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Appendix A Physical, Chemical, and Microbiological Constituents of MUS Waters The purpose of this appendix is to expand on some of the brief descriptions of constituents that may be found in either recharge or discharge waters of man- aged underground storage (MUS) systems. These include basic physicochemi- cal parameters, followed by inorganic and organic species, and finally microbes. PHYSICAL CHARACTERISTICS The first impressions of water quality are often based on visual observa- tions. Water is expected to be free of particles (turbidity), color, and odor. Ad- ditional important physical characteristics of MUS waters include dissolved oxygen, pH, oxidation-reduction potential (Eh), specific conductance, and tem- perature. Turbidity Suspended particles impede the passage of light through water by scattering and absorbing the light rays. This interference of light passage is called turbid- ity. Waters with greater turbidity will experience increased clogging of filters and increased head loss development during infiltration. The particles contribut- ing to turbidity can also harbor pathogens and enhance their survival in the pres- ence of a disinfectant. Color Color in a water is usually the result of an elevated organic content, such as humic and fulvic acids. The color of potable waters is typically determined by visually comparing a water sample to known color solutions prepared from a standard platinum-cobalt solution. Old water under anaerobic conditions may appear black or gray in color due to the presence of metallic sulfides. Odor The generation of gases during decomposition of organic matter or reduc- 297

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298 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER tion of dissolved sulfate often creates odorous compounds. Most odorous gases, such as hydrogen sulfide and the sulfur-bearing mercaptans, are formed under anaerobic conditions, so providing adequate dissolved oxygen is the first step toward controlling odors. The control of odors is among the priority issues with respect to public acceptance of a project. Dissolved Oxygen Adequate dissolved oxygen in surface waters is required for aerobic respira- tion and is needed to protect fish and other aquatic life. The presence of dis- solved oxygen (DO) leads to oxidizing conditions that minimize the formation of noxious odors and prevents the solubilization of certain metals (e.g., iron, manganese); however, introduction of DO into anaerobic or reduced aquifers may oxidize sulfide minerals and increase the release of metals. The inverse situation may occur as well; MUS activities that low DO water into a previously oxidized part of the aquifer may lead to reductive dissolution of minerals and the release of metals. pH The hydrogen ion concentration is an important quality parameter for all waters. The usual means of expressing hydrogen ion concentration is pH, which is defined as the negative logarithm of the hydrogen ion concentration. pH influ- ences the surface charge on solid surfaces, the distribution of acidic and basic compounds, the form of a chemical in solution, the solubility of compounds, the physical shape of organic molecules, and the toxicity of the medium. Oxidation-Reduction p\Potential (ORP) Eh is another critical parameter because of the effect of high Eh waters on iron-bearing minerals. Such solutions, which often contain high levels of dis- solved oxygen, alter primary minerals to iron oxyhydroxides, thus changing the water chemistry as well as altering the aquifer properties. Eh and pH are also primary controls on the population of subsurface bacteria that biodegrade certain organic contaminants, as well as on those that cause illness. Some sulfate- reducing bacteria, for example, survive or thrive only in the absence of dissolved oxygen.

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APPENDIX A 299 Specific Conductance Specific conductance is a measure of how well a given water sample con- ducts an electrical current. It is defined as the "reciprocal of the resistance in ohms measured between opposite faces of a centimeter cube of an aqueous solu- tion at a specified temperature” (Hem, 1985). It is a straightforward measure- ment that can be made with reasonable accuracy in the field. It is, therefore, often used as a proxy in lieu of the total dissolved solids (TDS) in a solution. The relationship between conductivity and TDS depends on the actual dissolved anions and cations (i.e., sodium chloride and calcium sulfate solutions of the same strength would have different specific conductances), so it is only a gen- eral indicator. However, if the dissolved salts are known to be of seawater ori- gin, the correlation may be quite good. Specific conductance also depends on temperature. Temperature Water temperature can be important for several reasons. In the case of re- charge water, it can affect the speed (“kinetics) of reactions in the subsurface. In general, higher temperatures increase the rate of most chemical reactions. Reac- tions involving dissolved gases (e.g., limestone dissolution, which involves dis- solved carbon dioxide) are also affected by temperature. Bacteria involved in clogging and oxidation-reduction reactions (including those related to aesthetic concerns) are more or less active depending on temperature. In the case of dis- charge water, higher temperatures generally have lower dissolved oxygen, and this might impact use of the water for environmental purposes. INORGANIC CONSTITUENTS Inorganic chemical constituents of concern in MUS source waters are sum- marized in Table 4-2. Inorganic chemicals of concern can be grouped as nutri- ents, nonmetals, and metals. Nitrogen and phosphorous species are known as nutrients because they are essential for growth of microorganisms and plants. The nonmetals of concern are hydrogen ions and dissolved salts, such as chlo- ride, sulfate, and boron. The metals of concern are often present at trace con- centrations, and many are classified as priority pollutants. Examples of toxic metals include arsenic, cadmium, mercury, lead, and chromium. Iron and man- ganese are metals that influence the aesthetic quality of the water. The presence of inorganic constituents in excessive quantities will interfere with many benefi- cial uses of the water due to aesthetic issues or because of their toxicity.

