Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.     

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.     

Organic matter and modeling redox reactions during river bank filtration in an alluvial aquifer of the Lot River, France

A 3 year study of the infiltration of Lot River water into a well field located in an adjacent gravel and clay alluvial aquifer was conducted to assess the importance of organic matter regarding the redox processes which influence groundwater quality in a positive (denitrification) or negative (Mn dissolution) manner. Chloride was used to quantify the mixing of river water with groundwater. According to modeling with PHREEQC, the biodegradation of the infiltrated dissolved organic carbon (DOCi) is not sufficient to explain the observed consequences of the redox reactions (dissolved O2 depletion, denitrification, Mn dissolution). Another electron donor source must therefore be involved: we propose solid organic carbon (SOC) as a likely candidate, if made available for degradation by prior hydrolysis. Its contribution to redox reactions could be significant (30-80% of the total organic carbon consumed by redox reactions during river bank filtration). We show here also that even though the first few meters of infiltration are highly reactive, significant redox reactions can take place further in the aquifer, possibly affecting groundwater quality away from the river bank.     

Geochemical reactions resulting from in situ oxidation of PCE-DNAPL by KMnO4 in a sandy aquifer

Although the potential for KMnO4 to destroy chlorinated ethenes in situ was first recognized more than a decade ago, the geochemical processes that accompany the oxidation have not previously been examined. In this study, aqueous KMnO4 solutions (10-30 g/L) were injected into an unconfined sand aquifer contaminated by the dense non-aqueous-phase liquid (DNAPL) tetrachloroethylene (PCE). The effects of the injections were monitored using depth-specific, multilevel groundwater samplers, and continuous cores. Two distinct geochemical zones evolved within several days after injection. In one zone where DNAPL is present, reactions between KMnO4 and dissolved PCE resulted in the release of abundant chloride and hydrogen ions to the water. Calcite and dolomite dissolved, buffering the pH in the range of 5.8-6.5, releasing Ca, Mg, and CO2 to the pore water. In this zone, the aqueous Ca/Cl concentration ratio is close to 5:12, consistent with the following reaction for the oxidation of PCE in a carbonate-rich aquifer: 3C2Cl4 + 5CaCO3(s) + 4KMnO4 + 2H+ --> 11CO2 + 4MnO2(s) + H2O + 12Cl- + 5Ca2+ + 4K+. In addition to Mg from dolomite dissolution, increases in the concentration of Mg as well as Na may result from exchange with K at cation-exchange sites. In the second zone, where lesser amounts of PCE were present, KMnO4 persisted in the aquifer for more than 14 months, and the porewater pH increased graduallyto between 9 and 10 as a resultof reaction between KMnO4 and H2O. A small increase in SO4 concentrations in the zones invaded by KMnO4 suggests that KMnO4 injections caused oxidation of sulfide minerals. There are important benefits of carbonate mineral buffering during DNAPL remediation by in situ oxidation. In a carbonate-buffered system, Mn(VII) is reduced to Mn(IV) and is immobilized in the groundwater by precipitating as insoluble manganese oxide. Energy-dispersive X-ray spectroscopy analyses of the manganese oxide coatings on aquifer mineral grains have detected the impurities Al, Ca, Cl, Cu, Pb, P, K, Si, S, Ti, U, and Zn indicating that, similar to natural systems, precipitation of manganese oxide is accompanied by coprecipitation of other elements. In addition, the consumption of excess KMnO4 by reaction with reduced minerals such as magnetite will be minimized because the rates of these reactions increase with decreasing pH. Aquifer cores collected after the KMnO4 injections exhibit dark brown to black bands of manganese oxide reaction products in sand layers where DNAPL was originally present. Mineralogical investigations indicate that the manganese oxide coatings are uniformly distributed over the mineral grains. Observations of the coatings using transmission electron microscopy indicate that they are on the order of 1 microm thick, and consequently, the decrease in porosity through the formation of the coatings is negligible.     

Can arsenic occurrence rates in bedrock aquifers be predicted?

