Pore-water response on seasonal environmental changes in intertidal sediments of the Weser Estuary,Germany

In order to determine time-dependent changes in estuarine pore-water chemistry and flux variations across the sediment-water interface, sediment cores of an intertidal mud flat in the Weser Estuary were taken monthly over a one-year period. Sediment temperature, pH, Eh, Cl^–, O₂, NO ₃ ^– , and SO ₄ ^2– pore-water concentrations were measured and showed variations that relate to the changes of surface temperature and estuarine water composition. Fick's first law was applied to quantify diffusive fluxes from concentration gradients in the diffusive boundary layer and in the pore water. Total nitrate fluxes were calculated from flux chamber experiments. Diffusive oxygen fluxes increased from 5 mmol m^–2 d^–1 in winter to 18 mmol m^–2 d^–1 in early summer, while nitrate fluxes into the sediment increased from 3 mmol m^–2 d^–1 in winter to 60 mmol m^–2 d^–1 in early summer. Oxygen and nitrate fluxes into the sediment correlated linearly to sediment temperature. Sulfate fluxes increased from 0.5 mmol m^–2 d^–1 in winter to 10 mmol m^–2 d^–1 in August and September. Converted into carbon fluxes, the sum of these oxidants ranged from 10 mmol m^–2 d^–1 in winter to 80 mmol m^–2 d^–1 in summer. An estimation of the upper limit of the annual nitrate flux into the sediment showed that about 10% of the 250,000 t of nitrate discharged annually by the river may be decomposed within the inner Weser Estuary.     

Distribution of arsenic and other trace elements in the Holocene sediments of the Meghna River Delta, Bangladesh

Geochemical study of the Holocene sediments of the Meghna River Delta, Chandpur, Bangladesh was conducted to investigate the distribution of arsenic and related trace and major elements. The work carried out includes analyses of core sediments and provenance study by rare earth element (REE) analysis. Results showed that the cores pass downward from silty clays and clays into fine to medium sands. The uppermost 3 m of the core sediments are oxidized [average oxidation reduction potential (ORP) + 230 mV], and the ORP values gradually become negative with depths (−45 to −170 mV), indicating anoxic conditions prevail in the Meghna sediments. The REE patterns of all lithotypes in the study areas are similar and are comparable to the average upper continental crust. Arsenic and other trace elements (Pb, Zn, Cu, Ni, and Cr) have greater concentrations in the silts and clays compared to those in the sands. Positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed on Fe oxides in aquifer sediments.     

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.     

Erratum to: Geochemical and environmental magnetic characteristics of high arsenic aquifer sediments from Datong Basin,northern China

Geochemical and environmental magnetic studies were carried out to identify the effect of iron oxyhydroxides on arsenic mobilization in high arsenic aquifer system. Using high arsenic sediment samples from two boreholes, specifically drilled for this study, chemical composition and magnetic properties including magnetic susceptibility, saturation remnant magnetization, and isothermal remnant magnetization were measured. Results of correlation analysis of element contents show that arsenic and iron are closely associated with each other (r ² = 0.40, α = 0.05, n = 21). In contrast, the correlation of phosphorus with iron (r = 0.11, α = 0.05, n = 21) and arsenic (r ² = 0.18, α = 0.05, n = 21) was poor, which might result from competitive adsorption of phosphorus and arsenic on the surface of Fe-oxyhydroxides. The high correlation coefficients between arsenic contents and magnetic parameters suggest that the ferrimagnetic minerals including maghemite and hematite are the dominant carrier of arsenic in aquifer sediments. The results of sequential extraction experiments also revealed the association of arsenic with reducible iron oxides, such as maghemite and hematite in aquifer sediments. Therefore, under reducing conditions, reductive dissolution and desorption of arsenic from Fe-oxyhydroxides into the aqueous phase should be the dominant geochemical processes for its enrichment in groundwater at Datong. An erratum to this article can be found at     

Mobility of arsenic and trace element inventories in sediment cores from Masuda City,southwestern Japan

