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At least 1,603 records · Page 89Linked to original sources

Remote sensing-based actual evapotranspiration assessment in a data-scarce area of Brazil: A case study of the Urucuia Aquifer System

The large groundwater reserves of the Urucuia Aquifer System (UAS) enabled agricultural development and economic growth in the western Bahia State, in northeastern Brazil. Over the last several years, concern has grown around the aquifer’s diminishing water levels, and water balance (WB) studies are in demand. Considering the lack of measured actual evapotranspiration (ET a ), a major component of the water cycle, this work uses the Operational Simplified Surface Energy Balance (SSEBop) model to estimate ET a , and compares it to basin-scale estimates from the Soil Moisture Accounting Procedure (SMAP) monthly model and from an annual WB closure method, based on gridded meteorological data and the Gravity Recovery and Climate Experiment (GRACE) product. Additionally, a comparative assessment of different versions of the SSEBop parameterization was performed. Moderate Resolution Imaging Spectroradiometer (MODIS) imagery was used to implement eight different versions of the SSEBop algorithm over the UAS between 2000 and 2013. SSEBop and SMAP ET a yielded similar seasonal patterns, with correlation coefficient (r) up to 0.65, mean difference (MD) of 0.8 mm/month and mean absolute difference (MAD) of 18.5 mm/month. Comparison of SSEBop annual ET a estimates to annual SMAP and WB closure estimates yielded low MD (12.1 and −7.3 mm/year, respectively) and MAD (82.5 and 82.8 mm/year, respectively), but also low r values (0.00 and 0.37, respectively). The comparison of the different SSEBop versions indicated the need to incorporate a calibration step of the aerodynamic heat resistance (r ah ) parameter. SSEBop results were also used for land cover and drought monitoring. Analysis indicates that agriculture, associated with an increasing trend of atmospheric evaporative demand, is responsible for the decrease in groundwater levels and streamflow in the studied time period.

Urucuia Aquifer System↗

Comment on “An unconfined groundwater model of the Death Valley Regional Flow System and a comparison to its confined predecessor” by R.W.H. Carroll, G.M. Pohll and R.L. Hershey [Journal of Hydrology 373/3–4, pp. 316–328]

Carroll et al. (2009) state that the United States Geological Survey (USGS) Death Valley Regional Flow System (DVRFS) model, which is based on MODFLOW, is “conceptually inaccurate in that it models an unconfined aquifer as a confined system and does not simulate unconfined drawdown in transient pumping simulations.” Carroll et al. (2009) claim that “more realistic estimates of water availability” can be produced by a SURFACT-based model of the DVRFS that simulates unconfined groundwater flow and limits withdrawals from wells to avoid excessive drawdown. Differences in results from the original MODFLOW-based model and the SURFACT-based model stem primarily from application by Carroll et al. (2009) of head limits that can also be applied using the existing MODLOW model and not from any substantial difference in the accuracy with which the unconfined aquifer is represented in the two models. In a hypothetical 50-year predictive simulation presented by Carroll et al. (2009), large differences between the models are shown when simulating pumping from the lower clastic confining unit, where the transmissivity is nearly two orders of magnitude less than in an alluvial aquifer. Yet even for this extreme example, drawdowns and pumping rates from the MODFLOW and SURFACT models are similar when the head-limit capabilities of the MODFLOW MNW Package are applied. These similarities persist despite possible discrepancies between assigned hydraulic properties. The resulting comparison between the MODFLOW and SURFACT models of the DVRFS suggests that approximating the unconfined system in the DVRFS as a constant-saturated-thickness system (called a “confined system” by Carroll et al., 2009) performs very well.

