Arsenic sequestration by sorption processes in high-iron sediments

High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment-porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment-water interface (0-4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate-binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe-Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe²⁺) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution.     

Natural arsenic contamination in waters from the Pesariis village,NE Italy

High arsenic (As) concentrations, >900 μg/L, were measured in Ca–Mg–SO₄ waters from springs and drainages in the village of Pesariis in the Carnic Alps (NE Italy). Oxidation of the outcropping arsenian marcasite ore deposits of the area is proposed as the mechanism for As release into oxygenated waters during runoff. Nevertheless, the limited extension of the ore deposit and the relatively low As content of the mineralization suggest that sulfide weathering might not be the only process responsible for the highest As concentration in groundwaters. An additional mechanism involves As adsorption onto ferric iron particulate during oxidation, the drawdown in reducing environment at depth during water infiltration, and the release of ferrous iron and sorbed arsenic to the water columns by reductive dissolution of hydrous ferric oxides (HFO). This yields the observed Fe–As correlation. Newly formed HFO precipitates when groundwaters discharge to aerated conditions, leading to the removal of As, which strongly partitions into the iron-rich sediments, adsorbed onto the surface of amorphous Fe₂O₃·xH₂O. The calculated and measured As concentration in sediments exceeds 10% by weight. Furthermore, geochemical and isotopic data indicate that the As-rich reservoir partly mixes with shallower aquifers, commonly tapped for drinking supply, representing a natural hazard for inhabitants.     

乌江渡水库中溶解性硅的时空分布特征

在2003年10月-2004年9月期间每月一次采集了乌江干流上乌江渡水库大坝前开阔水域中的表层水;并于2003年10月、2004年4月和7月在同一采样点采集了分层水样及其底部的柱状沉积物。分别测定了其中溶解性硅(DSi)和叶绿素a(Chl-a)的浓度,同时还现场测定了水体中的温度(T),溶解氧(DO)和pH值。结果表明:乌江渡水库表层水中DSi的浓度范围为0.53~3.96 mg/L,平均值为1.74 mg/L;但沉积物孔隙水中DSi浓度大约是上覆水体中DSi浓度的7倍。分层期间,水体中DSi浓度在垂直方向上随水深增加而升高,而孔隙水中DSi浓度随沉积深度先增加后降低。同时还发现乌江渡水库中DSi与叶绿素a之间存在较好的反相关关系,这表明该水库中DSi的含量和分布可能主要受到浮游植物尤其是硅藻的生物活动调节。     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Reactive Transport Modeling of Subaqueous Sediment Caps and Implications for the Long-Term Fate of Arsenic, Mercury, and Methylmercury

A 1-D biogeochemical reactive transport model with a full set of equilibrium and kinetic biogeochemical reactions was developed to simulate the fate and transport of arsenic and mercury in subaqueous sediment caps. Model simulations (50?years) were performed for freshwater and estuarine scenarios with an anaerobic porewater and either a diffusion-only or a diffusion plus 0.1-m/year upward advective flux through the cap. A biological habitat layer in the top 0.15?m of the cap was simulated with the addition of organic carbon. For arsenic, the generation of sulfate-reducing conditions limits the formation of iron oxide phases available for adsorption. As a result, subaqueous sediment caps may be relatively ineffective for mitigating contaminant arsenic migration when influent concentrations are high and sorption capacity is insufficient. For mercury, sulfate reduction promotes the precipitation of metacinnabar (HgS) below the habitat layer, and associated fluxes across the sediment–water interface are low. As such, cap thickness is a key design parameter that can be adjusted to control the depth below the sediment–water interface at which mercury sulfide precipitates. The highest dissolved methylmercury concentrations occur in the habitat layer in estuarine environments under conditions of advecting porewater, but the highest sediment concentrations are predicted to occur in freshwater environments due to sorption on sediment organic matter. Site-specific reactive transport simulations are a powerful tool for identifying the major controls on sediment- and porewater-contaminant arsenic and mercury concentrations that result from coupling between physical conditions and biologically mediated chemical reactions.     