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300 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER Nutrients Nitrogen and phosphorus are essential nutrients for growth of biomass. Their presence in water can stimulate growth of algae and microorganisms. This creates nuisance conditions during storage of the water and can accelerate biomass clogging in the subsurface. Nitrogen exists in several oxidation states with ammonia, nitrogen gas, nitrite, and nitrate being the common forms in wa- ter supplies. Chemical and biological reactions can convert one nitrogen form to another. Unionized ammonia (NH3) is toxic to fish and other aquatic life. At the pH of most natural waters, ammonia is mostly in the cationic form (NH4+). As water containing NH4+ contacts soil, NH4+ is usually rapidly removed from solution by ion exchange processes. Nitrite is relatively unstable and is easily oxidized to nitrate. Nitrite is also toxic to fish, other aquatic life, and humans. Nitrate is the most oxidized form of nitrogen. Nitrate readily moves with water through the subsurface and can impact the quality of water on a large scale. Nitrate is limited to 10 mg/L as nitrogen in drinking water because of its serious toxicity to infants. The usual aqueous forms of phosphorus are orthophosphate, polyphosphate, and organic phosphate. Phosphorus does not undergo change in oxidation state. Phosphates tend to precipitate and be removed by ion exchange in the subsurface. Salts Water in contact with the earth will naturally accumulate dissolved salts, such as sodium, calcium, magnesium, potassium, chloride, sulfate, and bicar- bonate. A gravimetric measurement technique that quantifies the residue of filtered water upon evaporation is termed total dissolved solids and provides an indicator of the total salt content. The TDS concentration is an important indica- tor of the usefulness of water for various applications. For example, drinking water has a recommended maximum TDS of 500 mg/L. Excessive dissolved salts influence the ability to recycle water in an MUS system as they impart a salty taste (aesthetic concern), accelerate corrosion of metals, form deposits, and can have a laxative effect in the case of sulfate. Metals, Metalloids, and Other Constituents Trace quantities of many metals (including metalloids), such as arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc are present in many waters. Organisms require most metals in trace quantities; therefore, the absence of trace metals in water is limiting to biomass growth. Many metals are classified as priority pollutants, so excessive amounts of these metals will interfere with beneficial uses of the water. Elevated iron and man- ganese in water imparts a metallic taste and causes staining of water fixtures.

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APPENDIX A 301 The most prevalent toxicity from use of recycled water for irrigation is from boron. The source of boron is usually household detergents or discharges from industrial plants. A guideline limit of <0.7 mg/L of boron allows for unre- stricted use of the water for irrigation of food crops. Boron levels above 3 mg/L are severely toxic to plants. While many of the metals listed above can be toxic (see Table A-1), the metal of most widespread concern in MUS systems is arsenic. This is not only because the maximum contaminant level is low, but also because it is associated with commonly occurring iron oxyhydroxides and sulfides in the subsurface. These minerals often release arsenic in response to changes in oxidation- reduction state. Arsenic is treated in considerable detail in Chapter 4. Radionuclides Radionuclides are unstable atoms that change their atomic state through the process of radioactive decay (U.S. Department of Health, Education, and Wel- fare, 1970). Radioactive decay results in the release of alpha, beta, or gamma radiation. The emission of alpha and beta particles transforms an isotope into a different element, while the emission of gamma radiation reduces the energy level of the element. When alpha, beta, or gamma radiation passes through ad- jacent atoms, it can dislodge electrons from their orbit and create ionized spe- cies. This ionization and deposition of energy can damage materials and lead to deleterious effects in human tissues including mutagenic, teratogenic, and acute toxicity. Consequently, human exposures to radionuclides are stringently con- trolled. Radionuclides in water supplies can be from natural or anthropogenic sources (Viessman and Hammer, 2005). Naturally occurring radioactive ele- ments of importance in water often emit alpha particles. These elements, such as radium-226, can leach from geological formations and enter groundwater. Radioactivity from radium is also widespread in surface waters because of fall- out from testing of nuclear weapons. Another source of radioactivity in water supplies is small releases from nuclear power plants and industrial users of ra- dioactive materials (e.g., weapons manufacture and testing; medical applica- tions; nuclear fuel processing, use, and disposal). Radionuclides are currently regulated in drinking water by the U.S. Environmental Protection Agency (EPA). The limit for gross alpha particle activity is 15 pCi/L, and the limit for the sum of 226Rd and 228Rd is 5 pCi/L. The measurement unit of pCi/L is 10-12 curie per liter, with a curie being the radioactivity of 1 gram of radium. The activity from beta radiation is primarily from nuclear weapons testing, and the allowable amount is up to 4 mrem/yr, which is a measure of equivalent absorbed dose. Uranium has several radioactive isotopes, and the uranium concentration must be less than 30 µg/L. A study by the National Academy of Sciences (1977) concluded that natural background radiation can be estimated to cause 4.5 to 45 fatal cases of cancer

