Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Modelling the closure-related geochemical evolution of groundwater at a former uranium mine

A newly developed reactive transport model was used to evaluate the potential effects of mine closure on the geochemical evolution in the aquifer downgradient from a mine site. The simulations were conducted for the K?nigstein uranium mine located in Saxony, Germany. During decades of operation, uranium at the former mine site had been extracted by in situ acid leaching of the ore underground, while the mine was maintained in a dewatered condition. One option for decommissioning is to allow the groundwater level to rise to its natural level, flooding the mine workings. As a result, pore water containing high concentrations of dissolved metals, radionuclides, and sulfate may be released. Additional contamination may arise due to the dissolution of minerals contained in the aquifer downgradient of the mine. On the other hand, dissolved metals may be attenuated by reactions within the aquifer. The geochemical processes and interactions involved are highly non-linear and their impact on the quality of the groundwater and surface water downstream of the mine is not always intuitive. The multicomponent reactive transport model MIN3P, which can describe mineral dissolution-precipitation reactions, aqueous complexation, and oxidation-reduction reactions, is shown to be a powerful tool for investigating these processes. The predictive capabilities of the model are, however, limited by the availability of key geochemical parameters such as the presence and quantities of primary and secondary mineral phases. Under these conditions, the model can provide valuable insight by means of sensitivity analyses.     

The solid-phase controls on the mobility of heavy metals at the Copper Cliff tailings area, Sudbury, Ontario, Canada

The Copper Cliff Tailings Disposal Area, located near Sudbury, Ontario, covers an area of approximately 2200 ha and constitutes more than 10% of the total area of all mine tailings in Canada. The area has been utilized since 1936, receiving sulphide-containing tailings from the Inco Sudbury operations. Field measurements of pore-gas oxygen and carbon dioxide in the vadose zone indicate that sulphide oxidation has progressed to depths of 1.6 m to 1.7 m within the tailings. The oxidation of sulphide minerals within the vadose zone, and the accompanying dissolution of carbonate and aluminosilicate minerals within these tailings releases SO₄, Fe(II) and other metals to the pore water. In the vadose and saturated zones, concentrations of Fe and Ni exceed 10100 mg/l and 2210 mg/l, respectively. These high concentrations of dissolved metals are attenuated by a series of precipitation, coprecipitation and adsorption reactions. The precipitation of secondary sulphate and hydroxide phases also create hardpan layers at or near the oxidation front. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary-phase precipitation is occurring at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of jarosite, gypsum and goethite within the shallow tailings, suggesting that these phases are controlling the dissolved concentrations of Fe, SO₄ and Ca. Extraction experiments conducted on the tailings solids indicate that the constituents contained in the water-soluble fraction of the shallow, weathered tailings are derived from the original pore water and the dissolution of highly soluble phases such as gypsum. The acid-leachable fraction of the weathered tailings accounts for up to 25% of the heavy metals, and the reducible fraction may contain up to 100% of the heavy metals within the shallow, weathered tailings. Based on the pore water profiles and the geochemistry of the tailings solids, a relative mobility scale of Fe=Mn=Ni=Co>Cd Zn>Cr=Pb>Cu can be determined.     

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.     

Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions

Dissolved arsenic (As) concentrations detected in groundwater bodies of the Emilia-Romagna Region (Italy) exhibit values which are above the regulation limit and could be related to the natural composition of the host porous matrix. To support this hypothesis, we present the results of a geochemical modeling study reproducing the main trends of the dynamics of As, Fe, and Mn concentrations as well as redox potential and pH observed during batch tests performed under alternating redox conditions. The tests were performed on a natural matrix extracted from a deep aquifer located in the Emilia-Romagna Region (Italy). The solid phases implemented in the model were selected from the results of selective sequential extractions performed on the tested matrix. The calibrated model showed that large As concentrations have to be expected in the solution for low crystallinity phases subject to dissolution. The role of Mn oxides on As concentration dynamics appears significant in strongly reducing environments, particularly for large water–solid matrix interaction times. Modeled data evidenced that As is released firstly from the outer surface of Fe oxihydroxides minerals exhibiting large concentrations in water when persistent reducing conditions trigger the dissolution of the crystalline structure of the binding minerals. The presence of organic matter was found to strongly affect pH and redox conditions, thus influencing As mobility.

Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column.The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))).In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction.The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Arsenic in groundwater and sediment in the Mekong River delta, Vietnam

A study of groundwater and sediment during 2007-2008 in the Mekong River delta in Vietnam (MDVN) revealed that 26%, 74%, and 50% of groundwater samples were above the US EPA drinking water guidelines for As (10 μg/L), Mn (0.05 mg/L), and Fe (0.3 mg/L). The range of As, Fe, and Mn concentrations in the MDVN were <0.1-1351 μg/L, <0.01-38 mg/L, and <0.01−14 mg/L, respectively. Elevated levels of As were found in groundwater at sampling sites close to the Mekong River and in wells less than 60−70 m deep. An inverse relationship was found between As and Mn concentrations in groundwater. Sediment samples from An Giang and Dong Thap had the highest As concentrations (18 mg/kg and 38 mg/kg, respectively). Arsenic sediment occurred mainly in the poorly crystalline Fe oxide phases. Reductive dissolution of the Fe oxide phase is not necessarily the dominant mechanism of As release to groundwater.     

