Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 microg/L to 191 microg/L with a mean concentration of 33 microg/L. Groundwater is mainly Ca-HCO(3) type with high concentrations of dissolved As, Fe, and Mn, but low level of SO(4). The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 microg/L. Deeper aquifer (>100 m depth) has a mean arsenic concentration of 18 microg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Phosphorus release in aerobic sludge digestion.

The objectives of this study are to examine the phosphorus release in aerobic sludge digestion and to better understand its governing mechanisms. In this study, phosphorus release was examined using the secondary sludge from both conventional and biological nutrient removal processes. The experiments were carried out at room temperature (22 +/- 2 degrees C), with or without automatic control of pH (4.5 to 7.8), and under three aeration schemes: fully aerobic (dissolved oxygen [DO] at 3 to 4 mg/L), low DO (0.2 to 0.8 mg/L), and cyclic (with alternate on/off aeration). The released phosphorus concentrations were 20 to 80 mg/L for the conventional sludge and 60 to 130 mg/L for the biophosphorus sludge. Higher phosphorus release also occurred at low pH (<6.0). As for the effect of DO, fully aerobic digestion caused higher phosphorus release than the low-DO and cyclic operations. For better understanding, the solid phosphorus in sludge was conceptually categorized into three forms: inorganic phosphorus precipitates, organic cellular phosphorus, and polyphosphate (poly-P) in polyphosphate-accumulating organisms. Dissolution of inorganic phosphorus precipitates is controlled by physical and chemical conditions, with pH being the most important in this study. Lowering the pH to 4 to 6 clearly promoted the release of inorganic phosphorus. Polyphosphate hydrolysis, on the other hand, was found to be regulated biologically (sensitive to occurrence of anaerobic conditions) and was insignificant in the glutaraldehyde-fixed sludge. Phosphorus release from organic phosphorus should correlate with the volatile solid (VS) digestion, which lyses the cells and frees the phosphorus covalently bonded with the organic matters. The amounts of phosphorus released per unit VS digested (deltaP/deltaVS) were therefore calculated for experiments with long periods of constant pH (to minimize interferences from dissolution/precipitation of inorganic phosphorus). The results suggested that some poly-P was hydrolyzed and released accompanying the aerobic VS digestion, but at rates far lower than those under anaerobic conditions.     

Geochemistry of a septic-system plume in a coastal barrier bar, Point Pelee, Ontario, Canada

The major ion and trace metal geochemistry of a septic system plume in a shallow sand aquifer was characterized to assess geochemical processes controlling the transport of nutrients and their release to a nearby wetland. The plume was generated from a 16-year-old tile bed, and is more than 60 m long, 40 m wide and 7 m thick. The groundwater pH at the site is near neutral, but up to 0.4 units lower in the plume core as a result of H⁺ generated from NH₃ and DOC oxidation in the unsaturated zone. The plume can be divided into distinct redox zones, which show differences in nutrient mobility. Proximal to the tile bed, there is a shallow suboxic zone, with intermediate Eh values (>400 mV), low concentrations of dissolved oxygen (<1.0 mg/l), and elevated concentrations of Mn (1–3 mg/l) and nutrients (10–80 mg/l NO₃–N, 1–15 mg/l NH₃–N, 0.1–1.5 mg/l PO₄–P, 6–13 mg/l dissolved organic carbon). At the base of the aquifer, there is a reduced zone (Eh<200 mV) with elevated concentrations of Fe (1–14 mg/l), PO₄ and NH₃, but negligible concentrations of NO₃ (<0.01 mg/l N). Distal from the tile bed, the shallow groundwater is suboxic to oxic, and has elevated concentrations of NO₃ and NH_3, but negligible PO₄. In the lower reduced zone, elevated concentrations of PO₄ occur up to 60 m away. The release of groundwater containing even very low concentrations of PO₄ (<0.02 mg/l P) can lead to the development of eutrophic conditions in surface water bodies. Geochemical calculations indicate that, in the Mn-rich zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, rhodochrosite, calcite and ferrihydrite. In the reduced zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, vivianite, calcite and siderite. Formation of these phases, or related phases, are likely limiting the concentrations of dissolved PO₄, Fe and Mn and controlling the geochemical evolution of the plume.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Spatial distribution and vertical variation of arsenic in Guangdong soil profiles, China

