Peter B. McMahon

Groundwater depletion and sustainability of irrigation in the US High Plains and Central Valley

Aquifer overexploitation could significantly impact crop production in the United States because 60% of irrigation relies on groundwater. Groundwater depletion in the irrigated High Plains and California Central Valley accounts for ∼50% of groundwater depletion in the United States since 1900. A newly developed High Plains recharge map shows that high recharge in the northern High Plains results in sustainable pumpage, whereas lower recharge in the central and southern High Plains has resulted in focused depletion of 330 km3 of fossil groundwater, mostly recharged during the past 13,000 y. Depletion is highly localized with about a third of depletion occurring in 4% of the High Plains land area. Extrapolation of the current depletion rate suggests that 35% of the southern High Plains will be unable to support irrigation within the next 30 y. Reducing irrigation withdrawals could extend the lifespan of the aquifer but would not result in sustainable management of this fossil groundwater. The Central Valley is a more dynamic, engineered system, with north/south diversions of surface water since the 1950s contributing to ∼7× higher recharge. However, these diversions are regulated because of impacts on endangered species. A newly developed Central Valley Hydrologic Model shows that groundwater depletion since the 1960s, totaling 80 km3, occurs mostly in the south (Tulare Basin) and primarily during droughts. Increasing water storage through artificial recharge of excess surface water in aquifers by up to 3 km3 shows promise for coping with droughts and improving sustainability of groundwater resources in the Central Valley.

Redox Processes and Water Quality of Selected Principal Aquifer Systems

Reduction/oxidation (redox) conditions in 15 principal aquifer (PA) systems of the United States, and their impact on several water quality issues, were assessed from a large data base collected by the National Water-Quality Assessment Program of the USGS. The logic of these assessments was based on the observed ecological succession of electron acceptors such as dissolved oxygen, nitrate, and sulfate and threshold concentrations of these substrates needed to support active microbial metabolism. Similarly, the utilization of solid-phase electron acceptors such as Mn(IV) and Fe(III) is indicated by the production of dissolved manganese and iron. An internally consistent set of threshold concentration criteria was developed and applied to a large data set of 1692 water samples from the PAs to assess ambient redox conditions. The indicated redox conditions then were related to the occurrence of selected natural (arsenic) and anthropogenic (nitrate and volatile organic compounds) contaminants in ground water. For the natural and anthropogenic contaminants assessed in this study, considering redox conditions as defined by this framework of redox indicator species and threshold concentrations explained many water quality trends observed at a regional scale. An important finding of this study was that samples indicating mixed redox processes provide information on redox heterogeneity that is useful for assessing common water quality issues. Given the interpretive power of the redox framework and given that it is relatively inexpensive and easy to measure the chemical parameters included in the framework, those parameters should be included in routine water quality monitoring programs whenever possible.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO2 production. Although sulfate concentrations are low (approximately 0.05–0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4–20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Ficks Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO2 production (about 10−5 mmoll−1 year−1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2–6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments.

Biotransformation of caffeine, cotinine, and nicotine in stream sediments: Implications for use as wastewater indicators

Microbially catalyzed cleavage of the imadazole ring of caffeine was observed in stream sediments collected upstream and downstream of municipal wastewater treatment plants (WWTP) in three geographically separate stream systems. Microbial demethylation of the N-methyl component of cotinine and its metabolic precursor, nicotine, also was observed in these sediments. These findings indicate that stream sediment microorganisms are able to substantially alter the chemical structure and thus the analytical signatures of these candidate waste indicator compounds. The potential for in situ biotransformation must be considered if these compounds are employed as markers to identify the sources and track the fate of wastewater compounds in surface-water systems.

Bacterial metabolism and the δ13C composition of ground water, Floridan aquifer system, South Carolina

Viable bacteria are present (10 5 -10 7 cells per gram sediment) in the clastic water-table and Hawthorn aquifers that overlie and recharge the Floridan aquifer near Hilton Head Island, South Carolina. Incubation of cored sediments shows that indigenous bacteria are capable of producing carbon dioxide (CO 2 ) as they metabolize sedimentary organic material. Estimated in situ CO 2 production rates, based on dissolved inorganic carbon (DIC) changes and ground-water flow rates, are in the range of 10 -2 mmol . L -1 , yr -1 . Two independent lines of evidence, (1) isotope balance calculations on DIC along ground-water flow paths and (2) direct measurement of the isotopic composition of CO 2 produced by incubation of Hawthorn sediment, suggest that bacterially produced CO 2 in the Hawthorn aquifer is much heavier isotopically (δ 13 C ∼ -10‰ to -15‰) than associated sedimentary organic material (δ 13 C ∼ -21‰). The relatively heavy δ 13 C values of DIC in water from the Floridan aquifer, which receives much of its recharge from the overlying Hawthorn, reflect this source of isotopically heavy CO 2 .

