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Prospects for Managed Underground Storage Recoverable Water 4 Water Quality Considerations INTRODUCTION Water quality is characterized by the chemical (organic and inorganic), physical, and microbiological nature of the water. The monitoring and testing that go along with this characterization must focus on both constituents of concern to human health and those that affect operations of the water systems. The development of a system for managed underground storage (MUS) of water involves the testing and characterization of the source water, the aquifer geochemistry and native water quality, the stored water, and the recovered water. The subsurface has the capacity to attenuate many chemical constituents and pathogens via physical, chemical, and biological processes. Critical to MUS is an understanding of the mixing of often chemically and microbiologically different waters, which may react with each other and with materials comprising the aquifer matrix. The reactions that occur can ultimately improve or diminish the stored water quality chemically and microbiologically. Water quality changes can be variable in both space and time. Furthermore, among the potential suite of reactions are those that can cause clogging or dissolution of the aquifer matrix and so affect MUS operation. The consequences of the potential reactions during storage underscore the importance of a comprehensive aquifer characterization to fully understand the water quality changes that may occur during MUS. An understanding of temporal changes in the quality of water prior to and during storage is critical and is intertwined with the application, treatment requirements, and use of the water after it is recovered. This understanding may also influence the treatment of waters prior to storage. “Successful” MUS is therefore much more than a function of effective hydrologic engineering; MUS must also consider the broad spectrum of processes—microbiologic, hydrochemical, geochemical, and hydrogeologic—as they influence water quality and performance of the system. The mix of constituents in source waters for MUS varies, depending on the natural purity of the water and constituent inputs and modifications through human activities (e.g., agricultural, industrial, commercial, and residential land use, engineered treatment processes). Public concerns about these constituents may vary depending on whether the classification is “health-related” or “aesthetic.” The purposes of this chapter are to describe: (1) the range of constituents in MUS waters; (2) hydrogeochemical and microbiological processes involved as source waters interact with the native ground water and rocks or sediments comprising the aquifer, and the impact of these processes on MUS performance; and (3) predictive tools for water quality and aquifer changes.
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Prospects for Managed Underground Storage Recoverable Water CONSTITUENTS IN WATERS THAT CAN AFFECT PERFORMANCE AND OPERATION OF MUS Constituents Two overlapping sets of water quality parameters are important to MUS performance and so must be considered in designing MUS systems. Constituents regulated in drinking water (as described by the Safe Drinking Water Act [SDWA]) comprise a well-defined list with concentrations that must be met in drinking water supplies for either human health or aesthetic reasons. While the SDWA prescribes the list of both chemicals and microorganisms that have been the primary impetus for water quality goals, this list is not sufficient to evaluate the quality of the various waters (source water, native groundwater, stored water, etc.) for an MUS system. In order to establish a sustainable MUS system, constituents that lead to aquifer clogging or dissolution, or other reactions that improve or degrade water quality during MUS operations must also be evaluated. The constituent concentrations that are important for operations are not embodied in a regulatory list, but emerge from consideration of the reactions that can impact MUS performance and the particular type of MUS system (e.g., type of source water, recharge method, native groundwater characteristics, and aquifer geochemistry). Importantly, the microbial and chemical water quality can improve or degrade during any stage of MUS. The list of contaminants developed under the SDWA includes the list of chemical and microbiological constituents that have established legal enforceable maximum contaminant levels (MCLs) and/or treatment technology requirements and MCLGs (maximum contaminant level goals). Total coliform bacteria are used from a regulatory monitoring perspective to judge drinking water microbiological safety. There is also emerging concern about “new” (previously unmonitored) chemicals and constituents that occur in water as a consequence of human activities and are not regulated (e.g., endocrine disrupting chemicals, pharmaceuticals, personal care products). For many of the chemicals in this classification, analytical techniques appropriate for environmental samples are relatively new and complex. The World Health Organization also has developed a list of constituents of interest in water for health goals that includes some compounds that are not regulated by the U.S. Environmental Protection Agency (EPA) including, for example, the cyanobacterial toxins that can be found in surface waters. To fully appreciate the broad water quality characteristics found in MUS systems from the ambient groundwater to the source, stored, and recovered water, the physical, chemical, and microbiological water quality constituents need to be understood and measured. These are described briefly in the following sections, and extended descriptions are available in Appendix A.