Geochemical assessment of arsenic contamination in well water and sediments from several communities in the Nawalparasi District of Nepal

Arsenic contamination of well water is a serious issue in the Nawalparasi District of the Terai region in Nepal. A local investigation was carried out on 137 tube wells in 24 communities of the district in December 2011. The investigation revealed that the average arsenic concentration in the tube wells was 350 μg/L, and that nearly 98 % of the wells exceeded the WHO guideline arsenic level limit of 10 μg/L. Highly contaminated well water, with more than 400 μg/L of arsenic, was found within the limited depth ranges of 18–22 and 50–80 m. High arsenic levels exceeding 500 μg/L were detected in shallower wells at Patkhauli, Mahuawa, Thulokunwar, and Goini located between 27.517° and 27.543°N and between 83.648° and 83.748°E. Boring sampling at five communities of Kashiya, Goini, Sanokunwar, Thulokunwar, and Mahuawa revealed two aquifers located at the two depths around 14–22 and 41–50 m in each community. Dark gray or black-colored peaty clay layers rich in organic matter were distributed at depths of 18–21 m beside the upper aquifers with high arsenic concentration in each community. Positive correlations were shown between iron and arsenic in the sediments from the five communities. It can be inferred that these results were caused by dissolution of iron-oxyhydroxide molecules with arsenic from solid phases. Microbial metabolisms have a great potential to induce the dissolution and release arsenic attached on the solid phases into aqueous phases depending on the level of redox potential and pH.     

Speciation,fractionation and plant availability of arsenic as induced by sorbents mixed with soil of Zarshuran (Iran)

The aim of this work was to investigate the effects of sorbent (natural and modified zeolite and bentonite, iron filings and ferric sulfate) on the speciation and bioavailability of arsenic in contaminated soil. The soil used in this experiment was collected from Zarshuran area (Western Azerbaijan province, NW Iran). The sorbents were added to the soil in various rates separately. After a month of incubation, sunflower was planted in pots. After harvest, soil and plant samples of each pot were analyzed. Then various species of arsenic were estimated in soil solutions by MINTEQ software program. Water-soluble arsenate, arsenite and exchangeable arsenic from each pot measured. The results showed that the sorbents had no effect on the speciation of arsenic. Mobility of arsenite in the soil solutions has not changed. Soils treated with natural bentonite and zeolite increased soluble arsenate concentration and decreased exchangeable arsenic concentration. Although Fe-zeolite increased soluble arsenate concentration, Fe-bentonite, iron filings and ferric sulfate decreased soluble arsenate concentration and exchangeable arsenic concentration. Finally, iron filings (containing 354 mmol Fe⁺³) vigorously increases in the plants biomass and decreases in the arsenic concentration in plants tissue, is suggested as the best sorbent for arsenic stabilization in the region.     

Geochemical mobility of arsenic in the surficial waters from Argentina

The presence of arsenic (As) in surface water constitutes an important environmental risk, where mobility and adsorption processes are responsible for its behavior in the sediment–water interface. Therefore, the assessment of adsorption, mobility and water availability of arsenic in freshwater sediments, with agricultural, livestock and urban soil uses was performed. Arsenic concentrations in sediments ranged from 5.4 to 15.9 mg kg^?1 (total) and 2.8 to 6.5 mg kg^?1 (labile), and those of iron and manganese were 11,563–23,500 and 140.6–662.1 mg kg^?1, respectively. The As levels in water were significantly lower than those of sediments. Results would suggest that As co-precipitation and adsorption on Fe oxides are probably the major route of immobilization, determining its low lability. Manganese did not present an outstanding contribution to the retention, and cation-exchange capacity, pH and organic matter of sediments did not show an influence on the mobility of As.     

High-resolution profiles of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment

The remobilization of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment cores at Yingkou was assessed using diffusive equilibrium in thin films and diffusive gradients in thin films techniques. A relatively anoxic system (+33.7 to ?224.1 mV) in the sediment cores might cause the reductive release of iron, manganese and cobalt into pore water from the estuarine sediment. High-average concentrations of iron (47.85 μg ml^?1) and manganese (3.81 μg ml^?1) were observed using diffusive equilibrium in thin films on the sediment core, but the concentration of cobalt (18.02 ng ml^?1) was relatively low. A strong correlation between iron and cobalt was observed based on the vertical profiles of the metals. Manganese and iron were more readily released from the solid phase to the solution. The peak cobalt, copper and zinc concentrations were observed in the upper layer (2–4 cm) measured using diffusive gradients in thin films. However, the peak iron, manganese and cobalt concentrations were located in the deeper layer (≥7 cm). In addition, the concentration profiles measured using diffusive gradients in thin films of cobalt, copper and zinc were independent of the iron, manganese and cobalt distribution with respect to depth.     