A high percentage (31%) of groundwater samples from bedrock aquifers in the greater Augusta area, Maine was found to contain greater than 10 μg L(-1) of arsenic. Elevated arsenic concentrations are associated with bedrock geology, and more frequently observed in samples with high pH, low dissolved oxygen, and low nitrate. These associations were quantitatively compared by statistical analysis. Stepwise logistic regression models using bedrock geology and/or water chemistry parameters are developed and tested with external data sets to explore the feasibility of predicting groundwater arsenic occurrence rates (the percentages of arsenic concentrations higher than 10 μg L(-1)) in bedrock aquifers. Despite the under-prediction of high arsenic occurrence rates, models including groundwater geochemistry parameters predict arsenic occurrence rates better than those with bedrock geology only. Such simple models with very few parameters can be applied to obtain a preliminary arsenic risk assessment in bedrock aquifers at local to intermediate scales at other localities with similar geology.     

Sedimentological control on Mn, and other trace elements, in groundwater of the Bengal delta

To reveal what controls the concentration and distribution of possibly hazardous (Mn, U, Se, Cd, Bi, Pb) and nonhazardous (Fe, V, Mo, PO(4)) trace elements in groundwater of the Bengal delta, we mapped their concentrations in shallow groundwater (<60 mbgl) across 102 km(2) of West Bengal. Only Mn is a potential threat to health, with 55% of well water exceeding 0.3 mg/L, the current Indian limit for drinking water in the absence of an alternate source, and 75% exceeding the desirable limit of 0.1 mg/L. Concentrations of V are <3 μg/L. Concentrations of U, Se, Pb, Ni, Bi, and Cd, are below WHO guideline values. The distributions of Fe, Mn, As, V, Mo, U, PO(4), and δ(18)O in groundwater reflect subsurface sedimentology and sources of water. Areas of less negative δ(18)O reveal recharge by sources of evaporated water. Concentrations of Fe, As, Mo, and PO(4) are high in palaeo-channel groundwaters and low in palaeo-interfluvial groundwaters. Concentrations of U, V, and Mn, are low in palaeo-channel groundwaters and high in palaeo-interfluvial groundwaters. Concentrations of Fe and Mn are highest (18 and 6 mg/L respectively) at dual reduction-fronts that form strip interfaces at depth around the edges of palaeo-interfluvial aquifers. The fronts form as focused recharge carries dissolved organic carbon into the aquifer margins, which comprise brown, iron-oxide bearing, sand. At the Mn-reduction front, concentrations of V and Mo reach peak concentrations of 3 μg/L. At the Fe-reduction front, concentrations of PO(4) and As reach concentrations 3 mg/L and 150 μg/L respectively. Many groundwaters contain >10 mg/L of Cl, showing that they are contaminated by Cl of anthropogenic origin and that organic matter from in situ sanitation may contribute to driving reduction.     

Field evaluation of in situ source reduction of trichloroethylene in groundwater using bioenhanced in-well vapor stripping

Two technologies in combination, cometabolic bioremediation and in-well vapor stripping, were applied to reduce trichloroethylene (TCE) concentrations in groundwater at a contaminant source area without the need to pump contaminated groundwater to the surface for treatment. The vapor-stripping well reduced source TCE concentrations (as high as 6-9 mg/L) by over 95%. Effluent from the well then flowed to two bioremediation wells, where additional reductions of approximately 60% were achieved. TCE removal was extensively monitored (for research and not regulatory purposes) using an automated system that collected samples about every 45 min at 55 locations over an area of approximately 50 x 60 m2. During 4.5 months of system operation, total TCE mass removal was 8.1 kg, 7.1 kg of which resulted from in-well vapor stripping and 1.0 kg from biotreatment. The system reduced the average TCE concentration of about 3000 microg/L in the source-zone groundwater to about 250 microg/L in water leaving the treatment zone, effecting greater than 92% TCE removal. A 6 month rebound study after system operation ceased found TCE concentrations then increased significantly in the treatment zone due to diffusion from the fractured rock below and perhaps other processes, with mass increases of about 1.5 kg in the lower aquifer and 0.3 kg in the upper aquifer.     

Long-term natural attenuation of carbon and nitrogen within a groundwater plume after removal of the treated wastewater source