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Prospects for Managed Underground Storage Recoverable Water Physical Characteristics The first impressions of water quality are often based on visual observations. Water is expected to be free of particles (turbidity), color, taste, and odor. Turbidity may increase clogging, and these particles can also harbor pathogens and enhance their survival in the presence of a disinfectant. Color is often the result of dissolved organic matter, for example, humic and fulvic acids. Taste is often related to the presence of iron or manganese in the water. It may also be due to high levels of chlorine used as a disinfectant. Odor may be caused by decomposition of organic matter or reduction of dissolved sulfate; the control of odors is among the priority issues with respect to public acceptance of a project. Additional important physicochemical characteristics of MUS waters include dissolved oxygen, pH, oxidation-reduction potential (Eh), specific conductance, and temperature. Dissolved oxygen (DO) is required by any aquatic organisms that respire aerobically (i.e., breathe oxygen). The presence of DO tends to minimize odors, but it may cause oxidation of sulfide minerals or organic matter in aquifers that can lead to the release of arsenic and other metals. The DO content of recharged water is affected by temperature and so can vary significantly with the season. Dissolved oxygen saturation (with respect to atmospheric oxygen content) is a strong function of temperature within the relevant environmental range. For fresh water (< 2000 mg/L of total dissolved solids [TDS]), the oxygen saturation ranges from approximately 7 mg/L at 35°C to 12.8 mg/L at 5°C. Water treatment processes, such as ozonation and chlorination, also affect the DO. The pH is a measure of the hydrogen-ion concentration, or the acidity, of water. It influences everything from the ability of a mineral to adsorb toxic metals to the dissolution of the aquifer materials. Oxidation-reduction potential (ORP or Eh) is another critical parameter because it indicates processes such as iron dissolution or precipitation and proportions of various dissolved nitrogen species such as ammonia. Along with pH, Eh provides a measure useful for gauging conditions that favor the persistence of certain organic contaminants or the survival of certain pathogens. Specific conductance is a measure of how well a given water sample conducts an electrical current and can give a good estimate of the TDS in a solution. Finally, temperature affects the speed (kinetics) of chemical reactions in the subsurface, whether they are mediated by bacteria or not. Organic Constituents Four classes of organic constituents are particularly important to MUS systems: total organic carbon, disinfection by-products, other regulated organics (aside from disinfection by-products), and so-called emerging contaminants. Total organic carbon includes both dissolved organic carbon (DOC) and particulate organic carbon (POC) and is composed primarily of natural organic matter (NOM). DOC can lead to the formation of disinfection by-products. In addi-
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Prospects for Managed Underground Storage Recoverable Water tion, the degradation of labile dissolved and particulate organic carbon in recharge water can lead to reductions in DO, ORP, and pH and can also cause clogging through stimulation of biomass growth. Disinfection by-products, or DBPs, are formed as a consequence of reactions between disinfection chemicals (chlorine, chloramine, and ozone) used to treat microbial pathogen contaminants and DOC. They are often small, halogenated (e.g. chlorinated, brominated) or nitrogen-containing organic compounds. Because the precursor organic matter is of variable composition, the DBPs produced encompass a spectrum of chemicals including the regulated trihalomethanes (THMs) and haloacetic acids (HAAs). Regulated trace organic contaminants, such as petroleum hydrocarbons, chlorinated solvents, and regulated pesticides, are known toxins or carcinogens and are problematic in thousands of contaminated sites around the country. Their behavior must be considered for any particular MUS if they are present in either the source water or the groundwater system. Unlike DBPs, these chemicals are not created in situ. Methods to monitor these chemicals in drinking water supplies are well established and routinely available. The fate and transport of these chemicals in groundwater are relatively well understood (compared to emerging contaminants) as a consequence of prior groundwater studies. The behavior of these compounds in standard water treatment facilities is also well known. For these reasons, the discussion of this group of contaminants in this report is limited, and the reader is referred to more comprehensive reviews. Emerging contaminants are any synthetic or naturally occurring chemicals or