Hydrogeochemistry and arsenic contamination of groundwater in the Rayen area, southeastern Iran

High As contents in groundwater were found in Rayen area and chosen for a detailed hydrogeochemical study. A total of 121 groundwater samples were collected from existing tube wells in the study areas in January 2012 and analyzed. Hydrogeochemical data of samples suggested that the groundwater is mostly Na–Cl type; also nearly 25.62 % of samples have arsenic concentrations above WHO permissible value (10 μg/l) for drinking waters with maximum concentration of aqueous arsenic up to 25,000 μg/l. The reducing conditions prevailing in the area and high arsenic concentration correlated with high bicarbonate and pH. Results show that arsenic is released into groundwater by two major phenomena: (1) through reduction of arsenic-bearing iron oxides/oxyhydroxides and Fe may be precipitated as iron sulfide when anoxic conditions prevail in the aquifer sediments and (2) transferring of As into the water system during water–acidic volcanic rock interactions.     

Geochemical fractionation of manganese in the Riogrande II reservoir, Antioquia, Colombia

The Riogrande II reservoir in Colombia has a total storage capacity of 240 million m³ and lies 2,270 m above sea level. The reservoir is used for power generation, water supply and environmental improvement. Dissolved manganese (Mn) is removed from reservoir water dedicated to domestic use by purification processes. Removal of Mn, however, poses a major challenge to purification processes and warrants the study of ways to naturally reduce dissolved Mn levels in the reservoir. The source of Mn within the reservoir is not well understood, however, presumably arises from sediment mobilization initiated by variation in pH, redox potential (ORP or Eh), dissolved oxygen (O₂) and ionic strength conditions. This study investigated conditions within the reservoir to further understand Mn transfer from the sediment into the water column. O₂, pH, oxidation–reduction potential (ORP or Eh), organic matter content and electric conductivity were measured in water samples and sediment from the reservoir. Sequential extraction (SE) procedures were used to test the specific effects exerted by each of these conditions on Mn mobilization from the sediments. The European Community Bureau of Reference (BCR) sequential extraction procedure was used to quantify metals in sediment (referred to as the BCR extraction below). Statistical analysis of geochemical data from water samples (both water column and sediment pore water) and sediments demonstrated the conditions under which Mn can be released from sediments into the water column. The results indicated a primarily oxic water column and anoxic reducing conditions in the sediment (ORP or Eh ≤ ?80 mV). The pH of water in contact with bottom sediments varied from 7.6 to 6.8. The pH of sedimentary pore water varied from 6.8 to 4.7. The sediments contained significant amounts of organic matter (20 %). Chemical extractions showed that the exchangeable fraction contained over 50 % of the total Mn within sediments. Microscopic analysis using scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS) indicated that Mn does not occur within well-crystallized mineral phases in the Riogrande II sediments. A large proportion of Mn exists instead as material adsorbed onto the surfaces of recently deposited sediment particles. Bacterial oxidation of organic matter may cause the observed anoxic conditions at the bottom of the reservoir. Mineralization of organic matter therefore contributes to reducing conditions within the sediments. Mobilization of Mn from the sediment into the water column may result from reductive dissolution of this fraction. Manganese release by this mechanism diminishes the water quality of the Riogrande II reservoir and warrants further study.     