Disposal of treated wastewater for more than 60 years onto infiltration beds on Cape Cod, Massachusetts produced a groundwater contaminant plume greater than 6 km long in a surficial sand and gravel aquifer. In December 1995 the wastewater disposal ceased. A long-term, continuous study was conducted to characterize the post-cessation attenuation of the plume from the source to 0.6 km downgradient. Concentrations and total pools of mobile constituents, such as boron and nitrate, steadily decreased within 1-4 years along the transect. Dissolved organic carbon loads also decreased, but to a lesser extent, particularly downgradient of the infiltration beds. After 4 years, concentrations and pools of carbon and nitrogen in groundwater were relatively constant with time and distance, but substantially elevated above background. The contaminant plume core remained anoxic for the entire 10-year study period; temporal patterns of integrated oxygen deficit decreased slowly at all sites. In 2004, substantial amounts of total dissolved carbon (7 mol C m(-2)) and fixed (dissolved plus sorbed) inorganic nitrogen (0.5 mol N m(-2)) were still present in a 28-m vertical interval at the disposal site. Sorbed constituents have contributed substantially to the dissolved carbon and nitrogen pools and are responsible for the long-term persistence of the contaminant plume. Natural aquifer restoration at the discharge location will take at least several decades, even though groundwater flow rates and the potential for contaminant flushing are relatively high.     

Influence of net groundwater discharge on the chemical composition of a coastal environment: Flanders Bay, Long Island, New York

Seasonal (October 1997 and May 1998) concentrations of dissolved (< 0.45 micron) trace metals (Ag, Al, Cd, Cu, Fe, Mn), inorganic nutrients (NO3, PO4, Si), DOC and DON were measured at seven wells during periods of low and high groundwater flow, in the aquifer around Flanders Bay in Eastern Long Island, New York. Similar measurements were made in surface waters of Flanders Bay, a shallow coastal embayment with restricted water flushing and river input. Dissolved constituents in the groundwater were classified according to their behavior under different flow conditions as follows: (1) peak during high flow (DOC, pH, Si, NO3, Al and Cu); (2) peak during low flow (salinity, DON, Ag, Cd, Mn); and (3) concentrations independent of flow conditions (PO4 and Fe). The primarily urban and agricultural land use on the North Fork of Long Island was reflected in higher concentrations of nutrients, Cu and Cd in groundwater, compared to samples from the South Fork which is mostly open parkland. Principal component analysis indicated that groundwater seepage could influence the chemical composition of Flanders Bay with respect to the major geochemical carriers (e.g. Fe and Mn). However, mass balance estimates for Cu indicated that, during low flow conditions, net groundwater Cu input was about 10% of the total input. In contrast, during high flow, net groundwater flow could account for up to 58% of all Cu inputs. Nevertheless, a large imbalance, which accounted for up to 70% of the outflux during low aquifer recharge, suggested that the Cu budget of the Bay was not adequately described by the inputs considered (river, net groundwater flow, atmospheric deposition, and tidal exchange). Important missing components of the Cu mass balance in Flanders Bay may include groundwater circulation driven by tides and waves as well as diffusive benthic fluxes.     

Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer

Evidence of seepage from animal waste holding lagoons at a dairy facility in the San Joaquin Valley of California is assessed in the context of a process geochemical model that addresses reactions associated with the formation of the lagoon water as well as reactions occurring upon the mixture of lagoon water with underlying aquifer material. Comparison of model results with observed concentrations of NH4+, K+, PO4(3-), dissolved inorganic carbon, pH, Ca2+, Mg2+, SO4(2-), Cl-, and dissolved Ar in lagoon water samples and groundwater samples suggests three key geochemical processes: (i) off-gassing of significant quantities of CO2 and CH4 during mineralization of manure in the lagoon water, (ii) ion exchange reactions that remove K+ and NH4+ from seepage water as it migrates into the underlying anaerobic aquifer material, and (iii) mineral precipitation reactions involving phosphate and carbonate minerals in the lagoon water in response to an increase in pH as well as in the underlying aquifer from elevated Ca2+ and Mg2+ levels generated by ion exchange. Substantial off-gassing from the lagoons is further indicated by dissolved argon concentrations in lagoon water samples that are below atmospheric equilibrium. As such, Ar may serve as a unique tracer for lagoon water seepage since under-saturated Ar concentrations in groundwater are unlikely to be influenced by any processes other than mechanical mixing.     

Noble gas excess air applied to distinguish groundwater recharge conditions

The application of geochemical tracers in groundwater studies can provide valuable insights into the rates and sources of groundwater recharge, residence times, and flow dynamics that are of significant value in the management of this important natural resource. This paper demonstrates the application of noble gas excess air to distinguish groundwater bodies with different recharge histories in a layered sandstone aquifer system in the east of England. The sampled groundwaters are all supersaturated with respect to neon, indicating the presence of excess air. The lowest excess air concentrations occur where the aquifer is unconfined (deltaNe, the proportion of neon in excess of saturation, = 12-26%) and recharge occurs directly to the outcrop. Groundwater in the confined part of the aquifer can be divided into two hydrochemical types based upon the dissolved ion chemistry: Type 1 groundwaters contain more excess air (deltaNe = 115-120%) than Type 2(deltaNe = 22-62%). The difference in excess air concentrations confirms that groundwater enters the confined aquifer along two discrete pathways. Furthermore, excess neon concentrations predicted from the magnitude of annual water table fluctuation observed in the different recharge areas are in good agreement with those measured in the corresponding groundwaters. We therefore recommend that excess air may be usefully employed as a direct indicator of the volume of long-term net annual groundwater recharge.     