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302 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER per year per million people, and less than 1 percent of the risk is attributed to radionuclides in drinking water. Consequently, in most water supplies, it is not possible to measure any adverse health effects from radionuclides with certainty. Monitoring for radionuclides in water supplies is straightforward, and it is pru- dent to periodically monitor the radionuclide activity in the source and extracted waters in MUS systems to ensure the safety of the consumer. ORGANIC CONSTITUENTS Residual organic carbon is a concern in underground storage systems be- cause some of these compounds are associated with a broad spectrum of poten- tial health concerns (Asano, 1998). Three groups of residual organic chemicals require attention: (1) natural organic matter (NOM) present in most water sup- plies, (2) soluble microbial products (SMPs) formed during the wastewater treatment process and resulting from the decomposition of organic compounds (Barker and Stuckey, 1999), and (3) synthetic organic compounds (SOC) added by consumers and generated as disinfection by-products (DBPs) during the dis- infection of water and wastewater. Natural Organic Matter and Soluble Microbial Products Natural organic matter and soluble microbial products are mixtures of com- pounds that cannot be effectively measured individually. When NOM and SMPs are measured as a group as dissolved organic carbon, the concentrations of organic carbon are typically measured in the milligram-per-liter range. Most waters contain NOM and reclaimed waters contain a mixture of NOM and SMPs. These compounds are not known to present significant health concerns. The primary concern above NOM and SMPs is their potential to form disinfec- tion by-products and to stimulate biological growth in distribution systems, in wells, or in situ. Synthetic organic compounds and disinfection by-products are measured individually at concentrations of microgram or nanogram per liter. When a pool of organic carbon exists, the synthetic organic carbon compounds and disinfection by-products may represent less than 1 percent of the total or- ganic carbon. However, concerns about both human and aquatic health effects are generally associated with SOCs and DBPs. Most waters used in underground storage systems receive limited charac- terization of NOM and/or SMPs that comprise the bulk of the organic carbon compounds present. Typically, these compounds are quantified by dissolved organic carbon measurements and ultraviolet absorbance (UVA) (Ma and Yin, 2001). UVA provides a relative measure of the aromatic content of the dis- solved organic carbon and serves as a predictor of disinfection by-product for- mation potential. DBP formation potential tests are also used to characterize the reactivity of NOM and SMPs with disinfectants. Advanced characterization of

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APPENDIX A 303 NOM and SMPs has been done for research purposes. Separation techniques used for bulk organic carbon include molecular weight fractionation, size exclu- sion chromatography and fractionation based on hydrophobicity (Croue et al., 2000). Spectroscopic characterization of organic carbon isolates may be done using 13C nuclear magnetic spectroscopy, Fourier transform infrared spectros- copy, and fluorescence spectroscopy (Fox et al., 2001). In addition, elemental analysis may be done to determine the elemental composition of organic com- pound mixtures. The majority of these techniques do not identify significant differences in organic compound structure, function, and reactivity when com- paring NOM samples with mixtures of NOM and SMPs in reclaimed waters. SMPs do have elevated levels of organic nitrogen and associated fluorescence compared to NOMs. Organic compounds are removed during subsurface storage by a combina- tion of filtration, sorption, oxidation-reduction and biodegradation. Biodegrada- tion is the primary sustainable removal mechanism for organic compounds dur- ing subsurface transport. The concentrations of NOM and SMPs are reduced during subsurface transport as high-molecular-weight compounds are hydro- lyzed into lower-molecular-weight compounds and the lower-molecular-weight compounds serve as substrate for microorganisms. As the concentrations of NOM and SMPs are decreased, the disinfection by-product potential associated with these compounds is also decreased (AwwaRF, 2001). Synthetic organic compounds at concentrations too low to directly support microbial growth may be co-metabolized as NOM and SMPs serve as the primary substrate for growth. Given sufficient surface area and contact time, the water used for underground storage may approach the quality of native groundwaters with respect to organic carbon content. Total Organic Carbon The performance of sustainable underground storage systems with respect to organic carbon transformations has often been quantified by measuring total organic carbon (TOC). While total organic carbon does not provide any sig- nificant information regarding health effects, it has often been used as a surro- gate for organic carbon removal for several reasons. TOC is simple to measure, and most laboratories can measure it rapidly and accurately. The second reason is that 1 mg of organic carbon may be composed of millions of different com- pounds and these compounds cannot be individually quantified. Furthermore, if all these compounds could be quantified, using the data collected would be very difficult to interpret. A health effects study completed in Los Angeles County determined there were no impacts of groundwater recharge from reclaimed wa- ter. The California Department of Health Services estimated that the maximum TOC concentration from reclaimed water in the drinking water supply was 1 mg/L. Presently, California has a guideline of 0.5 mg/L of TOC from recycled water that may be used for drinking water. The State of Washington has a pro-

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304 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER posed rule of 1 mg/L of TOC for direct injection with reclaimed water and Flor- ida has limit of 3 mg/L of TOC for groundwater recharge with reclaimed water. When TOC concentrations for reclaimed water are set at 1 mg/L or less, the target that concentration is below the TOC concentration of most surface water sources. The result is there must be significant dilution of the reclaimed water used for recharge, or extensive treatment of the reclaimed water is required. Since most reclaimed waters contain refractory NOM and SMPs in excess of 2 mg TOC/L, treatment by nanofiltration or reverse osmosis is necessary to reduce the TOC concentration to below 1 mg/L. Efforts to develop surrogates for organic carbon removal other than TOC are currently ongoing and were summarized at the Water Reuse Foundation Re- search Conference in May 2006. The fact that TOC concentrations below 1 mg/L can still contain elevated concentrations of synthetic organic compounds with significant health concerns such as N-Nitrosodimethylamine (NDMA). Since refractory TOC concentrations depend on the original drinking water source and SMP production during wastewater treatment, a measure of micro- bial activity was suggested as a surrogate during subsurface transport where the major sustainable removal mechanism is biodegradation. The mosquito repel- lent DEET (N, N-diethyl-m-toluamide, a personal care product, was suggested as a marker since it is biodegradable and almost all other biodegradable com- pounds were removed before DEET. Synthetic Organic Carbon Many waters used in underground storage systems are analyzed for con- taminants regulated by the Safe Drinking Water Act, which includes maximum contaminant levels (MCLs) for 51 synthetic organic compounds. Since many of the compounds were regulated by the Safe Drinking Water Act because of groundwater contamination issues, these compounds are not often detected in water sources being considered for underground storage. Exceptions to the case include chlorinated disinfection by-products and specific agricultural chemicals. When reclaimed waters are used as a water source, monitoring for emerging contaminants of concern may be applied in specific states such as California. Trace Organics Trace organics in both wastewater and surface waters impacted by human and animal waste streams are of interest if used for MUS systems. The behavior of selected trace organics during underground storage has been studied to iden- tify and quantify processes that affect organic contaminant attenuation during subsurface transport. The majority of this research has focused on the use of reclaimed water as a source water and also the use of sewage-contaminated sur- face waters in bank filtrations systems. For trace organic compounds, the prin-

