Hydrogeochemical characteristics and its role in controlling arsenic mobilization in a shallow aquifer

The relevance of groundwater hydrogeochemistry to explain the occurrence and distribution of arsenic in groundwater is of great interest. The insightful discussions on the control of shallow groundwater (< 50 m) hydrogeochemistry in arsenic mobilization are known to be a viable tool to explain the arsenic menace in shallow groundwater. The present investigation emphasizes the hydrogeochemical driver and/or control over the reductive dissolution of Fe-bearing host minerals and thereby releasing arsenic into the shallow groundwater of the study area. The study suggests that hydrogeochemical evolution is mainly governed by carbonate minerals dissolution, silicate weathering, and competitive ion-exchange processes in the shallow aquifers (< 50 m). The present study also indicates the prevalence of carbonate minerals dissolution over silicate weathering. The emergence of Cl⁻ concentration in the shallow groundwater founds the possibilities of anthropogenic inputs into the shallow aquifers (< 50 m). The reducing environment in shallow aquifers (< 50 m) of the study area is evident in the reductive dissolution of Fe- bearing shallow aquifer minerals which absorb arsenic in the solid phase and mobilize arsenic onto shallow groundwater. The study opted for many statistical approaches to delineate the correlation among major and minor ionic constituents of the groundwater which are very helpful to understand the comprehensive mechanism of arsenic mobilization into shallow groundwater.

     

Laboratory-scale analysis of transportation and natural attenuation of diesel fuel in aquifer

Processes that control the distribution and natural attenuation (NA) of petroleum hydrocarbons dissolved from the released diesel fuel in a bench-scale model aquifer were evaluated. The experimental results obtained in two-dimensional aqueous-phase petroleum hydrocarbon concentrations indicated that the total petroleum hydrocarbon (TPH) in the aquifer migrated in longitudinal and lateral directions. The TPH plume of 2 mg L^?1 spread to the entire area of the aquifer, and the maximum concentration at the center of the plume was 44.15 mg L^?1 after 90 days of release. After diesel fuel release, the NA of TPH was evaluated and quantified. Experimental data indicated that the NA of TPH was immediately implemented to prevent migration of the plume into the downgradient of the aquifer, but controlling the TPH plumes using NA mechanisms requires a long time.     

A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump

At the abandoned As mine in Nishinomaki, Japan, discharged water from the mining and waste dump area is acidic and rich in As. However, the As concentration in the drainage has been decreased to below the maximum contaminant level (0.01 mg/l for drinking water, Japan) without any artificial treatments before mixing with a tributary to populated areas. This implies that the As concentration in water from the waste dump area has been naturally attenuated. To elucidate the reaction mechanisms of the natural attenuation, analysis of water quality and characterization of the precipitates from the stream floor were performed by measuring pH, ORP and electric conductivity on-site, as well as X-ray diffraction, ICP-mass spectrometry and ion-chromatography. Selective extractions and mineral alteration experiments were also conducted to estimate the distribution of As in constituent phases of the precipitates and to understand the stability of As-bearing phases, respectively. The water contamination resulted from oxidation of sulfide minerals in the waste rocks, i.e., the oxidation of pyrite and realgar and subsequent release of Fe, SO₄, As(V) and proton. The released Fe(II) transformed to Fe(III) by bacterial oxidation; schwertmannite then formed immediately. While the As concentrations in the stream were lowered nearly to background level downstream, those in the ochreous precipitates were up to several tens of mg/g. The As(V) was effectively removed by the formed schwertmannite and had been naturally attenuated. Although schwertmannite is metastable with respect to goethite, the experiments show that the transformation of schwertmannite to goethite may be retarded by the presence of absorbed As(V) in the structure. Therefore, the attenuation of As in the drainage and the retention of As by schwertmannite are expected to be maintained for the long term.     