microorganisms that are not commonly monitored in the environment but have the potential to enter the environment and cause known or suspected adverse ecological and/or human health effects (http://toxics.usgs.gov/regional/emc/). They are widespread and include antibiotics and other pharmaceuticals, personal care products, hormones, and many other compounds. Inorganic Constituents Inorganic chemical constituents of concern in MUS source waters can be grouped as nutrients, nonmetals, and metals and metalloids. Nitrogen and phosphorous species are known as nutrients because they are essential for the growth of microorganisms and plants. However, they can also contribute to deleterious growth of algae or microorganisms in MUS systems. Nitrogen is soluble in several forms, including nitrate and nitrite. Phosphorus is generally poorly soluble as phosphate. The nonmetals of concern include species such as chloride and sulfate and occasionally borate. Typically, these are part of a larger problem of salinization either in the case of recharge into brackish groundwater or due to evaporation in arid regions. The metals and metalloids of concern are often present at trace concentrations, and many are classified as priority pollutants. Examples of these include arsenic, cadmium, mercury, lead, and chromium. They are associated with a wide variety of problems from developmental delays in children to various cancers, bone disease, and skin problems. Radionuclides
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Prospects for Managed Underground Storage Recoverable Water of greatest concern are uranium and radon, both of which are carcinogens. Iron and manganese, except at very high levels, are primarily of concern because they influence the aesthetic quality of the water. Iron can be related to clogging problems as well. Microbial Constituents Important human pathogens for MUS systems are those microorganisms including bacteria, parasites, and viruses that come from both human and animal fecal pollution and naturally-occurring microorganisms that reside and grow in the aquatic environment such as cyanobacteria (toxic algae) and Legionella. Often the distinction between human and animal sources using microbial source tracking techniques is advantageous with regard to developing strategies to control the source. In the United States, waterborne outbreaks (common-source epidemics associated with contamination of the drinking water) have occurred in both community and non-community systems. Groundwater was the supply most often associated with these outbreaks (compared to springs, surface water, or contamination of the distribution system) often because disinfection was inadequate or not used to treat microbially contaminated wells (Liang et al., 2006). From 1989 to 2002, 64 percent of drinking water outbreaks were from a groundwater supply, and more recently from the 2001 to 2002 and 2003 to 2004 reports, groundwater was associated with 92 percent and 52 percent of the drinking water outbreaks, respectively (Blackburn et al., 2004;Liang et al., 2006). Bacteria, including fecal bacteria such as Campylobacter (associated with animal and human wastes) and aquatic (nonfecal) bacteria such as Legionella as well as enteric viruses from human fecal wastes, were the most common causes of the illnesses. Native Groundwater and Aquifer Geochemistry Native Groundwater Geochemistry and Associated Aquifer Classification Native groundwater quality in an aquifer is important to consider in planning an MUS system because it provides information about constituents likely to dissolve into stored water as it equilibrates with the aquifer matrix. Knowledge of native groundwater quality is also critical to evaluating the potential for chemical reactions occur as recharged and native waters mix in the transition zone. In addition, native groundwater chemistry provides a useful means for aquifer classification that is related to the aquifer mineral matrix. In uncontaminated groundwaters, major ions typically originate from the weathering of aquifer minerals. Hence, there is a strong association between the major ions identified and the mineral composition of the aquifer. Major cations include Ca2+, K+, Na+, and Mg2+, and major anions include Cl−, HCO3−, SO42−,