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APPENDIX A 305 cipal attenuating processes are biological transformation and sorption. The oc- currence of these processes differs depending on compound structure, soil, and biogeochemical conditions. The capacity of biodegradation and sorption to at- tenuate organic contaminants may vary considerably depending upon the under- ground storage system. Geochemical factors such as changes in redox condi- tions and the formation of organic complexes may also affect transformations during subsurface transport. Attempts to develop time-distance relationship for the attenuation processes have been successful for specific types of systems such as flow through porous media in sand and gravel aquifers. Initial research ac- tivities focused on the fate of compounds present at microgram-per-liter concen- trations in source waters. These compounds included clofibric acid, surfactants such as alkylphenolethoxylates, disinfection by-products, nitrilotriacetic acid, and ethylenediaminetetraacetic acid (EDTA). As analytical techniques im- proved to detect compounds at nanogram per liter concentrations, concerns about pharmaceuticals and personal care products (PPCPs) and endocrine dis- rupting compounds (EDC) led to additional research on these emerging con- taminants of concern. As a result of this research, certain anthropogenic com- pounds have been determined to be persistent in most underground storage sys- tems; however, the health effects associated with these compounds at nanogram- per-liter concentrations have not been assessed. Emerging disinfection by- products such as N-nitrosodimethylamine have also been studied during subsur- face transport. The occurrence and significance of anthropogenic compounds in surface waters impacted by wastewater discharges in the United States was described in a survey by Kolpin et al. (2002), who conducted a survey of 139 streams in the United States for 93 organic waste contaminants, and a wide range of pharma- ceuticals and personal care products were measured creating concerns over the safety of surface waters as drinking water supply. The widespread occurrence of these compounds in the United States and Europe was discussed by Daughton and Ternes (1999), who suggested that impacts to aquatic life and other envi- ronmental impacts were possible; however, the concentrations of pharmaceuti- cals were too low to have a defined impact on human health. Nevertheless, con- cern over these emerging contaminants has resulted in active research on the fate and transport of these compounds in the environment. Research on the fate of these compounds during bank filtration has been occurring to a large extent in Europe and to a lesser extent in the United States (Heberer et al., 2001). Sev- eral monitoring studies carried out in Berlin, Germany, between 1996 and 2000 identified pharmaceuticals such as clofibric acid, diclofenac, ibuprofen, propy- phenazone, primidone and carbamazepine at individual concentrations up to the nanogram-per-liter level in influent and effluent samples from WWTPs and in all surface water samples collected downstream from the waste water treatment plants (Heberer, 2002). The persistence of carbamazepine has led researchers to suggest that carbamazepine be used as a universal indicator of anthropogenic contamination.

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306 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER MICROORGANISMS The microorganisms of concern associated with public health risks in groundwaters and source waters used for MUS may be divided into two major categories; those that are associated with fecal pollution of ground- and surface water and those that may be naturally-occurring. Groundwater has been shown to be a major source associated with waterborne disease outbreaks in the United States, because it is often used without treatment. In addition as already men- tioned, the nature (perceived as protected) of groundwater and its use (as a pota- ble supply) dictates the absence of “indicator” organisms and pathogens associ- ated with contamination and public health risk as well as absence of pathogens. All surface waters will have some level of algae, bacteria, and parasites; if there are sewage inputs there will also be enteric viruses and other microbes of fecal origin. Thus unless this water is pretreated to drinking water standards or infiltration systems are used to effectively remove some percentage of the mi- croorganisms, then the source or stored water will contain these microbes. The native groundwater could also contain some bacteria and protozoa that may or may not pose a risk to human health. The targeted microbial contamination level associated with acceptable risks would depend on the use of the recovered water. For potable purposes a maximum contaminant level goal (MCLG) of zero is the target for those microorganisms associated with disease. Finally, both regrowth and attenuation (usually due to die-off) of bacteria and the free-living protozoa can occur depending on the conditions. For enteric viruses and proto- zoa long-term survival is of concern and interest. As a part of the attenuation via filtration or dilution (diffusion) the concentrations of the microorganisms which may migrate and be transported into other aquifers has also been an area of re- search. Monitoring for the wide range of microorganisms in source, stored and re- covered water has not been widely implemented. Thus there is often a presump- tion of microbial water quality based on the monitoring of selected “indicator” species. As mentioned the primary research has focused on drinking water MUS systems and thus those microbes associated with fecal pollution and standards and rules for potable water have been the target of most of the controversy and studies. The bacterial pathogens are rarely monitored for, a select group of vi- ruses may be monitored for on occasion, and the protozoa are monitored for in surface waters but not generally groundwaters. None of these groups of mi- crobes are monitored for in reclaimed waters on a routine basis (the exception being Florida which requires monitoring of Cryptosporidium and Giardia in reclaimed wastewaters). Table A-1 gives the list of some of the routine and emerging microorgan- isms that may be of concern in MUS systems. These all have an MCLG of zero in drinking water.