Total of 260 soil profiles were reported to investigate the arsenic spatial distribution and vertical variation in Guangdong province. The arsenic concentration followed an approximately lognormal distribution. The arsenic geometric mean concentration of 10.4 mg/kg is higher than that of China. An upper baseline concentration of 23.4 mg/kg was estimated for surface soils. The influence of soil properties on arsenic concentration was not important. Arsenic spatial distributions presented similar patterns that high arsenic concentration mainly located in limestone, and sandshale areas, indicating that soil arsenic distribution was dependent on bedrock properties than anthropogenic inputs. Moreover, from A- to C-horizon arsenic geometric mean concentrations had an increasing tendency of 10.4, 10.7 to 11.3 mg/kg. This vertical variation may be related to the lower soil organic matter and soil degradation and erosion. Consequently, the soil arsenic export into surface and groundwaters would reach 1040 t year-1 in the study area.     

Effect of design parameters in horizontal flow constructed wetland on the behaviour of volatile fatty acids and volatile alkylsulfides

A pilot-scale horizontal flow constructed wetland (HFCW) system planted with common reed (Phragmites sp.) was constructed to study how hydraulic loading rate (HLR), aspect ratio, water depth, and granular medium affect to the fate of several organic matter degradation intermediates namely, acetic acid (HAc), isovaleric acid (Isoval), and dimethylsulfide (DMS). ANOVA statistical analysis performed on the data set of 8 months of operation shows that the HLR and the water depth are two major factors that control the performance of HFCWs for the target analytes. A clear difference in the HFCW effluent concentrations was obtained according to water depth. Effluents of the shallow water depth contained lower DMS (1.05-1.44 microg l-1), HAc (7.91-10.9 mg l-1), and Isoval (0.11-0.15 mg l-1) concentrations than the deeper beds (DMS: 1.68-2.40 microg l-1; HAc: 9.29-14.4 mg l-1, and Isoval: 0.20-0.31 mg l-1). Such differences could be accounted to the different formation and consumption rates of the organic matter degradation intermediates, which is related with the redox potentials (E). Indeed, it could lead to different biochemical reactions of organic matter degradation according with the E value. HLR has a statistically significant influence on the effluent HAc, Isoval, and DMS concentrations. Seasonal variability of effluent HAc concentration shows that it is independent on the HAc loading. While the loading showed no seasonal pattern, the removal efficiency was clearly higher in cold months, which suggests a predominant internal production of HAc in HFCWs in the warm season from the accumulated organic particulate matter. Similar results were also found when Isoval and DMS were considered.     

Oxidation-reduction potential changes in aeration tanks and microprofiles of activated sludge floc in medium- and low-strength wastewaters.

Real-time control of aeration tank operation is key to high-efficiency pollutant removal and energy savings. One of the aims of this study was to examine the potential for using redox potential (oxidation-reduction potential [ORP]) to indicate wastewater quality online in aeration tanks treating medium (chemical oxygen demand [COD] of 70 to 150 mg/L) and low (COD of 15 to 30 mg/L) pollutant-concentration wastewaters. The field-scale data provide a good relationship between ORP values and nutrient removal along the length of the aeration tanks. The ORP values increased dramatically as organic matter was removed along the aeration tanks, indicating the improvement of the bulk liquor redox status. Dissolved oxygen higher than 1.0 mg/L was necessary for good biodegradation and improvement of the liquid redox status. Nitrification occurred at higher ORP values (380 to 420 mV) than was the case for organic substrate oxidation (250 to 300 mV). The microprofiles obtained from microelectrode measurements substantiate the heterogeneity of the microbial processes inside activated sludge flocs. Because of microbial oxygen utilization, the aerobic region in the activated sludge floc was limited to the top layer (0.1 to 0.2 mm) of the activated sludge aggregate present in medium-strength wastewater, with an anoxic zone dominating inside the flocs. When dissolved oxygen in the bulk water was higher than 4.0 mg/L, the anoxic zone inside the floc disappeared. At low wastewater pollutant concentrations, the ORP and dissolved oxygen inside the activated sludge aggregates were higher than those from medium-strength wastewater. The prospect of using ORP as an online control approach for aeration tank operation and the potential reasons for activated sludge floc size varying with pollutant strengths are also discussed.     