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Prospects for Managed Underground Storage Recoverable Water and sometimes NO3− (Table 4-1) (Freeze and Cherry, 1979; Hem, 1985). Concentrations of nitrate sufficiently high to warrant its inclusion as a major anion are generally attributable to anthropogenic influence. The fingerprint of the major cations and anions in groundwaters (e.g., their concentrations and relative proportions) can be used to distinguish among hydrochemical units in the subsurface. For example, aquifers comprised of limestone (mostly calcium and/or calcium-magnesium carbonate minerals) will typically exhibit calcium as the dominant cation and bicarbonate as the dominant anion. Table 4-1 summarizes some hydrochemical attributes typical of groundwaters contained within different types of aquifer rocks. This table generalizes compositions typical of potable aquifers that have low (less than 1,000-2,000 mg/L) TDS. Although trace metals and metalloids in groundwater are often associated with contamination, they can also occur naturally in groundwaters as a consequence of water-rock interactions. Recent work (Lee and Helsel, 2005) suggests that background (without anthropogenic contamination) trace element concentrations of barium, chromium, copper, lead, nickel, molybdenum, and selenium have a 1.0 to 1.5 percent likelihood of exceeding federal drinking water standards. The authors report that arsenic is an exception, with a 7 percent likelihood of exceeding the federal drinking water standard. Unlike trace metals, regulated organic contaminants occur in groundwater solely because of human activities. Regulated industrial chemicals occur in groundwater as a consequence of point source discharges via leaks, spills, or historical disposal. In addition, regional contamination of groundwaters can occur from nonpoint or widely distributed sources related to land use. Examples of such chemicals include pesticides and nutrients (Scanlon et al., 2005). TABLE 4-1 Typical Major Ion Chemistry in Groundwaters Associated with Potable Aquifers in Different Types of Rock Matrix pHa Major dissolved speciesb Carbonate Circumneutral to basic Ca2+, Mg2+, HCO3− Unconsolidated and consolidated siliciclastic sediments Siliciclastic; alluvium, glacial Circumneutral to acidic Ca2+, Na+, HCO3−; SO42 ; mixed cation Fractured Bedrock (igneous, metamorphic, brittle sedimentary) Basic Mg2+, Ca2+, Na+, HCO3−; SiO2 amore acidic near recharge areas. bions and dissolved chemicals (see glossary for definitions). Na+, Mg2+, Cl− are generally higher proximal to saline water bodies and within deeper “formation” waters; NO3− in high-recharge areas and unconfined aquifers. SOURCE: Freeze and Cherry (1979); Hem (1985).
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Prospects for Managed Underground Storage Recoverable Water The microbiological quality associated with bacteria that naturally reside in the system is not well studied. Those involved in biochemical processes or bioremediation have been the primary focus of in situ studies. Many of the bacteria are anaerobic or facultative aerobes. There is a large emphasis in the literature on groundwaters impacted by microorganisms of surface water or wastewater origin. Regulatory Classification of a Potable Aquifer In addition to the water chemistry-based classification system for aquifers described above, there exist regulatory aquifer classifications that define an aquifer as ”potable” or ”non-potable” or describe its relative vulnerability to surface sources of contamination. Although aquifers within either classification can be considered for MUS, the regulatory designation may affect operational requirements, particularly source water quality, for the MUS system. Chapter 5 further describes regulation pertinent to MUS. Most aquifers are protected by generic antidegradation policies such that no anthropogenic activity can lead to a measurable or perceived decline in water quality. This is due partly to the fact that groundwater is more difficult to clean up once contaminated. Protection of a potable aquifer is a key consideration for an MUS system and is addressed through water quality monitoring associated with drinking water applications. Federal regulations classify (or designate) potable aquifers based on the following criteria: current use of the groundwater, water availability, and water quality as indicated by total dissolved solids. It is presumed that an aquifer classified as an underground source of drinking water (USDW) will meet the coliform bacteria regulatory requirement (<1/100 ml), yet the Ground Water Rule (http://www.epa.gov/safewater/disinfection/gwr) now recognizes the need for disinfection of groundwater used for potable purposes. Specific regulatory text describing an underground source of drinking water is provided in Box 4-1. By law, state water quality regulations are at least as stringent as federal regulations. As a result, potable aquifer designations in some states are more detailed or involved than the federal regulation requires. Florida is among the many states that provide examples of additional regulatory classifications for aquifers. The Florida code defines three categories of aquifers for potable use based on the TDS of water in the aquifer and whether the aquifer serves as a single source of drinking water. It also lists two nonpotable use classifications for aquifers with high TDS for which there is no reasonable expectation that the aquifer will serve as a source of future drinking water. Confined aquifers so classified may be used for wastewater injection.