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APPENDIX A 307 TABLE A-1 Pathogens and Microorganisms of Possible Concern with MUS Systems Relationship Occurrence Other Key to Ground- Microbe Sources water in Water Points Bacteria Toxins found Not routinely Cyanobacteria Naturally- Unknown in surface monitored for yet occurring could be sta- waters alone in MUS. In Surface Wa- ble in MUS with seasonal On the CCL ters aquifers blooms Aerotolerant Can cause Animal/ bird Associated Campylobacter Guillian Barré and human with Stable in non- Syndrome fecal wastes groundwater disinfected outbreaks waters Possibly Unknown Grows at low Emerging human Arcobacter animal and Identified in temperatures pathogen human wastes groundwater with massive contamina- tion Emerging cause Human sewage Association Detected by Helicobacter of ulcers and with human PCR in sew- disease and age and cancer; on the CCL exposure to groundwater groundwater Grows along No studies on Naturally- Found in Legionella with increased enhancement of occurring in groundwater amoeba and populations un- aquatic envi- and cause of heterotrophs der MUS ronment the distribu- tion system in biofilms seeding a Viruses . Adenoviruses Human Detected in High concentra- Wastewater ground-, sur- tions in sewage, face, and long-term survival drinking water in water; more resistant to UV Coxsackie Human CB5 found to Cause of chronic wastewater be one of the diseases. most preva- lent viruses in sewage and polluted wa- ters. table continues

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322 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER problems factories p-Dichlorobenzene 0.075 0.075 Anemia; liver, Discharge from kidney or industrial spleen chemical damage; factories changes in blood 1,2-Dichloroethane zero 0.005 Increased risk Discharge from of cancer industrial chemical factories 1,1-Dichloroethylene 0.007 0.007 Liver problems Discharge from industrial chemical factories cis-1,2-Dichloroethylene 0.07 0.07 Liver problems Discharge from industrial chemical factories trans-1,2- 0.1 0.1 Liver problems Discharge from Dichloroethylene industrial chemical factories Dichloromethane zero 0.005 Liver prob- Discharge from lems; in- drug and creased risk of chemical cancer factories 1,2-Dichloropropane zero 0.005 Increased risk Discharge from of cancer industrial chemical factories Di(2-ethylhexyl) adipate 0.4 0.4 Weight loss, Discharge from liver problems, chemical or possible factories reproductive difficulties. Di(2-ethylhexyl) phthalate zero 0.006 Reproductive Discharge from difficulties; rubber and liver problems; chemical increased risk factories of cancer

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APPENDIX A 323 Dinoseb 0.007 0.007 Reproductive Runoff from difficulties herbicide used on soybeans and vegetables Dioxin (2,3,7,8-TCDD) zero 0.0000000 Reproductive Emissions from 3 difficulties; waste incinera- increased risk tion and other of cancer combustion; discharge from chemical factories Diquat 0.02 0.02 Cataracts Runoff from herbicide use Endothall 0.1 0.1 Stomach and Runoff from intestinal prob- herbicide use lems Endrin 0.002 0.002 Liver problems Residue of banned insec- ticide 9 Epichlorohydrin zero TT Increased Discharge from cancer risk, industrial and over a chemical long period of factories; an time, stomach impurity of problems some water treatment chemicals Ethylbenzene 0.7 0.7 Liver or kid- Discharge from neys problems petroleum refineries Ethylene dibromide zero 0.00005 Problems with Discharge from liver, stomach, petroleum reproductive refineries system, or kidneys; increased risk of cancer Glyphosate 0.7 0.7 Kidney prob- Runoff from lems; repro- herbicide use ductive difficulties Heptachlor zero 0.0004 Liver damage; Residue of

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324 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER increased risk banned of cancer termiticide Heptachlor epoxide zero 0.0002 Liver damage; Breakdown of increased risk heptachlor of cancer Hexachlorobenzene zero 0.001 Liver or kidney Discharge from problems; metal refineries reproductive and agricultural difficulties; chemical increased risk factories of cancer Hexachlorocyclo- 0.05 0.05 Kidney or Discharge from pentadiene stomach prob- chemical lems factories Lindane 0.0002 0.0002 Liver or kidney Run- problems off/leaching from insecti- cide used on cattle, lumber, gardens Methoxychlor 0.04 0.04 Reproductive Run- difficulties off/leaching from insecti- cide used on fruits, vegetables, alfalfa, livestock Oxamyl (Vydate) 0.2 0.2 Slight nervous Runoff/leach- system effects ing from insecticide used on apples, potatoes, and tomatoes Runoff from Polychlorinated zero 0.0005 Skin changes; landfills; biphenyls (PCBs) thymus gland discharge of problems; waste immune chemicals deficiencies; reproductive or nervous system difficulties; increased risk

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APPENDIX A 325 of cancer Pentachlorophenol zero 0.001 Liver or kidney Discharge from problems; wood preserv- increased ing factories cancer risk Picloram 0.5 0.5 Liver problems Herbicide runoff Simazine 0.004 0.004 Problems with Herbicide blood runoff Styrene 0.1 0.1 Liver, kidney, Discharge from or circulatory rubber and system plastic problems factories; leaching from landfills Tetrachloroethylene zero 0.005 Liver Discharge from problems; factories and increased risk dry cleaners of cancer Toluene 1 1 Nervous Discharge from system, petroleum kidney, or liver factories problems Toxaphene zero 0.003 Kidney, liver, Runoff/leach- or thyroid ing from insec- problems; ticide used on increased risk cotton and of cancer cattle 2,4,5-TP (Silvex) 0.05 0.05 Liver problems Residue of banned herbicide 1,2,4-Trichlorobenzene 0.07 0.07 Changes in Discharge from adrenal glands textile finishing factories 1,1,1-Trichloroethane 0.20 0.2 Liver, nervous Discharge from system, or metal circulatory degreasing problems sites and other factories