Death Valley↗

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands: Pahranagat Valley, Nevada, USA

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium ( 87 Sr/ 86 Sr) and uranium ( 234 U/ 238 U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87 Sr/ 86 Sr and 234 U/ 238 U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge’s irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Nevada↗

Processes affecting transport of uranium in a suboxic aquifer

At the Naturita site in Colorado, USA, groundwaters were sampled and analyzed for chemical composition and by culture and culture-independent microbiological techniques. In addition, sediments were extracted with a dilute sodium carbonate solution to determine quantities of labile uranium within the sediments. Samples from the upgradient portion of the contaminated aquifer , where very little dissolved Fe(II) is found in the groundwater, have uranium content that is controlled by U(VI) adsorption and few metal-reducing bacteria are observed. In the extreme downgradient portion of the aquifer, where dissolved Fe(II) is observed, uranium content of the sediments includes significant quantities of reduced U(IV) and diverse populations of Fe(III)-reducing bacteria were present in the subsurface with the potential of reducing U(VI) to U(IV).

Physics and Chemistry of the Earth↗

Microbial pathogens and contaminants of emerging concern in groundwater at an urban subsurface stormwater infiltration site

Urban stormwater may contain a variety of pollutants, including viruses and other pathogens, and contaminants of emerging concern (pharmaceuticals, artificial sweeteners, and personal care products). In vulnerable geologic settings, the potential exists for these contaminants to reach underlying aquifers and contaminate drinking water wells. Viruses and other pathogens, as well as other contaminants of emerging concern, were measured in stormwater and groundwater at an urban site containing a stormwater cistern and related subsurface infiltration gallery, three shallow lysimeter wells, and a monitoring well. Five of 12 microbial targets were detected more than once across the eight rounds of sampling and at multiple sampling points, with human-specific Bacteroides detected most frequently. The microbial and chemical contaminants present in urban stormwater were much lower in the water table monitoring well than the vadose zone lysimeters. There may be numerous causes for these reductions, but they are most likely related to transit across fine-grained sediments that separate the water table from the vadose zone at this location. Precipitation amount prior to sample collection was significantly associated with microbial load. A significant relation between microbial load and chloride-bromide ratio was also observed. The reduction in number and concentrations of contaminants found in the monitoring well indicates that although geologically sensitive aquifers receiving urban stormwater effluent in the subsurface may be prone to contamination, those with a protective cap of fine-grained sediments are less vulnerable. These results can inform stormwater infiltration guidance relative to drinking water wells, with an emphasis on restricting infiltration near water supply wells finished in geologically sensitive aquifers to reduce public health risks.

Minnesota↗

Modeling CO2 degassing and pH in a stream-aquifer system

Pinal Creek, Arizona receives an inflow of ground water with high dissolved inorganic carbon (57-75 mg/l) and low pH (5.8-6.3). There is an observed increase of in-stream pH from approximately 6.0-7.8 over the 3 km downstream of the point of groundwater inflow. We hypothesized that CO2 gas-exchange was the most important factor causing the pH increase in this stream-aquifer system. An existing transport model, for coupled ground water-surface water systems (OTIS), was modified to include carbonate equilibria and CO2 degassing, used to simulate alkalinity, total dissolved inorganic carbon (C(T)), and pH in Pinal Creek. Because of the non-linear relation between pH and C(T), the modified transport model used the numerical iteration method to solve the non-linearity. The transport model parameters were determined by the injection of two tracers, bromide and propane. The resulting simulations of alkalinity, C(T) and pH reproduced, without fitting, the overall trends in downstream concentrations. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that C(T) and pH in stream water were controlled by the mixing of ground water with stream water and CO2 degassing. The relative importance of these two processes varied spatially depending on the hydrologic conditions, such as stream flow velocity and whether a reach gained or lost stream water caused by the interaction with the ground water. The coupled transport model with CO2 degassing and generalized sensitivity analysis presented in this study can be applied to evaluate carbon transport and pH in other coupled stream-ground water systems.An existing transport model for coupled groundwater-surface water systems was modified to include carbonate equilibria and CO2 degassing. The modified model was used to simulate alkalinity, total dissolved inorganic carbon (CT) and pH in Pinal Creek. The model used the numerical iteration method to solve the nonlinear relation between pH and CT. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that CT and pH in the stream water were controlled by the mixing of groundwater with stream water and CO2 degassing.