Nature and origin of arsenic carriers in shallow aquifer sediments of Bengal Delta,India

Sediments from shallow aquifers in Bengal Delta, India have been found to contain arsenic. Rivers of Ganga-Brahmaputra system, responsible for depositing these sediments in the delta, have created a store of arsenic. Geomorphological domains with different depositional styles regulate the pattern of distribution of zones with widely different content of groundwater arsenic. The high arsenic zones occur as narrow sinuous strips confined to channel deposits. A few iron-bearing clastic minerals and two post-depositional secondary products are arsenic carriers. Secondary siderite concretions have grown on the surface of the clastic carriers in variable intensity. The quantity of arsenic in all clastic carriers is in excess of what is generally expected. Excess arsenic is contributed by the element adsorbed on the concretion grown on the surface of the carriers, which adds up to the arsenic in the structure of the minerals. Variable abundance of concretions is responsible for the variable quantity of arsenic in the carriers and the sediment samples. Fe²⁺ for the growth of siderite concretions is obtained from the iron-bearing clastic carriers. The reaction involves reduction of trivalent iron to bivalent and the required electron is obtained by transformation of As³⁺ to As⁵⁺. It is suggested that oxidation of As³⁺ to As⁵⁺ is microbially mediated. In the Safe zone arsenic is retained in the carriers and groundwater arsenic is maintained below 0.05 mg/l. In the Unsafe zone sorbed arsenic is released from the carriers in the water through desorption and dissolution of concretion, thereby elevating the groundwater arsenic level to above 0.05 mg/l.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

The effect of aquifer heterogeneity on natural attenuation rate of BTEX

Monitored natural attenuation can be a viable option for remediation of groundwater contamination by BTEX compounds. Under the field conditions, the rate of contaminant mass attenuation through natural processes, such as biodegradation, to a large extent affected by the groundwater flow regime, which is primarily controlled by the aquifer heterogeneity. Numerical simulation techniques were used to describe quantitatively the relationship between biodegradation rate of BTEX and aquifer heterogeneity. Different levels of aquifer heterogeneity were described by random hydraulic conductivity fields (K) having different statistical parameters, the coefficient of variation (CV) and the correlation length (h). The Turning Bands Algorithm was used to generate such K fields. Visual MODFLOW/RT3D was used to simulate the fate and transport of dissolved BTEX plume within heterogeneous aquifers. The multispecies reactive transport approach described BTEX degradation using multiple terminal electron-accepting processes. First-order biodegradation rate constants were calculated from simulated BTEX plumes in heterogeneous flow fields. The results showed that aquifer heterogeneity significantly affected biodegradation rate; it decreased with increasing CV when h was in the range of up to 12 m, whereas it increased with increasing CV when h was greater than about 12 m. For well characterized aquifers, this finding could be of great value in assessing the effectiveness of natural attenuation during feasibility studies at BTEX contaminated sites.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

浅层地下水氯代烃污染天然衰减速率的估算

天然衰减恢复技术是恢复和控制浅层地下水氯代烃污染的技术之一,如何简便获取可靠的氯代烃衰减速率常数是该技术应用的一个关键。趋势线分析方法是一种简便有效的方法,在污染羽状体稳定的条件下,通过地下水流向上至少3口监测井的资料,能够比较准确地估算出污染物的天然衰减速率常数和生物降解速率常数。某氯代烃污染典型区的应用实例研究表明,该区四氯乙烯(PCE)的天然衰减速率常数和生物降解速率常数分别为0·000925d-1和0·000537d-1,证实该区浅层地下水中的PCE存在天然生物降解,但降解速率比较缓慢。忽略吸附作用的天然衰减容量计算所得出的天然衰减速率常数明显小于实际结果,说明尽管典型区包气带及含水层介质的有机碳含量很少,但它们对PCE的吸附作用不容忽视。     

Distribution of arsenic and its mobility in shallow aquifer sediments from Ambikanagar, West Bengal, India

Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As³⁺ vs. As⁵⁺), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg⁻¹, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As³⁺ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO₄ reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As³⁺ and presence of As⁵⁺ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.     