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326 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER 1,1,2-Trichloroethane 0.003 0.005 Liver, kidney, Discharge from or immune industrial system chemical problems factories Trichloroethylene zero 0.005 Liver prob- Discharge from lems; metal degreas- increased risk ing sites and of cancer other factories Vinyl chloride zero 0.002 Increased risk Leaching from of cancer PVC pipes; discharge from plastic factories Xylenes (total) 10 10 Nervous Discharge from system petroleum damage factories; discharge from chemical factories Radionuclides MCL or Sources of 1 MCLG Potential Health Effects 1 Contaminant TT Contaminant in 2 (mg/L) from Ingestion of Water 2 (mg/L) Drinking Water 7 Alpha particles None 15 pico- Increased risk of cancer Erosion of natural ---------- curies deposits of certain zero per Liter minerals that are (pCi/L) radioactive and may emit a form of radiation known as alpha radia- tion 7 Beta particles None 4 mil- Increased risk of cancer Decay of natural and and photon ---------- lirems man-made deposits of emitters zero per year certain minerals that are radioactive and may emit forms of radiation known as photons and beta radiation 7 Radium 226 and None 5 pCi/L Increased risk of cancer Erosion of natural Radium 228 ---------- deposits (combined) zero

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APPENDIX A 327 Uranium Zero 30 ug/L Increased risk of cancer, Erosion of natural as of kidney toxicity deposits 12/08/0 3 Notes: 1 Definitions: Maximum Contaminant Level (MCL) - The highest level of a contaminant that is allowed in drinking water. MCLs are set as close to MCLGs as feasible using the best available treatment technology and taking cost into consideration. MCLs are enforceable standards. Maximum Contaminant Level Goal (MCLG) - The level of a contaminant in drinking water below which there is no known or expected risk to health. MCLGs allow for a margin of safety and are non- enforceable public health goals. Maximum Residual Disinfectant Level (MRDL) - The highest level of a disinfectant allowed in drinking water. There is convincing evidence that addition of a disinfectant is necessary for control of microbial contaminants. Maximum Residual Disinfectant Level Goal (MRDLG) - The level of a drinking water disinfectant below which there is no known or expected risk to health. MRDLGs do not reflect the benefits of the use of disinfectants to control microbial contaminants. Treatment Technique - A required process intended to reduce the level of a contaminant in drinking water. 2 Units are in milligrams per liter (mg/L) unless otherwise noted. Milligrams per liter are equivalent to parts per million. 3 EPA's surface water treatment rules require systems using surface water or groundwater under the direct influence of surface water to (1) disinfect their water, and (2) filter their water or meet criteria for avoiding filtration so that the following contaminants are controlled at the following levels: • Cryptosporidium: (as of1/1/02 for systems serving >10,000 and 1/14/05 for systems serving <10,000) 99% removal. • Giardia lamblia: 99.9% removal/inactivation • Viruses: 99.99% removal/inactivation • Legionella: No limit, but EPA believes that if Giardia and viruses are removed/inactivated, Legionella will also be controlled. • Turbidity: At no time can turbidity (cloudiness of water) go above 5 nephelolometric turbidity units (NTU); systems that filter must ensure that the turbidity go no higher than 1 NTU (0.5 NTU for conventional or direct filtration) in at least 95% of the daily samples in any month. As of January 1, 2002, turbidity may never exceed 1 NTU, and must not exceed 0.3 NTU in 95% of daily samples in any month. • HPC: No more than 500 bacterial colonies per milliliter. • Long Term 1 Enhanced Surface Water Treatment (Effective Date: January 14, 2005); Surface water systems or (GWUDI) systems serving fewer than 10,000 people must comply with the applicable Long Term 1 Enhanced Surface Water Treatment Rule provisions (e.g. turbidity standards, individual filter monitoring, Cryptosporidium removal requirements, updated watershed control requirements for unfiltered systems). • Filter Backwash Recycling; The Filter Backwash Recycling Rule requires systems that recycle to return specific recycle flows through all processes of the system's existing conventional or direct filtration system or at an alternate location approved by the state. 4 more than 5.0% samples total coliform-positive in a month. (For water systems that collect fewer than 40 routine samples per month, no more than one sample can be total coliform-positive per month.) Every sample that has total coliform must be analyzed for either fecal coliforms or E. coli if two consecutive TC-positive samples, and one is also positive for E.coli fecal coliforms, system has an acute MCL violation. 5 Fecal coliform and E. coli are bacteria whose presence indicates that the water may be contaminated with human or animal wastes. Disease-causing microbes (pathogens) in these wastes can cause diarrhea, cramps, nausea, headaches, or other symptoms. These pathogens may pose a special health risk for infants, young children, and people with severely compromised immune systems. 6 Although there is no collective MCLG for this contaminant group, there are individual MCLGs for some of the individual contaminants: • Trihalomethanes: bromodichloromethane (zero); bromoform (zero); dibromochloromethane (0.06 mg/L). Chloroform is regulated with this group but has no MCLG. • Haloacetic acids: dichloroacetic acid (zero); trichloroacetic acid (0.3 mg/L). Monochloroacetic acid, bromoacetic acid, and dibromoacetic acid are regulated with this group but have no MCLGs.