Pore water geochemistry near the sediment-water interface of a zoned, freshwater wetland in the southeastern United States

 Sediment and its associated pore water were collected from a zoned, freshwater, riparian wetland, located in the Talladega National Forest, northeastern Hale County, Alabama, to study the porewater chemistry and its spatial changes within and between the wetland ecological zones. Obvious changes in pH, Eh and element concentrations were observed between the different wetland ecological zones. Major cations (Ca, Mg, and Na) and trace elements (B, Ba, Sr, and Mn) have very good spatial correlation with Fe and Mn distributions, both in the pore water and the sediment, suggesting that adsorption on, and desorption from, iron and manganese oxyhydroxides are important processes controlling the distributions of these elements in the wetland sediment. However, an equilibrium adsorption model is not able to explain the distribution of trace elements between the pore water and sediment. A redox kinetic model gives similar vertical profiles for iron and the correlated elements as those measured in the field and thus suggests that the relative rates of ferrous iron oxidation and the reductive dissolution of ferric iron in the sediment are important variables determining the distributions of these elements in the wetland pore waters. Received: 31 October 1996 · Accepted: 27 May 1997     

Salinization of porewater in a multiple aquitard-aquifer system in Jiangsu coastal plain,China

Chemical and isotopic compositions were analyzed in porewater squeezed from a clayey aquitard in Jiangsu coastal plain, eastern China, to interpret the salinity origin, chemical evolution and water-mass mixing process. A strong geochemical fingerprint was obtained with an aligned Cl/Br ratio of 154 in the salinized aquitard porewater over a wide Cl^? concentration range (396–9,720 mg/L), indicating that porewater salinity is likely derived from a mixing with old brine with a proportion of less than 20%. Very small contributions of brine exerted limited effects on water stable isotopes. The relationships between porewater δ¹⁸O and δD indicate that shallow and intermediate porewaters could be original seawater and were subsequently diluted with modern meteoric water, whereas deep porewaters with depleted stable isotopic values were probably recharged during a cooler period and modified by evaporation and seawater infiltration. The cation–Cl relationship and mineralogy of associated strata indicate that porewater has been chemically modified by silicate weathering and ion-exchange reactions. ⁸⁷Sr/⁸⁶Sr ratios of 0.7094–0.7112 further confirm the input source of silicate minerals. Numerical simulations were used to evaluate the long-term salinity evolution of the deep porewater. The alternations of boundary conditions (i.e., the third aquifer mixed with brine at approximately 70 ka BP, followed by recharge of glacial meltwater at 20–25 ka BP, and then mixing with Holocene seawater at 7–10 ka BP) are responsible for the shift in porewater salinity. These timeframes correspond with the results of previous studies on ancient marine transgression-regression in Jiangsu coastal plain.     

Role of Quaternary stratigraphy on arsenic-contaminated groundwater from parts of Barak Valley, Assam, North–East India

Groundwater arsenic survey in Cachar and Karimganj districts of Barak Valley, Assam shows that people in these two districts are drinking arsenic-contaminated (max. 350 μg/l) groundwater. 66% of tubewells in these two districts have arsenic concentration above the WHO guideline value of 10 μg/l and 26% tubewells have arsenic above 50 μg/l, the Indian standards for arsenic in drinking water. 90% of installed tubewells in these two districts are shallow depth (14–40 m). Shallow tubewells were installed in Holocene Newer Alluvium aquifers are characterised by grey to black coloured fine grained organic rich argillaceous sediments and are mostly arsenic contamination in groundwater. Plio-Pleistocene Older Alluvium aquifers composed of shale, ferruginous sandstone, mottle clay, pebble and boulder beds, which at higher location or with thin cover of Newer Alluvium sediments are safe in arsenic contamination in groundwater. 91% of tubewell water samples show significantly higher concentrations of iron beyond its permissible limit of 1 mg/l. The iron content in these two districts varies from 0.5 to as much as 48 mg/l. Most of the arsenic contaminated villages of Cachar and Karimganj districts are located in entrenched channels and flood plains of Newer Alluvium sediments in Barak-Surma-Langai Rivers system. However, deeper tubewells (>60 m) in Plio-Pleistocene Older Alluvium aquifers would be a better option for arsenic-safe groundwater. The arsenic in groundwater is getting released from associated Holocene sediments which were likely deposited from the surrounding Tertiary Barail hill range.     