The vertical distribution of arsenic and other trace and major elements has been studied in four sediment cores from Masuda City, Nagashima and Okite in the Shimane Prefecture of southwestern Japan. The sediment cores were also subjected to leaching techniques and ¹⁴C dating. The stratigraphic sequences in the cores consist of silt and sandy silt at top, passing downward into gray to black clays. Elevated values of As, Pb, Zn, Cu, Ni, Cr, and V are present in several horizons while abundances of these elements tend to be higher in the black and gray clays, probably due to adsorption onto clay sediments. Higher concentrations of Fe and total sulfur (TS) occur in black clays. The correlations of the trace metals with iron suggest their adsorption onto Fe (oxy)hydroxides, whereas correlations with sulfur in some cores indicate that they were precipitated as Fe-sulfides. Age determinations suggest that clay horizons at ∼5 m depth were deposited at around 5,000 and 6,000 years BP (¹⁴C ages) during the transgressive phase of sea level change. The results of the leaching techniques in the core samples show that higher amounts of As were extracted with deionized water. Even at neutral pH, As can be released from sediments to groundwater, and therefore groundwater pollution is a concern in Masuda City and the surrounding area.     

Geological and geochemical examination of arsenic contamination in groundwater in the Holocene Terai Basin, Nepal

Geological and geochemical study has been carried out to investigate arsenic contamination in groundwater in Nawalparasi, the western Terai district of Nepal. The work carried out includes analyses of core sediments, provenance study by rare earth elements analyses, ¹⁴C dating, and water analyses. Results showed that distribution of the major and trace elements are not homogeneous in different grain size sediments. Geochemical characteristics and sediment assemblages of the arsenic contaminated (Nawalparasi) and uncontaminated (Bhairahawa) area have been compared. Geochemical compositions of sediments from both the areas are similar; however, water chemistry and sedimentary facies vary significantly. Extraction test of sediment samples showed significant leaching of arsenic and iron. Chemical reduction and contribution from organic matter could be a plausible explanation for the arsenic release in groundwater from the Terai sediments.     

Microcosm studies on iron and arsenic mobilization from aquifer sediments under different conditions of microbial activity and carbon source

Microcosm experiments were conducted to understand the mechanism of microbially mediated mobilization of Fe and As from high arsenic aquifer sediments. Arsenic-resistant strains isolated from aquifer sediments of a borehole specifically drilled for this study at Datong basin were used as inoculated strains, and glucose and sodium acetate as carbon sources for the experiments. In abiotic control experiments, the maximum concentrations of Fe and As were only 0.47 mg/L and 0.9 μg/L, respectively. By contrast, the maximum contents of Fe and As in anaerobic microcosm experiments were much higher (up to 1.82 mg/L and 12.91 μg/L, respectively), indicating the crucial roles of microbial activities in Fe and As mobilization. The observed difference in Fe and As release with different carbon sources may be related to the difference in growth pattern and composition of microbial communities that develop in response to the type of carbon sources.     

Ammonium regeneration in intertidal sediments of the Yangtze estuary during air-exposure

The influences of exposure to the atmosphere on ammonium cycle in the intertidal surface sediments were in situ studied with a geochemical approach at a typical station in the Yangtze Estuary during three tidal cycles in September 2003. During an about 8-h emersion period of each diurnal tide, six high-resolution vertical profiles of adsorbed and dissolved ammonium were measured. It was observed that both adsorbed and dissolved ammonium generally had an increasing trend in sediment cores during the exposure. The rate of ammonium regeneration in sediments was estimated using the accumulation amount of ammonium including adsorbed and soluble fractions during the daytime emersion. The calculation result showed that there was relatively high ammonification rate (˜500 nmol N cm⁻³ day⁻¹), which reflected that organic nitrogen in sediments was quickly decomposed with a residence time of ˜52.7 days. Due to the dramatic temperature difference observed in sediment profiles, free convection was considered an important mechanism of regulating the efflux of produced ammonium into overlying waters. The total estimated amount of regenerated ammonium was ˜1.35×10⁵ t N year⁻¹ in the intertidal flat of the Yangtze Estuary, which occupied 7.6% of the total inorganic nitrogen annually transported to the estuarine ecosystem.     