Journal of Hydrology↗

Effects of dynamic redox zonation on the potential for natural attenuation of trichloroethylene at a fire-training-impacted aquifer

Hydrogeochemical and microbiological methods were used to characterize temporal changes along a transect of an aquifer contaminated by mixed hydrocarbon and solvent wastes from fire training activities at Wurtsmith Air Force Base (Oscoda, MI). Predominant terminal electron accepting processes (TEAPs) as measured by dissolved hydrogen indicated reoxygenation along the transect between October 1995 and October 1996, possibly because of recharge, fluctuations in water table elevation, or microbial activity. Microbiological analyses using universal and archaeal probes revealed a relationship between groundwater hydrogen concentration, TEAP, and predominant bacterial phylogeny. Specifically, a raised water table level and evidence of methanogenesis corresponded to an order of magnitude increase in archaeal 16S rRNA relative to when this zone was unsaturated. Spatial microbial and geochemical dynamics did not result in measurable differences in trichloroethylene (TCE) mineralization potential in vadose, capillary fringe, and saturated zone soils during a 500-day microcosm experiment using unprocessed contaminated soil and groundwater. Aerobic systems indicated that methane, but not toluene, may serve as cosubstrate for TCE cometabolism. Anaerobic microcosms demonstrated evidence for methanogenesis, CO2 production and hydrogen consumption, yet dechlorination activity was only observed in a microcosm with sulfate-reduction as the dominant TEAP. Mass balance calculations indicated less than 5% mineralization, regardless of redox zone or degree of saturation, at maximum rates of 0.01-0.03 ??mol/g soil??d. The general lack of dechlorination activity under laboratory conditions corroborates the limited evidence for natural dechlorination at this site, despite abundant electron donor material and accumulated organic acids from microbial degradation of alkylbenzenes. Thus, the short-term temporal dynamics in redox conditions is unlikely to have measurable effects on the long-term natural remediation potential of the aquifer.

Physics and Chemistry of the Earth, Part B: Hydrol↗

Pesticides and pesticide degradates in groundwater used for public supply across the United States: Occurrence and human-health context

This is the first assessment of groundwater from public-supply wells across the United States to analyze for >100 pesticide degradates and to provide human-health context for degradates without benchmarks. Samples from 1204 wells in aquifers representing 70% of the volume pumped for drinking supply were analyzed for 109 pesticides (active ingredients) and 116 degradates. Among the 41% of wells where pesticide compounds were detected, nearly two-thirds contained compound mixtures and three-quarters contained degradates. Atrazine, hexazinone, prometon, tebuthiuron, four atrazine degradates, and one metolachlor degradate were each detected in >5% of wells. Detection frequencies were largest for aquifers with more shallow, unconfined wells producing modern-age groundwater. To screen for potential human-health concerns, benchmark quotients (BQs) were calculated by dividing concentrations by the human-health benchmark, when available. For degradates without benchmarks, estimated values (estimated benchmark quotients (BQE)) were first calculated by assuming equimolar toxicity to the most toxic parent; final analysis excluded degradates with likely overestimated toxicity. Six pesticide compounds and 1.6% of wells had concentrations approaching levels of potential concern (individual or summed BQ or BQE values >0.1), and none exceeded these levels (values >1). Therefore, although pesticide compounds occurred frequently, concentrations were low, even accounting for mixtures and degradates without benchmarks.