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Prospects for Managed Underground Storage Recoverable Water BOX 4-1 Federal Language Designating an Aquifer as ‘Potable’ According to Section 144.3, Title 40, of the Code of Federal Regulations, an underground source of drinking water (USDW) “means an aquifer or its portion: (a) (1) Which supplies any public water system; or (2) Which contains a sufficient quantity of groundwater to supply a public water system; and (i) Currently supplies drinking water for human consumption; or (ii) Contains fewer than 10,000 mg/l total dissolved solids; and (b) Which is not an exempted aquifer.” The same section states, “Exempted aquifer means an ‘aquifer’ or its portion that meets the criteria in the definition of ‘underground source of drinking water’ but which has been exempted according to the procedures in Sec. 144.7” (Title 40 of the Code of Federal Regulations). Source Waters Differences between the source water and native groundwater lead to reactions during storage that can impact recovered water and either improve or degrade its quality and/or impact MUS performance. To assess the potential for such reactions, evaluation of the source water quality is essential. With a few important and notable exceptions, source water is the origin of most anthropogenic organic and microbial contaminants in stored groundwater. The exceptions include organic disinfection by-products that can be formed in the groundwater system through reaction of residual chemical disinfectants with natural organic matter. This statement also presumes that the groundwater system has not received contaminants through prior anthropogenic activities (e.g. spills, leaks, or nonpoint chemical use) that could contaminate the stored water. Surface waters, other groundwaters (from interbasin or interaquifer transfers), urban stormwater runoff, and treated or reclaimed wastewater are all potential sources for MUS. Typical constituent classes of concern to MUS from a water quality perspective that are associated with different water sources are listed in Table 4-2. In many cases, it is mandated that the source water be treated prior to storage, with the treatment level often defaulting to creating water that meets drinking water standards. However, poorer-quality waters may be used. The feasibility of using lower-quality source waters depends on issues such as planned end use of the stored water, aquifer classification, post storage treatment, and in situ reactions that occur during recharge or storage. Use of such waters for recharge is also constrained by regulatory limitations. For those waters used for other purposes, the main concern may be potential or measurable water quality degradation in nearby groundwaters.