Cu and Fe associated with humic acids in sediments of a tropical coastal lagoon

The amount of Cu and Fe associated with humic acids was estimated in five sediment cores from a tropical coastal lagoon (Piratininga Lagoon, Rio de Janeiro, Brazil). Core samples were analysed for humic acid contents, total Fe and Cu content. Fe and Cu associated with humic acids were also measured. Results show amounts of humic acids ranging from 0.7 to 21.7% of the dry weight of sediment (average 4.6%, standard deviation 4.4%). Concentrations of Fe and Cu ranged from 0.3 to 6.0% (average 2.2%, S.D. 1.2%) and from <1.0 to 65.0 μg g⁻¹ (average 28.6 μg g⁻¹, S.D. 16.4 μg g⁻¹), respectively. The results of strongly bound metals show that while humic acids are the main carrier for Cu, Fe does not seems to be significantly associated with this organic matter.     

Arsenic in the groundwater of Ouro Preto (Brazil): its temporal behavior as influenced by the hydric regime and hydrogeology

In the city of Ouro Preto (MG), water catchment for public supply originates from superficial drainage, springs, old abandoned mines and some driven wells. In the rocks of the region, As is originally found in gold-enriched sulphide-bearing mineral deposits. The weathering process introduces As into the hydrological system by dissolution of this element into the leachate. Measurement of the As content in the groundwater of some catchments was carried out during 1 year and these measurements demonstrated high As content—up to 224 μg L⁻¹ of As(V)—during the rainy season (the maximum concentration limit according to World Health Organization is 10 μg L⁻¹). Lower values were observed during the dry season and in some sampling stations, As was not even detected. The As concentration variability during 1 year shows a strict and direct relationship to seasonal and hydrological conditions. For city authorities, responsible for public water supply, it is necessary to perform a complete inventory of the water sources used and constantly monitor the As content in the water.     

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.     

A 1,800-year record of arsenic concentration in the penguin dropping sediment,Antarctic

Heavy/toxic metals have been widely investigated in the Antarctic. However, there are rare reports on arsenic up to now. Here, we analyzed a 1,800-year record of arsenic concentration in lake sediments affected by penguin droppings. We found that arsenic enriches in the penguin dropping sediments with 12.41 ± 0.45 μg/g (on dry weight), which is about two times higher than the one in the background sediments with absence of penguin. Historical change in arsenic concentration was found to significantly correlate with the fluctuation of penguin number, indicating that penguin activity will result in the enrichment of arsenic somewhere in the maritime Antarctic.     

Microbial effects on geochemical behavior of arsenic in As-contaminated sediments

The purpose of this study is to investigate the contamination level and chemical speciation of As in sediments from the Hwachon Au mine area, and to study the effects of indigenous bacteria on geochemical behavior of As in As-contaminated sediments from the mine. Concentrations of heavy metal and metalloids in one composite sample of 9 Hwachon sediments were 24.9 As mg/kg, 16.6 Cd mg/kg, 230 Pb mg/kg and 1080 Zn mg/kg. This indicates that this area was seriously contaminated with As, Cd and Zn. From the result of sequential extraction analysis, most of As (87.9%) existed as a phase of As which coprecipitated with Fe oxyhydroxides. Under aerobic condition, As concentration leached from sediments were 4 times higher in non-sterile than in sterile condition. This enrichment of As leaching could be caused by increase of pH and exudation secreted during microbial metabolism. On the other hand, under anaerobic condition, As concentration has dramatically increased in non-sterile solution with time. This As leaching has begun on 4–5th days of incubation and the highest concentration of 511 As μg/l was recorded on about 11th day. Arsenic leaching under anaerobic condition was caused by microbial enhancement of Fe leaching. Total Fe concentration increased from the 4th day, and this Fe leaching might cause lixiviation of As which had been coprecipitated with Fe oxyhydroxide.     

Distribution of iron in the surface and groundwaters of East Godavari district,Andhra Pradesh,India

With the progradation of Godavari delta in the east coast of India, increase in iron (Fe) concentrations in the groundwater was observed. High concentrations of Fe (>10 mg/l) were observed in khondalite and charnockite formations. A lower portion of the Godavari river basin, viz. East Godavari district was chosen for the study of the distribution of iron with special reference to the existing geological formations and the geomorphology of the area. The concentration of iron was observed to vary from below detection limit to 69 mg/l in the groundwater while it was less than 1 mg Fe/l in river and spring waters. The Fe of river water was reduced due to seawater mixing and the electrical conductivity (EC) was increased approximately to half of the seawater conductivity. Unlike the mixing of seawater at the surface, the same seawater mixing with groundwater yielded a water having similar order of EC with relatively high Fe. Fe was inversely related with nitrate in the groundwater. Fe was found to correlate considerably better with manganese in fluvial and coastal alluvium zones. The locations having higher Fe in delta are suspected to be related to palaeo channels. The association between Fe and Mn and their negative association with NO₃ may be due to the possible autotrophic denitrification that might have taken place in the subsurface.     