Fluoride removal by calcite: evidence for fluorite precipitation and surface adsorption

Fluoride contamination of groundwater, both anthropogenic and natural, is a major problem worldwide. In this study, fluoride removal by crushed limestone (99% pure calcite) was investigated by batch studies and surface-sensitive techniques from solutions with fluoride concentrations from 150 micromol/L (3 mg/L) to 110 mM (approximately 2100 mg/L). Surface-sensitive techniques, including atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) as well as zeta potential measurements, confirm that, in addition to precipitation reactions, adsorption of fluoride also occurs. Results indicate that fluoride adsorption occurs immediately over the entire calcite surface with fluorite precipitating at step edges and kinks, where dissolved Ca2+ concentration is highest. The PHREEQ geochemical model was applied to the observed data and indicates that existing models, especially at low fluoride concentrations and high pH (>7.5) are not equipped to describe this complex system, largely because the PHREEQ model includes only precipitation reactions, whereas a combination of adsorption and precipitation parameters are required.     

Fate and origin of 1,2-dichloropropane in an unconfined shallow aquifer

A shallow aquifer with different redox zones overlain by intensive agricultural activity was monitored for the occurrence of 1,2-dichloropropane (DCP) to assess the fate and origin of this pollutant. DCP was detected more frequently in groundwater samples collected in aerobic and nitrate-reducing zones than those collected from iron-reducing zones. Simulated DCP concentrations for groundwater entering an iron-reducing zone were calculated from a fate and transport model that included dispersion, sorption, and hydrolysis but not degradation. Simulated concentrations were well in excess of measured values, suggesting that microbial degradation occurred in the iron-reducing zone. Microcosm experiments were conducted using aquifer samples collected from iron-reducing and aerobic zones to evaluate the potential for microbial degradation of DCP and to explain field observations. Hydrogenolysis of DCP and production of monochlorinated propanes in microcosm experiments occurred only with aquifer materials collected from the iron-reducing zone, and no dechlorination was observed in microcosms established with aquifer materials collected from the aerobic zones. Careful analyses of the DCP/1,2,2-trichloropropane ratios in groundwater indicated that older fumigant formulations were responsible for the high levels of DCP present in this aquifer.     

Fate of pharmaceutical and trace organic compounds in three septic system plumes, Ontario, Canada

Three high volume septic systems in Ontario, Canada, were examined to assess the potential for onsite wastewatertreatment systems to release pharmaceutical compounds to the environment and to evaluate the mobility of these compounds in receiving aquifers. Wastewater samples were collected from the septic tanks, and groundwater samples were collected below and down gradient of the infiltration beds and analyzed for a suite of commonly used pharmaceutical and trace organic compounds. The septic tank samples contained elevated concentrations of several pharmaceutical compounds. Ten of the 12 compounds analyzed were detected in groundwater at one or more sites at concentrations in the low ng L(-1) to low microg L(-1) range. Large differences among the sites were observed in both the number of detections and the concentrations of the pharmaceutical compounds. Of the compounds analyzed, ibuprofen, gemfibrozil, and naproxen were observed to be transported atthe highest concentrations and greatest distances from the infiltration source areas, particularly in anoxic zones of the plumes.     

Geochemical and geophysical examination of submarine groundwater discharge and associated nutrient loading estimates into Lynch Cove, Hood Canal, WA