Speciation of arsenic in sulfidic waters

Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH₂S from 10^-7.5 to 10^-3.0 M, ΣAs from 10^-5.6 to 10^-4.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH)₃ ⁰, and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10^-4.3 M at neutral pH. Conversion from neutral As(OH)₃ ⁰ to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

Geochemical heterogeneity and isotope geochemistry of natural attenuation processes in a gasoline-contaminated aquifer at the Hnevice site,Czech Republic

The geochemical processes, water–rock interactions and stable isotopes distribution (δ¹³C of DIC and δ¹⁸O and δ³⁴S of \({\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} \)) were investigated in the gasoline-contaminated aquifer at the Hnevice site, 50  km northwest of Prague, Czech Republic. Diesel, gasoline and oil leaks originate from a large fuel storage area causing heavy contamination of the saturated and unsaturated zones in an area of about 0.7  km². Groundwater investigations were conducted using five multilevel sampler wells with emphasis on redox parameters and degradation by-products and a solid-phase study focused on iron speciation and determination of principal and secondary minerals. Based on the study of groundwater and solid-phase geochemistry, four different geochemical zones were described. Zone I is thought to be background consisting of an aerobic aquifer and the absence of reduced species in significant concentrations. Zone II is situated in the plume core with methanogenic, sulphate and iron-reducing conditions accompanied by ankerite and kutnahorite precipitates and significant depletion of the oxidation capacity of the aquifer. Zone III is a mixing (corona) zone, situated at the fringe of the plume with high biodegradation rates and Fe(III)-precipitants. In zone IV, reoxidation of Fe(II) minerals (with e.g. the occurrence of psilomelane and cornelite) is typical.     

Pollutant transport in a shallow unconfined aquifer in Perry,Ohio

The groundwater system in northern Perry Township in Lake County, Ohio, is a shallow, unconfined aquifer consisting of periglacial lake beach deposits and less permeable lacustrine plain deposits. Groundwater flow is generally toward Lake Erie from south to north and is controlled by the top of the Ashtabula Till, but strong, local variations are caused by northward flowing streams During the study period, water levels in most wells exhibited a seasonal fluctuation of less than 0 3 m from their mean values. The areal distributions of chloride and nitrate concentrations indicate that road salt runoff easily infiltrates the aquifer and that nitrate may be sourced from fertilizer application. Ground-water flow and solute transport models indicate that in excess of 27 years are required to obtain chemical steady-state under hydrologic steady-state conditions. The simulations also demonstrate that nitrate loading must occur in more than one cultivated field in order to obtain the observed wide-spread nitrate distribution.     

Speciation studies of arsenic in the environment and in human

Arsenic is the 20th most abundant element in the Earth crust. Humans are exposed to naturally occurring and anthropogenic sources of arsenic compounds in the environment. A wide variety of adverse health effects have been attributed to chronic exposure to high levels of arsenic. More than two-dozen arsenic compounds （species） are present in the environment and in biological systems. The various arsenic species have dramatically different behavior and toxicity. This presentation briefly describes arsenic speciation analysis, human exposure to and metabolism of arsenic species. Environmental issues on arsenic in Canada are briefly discussed. These include （1） the arsenic waste left from previous gold mining and smelting activities; （2） the domestic use of wood treated with chromated copper arsenate; and （3） use of well water as the source of drinking water by approximately one third of the Canadian population.     

利用观测孔中地下水位潮汐效应计算天津滨海新区含水层参数

在沿海地区,尤其是围海造陆工程形成的陆域地区地下水水位受潮汐影响较大,使传统水文地质试验求取含水层参数存在较大误差。因此通过合理概化地下水在潮汐作用下运动规律,建立数学模型,推导解析公式求取沿海含水层参数具有重要意义。分析天津滨海新区两处观测孔地下水位及潮汐波动特征,在滞后时间不明显的情况下,利用观测孔水位变幅数据计算了含水层水头扩散系数,并根据承压含水层储水系数经验值进一步获得含水层渗透系数。通过两个观测孔分别计算,对比计算结果互相验证发现,该方法取得了令人满意的结果。利用地下水潮汐效应计算含水层参数可以广泛应用于沿海地区水文地质工作中。     

Of sand and mud: Sedimentological criteria for identifying the turbidity maximum zone in a tidally influenced river