Geographical distribution of arsenic in sediments within the Rio Conchos Basin,Mexico

Arsenic (As) content of sediments from the Rio Conchos and Rio San Pedro in northern Mexico were measured to determine if this toxic metalloid had accumulated to unsafe levels to humans and aquatic life. The spatial distribution of As in each of the six clusters of river and arroyo sediments was analyzed to determine variations with respect to background levels and to infer about potential As sources and sinks. In the northern part of the study area, background concentrations varied little throughout the area and concentrations in river sediments were close to background levels. In the southern part, however, the content of As in arroyo sediment contained a wider range of values and anomalous concentrations. The latter could be traced in part to the presence of mine tailings. As concentrations were below the limit in all studied river stretches and thus do not pose an immediate threat to the river environment, but As content in reservoir sediments exceeded the guideline values. Reservoirs seem to act as a sink for As, warranting closer observation and monitoring.     

Redox zonation and oscillation in the hyporheic zone of the Ganges-Brahmaputra-Meghna Delta: Implications for the fate of groundwater arsenic during discharge

Riverbank sediment cores and pore waters, shallow well waters, seepage waters and river waters were collected along the Meghna Riverbank in Gazaria Upazila, Bangladesh in Jan. 2006 and Oct.–Nov. 2007 to investigate hydrogeochemical processes controlling the fate of groundwater As during discharge. Redox transition zones from suboxic (0–2 m depth) to reducing (2–5 m depth) then suboxic conditions (5–7 m depth) exist at sites with sandy surficial deposits, as evidenced by depth profiles of pore water (n = 7) and sediment (n = 11; diffuse reflectance, Fe(III)/Fe ratios and Fe(III) concentrations). The sediment As enrichment zone (up to ∼700 mg kg⁻¹) is associated with the suboxic zones mostly between 0 and 2 m depth and less frequently between 5 and 7 m depth. The As enriched zones consist of several 5–10 cm-thick dispersed layers and span a length of ∼5–15 m horizontally from the river shore. Depth profiles of riverbank pore water deployed along a 32 m transect perpendicular to the river shore show elevated levels of dissolved Fe (11.6 ± 11.7 mg L⁻¹) and As (118 ± 91 μg L⁻¹, mostly as arsenite) between 2 and 5 m depth, but lower concentrations between 0 and 2 m depth (0.13 ± 0.19 mg L⁻¹ Fe, 1 ± 1 μg L⁻¹ As) and between 5 and 6 m depth (1.14 ± 0.45 mg L⁻¹ Fe, 28 ± 17 μg L⁻¹ As). Because it would take more than a few hundred years of steady groundwater discharge (∼10 m yr⁻¹) to accumulate hundreds of mg kg⁻¹ of As in the riverbank sediment, it is concluded that groundwater As must have been naturally elevated prior to anthropogenic pumping of the aquifer since the 1970s. Not only does this lend unequivocal support to the argument that As occurrence in the Ganges-Brahmaputra-Meghna Delta groundwater is of geogenic origin, it also calls attention to the fate of this As enriched sediment as it may recycle As into the aquifer.     

Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province,Cambodia

Natural arsenic(As)contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue,particularly in South and Southeast Asia.A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region,however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry.The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn(hydr)oxides is an important control in As mobilization.Here,selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province,Cambodia,were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes(Fe,Mn and P)between groundwater and the associated solid aquifer matrix.In general,groundwater As is strongly affected by both pH and Eh throughout the study area.However,contrasting sorption behaviour is observed in two distinct sand-dominated(T-Sand)and clay dominated(T-Clay)transects,and plausibly attributed to differing dominant lithologies,biogeochemical and/or hydrogeological conditions.Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects,but to varying extents and in different ways.In T-Sand,which is typically highly reducing,correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter;in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur.Multiple linear regression analysis was conducted with groups categorised by transect and by Eh,and the output correlations support the contrasting sorption behaviours encountered in this study area.Irrespective of transect,however,the key biogeochemical processes which initially control As mobilization in such aquifers,may be "masked" by the re-setting of As concentrations through in-aquifer sorption/desorption processes.     