Geochemical tracer data (i.e., 222Rn and four naturally occurring Ra isotopes), electromagnetic (EM) seepage meter results, and high-resolution, stationary electrical resistivity images were used to examine the bi-directional (i.e., submarine groundwater discharge and recharge) exchange of a coastal aquifer with seawater. Our study site for these experiments was Lynch Cove, the terminus of Hood Canal, WA, where fjord-like conditions dramatically limit water column circulation that can lead to recurring summer-time hypoxic events. In such a system a precise nutrient budget may be particularly sensitive to groundwater-derived nutrient loading. Shore-perpendicular time-series subsurface resistivity profiles show clear, decimeter-scale tidal modulation of the coastal aquifer in response to large, regional hydraulic gradients, hydrologically transmissive glacial terrain, and large (4-5 m) tidal amplitudes. A 5-day 222Rn time-series shows a strong inverse covariance between 222Rn activities (0.5-29 dpm L(-1)) and water level fluctuations, and provides compelling evidence for tidally modulated exchange of groundwater across the sediment/water interface. Mean Rn-derived submarine groundwater discharge (SGD) rates of 85 +/- 84 cm d(-1) agree closely in the timing and magnitude with EM seepage meter results that showed discharge during low tide and recharge during high tide events. To evaluate the importance of fresh versus saline SGD, Rn-derived SGD rates (as a proxy of total SGD) were compared to excess 226Ra-derived SGD rates (as a proxy for the saline contribution of SGD). The calculated SGD rates, which include a significant (>80%) component of recycled seawater, are used to estimate associated nutrient (NH4+, Si, PO4(3-), NO3 + NO2, TDN) loads to Lynch Cove. The dissolved inorganic nitrogen (DIN = NH4 + NO2 + NO3) SGD loading estimate of 5.9 x 10(4) mol d(-1) is 1-2 orders of magnitude larger than similar estimates derived from atmospheric deposition and surface water runoff, respectively.     

Arsenic removal from groundwater by household sand filters: comparative field study, model calculations, and health benefits

Arsenic removal efficiencies of 43 household sand filters were studied in rural areas of the Red River Delta in Vietnam. Simultaneously, raw groundwater from the same households and additional 31 tubewells was sampled to investigate arsenic coprecipitation with hydrous ferric iron from solution, i.e., without contact to sand surfaces. From the groundwaters containing 10-382 microg/L As, < 0.1-48 mg/L Fe, < 0.01-3.7 mg/L P, and 0.05-3.3 mg/L Mn, similar average removal rates of 80% and 76% were found for the sand filter and coprecipitation experiments, respectively. The filtering process requires only a few minutes. Removal efficiencies of Fe, phosphate, and Mn were > 99%, 90%, and 71%, respectively. The concentration of dissolved iron in groundwater was the decisive factor for the removal of arsenic. Residual arsenic levels below 50 microg/L were achieved by 90% of the studied sand filters, and 40% were even below 10 microg/L. Fe/As ratios of > or = 50 or > or = 250 were required to ensure arsenic removal to levels below 50 or 10 microg/L, respectively. Phosphate concentrations > 2.5 mg P/L slightly hampered the sand filter and coprecipitation efficiencies. Interestingly, the overall arsenic elimination was higher than predicted from model calculations based on sorption constants determined from coprecipitation experiments with artificial groundwater. This observation is assumed to result from As(lll) oxidation involving Mn, microorganisms, and possibly dissolved organic matter present in the natural groundwaters. Clear evidence of lowered arsenic burden for people consuming sand-filtered water is demonstrated from hair analyses. The investigated sand filters proved to operate fast and robust for a broad range of groundwater composition and are thus also a viable option for mitigation in other arsenic affected regions. An estimation conducted for Bangladesh indicates that a median residual level of 25 microg/L arsenic could be reached in 84% of the polluted groundwater. The easily observable removal of iron from the pumped water makes the effect of a sand filter immediately recognizable even to people who are not aware of the arsenic problem.     

Shifts in biodegradation kinetics of the herbicides MCPP and 2,4-D at low concentrations in aerobic aquifer materials

Biodegradation kinetics of two phenoxy acid herbicides, MCPP [(+/-)-2-(4-chloro-2-methylphenoxy)propanoic acid; mecoprop] and 2,4-D [2,4-dichlorophenoxyacetic acid] were studied in laboratory batch microcosms at low concentrations (0.025-100 microg/L) using 14C technique with sediments and groundwater from a shallow aerobic sandy aquifer. Below a certain threshold concentration of approximately 1 microg/L for 2,4-D and 10 microg/L for MCPP, the biodegradation followed first-order nongrowth kinetics, and no adaptation was observed within the experimental period of 341 d. Half-lifes for ultimate degradation were 500 d for 2,4-D and 1100 d for MCPP at 10 degrees C in unpolluted aquifer sediment in this environmentally relevant concentration regime. Above the threshold concentrations, the biodegradation rate accelerated gradually due to selective growth of specific biomass, which was ascertained from 14C most probable number enumerations of specific phenoxy acid degraders. Atthe highest concentration tested (100 microg/ L), specific degraders increased from 10(-1) to 10(5) cells/g during the experiment, and half-lifes after adaptation decreased to approximately 5 d. The enhanced rate of degradation by adapted systems was maintained during degradation of the last residuals measured to less than 0.1 microg/L. In situ long-term preexposure of the aquifer sediment also resulted in significant higher degradation rates of the phenoxy acids.     