Role of Microbial Processes in Linking Sandstone Diagenesis with Organic-rich Clays

ABSTRACT Numerous chemical reactions within clay sequences have been proposed to produce dissolved material for diagenesis of deeply-buried sands. However, reactions responsible for solubilizing inorganic and organic constituents in clays at intermediate depths, and their importance to sandstone diagenesis, have not been evaluated. Results from this study show that the processes of microbial organic-acid production (via fermentation) in clays and microbial organic-acid consumption (via sulfate reduction) in sands effectively link organic-rich clays to sandstone diagenesis in the Black Creek Formation of South Carolina. Diagenetic processes have resulted in the formation of 10 volume percent calcite cement, 0.1 volume percent authigenic pyrite, and 1.5 volume percent secondary porosity in Black Creek sands. However, the distribution of these diagenetic processes is not uniform, resulting in net destruction of porosity in some parts of the sand and net porosity enhancement in other parts. Mass balance-derived rates of microbial organic-acid production (10-5 mmole carbon 1-1 yr-1) and microbial CO2 production (4 10-5 mmole l-1 yr-1) show that microbial processes can account for all organic carbon in the calcite cements (at least 11% of carbonate carbon based on isotope-balance calculations), all observed authigenic pyrite, and all observed secondary porosity. These findings show that microbial processes can serve to link organic-rich clays with sandsto e diagenesis at intermediate depths.

Denitrification in marine shales in northeastern Colorado

Parts of the South Platte River alluvial aquifer in northeastern Colorado are underlain by the Pierre Shale, a marine deposit of Late Cretaceous age that is <1000 m thick. Ground water in the aquifer is contaminated with NO3-, and the shale contains abundant potential electron donors for denitrification in the forms of organic carbon and sulfide minerals. Nested piezometers were sampled, pore water was squeezed from cores of shale, and an injection test was conducted to determine if denitrification in the shale was a sink for alluvial NO3− and to measure denitrification rates in the shale. Measured values of NO3−, N2, NH4+, δ15N[NO3−], δ15N[N2], and δ15N[NH4+] in the alluvial and shale pore water indicated that denitrification in the shale was a sink for alluvial NO3−. Chemical gradients, reaction rate constants, and hydraulic head data indicated that denitrification in the shale was limited by the slow rate of NO3− transport (possibly by diffusion) into the shale. The apparent in situ first-order rate constant for denitrification in the shale based on diffusion calculations was of the order of 0.04–0.4 yr−1, whereas the potential rate constant in the shale based on injection tests was of the order of 60 yr−1. Chemical data and mass balance calculations indicate that organic carbon was the primary electron donor for denitrification in the shale during the injection test, and ferrous iron was a minor electron donor in the process. Flux calculations for the conditions encountered at the site indicate that denitrification in the shale could remove only a small fraction of the annual agricultural NO3-input to the alluvial aquifer. However, the relatively large potential first-order rate constant for denitrification in the shale indicated that the percentage of NO3− uptake by the shale could be considerably larger in areas where NO3− advection.

