 31 JTylosin 100 ng/L ND ND

Table 2

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MMID 2012 PPCP Test Summary Pharmaceuticals

Biobrimstone Pretreatment

PharmaceuticalsReporting Limit Testing Date Influent Treated Effluent

1/5/2012 Influent Bag 1 Acid Bag 2 NeutralAcetaminophen 500 ng/L ? NR 87000E/150000AA 87000E/120000AABisphenol-A 1500 ng/L 100% reduction 2500 ND/ND ND/NDCaffeine 500 ng/L 33% reduction 150000E 180000E/190000 100000E/120000Carbamazepine 100 ng/LCotinine 100 ng/LIbuprofen 250 ng/L 60% reduction 35000E 16000E/13000E 15000E/14000EIopromide 500 ng/LLincomycin 100 ng/LNaproxen 500 ng/L 33% reduction 18000E 16000E/16000E 12000E/18000ESulfamethoxazole 250 ng/L ? 860 120J/2600 1500/2200Trimethoprim 100 ng/L ? 310 1300/1600 780/990Diltiazem 50 ng/LFluoxetine 250 ng/LGemfibrozil 500 ng/L ? 990 3000/1700 3200E/3100Triclosan 500 ng/L ~50% reduction 28000E 22000E/4200 15000E/3600Triclocarban 100 ng/LTylosin 100 ng/L

Table 3

*Detection limit for Bisphenol-A raised above influent levels of 2500**Filtrate levels higher than in the influent.

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MMID 2012 PPCP Test Summary Pharmaceuticals

Biobrimstone Pretreatment

PharmaceuticalsReporting Limit Testing Date Influent Treated Effluent

2/9/2012 Influent Bag 1 Acid Bag 2 NeutralAcetaminophen 500 ng/L 17%/9% 120,000 100000 110000Bisphenol-A 3000 ng/L* ND ND/ND ND/ND

Caffeine 500 ng/L33%/22% reduction 140000 94000 110000

Carbamazepine 100 ng/LCotinine 100 ng/L

Ibuprofen 250 ng/L64%/18% reduction 23000 13000 19000

Iopromide 500 ng/LLincomycin 100 ng/LNaproxen 500 ng/L 8%16% reduction 13000 12000 11000Sulfamethoxazole 250 ng/L 35%/** 1200 790 1500Trimethoprim 100 ng/L 25%/** 510 380 750**Diltiazem 50 ng/LFluoxetine 250 ng/LGemfibrozil 500 ng/L ** 1100 1800** 1600**

Triclosan 500 ng/L62%/61%% reduction 1500 580 590J

Triclocarban 100 ng/LTylosin 100 ng/L

PPCP RE-TREATMENT SUMMARY TABLE

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