Biogeochemistry and bacteriology of ferrous iron oxidation in geothermal habitats

A survey of hot, acid springs in Yellowstone Park has shown that high concentrations of ferrous and ferric iron are often present. Total ionic iron concentrations in different springs ranged from less than 1 ppm to greater than 200 ppm, and up to 50% of the ionic iron was in the ferrous form. Some of these springs also have high concentrations of reduced sulfur species (S^2? and S⁰). Significant populations of the bacterium Sulfolobus, acidocaldarius, an autotrophic organism able to live and oxidize sulfur compounds at low pH and high temperature, were present in most of these springs. The role of this organism in the oxidation of ferrous iron was investigated by incubating natural samples of water and assaying for disappearance of ferrous iron. Controls in which bacterial activity was inhibited by addition of 10% NaCl were also run. Bacterial oxidation of ferrous iron occurred in most but not all of the spring waters. The temperature optimum for oxidation varied from spring to spring, but significant oxidation occurred at temperatures of 80–85°C, but not at 90°C. Thus, 85–90°C is the upper temperature at which bacterial iron oxidation occurs; a similar upper limit has previously been reported for sulfur oxidation in the same kinds of springs. The steady-state concentrations of ferrous and ferric iron are determined by the rate at which these ions move into the spring pools with the ground water (flow rate), by the rate at which ferric iron is reduced to the ferrous state by sulfide, and by the rate of bacterial oxidation. The bacterial oxidation rate is faster than the flow rate, so that the rate of reduction of ferric iron is probably the rate-controlling reaction. In several springs, no decrease in ferrous iron occurred, even though high bacterial populations were present. It was shown that in these springs, ferrous iron oxidation occurred but the ferric iron formed was reduced back to the ferrous state again. These springs were all high in suspended sediment and the reductant was shown to be present in the sediment. X-ray diffraction revealed that the sediment contained three major ingredients, elemental sulfur, natroalunite, and quartz. Chemical analyses showed a small amount of sulfide, too little to reduce the ferric iron. Elemental sulfur itself did not reduce ferric iron but when elemental sulfur was removed from the sediment by CS₂ extraction, the activity of the sediment was abolished. It is hypothesized that the sulfide present in the sediment (possibly bound to natroalunite) reacts with elemental sulfur to form a reductant for ferric iron. The results show that bacteria can have a profound influence on the ferrous/ferric ratios of geothermal systems, but that temperature and mineral composition of the water may significantly influence the overall result.     

Adsorption kinetic control of As(III &; V) mobilization and sequestration by Mangrove sediment

Elevated concentrations of arsenic in the sediment and pore water in the Sundarban wetlands pose an environmental risk. Adsorption and desorption are hypothesized to be the major processes controlling arsenic retention in surface sediment under oxic/suboxic condition. This study aims to investigate sorption kinetics of As(III & V) and its feedback to arsenic mobilization in the mangrove sediment. It ranges from sand to silty clay loam and shows the adsorption of As(III & V) following the Langmuir relation. Estimates of the maximum adsorption capacity are 59.11 ± 13.26 μg g⁻¹ for As(III) and 58.45 ± 8.75 μg g⁻¹ at 30°C for As(V) in the pH range 4 to 8 and salinity 15–30 psu. Extent of adsorption decreases with increasing pH from 4 to 8 and desorption is the rate-limiting step in the reaction of arsenic with sediment. Arsenic in the sediment could be from a Himalayan supply and co-deposited organic matter drives its release from the sediment. Arsenic concentration in the sediment is well below its maximum absorption capacity, suggesting the release of sorbed arsenic in pore water by the microbial oxidation of organic matter in the sediment with less feedback of adsorption.     

Redox and pH conditions in the water column and in the sediments of an acidic mining lake

Physico-chemical parameters of the acidic mining lake (ML) 111 in the Lusatian region (Germany) were determined in April and August 1997 using a multiparameter probe for the water column and punch-in pH and Eh electrodes for the sediment, respectively. Samples of the sediment profile were taken by a gravity corer. Besides determination of the physico-chemical parameters, grain size and water contents were determined after sediment slicing.Differences in the redox state of the water body, deduced from oxygen saturation between April and August, could not be inferred. However, a shift in pH to lower values was apparent. Data support the conclusion that the enhanced oxygen content was consumed for oxidation of ferrous iron to ferric iron (oxides/hydroxides) coupled with the release of protons.In the sediment, different buffer systems of iron compounds could be detected within separate zones with values below and above pH 3. At higher pH values, the redox conditions are controlled and stabilized by the presence of Fe-oxide-hydroxides and possibly Fe-sulfates.     