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.     

Biodegradation and mineral weathering controls on bulk electrical conductivity in a shallow hydrocarbon contaminated aquifer

Geochemical and stable carbon isotope data from closely spaced vertical intervals in a hydrocarbon-impacted aquifer were used to assess the relationship between biodegradation, mineral weathering, and enhanced bulk conductivity zones. The results show that depth zones of enhanced bulk conductivity in the contaminated aquifer had higher total dissolved solids (TDS) compared to background groundwater. The higher TDS in contaminated groundwater were due to elevated ion concentrations from enhanced mineral weathering. Depth intervals with higher concentrations of major cations overlapped with zones with higher total petroleum hydrocarbons, which were the same zones where reduction of nitrate, iron, manganese, sulfate, and methanogenesis was occurring. Hence, the zones of higher bulk conductivity may be explained by mineral weathering related to hydrocarbon biodegradation. Our results suggest that biodegradation of hydrocarbons may impart changes to the aquifer geochemistry that can be indirectly observed using geophysical techniques. We therefore argue for inclusion of geophysical investigations as part of natural attenuation assessment programs.     

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.     

Removal of As,Mn, Mo,Se, U,V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.     

Behaviour and fate of nine recycled water trace organics during managed aquifer recharge in an aerobic aquifer

The fate of nine trace organic compounds was evaluated during a 12month large-scale laboratory column experiment. The columns were packed with aquifer sediment and evaluated under natural aerobic and artificial anaerobic geochemical conditions, to assess the potential for natural attenuation of these compounds during aquifer passage associated with managed aquifer recharge (MAR). The nine trace organic compounds were bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR), carbamazepine, oxazepam, iohexol and iodipamide. In the low organic carbon content Spearwood sediment, all trace organics were non-retarded with retardation coefficients between 1.0 and 1.2, indicating that these compounds would travel at near groundwater velocities within the aquifer. The natural aerobic geochemical conditions provided a suitable environment for the rapid degradation for BPA, E2, iohexol (half life <1day). Lag-times for the start of degradation of these compounds ranged from <15 to 30days. While iodipamide was persistent under aerobic conditions, artificial reductive geochemical conditions promoted via the addition of ethanol, resulted in rapid degradation (half life <1days). Pharmaceuticals (carbamazepine and oxazepam) and disinfection by-products (NDMA and NMOR) did not degrade under either aerobic or anaerobic aquifer geochemical conditions (half life >50days). Field-based validation experiments with carbamazepine and oxazepam also showed no degradation. If persistent trace organics are present in recycled waters at concentrations in excess of their intended use, natural attenuation during aquifer passage alone may not result in extracted water meeting regulatory requirements. Additional pre treatment of the recycled water would therefore be required.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Engineered and subsequent intrinsic in situ bioremediation of a diesel fuel contaminated aquifer

A diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO4(2-) and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.     

Transport of Escherichia coli and solutes during waste water infiltration in an urban alluvial aquifer

Recharge of waste water in an unconsolidated poorly sorted alluvial aquifer is a complex process, both physically and hydrochemically. The aim of this paper is to analyse and conceptualise vertical transport mechanisms taking place in an urban area of extensive wastewater infiltration by analysing and combining the water balance, the microbial (Escherichia coli) mass balance, and the mass balance for dissolved solutes. For this, data on sediment characteristics (grain size, organic carbon, reactive iron, and calcite), groundwater levels, and concentrations of E. coli in groundwater and waste water were collected. In the laboratory, data on E. coli decay rate coefficients, and on bacteria retention characteristics of the sediment were collected via column experiments. The results indicated that shallow groundwater, at depths of 50 m below the surface, was contaminated with E. coli concentrations as high as 10(6) CFU/100 mL. In general, E. coli concentrations decreased only 3 log units from the point of infiltration to shallow groundwater. Concentrations were lower at greater depths in the aquifer. In laboratory columns of disturbed sediments, bacteria removal was 2-5 log units/0.5 cm column sediment. Because of the relatively high E. coli concentrations in the shallow aquifer, transport had likely taken place via a connected network of pores with a diameter large enough to allow bacterial transport instead of via the sediment matrix, which was inaccessible for bacteria, as was clear from the column experiments. The decay rate coefficient was determined from laboratory microcosms to be 0.15 d(-1). Assuming that decay in the aquifer was similar to decay in the laboratory, then the pore water flow velocity between the point of infiltration and shallow groundwater, coinciding with a concentration decrease of 3 log units, was 0.38 m/d, and therefore, transport in this connected network of pores was fast. According to the water balance of the alluvial aquifer, determined from transient groundwater modelling, groundwater flow in the aquifer was mainly in vertical downward direction, and therefore, the mass balance for dissolved solutes was simulated using a 1D transport model of a 200 m column of the Quaternary Alluvium aquifer. The model, constructed with PHREEQC, included dual porosity, and was able to adequately simulate removal of E. coli, cation-exchange, and nitrification. The added value of the use of E. coli in this study was the recognition of relatively fast transport velocities occurring in the aquifer, and the necessity to use the dual porosity concept to investigate vertical transport mechanisms. Therefore, in general and if possible, microbial mass balances should be considered more systematically as an integral part of transport studies.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.     

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.