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Prospects for Managed Underground Storage Recoverable Water TABLE 4-2 Selected Constituents in Source Waters and Relative Concern for MUSa Constituents Untreated Groundwaterb SurfaceWaters Urban Stormwater Runoff Waters Treated to Drinking Water Standards Wastewater Treated for Non-potable and Indirect Potable Use Salinity Low Low or medium Low to medium Low High Nutrients (NO3−, etc.) Medium Medium Medium Low High Metalloids, including arsenic Low to medium Low Medium to high Low Low Mn, Mo, Fe, Ni, Co, V, Low to medium Low Medium Low Low Trace organics Low to medium Medium High Low Medium Total organic carbon (TOC) Low to medium Medium to high Medium Low Medium Disinfection by-products Low Medium Low High High Microorganisms Medium to high High Medium Low High aThe relative concerns shown in the table are based on committee consensus. b Assuming source is a potable aquifer. The case study in Box 4-2 illustrates a situation in Florida where stormwater is being used for groundwater resource augmentation. In addition, stormwater runoff has been used for groundwater recharge on Long Island, New York, and—mixed with other water types—in Orange County, California, for many decades. However, caution is always warranted with stormwater because of its highly variable chemical and microbiological nature. Even in the same location, the quality of stormwater runoff may vary with rainfall quantity and intensity, time since the last runoff event, and time of the year. Stormwater runoff from industrial areas, dry weather storm drainage flow, salt-laden snowmelt flow, construction site runoff, and flow originating from vehicle service areas are particularly problematical for artificial recharge (NRC, 1994). There are promising new techniques to assess the risks posed by the use of stormwater. Page et al. (2006) used a Hazard Analysis and Critical Control Point (HACCP) framework to evaluate the viability of a potential ASTR project (see Chapter 6). They collected data on the number and types of industries in subcatchments, the likely chemicals used by these industries, stormwater quality, pollutants (and potential pollutants), operational procedures for stormwater management, barriers to hazards entering stormwater and control points for pollutant management. While their results generally supported moving forward,
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Prospects for Managed Underground Storage Recoverable Water BOX 4-2 Drainage Wells in Orlando, Florida Since the early 1900s, drainage wells have been utilized for lake-level control and management of urban runoff. These wells are recognized as important components of groundwater resource augmentation and as such are now referred to as aquifer recharge wells. More than 400 of these wells divert approximately 30 million to 50 million gallons per day (Mgal/d) of lake overflow and stormwater runoff to the upper Floridan Aquifer System. The positive aspect of recharge wells is self-evident; however, concerns exist with regard to the introduction of untreated urban runoff (e.g., petroleum by-products, metals, nutrients, pesticides, and microbes) into the aquifer. Pre-recharge treatment strategies can be employed, including first-flush bypass, screens, filters, and disinfection systems. The Central Florida Aquifer Recharge Project (CH2M Hill, 2006) was designed to assess these water quality concerns and potential strategies, specifically addressing the fate of bacteria in the Floridan Aquifer System, the effectiveness of passive stormwater treatment for reducing bacteria, and the effectiveness and cost feasibility of physically reducing bacteria in lake water recharge. These goals were addressed through (1) installation of monitor wells, (2) completion of groundwater tracer tests to confirm communication between the recharge and monitor wells, and (3) implementation of a comprehensive monitoring plan that includes broad-spectrum analyses of organic and inorganic constituents as well as microbes. During wet- and dry-season sampling, attenuation of nearly all constituents was observed. For example, up to a six-order-of-magnitude reduction in microbial concentrations was observed over a lateral distance through the aquifer of up to 450 feet. Arsenic, however, exhibited a statistically significant increase along the flow path between the recharge and monitor wells. A high degree of air entrainment during recharge, confirmed by borehole video, may have contributed to the release of arsenic from the aquifer matrix. The conclusions of this important and well-designed study were contrary to expected results. Metal mobilization was not anticipated, and initial concerns regarding microbes and synthetic organics were found to be uncorroborated. Based on the results of this study, government agency-sponsored random sampling of private wells is under way to assess elevated levels of arsenic. they concluded that chemicals such as pesticides, herbicides, and endocrine