Continental United States↗

Factors associated with sources, transport, and fate of volatile organic compounds and their mixtures in aquifers of the United States

Factors associated with sources, transport, and fate of volatile organic compounds (VOCs) in groundwater from aquifers throughout the United States were evaluated using statistical methods. Samples were collected from 1631 wells throughout the conterminous United States between 1996 and 2002 as part of the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey. Water samples from wells completed in aquifers used to supply drinking water were analyzed for more than 50 VOCs. Wells were primarily rural domestic water supplies (1184), followed by public water supplies (216); the remaining wells (231) supplied a variety of uses. The median well depth was 50 meters. Age-date information shows that about 60% of the samples had a fraction of water recharged after 1953. Chloroform, toluene, 1,2,4-trimethylbenzene, and perchloroethene were some of the frequently detected VOCs. Concentrations generally were less than 1 ??g/L. Source factors include, in order of importance, general land-use activity, septic/sewer density, and sites where large concentrations of VOCs are potentially released, such as leaking underground storage tanks. About 10% of all samples had VOC mixtures that were associated with concentrated sources; 20% were associated with dispersed sources. Important transport factors included well/screen depth, precipitation/groundwater recharge, air temperature, and various soil characteristics. Dissolved oxygen was strongly associated with VOCs and represents the fate of many VOCs in groundwater. Well type (domestic or public water supply) was also an important explanatory factor. Results of multiple analyses show the importance of (1) accounting for both dispersed and concentrated sources of VOCs, (2) measuring dissolved oxygen when sampling wells to help explain the fate of VOCs, and (3) limiting the type of wells sampled in monitoring networks to avoid unnecessary variance in the data, or controlling for this variance during data analysis.

Environmental Science & Technology↗

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

Aerobic conditions in desert aquifers commonly allow high nitrate (NO 3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (??15N NO3 and ??18ONO3) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Oesert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO 3- is generally higher than groundwater NO 3- in terms of both concentration (up to 15 476 ??M, corresponding to 3.6 mg NO3--N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10 -8 to 10 -5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10 -3 to 6.0 ?? 10 -3 M in [Ca 2+ ], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Biodegradation of the surfactant linear alkylbenzenesulfonate in sewage-contaminated groundwater: A comparison of column experiments and field tracer tests

Transport and biodegradation of linear alkylbenzenesulfonate (LAS) in sewage-contaminated groundwater were investigated for a range of dissolved oxygen concentrations. Both laboratory column and an 80-day continuous injection tracer test field experiments were conducted. The rates of LAS biodegradation increased with increasing dissolved oxygen concentrations and indicated the preferential biodegradation of the longer alkyl chain LAS homologues (i.e., C12 and C13) and external isomers (i.e., 2-and 3- phenyl). However, for similar dissolved oxygen concentrations, mass removal rates for LAS generally were 2-3 times greater in laboratory column experiments than in the field tracer test. Under low oxygen conditions (<1 mg/L) only a fraction of the LAS mixture biodegraded in both laboratory and field experiments. Biodegradation rate constants for the continuous injection field test (0.002-0.08 day-1) were comparable to those estimated for a 3-h injection (pulsed) tracer test conducted under similar biogeochemical conditions, indicating that increasing the exposure time of aquifer sediments to LAS did not increase biodegradation rates.Transport and biodegradation of linear alkylbenzenesulfonate (LAS) in sewage-contaminated groundwater were investigated for a range of dissolved oxygen concentrations. Both laboratory column and an 80-day continuous injection tracer test field experiments were conducted. The rates of LAS biodegradation increased with increasing dissolved oxygen concentrations and indicated the preferential biodegradation of the longer alkyl chain LAS homologues (i.e., C12 and C13) and external isomers (i.e., 2- and 3-phenyl). However, for similar dissolved oxygen concentrations, mass removal rates for LAS generally were 2-3 times greater in laboratory column experiments than in the field tracer test. Under low oxygen conditions (<1 mg/L) only a fraction of the LAS mixture biodegraded in both laboratory and field experiments. Biodegradation rate constants for the continuous injection field test (0.002-0.08 day-1) were comparable to those estimated for a 3-h injection (pulsed) tracer test conducted under similar biogeochemical conditions, indicating that increasing the exposure time of aquifer sediments to LAS did not increase biodegradation rates.