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328 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER 7 MCLGs were not established before the 1986 Amendments to the Safe Drinking Water Act. Therefore, there is no MCLG for this contaminant. 8 Lead and copper are regulated by a Treatment Technique that requires systems to control the corrosiveness of their water. If more than 10% of tap water samples exceed the action level, water systems must take additional steps. For copper, the action level is 1.3 mg/L, and for lead is 0.015 mg/L. 9 Each water system must certify, in writing, to the state (using third-party or manufacturer's certification) that when acrylamide and epichlorohydrin are used in drinking water systems, the combination (or product) of dose and monomer level does not exceed the levels specified, as follows: • Acrylamide = 0.05% dosed at 1 mg/L (or equivalent) • Epichlorohydrin = 0.01% dosed at 20 mg/L (or equivalent) SOURCE: Reproduced from EPA Drinking Water Contaminants. Available on the web at http://www.epa.gov/safewater/contaminants/index.html. Last accessed July 5, 2007. REFERENCES Abbaszadegan, M., M. LeChevallier, and C. Gerba. 2003. Occurrence of viruses in US ground waters. J. Am Water Works Assoc. 95:107-120. Aruin, L.I. (1997) Helicobacter pylori infection is carcinogenic for humans. Arkhiv Patologii 59, 74–78. Atlas, R. M. 1999. Legionella: from environmental habitats to disease pathol- ogy, detection and control. Environ Microbiol 1:283-293. Awwa Research Foundation (AwwaRF). 2001. Soil Aquifer Treatment for Sus- tainable Water Reuse. Denver, CO: AwwaRF. Barker, D. J., and D. C. Stuckey. 1999. A Review of Soluble Microbial Prod- ucts (SMP) in Wastewater Treatment Systems. Water Science & Technol- ogy 33(14):3063- 3082. Benin, A. L., R. F. Benson, and R. E. Besser. 2002. Trends in Legionnaires Disease, 1980–1998: Declining Mortality and New Patterns of Diagnosis. Clinical Infectious Diseases 35:1039-1046. Blaser, M.J. (1990) Helicobacter pylori and the pathogenesis of gastro ⁄ - duodenal inflammation. J Infect Dis 161, 626–633. Borchardt, M. A., P. D. Bertz, S. K. Spencer, and D. A. Battigelli. 1990. Incidence of Enteric Viruses in Groundwater from Household Wells in Wisconsin. Appl Environ Microbiol. 69(2): 1172–1180. Centers for Disease Control and Prevention (CDC). 2006. Summary of Notifi- able Diseases—United States, 2004. Atlanta: CDC. Clark, C. G., L. Price, R. Ahmed, D. L. Woodward, P. L. Melito, F. G. Rodgers, F. Jamieson, B. Ciebin, A. Li, and A. Ellis. 2003. Characterization of Wa- terborne Outbreak–associated Campylobacter jejuni, Walkerton, Ontario. Emerging Infectious Diseases 9(10): 1232-1241. Croue, J., G. V. Korshin, and M. Benjamin. 2000. Characterization of Natural Organic Matter in Drinking Water. Denver, CO: AWWA Research Foun- dation and American Water Works Association. Daughton, C., and T. Ternes. 1999. Pharmaceuticals and Personal Care Prod- ucts in the Environment: Agents of Subtle Change? Environmental Health Perspectives, 107(6):907-937.

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APPENDIX A 329 Diergaardt, S. M., S. N. Venter, A. Spreeth, J. Theron, and V. S. Brozel. 2004. The occurrence of campylobacters in water sources in South Africa. Water Res. 38:2589. Ellis, W. A., S. D.Neill, J. J. O'Brien, H. W. Ferguson, and J. Hanna. 1977. Isolation of spirillum/vibrio-like organisms from bovine fetuses. Veterinary Record 100:451–452. Feldman, R. A., A. J. P. Eccersley, and J. M. Hardie. 1997. Transmission of Helicobacter pylori. Curr Opin Gastroenterol 13:8–12. Fields, B. S., R. F. Benson, and R. E. Besser. 2002. Legionella and Legionnaires' Disease: 25 Years of Investigation. Clinical Microbiology Reviews 15:506-526. Fiore, A. E., J. P. Nuorti, O. S. Levine, A. Marx, A. C. Weltman, S. Yeager, R. F. Benson, J. Pruckler, P. H. Edelstein, P. Greer, S. R. Zaki, B. S. Fields, and J. C. Butler. 1998. Epidemic Legionnaires' Disease Two Decades Later: Old Sources, New Diagnostic Methods. Clinical Infectious Diseases. 26(2): 426-433. Fisman, D. N., S. Lim, G A. Wellenius, C. Johnson, P. Britz, M. Gaskins, J.. Maher, M. A. Mittleman, C. V. Spain, and C. N. Haas. 2005. It's Not the Heat, It's the Humidity: Wet Weather Increases Legionellosis Risk in the Greater Philadelphia Metropolitan Area. Journal of Infectious Diseases 192:2066-2073. Fong, T.-T., L. S. Mansfield, D. L. Wilson, D. J. Schwab, S. L. Molloy, and J. B. Rose. 2007. Massive Microbiological Groundwater Contamination As- sociated with a Waterborne Outbreak in Lake Erie, South Bass Island, Ohio. Environmental Health Perspectives 115: 856–864. Fout, S., B. C. Martinson, M. W. N. Moyer, and D. R. Dahling. 2003. A multi- plex reverse transcription--PCR method for detection of human enteric vi- ruses in groundwater. Appl. Envir. Microbiology 69(6):3158-3164. Fox, P., K. Naranaswamy, and J. E. Drewes. 2001. Water Quality Transforma- tions during Soil Aquifer Treatment at the Mesa Northwest Water Reclama- tion Plant, USA. Water Science and Technology 43(10):343-350. Gardner, T. B. and D. R. Hill. Treatment of Giardiasis. Clinical Microbiology Reviews 14(1):114-128 Haas, C. N., J. Rose, and C. Gerba. 1999. Quantitative microbial risk assessment. New York:John Wiley & Sons. Hancock C. M., J. B. Rose, and M. Callahan. 1998. Cryptosporidium and Giardia in US groundwater. J Am Water Works Assoc 90(3):58-61. Havelaar, A.H., M. van Olphen, and Y. C. Drost. 1993. F-specific RNA bacteriophages are adequate model organisms for enteric viruses in fresh water. Applied Environmental Microbiology 59(9):2956-2962. Heberer, T., I. M.Verstraeten, M. T Meyer, A. Mechlinski, and K. Reddersen. 2001. Occurrence and Fate of Pharmaceuticals during Bank Filtration – Preliminary Results from Investigations in Germany and the United States. Water Resources Update 120:4-17.