disruptors, which were not monitored in real-time, required further research to validate that they were either absent or being removed effectively by the pretreatment system. SUBSURFACE PROCESSES THAT AFFECT WATER QUALITY IN MUS SYSTEMS Biogeochemical reactions, including water-rock interactions, that occur during MUS activities are dynamic in both space and time and are a consequence of mixing recharge water with water quality parameters that differ from the native groundwater in the aquifer. The reactions that occur result from mixing between native and recharged water, interaction between the recharged water and the aquifer media, and changing the environmental conditions of the recharged water (e.g., storing water underground that resided formerly at the surface and was open to the atmosphere). Departure from thermodynamic equilibrium among the
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Prospects for Managed Underground Storage Recoverable Water recharged water, native groundwater, and aquifer media is the driving force for the changes in water chemistry and/or physical aquifer characteristics (e.g., permeability) that occur in the recharge zone. Chemical reactions that control or influence concentrations of contaminants during storage include oxidation-reduction (redox) reactions, acid-base reactions, sorption-desorption reactions including ion exchange, mixing (diffusion-dispersion or mechanical dispersion), and precipitation-dissolution reactions. Nearly all of the important reactions are mediated by common soil microorganisms native to the environment. Also, many of the most common (or important) geochemical processes that occur in situ encompass multiple reaction categories (e.g., redox, acid-base). Because of the high importance of redox reactions to water quality and aquifer integrity during underground storage, these are described in greater detail than the other reaction types. Detailed and rigorous discussions of each of these types of reactions in aqueous systems can be found in several texts, including (Drever, 1997; Langmuir, 1997; Stumm and Morgan, 1996) Redox Reactions In a redox reaction, electrons are transferred between chemicals with a concomitant gain or release of energy. Species are termed oxidized if they are electron poor (e.g., nitrate, carbon dioxide, Fe(III) As(V)) and reduced if they are electron rich (e.g., nitrite, carbon in organic matter, Fe(II), As(III)). Only elements that can exist in multiple “electron” forms (species), such as carbon, nitrogen, arsenic, and iron, can participate in redox reactions. In a redox reaction, an oxidation reaction (in which one species loses an electron) must be coupled to a reduction reaction (in which one species gains an electron) because there exist no “free” (e.g., not part of an element) electrons. Although there are no free electrons within a system, the redox condition or potential of the system can be gauged by the dominant forms of redox- sensitive elements in the system and is often reported as the Eh or pε of the system. A lower value of Eh or pε indicates that the system is more reduced. Flowing rivers that are open to the atmosphere generally contain significant dissolved oxygen and are oxidizing. Many (but certainly not all) groundwaters have very low or immeasurable dissolved oxygen concentrations and have relatively high concentrations of more reduced species such as reduced iron (Fe2+) or reduced sulfur (S2−). The redox reactions that occur during groundwater storage are typically exothermic (reactions that release energy). Microorganisms often mediate these reactions, which otherwise occur very slowly, and gain energy for growth. In general, microorganisms oxidize organic matter by utilizing available electron acceptor(s) to gain energy, and therefore, organic matter can serve as a driver of redox potential changes within a system. It can be either in the dissolved phase or as part of the aquifer solids. The energy available from coupling the oxidation of DOC to the reduction of different elements is quite variable (Figure 4-1A). In general, the most energetically favorable coupling available dominates a system.
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Prospects for Managed Underground Storage Recoverable Water that has begun at a national scale should be encouraged, and MUS programs will be among the many beneficiaries of such investigations. Conclusion: A better understanding is needed of potential removal processes for microbes and contaminants in the different types of aquifer systems being considered for MUS. These studies need to assess spatial and temporal behavior during operation of an MUS system. This research will reduce the uncertainty regarding the extent of chemical and microbial removal in MUS systems. In addition, this information will help reduce impediments to public acceptance of a wide variety of source waters for MUS. Conclusion: In particular, changes in reduction-oxidation (redox) conditions in the subsurface are common and often