Environmental Science & Technology↗

Biophysical mechanisms of trichloroethene uptake and loss in baldcypress growing in shallow contaminated groundwater

Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass- carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass-carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.

Environmental Science & Technology↗

Assessment of nitrate-nitrogen distribution in Kansas groundwater, 1990-1998

Nitrate-nitrogen (nitrate-N) in groundwater is a potential problem in many parts of Kansas. From 1990 to 1998, 747 water samples were collected from domestic, irrigation, monitoring, and public water supply wells primarily from the western two-thirds of the state, and analyzed for nitrate-N by the Kansas Geological Survey. Nitrate-N concentrations of the 747 samples analyzed range from 29% with less than or equal to 3 mg/L, 51% between 3 and 10 mg/L, and 20% greater than or equal to 10 mg/L. Factors that show a statistically significant relationship with the occurrence of nitrate-N in Kansas groundwater in this assessment include geographic area of the state, depth of well, and age of well. Nitrate-N levels of wells screened in the High Plains aquifer in south-central Kansas showed a statistically higher concentration than samples collected from the High Plains aquifer in the western portion of the state. Comparison of nitrate-N with depth of well indicated that shallower wells throughout the state generally have higher nitrate-N values than deeper wells. Irrigation wells older than 1975 showed statistically higher nitrate-N concentration than wells installed during and since 1975, possibly related to changes in well-construction practices and regulations that occurred in 1975.

Kansas↗

Effects of environmental change on groundwater recharge in the Desert Southwest

Climate and other environmental conditions have varied in the past, and will almost certainly vary significantly in the near future. The response of groundwater recharge to changes in environmental conditions is thus a matter of active concem for water-resources management. The major mechanisms for this response of recharge are three-fold. First, changes in vegetation communities can shift the water balance at the base of the root zone, increasing or decreasing the amount of recharge. Second, variations in the amount of runoff can affect channel recharge. Finally, shifts in the seasonality of precipitation can strongly affect the fraction that is evapotranspired back into the atmosphere and thus affect the amount that becomes recharge. Increases in recharge (defined as the water flux across the water table) may in some cases significantly increase fluxes through regional aquifers, but in other cases, depending on the hydrogeology, may only result in increased streamflow or evapotranspiration within the recharge area. Basins with relatively low maximum elevations, deep water tables, thin soils, and highly permeable recharge areas experience the largest recharge response to increases in precipitation. The relatively well-known paleoenvironmental history of the American Southwest can be compared with various lines of evidence for changes in recharge. These lines of evidence include timing of speleothem formation, chloride profiles in thick vadose zones, changes in water table shown by subsurface calcite precipitation, and expanded groundwater discharge areas. This evidence indicates that the wettest periods of the past 25 ka, which were generally between 20 and 13 ka, were also periods of enhanced vadose zone fluxes and aquifer discharge. Climate-driven changes in recharge appear to have been substantially mediated through changes in vegetation. This evidence for strong recharge response to past environmental changes indicates that expected future climate and environmental change will also cause changes in recharge. The ability to adequately predict future changes in recharge will depend on developing process-based numerical models that can simulate coupled climate/vegetation/ vadose zone processes and incorporate the outputs into groundwater/surface water models that can resolve processes at scales ranging from the hillslope to the basin.