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330 PROSPECTS FOR MANAGED UNDERGROUND STORAGE OF RECOVERABLE WATER Heberer, T. 2002. Occurrence, Fate, and Removal of Pharmaceutical Residues in the Aquatic Environment: A Review of Recent Research Data. Toxicology Letters 131:5-17. Hem, J.D. 1985. Study and interpretation of the chemical characteristics of natural water, 3rd edition. USGS Water-Supply Paper 2254. Alexandria, VA: U.S. Government Printing Office. Hulten, K., S. W. Han, H. Enroth, P. D.Klein, A. R. Opekun, R. H. Gilman, D. G. Evans, L. Engstrand, D. Y. Graham, and F. El-Zaatari. 1996. Helicobacter pylori in the drinking water in Peru. Gastroenterology, 110:1031-1035. Keller D. W., R. Hajjeh, A. DeMaria, Jr, B. S. Fields, J. M. Pruckler, R. S. Benson, P. E. Kludt, S. M. Lett, L. A. Mermel, C. Giorgio, and R. F. Breiman. 1996. Community outbreak of Legionnaires’ disease: an investigation confirming the potential for cooling towers to transmit Legionella species. Clin Infect Dis. 22:257–261. Kolpin, D.W., E.T. Furlong, M.T. Meyer, E.M. Thurman, S.D. Zaugg, L.B. Barber, and H.T. Buxton. 2002. Pharmaceuticals, hormones and other organic waste water contaminants in U.S. streams, 1990-2000: A National Reconnaissance. Environmental Science and Technology 36:1202-1211. LeClerc, H., D. A. A. Mossel, S. C. Edberg, and C. B. Struijk. 2001. Advances in the bacteriology of the coliform group: Their suitability as markers of microbial water safety. Annu. Rev. Microbiol. 55:201-234. Ma, H., H. Allen, and Y. Yin. 2001. Characterization of Isolated Fractions of Dissolved Organic Matter from Natural Water and Wastewater Effluents. Water Research 35(4): 985-996. Mac Kenzie, W. R., N. J. Hoxie, M. E. Proctor, M. S. Gradus, K. A. Blair, D. E. Peterson, J. J. Kazmierczak, D. G. Addiss, K. R. Fox, J. B. Rose, and J. P. Davis. 1994. A Massive Outbreak in Milwaukee of Cryptosporidium Infection Transmitted through the Public Water Supply. N Engl J Med 331(15):1035. Mara, D., and N. Horan. 2003. The Handbook of Water and Wastewater Microbiology. San Diego, California:Academic Press. Marciano-Cabral, F., R. MacLean, A. Mensah, and L. LaPat-Polasko. 2003. Identification of Naegleria fowleri in Domestic Water Sources by Nested PCR. Appl Environ Microbiol. 69:5864–5869. Marston, B. J., J. F. Plouffe, T. M. File, B. A. Hackman, S. J. Salstrom, H. B. Lipman, M. S. Kolczak, and R. F. Breiman. 1997. Incidence of community- acquired pneumonia requiring hospitalization—results of a population- based active surveillance study in Ohio. Arch. Intern. Med. 157:1709-1718. National Academy of Sciences. 1977. Drinking Water and Health, Vol. 1. Washington, D.C: .National Academy Press. National Research Council. 2004. Indicators for Waterborne Pathogens. Washington, D.C.: National Academies Press.

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APPENDIX A 331 Rolle-Kampczyk, U., J. G. Fritz, U. Diez, I. Lehmann, M. Richter, and O. Herbarth. 2004. Well water – one source of Helicobacter pylori colonization. Int J Hyg Environ Health 207:363–368. Rose J. B, J. T. Lisle, and C. N. Haas. 1996. Role of Pathogen Monitoring in Microbial Risk Assessment. Pp. 73-98 in Modeling Disease Transmission and its Prevention by Disinfection. Cambridge, United Kingdom: Cambridge University Press. Rose, J.B., D. E. Huffman, and A. Gennaccaro. 2002. Risk and Control of Waterborne Cryptosporidiosis. FEMS Microbiology Reviews 26:113-123. Smith, H. V. and J. B. Rose. 1998. Waterborne Cryptosporidiosis: Current Status. Parasitology Today 14:14–22. Stout, J. E. and V. L. Yu. 1997. Current concepts: Legionellosis. N Engl J Med 337(10):682-687. U.S. Department of Health, Education, and Welfare. 1970. Radiological Health Handbook, U.S. Government Printing Office, Washington, D.C., Stock No. 017-011-00043-0. Vandenburg O. 2004. Arcobacter species in humans. Emerg Infect Dis 10:1863- 1867. Viessman, W. Jr. and M.J. Hammer. 2005. Water Supply and Pollution Control, 7th Edition. Upper Saddle River, NJ: Prentice Hall. Wesley, I.V. 1997. Helicobacter and Arcobacter: Potential Human Foodborne Pathogens? Trends Food Sci Technol 8(9):293-299.

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