Quantifying uranium complexation by groundwater dissolved organic carbon using asymmetrical flow field-flow fractionation

The long-term mobility of actinides in groundwaters is important for siting nuclear waste facilities and managing waste-rock piles at uranium mines. Dissolved organic carbon (DOC) may influence the mobility of uranium, but few field-based studies have been undertaken to examine this in typical groundwaters. In addition, few techniques are available to isolate DOC and directly quantify the metals complexed to it. Determination of U-organic matter association constants from analysis of field-collected samples compliments laboratory measurements, and these constants are needed for accurate transport calculations. The partitioning of U to DOC in a clay-rich aquitard was investigated in 10 groundwater samples collected between 2 and 30 m depths at one test site. A positive correlation was observed between the DOC (4-132 mg/L) and U concentrations (20-603 microg/L). The association of U and DOC was examined directly using on-line coupling of Asymmetrical Flow Field-Flow Fractionation (AsFlFFF) with UV absorbance (UVA) and inductively coupled plasma-mass spectrometer (ICP-MS) detectors. This method has the advantages of utilizing very small sample volumes (20-50 microL) as well as giving molecular weight information on U-organic matter complexes. AsFlFFF-UVA results showed that 47-98% of the DOC (4-136 mg C/L) was recovered in the AsFlFFF analysis, of which 25-64% occurred in the resolvable peak. This peak corresponded to a weight-average molecular weight of about 900-1400 Daltons (Da). In all cases, AsFlFFF-ICP-MS suggested that相似文献   

Humic acids enhance the microbially mediated release of sedimentary ferrous iron

Iron (Fe) is an essential element for many organisms, but high concentrations of iron can be toxic. The complex relation between iron, arsenic (As), bacteria, and organic matter in sediments and groundwater is still an issue of environmental concern. The present study addresses the effects of humic acids and microorganisms on the mobilization of iron in sediments from an arsenic-affected area, and the microbial diversity was analyzed. The results showed that the addition of 50, 100, and 500 mg/L humic acids enhanced ferrous iron (Fe(II)) release in a time-dependent and dose-dependent fashion under anaerobic conditions. A significant increase in the soluble Fe(II) concentrations occurred in the aqueous phases of the samples during the first 2 weeks, and aqueous Fe(II) reached its maximum concentrations after 8 weeks at the following Fe(II) concentrations: 28.95?±?1.16 mg/L (original non-sterilized sediments), 32.50?±?0.71 mg/L (50 mg/L humic acid-amended, non-sterilized sediments), 37.50?±?1.85 mg/L (100 mg/L humic acid-amended, non-sterilized sediments), and 39.00?±?0.43 mg/L (500 mg/L humic acid-amended, non-sterilized sediments). These results suggest that humic acids can further enhance the microbially mediated release of sedimentary iron under anaerobic conditions. By contrast, very insignificant amounts of iron release were observed from sterilized sediments (the abiotic controls), even with the supplementation of humic acids under anaerobic incubation. In addition, the As(III) release was increased from 50?±?10 μg/L (original non-sterilized sediments) to 110?±?45 μg/L (100 mg/L humic acid-amended, non-sterilized sediments) after 8 weeks of anaerobic incubation. Furthermore, a microbial community analysis indicated that the predominant class was changed from Alphaproteobacteria to Deltaproteobacteria, and clearly increased populations of Geobacter sp., Paludibacter sp., and Methylophaga sp. were found after adding humic acids along with the increased release of iron and arsenic. Our findings provide evidence that humic acids can enhance the microbially mediated release of sedimentary ferrous iron in an arsenic-affected area. It is thus suggested that the control of anthropogenic humic acid use and entry into the environment is important for preventing the subsequent iron contamination in groundwater.     

Evaluating mobilization and transport of arsenic in sediments and groundwaters of Aquia aquifer, Maryland, USA