Water Science and Application↗

Evaluation of prediction intervals for expressing uncertainties in groundwater flow model predictions

We tested the accuracy of 95% individual prediction intervals for hydraulic heads, streamflow gains, and effective transmissivities computed by groundwater models of two Danish aquifers. To compute the intervals, we assumed that each predicted value can be written as the sum of a computed dependent variable and a random error. Testing was accomplished by using a cross‐validation method and by using new field measurements of hydraulic heads and transmissivities that were not used to develop or calibrate the models. The tested null hypotheses are that the coverage probability of the prediction intervals is not significantly smaller than the assumed probability (95%) and that each tail probability is not significantly different from the assumed probability (2.5%). In all cases tested, these hypotheses were accepted at the 5% level of significance. We therefore conclude that for the groundwater models of two real aquifers the individual prediction intervals appear to be accurate.

Water Resources Research↗

Modeling the movement of a pH perturbation and its impact on adsorbed zinc and phosphate in a wastewater‐contaminated aquifer

[1] Chemical conditions were perturbed in an aquifer with an ambient pH of 5.9 and wastewater-derived adsorbed zinc (Zn) and phosphate (P) contamination by injecting a pulse of amended groundwater. The injected groundwater had low concentrations of dissolved Zn and P, a pH value of 4.5 resulting from equilibration with carbon dioxide gas, and added potassium bromide (KBr). Downgradient of the injection, breakthrough of nonreactive Br and total dissolved carbonate concentrations in excess of ambient values (excess TCO 2 ) were accompanied by a decrease in pH values and over twentyfold increases in dissolved Zn concentrations above preinjection values. Peak concentrations of Br and excess TCO 2 were followed by slow increases in pH values accompanied by significant increases in dissolved P above preinjection concentrations. The injected tracers mobilized a significant mass of wastewater-derived Zn. Reactive transport simulations incorporating surface complexation models for adsorption of Zn, P, hydrogen ions, and major cations onto the aquifer sediments, calibrated using laboratory experimental data, captured most of the important trends observed during the experiment. These include increases in Zn concentrations in response to the pH perturbation, perturbations in major cation concentrations, attenuation of the pH perturbation with transport distance, and increases in alkalinity with transport distance. Observed desorption of P in response to chemical perturbations was not predicted, possibly because of a disparity between the range of chemical conditions in the calibration data set and those encountered during the field experiment. Zinc and P desorbed rapidly in response to changing chemical conditions despite decades of contact with the sediments. Surface complexation models with relatively few parameters in the form of logK values and site concentrations show considerable promise for describing the influence of variable chemistry on the transport of adsorbing contaminants.

Water Resources Research↗

O2 reduction and denitrification rates in shallow aquifers

O 2 reduction and denitrification rates were determined in shallow aquifers of 12 study areas representing a wide range in sedimentary environments and climatic conditions. Zero‐ and first‐order rates were determined by relating reactant or product concentrations to apparent groundwater age. O 2 reduction rates varied widely within and between sites, with zero‐order rates ranging from <3 μmol L −1 yr −1 to more than 140 μmol L −1 yr −1 and first‐order rates ranging from 0.02 to 0.27 yr −1 . Moderate denitrification rates (10–100 μmol N L −1 yr −1 ; 0.06–0.30 yr −1 ) were observed in most areas with O 2 concentrations below 60 μmol L −1 , while higher rates (>100 μmol N L −1 yr −1 ; >0.36 yr −1 ) occur when changes in lithology result in a sharp increase in the supply of electron donors. Denitrification lag times (i.e., groundwater travel times prior to the onset of denitrification) ranged from <20 yr to >80 yr. The availability of electron donors is indicated as the primary factor affecting O 2 reduction rates. Concentrations of dissolved organic carbon (DOC) and/or sulfate (an indicator of sulfide oxidation) were positively correlated with groundwater age at sites with high O 2 reduction rates and negatively correlated at sites with lower rates. Furthermore, electron donors from recharging DOC are not sufficient to account for appreciable O 2 and nitrate reduction. These relations suggest that lithologic sources of DOC and sulfides are important sources of electrons at these sites but surface‐derived sources of DOC are not. A review of published rates suggests that denitrification tends to occur more quickly when linked with sulfide oxidation than with carbon oxidation.

Water Resources Research↗