Arsenic mobilization in alluvial soils of Punjab, North–West India under flood irrigation practices

A laboratory investigation was carried out to examine the mechanism of arsenic (As) mobilization under flooded conditions (24 and 240 h) in 18 alluvial soils of Punjab, North–West India. Total dissolved As increased from a range of 3–16 μg L^?1 (mean 9 μg L^?1) to a range of 33–1,761 μg L^?1 (mean 392 μg L^?1) with the increase in flooding period from 24 to 240 h. The amount of As mobilization varied depending upon redox potential (pe) created by flooding conditions. After 24 h of flooded conditions, pe of soil water suspension ranged from ?1.75 to 0.77 (mean ?0.24). Increasing the flooding period to 240 h, pe of soil water suspension decreased in the range of ?4.49 to ?2.74 (mean ?3.29). Pourbaix diagram identified arsenate (HAsO₄ ^2?) as predominant species in most of the alluvial soil–water suspensions under oxidized conditions, after 24 h of equilibration period, which ultimately transformed to arsenite (H₃AsO₃ ⁰) after 240 h of anaerobic condition due to more reduced status. The solid phase identified was orpiment (As₂S₃). Identification of iron and manganese species in alluvial soil water suspension by Pourbaix diagram indicated decline in both soluble Fe²⁺ and SO₄ ^2? concentration due to the formation of iron sulfide mineral phase after 240 h under anaerobic conditions. In these soils, decline in soluble Fe was also due to the precipitation of vivianite [Fe₃(PO₄)₂·8H₂O]. Elevated arsenic content and low pe value were measured in aquifers located in paddy growing fields comparative to aquifers of other sites. Large degree of variability in As concentrations was recorded in aquifers located at same sites. Thus, it is better to analyze each aquifer for their As content rather than to depends on the prediction on As content of neighbouring wells. The present investigation elucidates that flood irrigation practices in Punjab for growing paddy crop could induce the geochemical conditions favorable to mobilize arsenic from surface soils which could eventually elevate its content in the underlying shallow aquifers. Water abstracted from these aquifers by hand pumps or tube wells for drinking purposes could create hazards for local population due to loading with arsenic concentration above the safe limits. Thus, to avoid further contamination of shallow aquifers with arsenic, it is advisable to shift the flooded rice cultivation to other upland crops having lesser water requirement.     

Impacts of subsurface heat storage on aquifer hydrogeochemistry

The use of shallow aquifers for subsurface heat storage in terms of energy management and building climatisation can lead to a temperature rise in the aquifer to 70 °C and above. The influence of temperature changes on individual mineral and sorption equilibria, reaction kinetics and microbial activity is largely known. However, the impact of heating to temperatures as high as 70 °C on the aquifer overall system has not been quantified yet. Temperature-related changes in sediment ion exchange behaviour, dimension and rates of mineral dissolution and precipitation as well as microbially enhanced redox processes were studied in column experiments using aquifer sediment and tap water at 10, 25, 40, and 70 °C. At 70 °C, a change in sediment sorption behaviour for cations and organic acids was postulated based on temporal changes in pH, magnesium, and potassium concentration in the experimental solution. No clear changes of pH, TIC and major cations were found at 10–40 °C. Redox zoning shifted from oxic conditions towards nitrate and iron(III) reducing conditions at 25 and 40 °C and sulphate reducing conditions at 70 °C. This was attributed to (a) a temperature-related increase in microbial reduction activity, and (b) three times higher release of organic carbon from the sediment at 70 °C compared to the lower temperatures. The findings of this study predict that a temperature increase in the subsurface up to 25 °C and above can impair the usability of ground water as drinking and process water, by reducing metal oxides and thus possibly releasing heavy metals from the sediment. Generally, at 70 °C, where clear cation and organic carbon desorption processes were observed and sulphate reducing conditions could be achieved, a site-specific assessment of temperature effects is required, especially for long-term operations of subsurface heat storage facilities.     

Transformation of arsenic compounds in modern intertidal sediments of Iriomote Island, Japan

The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.