Hydrosulfide oxidation pathways in oxic solutions containing iron(III) chelates

The role of dissolved oxygen (DO2) on the oxidation of hydrosulfide ions (HS-; C(HS-)0 = 50-150 micromol/L) into polysulfides (S(n)2-; n = 2-9), colloidal sulfur, and oxysulfur species with iron(III) trans-1,2-diaminocyclohexanetetraacetate (iron(III)-cdta; C(Fe(III)0 = 50-300 micromol/L) complexes in alkaline solutions (pH 9-10.2) was investigated at 25 +/- 1 degree C. At higher pH, oxygen was seen to slow down the hydrosulfide conversion rate. For instance, the HS- half-life was 24.8 min in a DO2-saturated iron(III)-cdta solution compared to 11.3 min in the corresponding anoxic solution (pH 10.2, C(HS-)0 = 80 micromol/L, C(Fe(III))0 = 200 micromol/L). In anoxia, HS- oligomerizes into chain-like polysulfides which behave as autocatalysts on the HS- conversion rates. The presence of DO2 disrupts the HS- oligomerization process by generating thiosulfate precursors from polysulfides, a pathway that impedes the HS- uptake. At lower alkaline pH where the hydroxide-free Fe(3+)cdta(4-) is the prevailing iron(III)-cdta species, the "iron(II)-cdta + DO2" oxidative reaction becomes crucial. Oxidative regeneration of iron(III) as Fe(3+)cdta(4-) (being more reactive than Fe(3+)OH(-)cdta(4-)) offsets to some extent the restrictive role of oxygen on the accumulation of polysulfides. Thiosulfate and sulfate were the main end-products for the current experimental conditions to the detriment of colloidal sulfur, which did not form in DO2-saturated solutions.     

Has submarine groundwater discharge been overlooked as a source of mercury to coastal waters?

We measured the mercury (Hg) in groundwater, aquifer sediments, and surface water in Waquoit Bay (Massachusetts) and found that this toxic metal (range: <3.2-262 pM) was being released within the subterranean estuary, with similarly high levels (range: 18-256 pM) found in the surface waters of the bay. None of the dissolved species (DOC, chloride, and Fe) normally observed to influence Hg partitioning correlated well with the observed Hg concentrations. It was hypothesized that this was in part due to the variable loading in time and space of Hg onto the aquifer sands in combination with the seasonality of groundwater flow through the aquifer. Aquifer sediment samples from the study site ranged from <1 to 12.5 pmol of Hg/g of sediment, suggesting log Kd values on the order of 1. We hypothesize that this was due to the low organic carbon content typical of the aquifer sediments. Last, itwas estimated that submarine groundwater discharge supplied 0.47-1.9 nmol of Hg m(-2) day(-1) to the bay, which is an order of magnitude higher than the atmospheric deposition rate for the northeastern U.S.     

Vulnerability of recently recharged groundwater in principal [corrected] aquifers of the United States to nitrate contamination

Recently recharged water (defined here as <60 years old) is generally the most vulnerable part of a groundwater resource to nonpoint-source nitrate contamination. Understanding at the appropriate scale the interactions of natural and anthropogenic controlling factors that influence nitrate occurrence in recently recharged groundwater is critical to support best management and policy decisions that are often made at the aquifer to subaquifer scale. New logistic regression models were developed using data from the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) program and National Water Information System for 17 principal aquifers of the U.S. to identify important source, transport, and attenuation factors that control nonpoint source nitrate concentrations greater than relative background levels in recently recharged groundwater and were used to predict the probability of detecting elevated nitrate in areas beyond the sampling network. Results indicate that dissolved oxygen, crops and irrigated cropland, fertilizer application, seasonally high water table, and soil properties that affect infiltration and denitrification are among the most important factors in predicting elevated nitrate concentrations. Important differences in controlling factors and spatial predictions were identified in the principal aquifer and national-scale models and support the conclusion that similar spatial scales are needed between informed groundwater management and model development.