The influence of physicochemical parameters on bioavailability and bioaccessibility of heavy metals in sediments of the intertidal zone of Asaluyeh region,Persian Gulf,Iran

In this research, we have worked on the evaluation of heavy metal contamination in the sediments taken from the intertidal zone of Asaluyeh region using Modified Community Bureau of Reference sequential extraction method (mBCR), the simplified bioaccessibility extraction test (SBET), and calculated enrichment factor (EF). Also, potential influencing factors including sediment characteristics that may affect the heavy metals bioavailability and bioaccessibility were investigated. mBCR extraction analysis indicated that among the metals, Mn, Zn, V, Cu, and Cd exhibit relatively higher mobility, while Ti, Pb, Cr, and Ni occur mainly in the residual fractions. Based on the mean values, the bioaccessibility of metals decreased in the order: Mn (50.01%)>Cd (46.26%)>Zn (14.61%)>V (13.97%)>Pb (10.88%)>Ni (9.2%)>Ti (8.43%)>Cr (6.66%)>Cu (6.23%). The obtained results from the principal component analysis (PCA), EF and mBCR extraction showed that most anthropogenic-derived metals with higher solubility are more bioaccessible compared to those of natural origin. Multiple linear regression analysis demonstrated that the main physicochemical variables of the sediment influencing the bioaccessibility of metals include cation exchange capacity (CEC), pH, and particle size fraction.     

Occurrence,distribution and source of arsenic in deep groundwater wells in Maydavood area,southwestern Iran

Groundwater in some deep wells of Maydavood aquifer, southwestern Iran, contains relatively high concentrations of arsenic. Detailed hydrochemical analysis of these groundwaters (with ICP-OES instrument) showed that concentrations of iron, manganese, nickel, and vanadium are also high in them and concentrations of total arsenic in 81% of deep wells are greater than World Health Organization’s permissible value (10 ppb). XRF analysis of surrounding geological formations and aquifer sediments proposed that original source of arsenic in aquifer material can be attributed to minerals from Asmari Formation. It appears that a key mechanism for arsenic mobilizing to deep wells is microbial biodegradation of petroleum related organic matters (PROMs), which exist in aquifer sediments and originates from the bedrock of the aquifer (Gachsaran Formation). This process is followed by microbially mediated reductive dissolution of arsenic-bearing iron/manganese oxyhydroxides/oxides and further by nickel and vanadium mobilizing to groundwater. According to hydrogeochemical conditions and cluster analysis, water wells in Maydavood aquifer are divided to four subgroups: the wells with mildly reducing condition (subgroup I), moderately reducing condition (subgroup II), reducing condition (subgroup III), and high reducing condition (subgroup IV). Affected wells to arsenic are belonged to subgroups III and IV.     

Preliminary evidence of a link between surface soil properties and the arsenic content of shallow groundwater in Bangladesh

The extremely heterogeneous distribution of As in Bangladesh groundwater has hampered efforts to identify with certainty the mechanisms that lead to extensive mobilization of this metalloid in reducing aquifers. We show here on the basis of a high-resolution transect of soil and aquifer properties collected in Araihazar, Bangladesh, that revealing tractable associations between As concentrations in shallow (< 20 m) groundwater with other geological, hydrological, and geochemical features requires a lateral sampling resolution of 10–100 m. Variations in the electromagnetic conductivity of surface soils (5–40 mS/m) within a 500 m × 200 m area are documented with 560 EM31 measurements. The results are compared with a detailed section of groundwater As concentrations (5–150 μg/L) and other aquifer properties obtained with a simple sampling device, “the needle-sampler”, that builds on the local drilling technology. By invoking complementary observations obtained in the same area and in other regions of Bangladesh, we postulate that local groundwater recharge throughout permeable sandy soils plays a major role in regulating the As content of shallow aquifers by diluting the flux of As released from reducing sediments.