Groundwater and sediment samples were collected along a flow path in the Aquia aquifer (Paleocene), Maryland in order to examine and study the factors influencing "evolution" of arsenic (As) in these groundwaters. The Aquia crops out near Washington, DC, where it is unconfined, and extends approximately 90 km down dip to the south and east towards and beneath the Chesapeake Bay. The studied flow path was chosen owing to (i) the number of accessible wells, (ii) differences in total dissolved As concentrations in groundwaters from some of the sampled wells, which reach values >/=667 nmol kg(-1) or >/=50 ppb, and (iii) the distinct difference in total dissolved As concentrations in Aquia groundwaters between the northern and southern portions of the study area. In groundwater samples, in situ separation of inorganic As species [As(III) and As(V)] were performed by using anion exchange chromatography. Subsequently, As concentrations were determined by inductively coupled plasma mass spectrometry. In situ measurements of Fe concentrations and speciation, dissolved S(-II) concentrations, pH, alkalinity, and oxidation-reduction potential (Eh) were determined to establish the oxidation-reduction conditions and solution chemistry along the flow path. Concentrations of As in 12 analyzed groundwater samples range from approximately 0.75 to 1 072 nmol kg(-1), and As(III) concentrations ranging from 0.24 to 980 nmol kg(-1) appears to be the dominant form of As in solution. 50% of the studied wells yielded groundwaters with concentrations that exceed the US EPA's Maximum Contaminant Level for As in drinking water of 133 nmol kg(-1) or 10 ppb. In order to examine the solid phase speciation of As within the aquifer sediments, we collected a number of Aquia sediment samples from a drill core that was archived at the Maryland Geological Survey. These sediment samples were evaluated using a previously established sequential extractions procedure. Solid phase As concentrations range between 973 and 2,012 nmol kg(-1). Additionally, petrographic, X-Ray diffraction and diffuse reflectance spectroscopy analyses of the Aquia sediments reveal presence of glauconite, and smectite along with goethite and hematite within the samples. Here, we present the possible mechanisms responsible for the elevated As concentrations in the studied groundwaters of the Aquia aquifer.     

Elements Influencing Cost Allocation in the Pinal Creek Aquifer,Arizona, USA. Part I: Geochemical Fingerprinting and Source Delineation

This is the first in a three-article series in this volume of Environmental Forensics describing the framework that was developed to quantitatively allocate mass loading of metals to the Pinal Creek alluvial aquifer. This article describes geochemical fingerprinting, followed by spatial and temporal analysis of Pinal Creek monitoring well data (more than 600,000 records from hundreds of locations), which identified three distinct source areas and plumes on the basis of facility-specific differences in process geochemistry, ore mineralogy, and solution handling. The primary Webster Lake/Gulch source originated in 1926 (700 mg/L chlorine, 200 mg/L copper, 3000–9000 mg/L iron). Secondary contributions from the Bluebird/Oxhide/Live Oak Gulch/Davis Canyon leach complex in Upper Bloody Tanks Wash began circa 1962 (30–200 mg/L chlorine, 1500–3500 mg/L copper, <500 mg/L iron), and recent (1992–2001) contributions came from Miami Unit hydromining releases to Bloody Tanks Wash (30–70 mg/L chlorine, ～1000 mg/L copper, ～2000 mg/L iron). In Kiser Basin, where the plumes commingle, temporal evolution of the plume chemistry is reflected in a shift from a predominantly iron:copper-rich solution (10:1) to an increasingly copper-dominated signature (1:1) with the arrival of the secondary plume. Based on historical records and geochemical fingerprints, the original acid front migrated through the alluvium at ～0.5 m/day; however, later acidic releases traveled at ～2.3 m/day due to exhaustion of the available buffering capacity. The divisible nature of the plume supports quantitative allocation of contributions to the aquifer.     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.     

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.     

As(III) removal from groundwaters using fixed-bed upflow bioreactors

The application of biological oxidation of iron and manganese, as a potential treatment method for the removal of arsenic from contaminated groundwaters, was examined in this paper. This method was based on the growth of certain species of indigenous bacteria, which are capable of oxidizing the soluble iron and manganese ions; the oxidized forms can be subsequently removed from the aqueous stream by over 97%, through their transformation to insoluble oxides and separation by a suitable filter medium. Arsenic was removed by around 80%, under certain conditions, which were found to be sufficient for Fe(II) removal (dissolved oxygen 2.7 mg/l, redox 280-290 mV, pH 7.2, U 8.25 m/h). The specific treatment technique presents several advantages towards conventional physicochemical treatment methods, such as enhanced coagulation or direct adsorption since: (a) it does not require the addition of other chemicals for oxidizing and removing As(III), (b) it does not require close monitoring of a breakthrough point, as in conventional column adsorption processes and (c) it could find application for the removal of, at least, three groundwater contaminants (Fe, Mn, As).     

Biogeochemistry at a wetland sediment–alluvial aquifer interface in a landfill leachate plume

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring.Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.