Shallow ground-water quality beneath a major urban center: Denver, Colorado, USA

Abstract A survey of the chemical quality of ground water in the unconsolidated alluvial aquifer beneath a major urban center (Denver, Colorado, USA) was performed in 1993 with the objective of characterizing the quality of shallow ground-water in the urban area and relating water quality to land use. Thirty randomly selected alluvial wells were each sampled once for a broad range of dissolved constituents. The urban land use at each well site was sub-classified into one of three land-use settings: residential, commercial, and industrial. Shallow ground-water quality was highly variable in the urban area and the variability could be related to these land-use setting classifications. Sulfate (SO 4 ) was the predominant anion in most samples from the residential and commercial land-use settings, whereas bicarbonate (HCO 3 ) was the predominant anion in samples from the industrial land-use setting, indicating a possible shift in redox conditions associated with land use. Only three of 30 samples had nitrate concentrations that exceeded the US national drinking-water standard of 10 mg l −1 as nitrogen, indicating that nitrate contamination of shallow ground water may not be a serious problem in this urban area. However, the highest median nitrate concentration (4.2 mg l −1 ) was in samples from the residential setting, where fertilizer application is assumed to be most intense. Twenty-seven of 30 samples had detectable pesticides and nine of 82 analyzed pesticide compounds were detected at low concentrations, indicating that pesticides are widely distributed in shallow ground water in this urban area. Although the highest median total pesticide concentration (0.17 μg l − ) was in the commercial setting, the herbicides prometon and atrazine were found in each land-use setting. Similarly, 25 of 29 samples analyzed had detectable volatile organic compounds (VOCs) indicating these compounds are also widely distributed in this urban area. The total VOC concentrations in sampled wells ranged from nondetectable to 23 442 μg l − . Widespread detections and occasionally high concentrations point to VOCs as the major anthropogenic ground-water impact in this urban environment. Generally, the highest VOC concentrations occurred in samples from the industrial setting. The most frequently detected VOC was the gasoline additive methyl tert -butyl ether (MTBE, in 23 of 29 wells). Results from this study indicate that the quality of shallow ground water in major urban areas can be related to land-use settings. Moreover, some VOCs and pesitides may be widely distributed at low concentrations in shallow ground water throughout major urban areas. As a result, the differentiation between point and non-point sources for these compounds in urban areas may be difficult.

Potential for 4‐n‐nonylphenol biodegradation in stream sediments

The potential for in situ biodegradation of 4-nonylphenol (4-NP) was investigated in three hydrologically distinct streams impacted by wastewater treatment plants (WWTPs) in the United States. Microcosms were prepared with sediments from each site and amended with [U-ring-(14)C]4-n-nonylphenol (4-n-NP) as a model test substrate. Microcosms prepared with sediment collected upstream of the WWTP outfalls and incubated under oxic conditions showed rapid and complete mineralization of [U-ring-(14)C]4-n-NP to (14)CO(2) in all three systems. In contrast, no mineralization of [U-ring-(14)C]4-n-NP was observed in these sediments under anoxic (methanogenic) conditions. The initial linear rate of [U-ring-(14)C]4-n-NP mineralization in sediments from upstream and downstream of the respective WWTP outfalls was inversely correlated with the biochemical oxygen demand (BOD) of the streambed sediments. These results suggest that the net supply of dissolved oxygen to streambed sediments is a key determinant of the rate and extent of 4-NP biodegradation in stream systems. In the stream systems considered by the present study, dissolved oxygen concentrations in the overlying water column (8-10 mg/L) and in the bed sediment pore water (1-3 mg/L at a depth of 10 cm below the sediment-water interface) were consistent with active in situ 4-NP biodegradation. These results suggest WWTP procedures that maximize the delivery of dissolved oxygen while minimizing the release of BOD to stream receptors favor efficient biodegradation of 4-NP contaminants in wastewater-impacted stream environments.

Effects of carbon and nitrate on denitrification in bottom sediments of an effluent-dominated river

Nitrogen and carbon limitation of denitrification in the bed sediments of an effluent-dominated stream were investigated by quantifying the effects of nitrate and glucose additions on the rate of sediment N2O production. Bed sediment samples were collected from a 30-km stretch of the South Platte River where up to 95% of the base flow discharge consists of effluent from a water treatment plant in Denver, Colorado. The rate of denitrification in upstream sediment samples incubated under in situ nitrate and carbon conditions was primarily limited by nitrate supply. The stimulatory effect of nitrate additions on the rate of bed sediment denitrification decreased with increasing distance downstream of the treatment plant. Approximately 35 km downstream of the treatment plant, denitrification in the bed sediment samples was carbon limited. The observed decreases in the concentration of total inorganic nitrogen (as NH4 + NO3) dissolved in the river and the organic carbon content of the bed sediments with increasing distance downstream of the treatment plant suggest that bed sediment denitrification is a significant sink for nitrogen in this stretch of the river.