The thickness and lateral distribution of sand and mud beds and bedsets on channel bars from the tidally influenced Fraser River, British Columbia, Canada, are quantitatively assessed. Fifty‐six vibracores totalling ca 114 m of vertical section are used to tabulate bed thicknesses. Statistical calculations are undertaken for nine channel bars ranging from the freshwater and tidal zone, to the sustained brackish water and tidal zone. The data reveal that thickness trends can be organized into three groups that broadly correspond to time‐averaged hydrodynamic and salinity conditions in the various distributary channels. Thick sand beds (up to 30 cm) and thin mud beds (up to 5 cm) characterize the freshwater tidal zone. The tidal and freshwater to brackish‐water transition zone comprises thin sands (up to 10 cm) and thicker muds (up to 19 cm), and the sustained brackish water tidal zone consists of thin muds (up to 6 cm) with relatively thicker sands (up to 25 cm). The results suggest that the locus of mud deposition occurs in the tidal freshwater to brackish‐water zone, probably reflecting mud flocculation and deposition at the turbidity maximum. Landward of the turbidity maximum, mud deposition is linked to tidal influence (tidal backwater effect and reverse eddy currents on channel margins) as mud beds thin in the landward direction. These results support the hypothesis that mud deposition is greatest at the turbidity maximum and decreases in both the seaward and landward direction. This study also showcases that mud‐bed thicknesses are greatest towards the turbidity maximum and thin in both the landward and seaward direction. In the rock record, the apex of mud deposition probably marks the position of the palaeo‐turbidity maximum.     

Control mechanisms for dissolved phosphorus and arsenic in a shallow lake

This study investigated P and As sediment remobilisation in Lake Yangebup, a shallow lake with an overlying floc layer that covers the consolidated sediment. This floc is frequently resuspended into the water column, a process that was postulated to produce high P and As lakewater concentrations. Rate investigations using deionised water showed that P and As remobilisation reached steady state after 20 h in the consolidated sediment and within 1 h for the floc. Floc resuspension in lakewater showed no net release of either P and As, indicating that the floc was in constant equilibrium with the water column. A protocol to distinguish between desorption and dissolution was applied to both sediments and the response of remobilisation to varying slurry density and As addition measured. For the consolidated sediment, the concentration of Fe(II), P and As were unaffected above a slurry density ∼30 g L⁻¹ and added arsenate (10–100 μg L⁻¹) did not significantly change As and P remobilisation. It is shown that these results do not fit an adsorption/desorption equilibrium formulation for P and As remobilisation. Instead, the evidence suggests that the solubility of a thin, non-stoichiometric FeP_xFeAs_y oxyhydroxide surface coating determined the remobilisation process. Data scatter lead to some uncertainty in the floc results but suggest that dissolved P is controlled by dissolution, while dissolved As is controlled by adsorption/desorption. The results conclusively show that P and As remobilisation was lower from the floc than from the consolidated sediment and that the removal of the floc would not lower P and As lakewater concentrations. Implications of these results for the management of As in Lake Yangebup are outlined.     

Speciation of metals in natural waters

The form or speciation of a metal in natural waters can change its kinetic and thermodynamic properties. For example, Cu(II) in the free ionic form is toxic to phytoplankton, while copper complexed to organic ligands is not toxic. The form of a metal in solution can also change its solubility. For example, Fe(II) is soluble in aqueous solutions while Fe(III) is nearly insoluble. Natural organic ligands interactions with Fe(III) can increase the solubility by 20-fold in seawater. Ionic interaction models that can be used to determine the activity and speciation of divalent and trivalent metals in seawater and other natural elements will be discussed. The model is able to consider the interactions of metals with the major (Cl^-, SO₄ ^2-, HCO₃ ^-, CO₃ ^2-, Br^-, F^-) and minor (OH^-, H₂PO₄ ^-, HPO₄ ^2-, PO₄ ^3-, HS^-) anions as a function of temperature (0 to 50 °C), ionic strength [0 to 6 m (m = mol kg-¹)] and pH (1 to 13). Recently, it has been shown that many divalent metals are complexed with organic ligands. Although the composition of these ligands is not known, a number of workers have used voltammetry to determine the concentration of the ligand [L ⁿ ] and the stability constant (K _ML) for the formation of the complex