important outcomes of MUS operation. These changes can have both positive and negative influences on the physical properties and the chemical and biological reactivity of aquifer materials. For example, the existence of both oxidizing and reducing conditions might enhance the biodegradation of a suite of trace organic compounds of concern or, conversely, lead to accumulation of an intermediate product of concern. Redox changes can cause dissolution-precipitation or sorption-desorption reactions that lead to adverse impacts on water quality or clogging of the aquifer; however, such precipitation reactions can also sequester dissolved contaminants. Recommendation: Additional research should be conducted to understand potential removal processes for various contaminants and microbes and, particularly, to determine how changes in redox conditions influence the movement and reactions for many inorganic and organic constituents. Specific areas of research that are recommended include (1) bench-scale and pilot studies along with geochemical modeling to address potential changes in water quality with variable physical water conditions (pH, Eh, and DO); and (2) examination of the influence of sequential aerobic and anaerobic conditions or alternating oxidizing and reducing conditions on the behavior of trace organic compounds in MUS systems, especially during storage zone conditioning. Conclusion: Molecular biology methods have the potential for rapid identification of pathogens in water supplies. These noncultivable techniques have not been tested in a meaningful way to address background and significance of the findings. False negatives and false positives remain an issue that needs to be addressed. Recommendation: Research should be conducted to address the approaches and specific applicability of molecular biology methods for pathogen identification, particularly interpretation of results that cannot determine viability, for the different types of source waters and aquifer systems being considered for MUS. Conclusion: Pathogen removal or disinfection is often required prior to storing water underground. If primary disinfection is achieved via chlorination, disinfection by-products such as trihalomethanes and haloacetic acids are
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Prospects for Managed Underground Storage Recoverable Water formed. These have been observed to persist in some MUS systems. However, chlorine is the most cost-effective agent for control of biofouling in recharge wells; hence, it may not be possible to eliminate entirely the use of chlorine in MUS systems (e.g., periodic pulses of chlorine to maintain injection rates). Recommendation: To minimize formation of halogenated DBPs, alternatives to chlorination should be considered to meet primary disinfection requirements, such as ultraviolet, ozone, or membrane filtration. REFERENCES Allen-King, R. M., P. Grathwohl, and W. P. Ball. 2002. New modeling paradigms for the sorption of hydrophobic organic chemicals to heterogeneous carbonaceous matter in soils, sediments, and rocks. Advances in Water Resources 25:985-1016. Alvarez, M. E., M. Aguilar, A. Fountain, N. Gonzalez, O. Rascon, and D. Saenz. 2000. Inactivation of MS-2 phage and poliovirus in groundwater. Canadian Journal of Microbiology 46(2):159-165. Arthur, J. D., A. A. Dabous, and J. B. Cowart. 2005. Water-rock geochemical considerations for aquifer storage and recovery: Florida case studies. Pp. 327-339 in C.F. Tsang, and J. A. Apps (eds.) Underground Injection Science and Technology, Developments in Water Science. Amsterdam: Elsevier. Arthur, J.D., A. A. Dabous, and C. Fischler. 2007. Aquifer storage and recover in Florida: geochemical assessment of potential storage zones. Tallahassee, FL: Florida Geological Survey. Arthur, J. D., J. B. Cowart, and A. A. Dabous. 2001. Florida Aquifer Storage and Recovery Geochemical Study: Year Three Progress Report, Florida Geological Survey Open File Report 83. Arthur, J. D., A. A. DaBous, and C. Fischler, . 2007. Aquifer storage and recovery in Florida: Geochemcial assessment of potential storage zones. Pp. 185-197 in P. Fox (ed.) Management of Aquifer Recharge for Sustainability. Phoenix, AZ: Acacia Publishing. Atlas, R. M., and J. Philip (eds.) 2005. Bioremediation: Applied Microbial Solutions for Real-World Environmental Cleanup. Washington, DC: ASM Press. AwwaRF (American Water Works Association Research Foundation). 2001. Soil Aquifer Treatment for Sustainable Water Reuse.Denver, CO: AwwaRF. Banning, N., S. Toze, and B. J. Mee. 2002. Escherichia coli survival in groundwater and effluent measured using a combination of propidium iodide and the green fluorescent protein. Journal of Applied Microbiology 93(1):69-76. Baveye, P., P. Vandevivere, B. L. Hoyle, P. C. DeLeo, and D. S. de Lozada. 1998. Environmental impact and mechanisms of the biological clogging of saturated soils and aquifer materials. Critical Reviews in Environmental
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