An integrated colloid fractionation approach applied to the characterisation of porewater uranium-humic interactions at a depleted uranium contaminated site

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV-visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa-0.2 microm) and small (3-30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa-0.2 microm) iron (Fe)-aluminium (Al) colloids in addition to an association with small (3-30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.     

Physicochemical characterisation of depleted uranium (DU) particles at a UK firing test range

Depleted uranium (DU) particles were isolated from soils at Eskmeals, UK, where DU munitions have been tested against hard targets and unfired DU buried in soils for corrosion studies. Using electron microscopy and X-ray analyses, three classes of particles were identified: (1) DU aerosols and fragments, typically 1-20 μm diameter, composed mainly of uranium as UO₂ and U₃O₈, (2) solidified molten particles, typically 200-500 μm diameter, composed of U, mixed with Fe from target materials and (3) deposits and coatings, often of metaschoepite on sand grains up to 500 μm diameter. The first two particle types are derived from firing impacts, the last from corrosion of buried uranium metal. Alpha and mass spectrometry allowed quantitative elemental and isotopic characterisation of DU-containing particulate environmental samples.     

The distribution of depleted uranium contamination in Colonie, NY, USA

Uranium oxide particles were dispersed into the environment from a factory in Colonie (NY, USA) by prevailing winds during the 1960s and '70s. Uranium concentrations and isotope ratios from bulk soil samples have been accurately measured using inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) without the need for analyte separation chemistry. The natural range of uranium concentrations in the Colonie soils has been estimated as 0.7-2.1 μg g^− 1, with a weighted geometric mean of 1.05 μg g^− 1; the contaminated soil samples comprise uranium up to 500 ± 40 μg g^− 1. A plot of ²³⁶U/²³⁸U against ²³⁵U/²³⁸U isotope ratios describes a mixing line between natural uranium and depleted uranium (DU) in bulk soil samples; scatter from this line can be accounted for by heterogeneity in the DU particulate. The end-member of DU compositions aggregated in these bulk samples comprises (2.05 ± 0.06) × 10^− 3235U/²³⁸U, (3.2 ± 0.1) × 10^− 5236U/²³⁸U, and (7.1 ± 0.3) × 10^− 6234U/²³⁸U. The analytical method is sensitive to as little as 50 ng g^− 1 DU mixed with the natural uranium occurring in these soils. The contamination footprint has been mapped northward from site, and at least one third of the uranium in a soil sample from the surface 5 cm, collected 5.1 km NNW of the site, is DU. The distribution of contamination within the surface soil horizon follows a trend of exponential decrease with depth, which can be approximated by a simple diffusion model. Bioturbation by earthworms can account for dispersal of contaminant from the soil surface, in the form of primary uranium oxide particulates, and uranyl species that are adsorbed to organic matter. Considering this distribution, the total mass of uranium contamination emitted from the factory is estimated to be c. 4.8 tonnes.     

Uranium facilitated transport by water-dispersible colloids in field and soil columns

The transport of uranium through a sandy podzolic soil has been investigated in the field and in column experiments. Field monitoring, numerous years after surface contamination by depleted uranium deposits, revealed a 20 cm deep uranium migration in soil. Uranium retention in soil is controlled by the < 50 µm mixed humic and clayey coatings in the first 40 cm i.e. in the E horizon. Column experiments of uranium transport under various conditions were run using isotopic spiking. After 100 pore volumes elution, 60% of the total input uranium is retained in the first 2 cm of the column. Retardation factor of uranium on E horizon material ranges from 1300 (column) to 3000 (batch). In parallel to this slow uranium migration, we experimentally observed a fast elution related to humic colloids of about 1-5% of the total-uranium input, transferred at the mean porewater velocity through the soil column. In order to understand the effect of rain events, ionic strength of the input solution was sharply changed. Humic colloids are retarded when ionic strength increases, while a major mobilization of humic colloids and colloid-borne uranium occurs as ionic strength decreases. Isotopic spiking shows that both ²³⁸U initially present in the soil column and ²³³U brought by input solution are desorbed. The mobilization process observed experimentally after a drop of ionic strength may account for a rapid uranium migration in the field after a rainfall event, and for the significant uranium concentrations found in deep soil horizons and in groundwater, 1 km downstream from the pollution source.     

Estimation of dissolved organic carbon (DOC) concentrations in nanoliter samples using UV spectroscopy

A simple analytical system has been developed and tested for estimating dissolved organic carbon (DOC) concentrations in nanoliter samples of sediment porewaters. The system consists of a loop injector that introduces 200 nL of sample directly into the capillary tubing connected to a scanning UV-VIS detector equipped with a 35-nanoliter capillary flowcell. Analysis of DOC by spectroscopic and high-temperature catalytic oxidation (HTCO) methods on the same samples showed a strong linear correlation between UV absorbance at 254 nm and HTCO-DOC concentration, allowing the DOC quantification. The simplicity and the robustness of the UV system allow DOC measurements in the field at a rate of 30 samples/h. We have used the UV system successfully for determining high-resolution distributions of porewater DOC concentrations in sediments at millimeter scales.     

ICP-MS法测定水中银的测量不确定度评定

按照中华人民共和国国家计量技术规范JJF 1059-1999测量不确定度评定与表示的要求,通过电感耦合等离子体—质谱法测定水中银的实验,展示了电感耦合等离子体—质谱法测定水中银实验中的不确定度评定的全过程,得出了水样中银的质量浓度,为同类水中银的检测提供了经验。     

Speciation of aluminium, arsenic and molybdenum in excessively limed lakes

The possible existence of the potentially toxic oxyanions of Al (Al(OH)₄⁻), As (HAsO₄²⁻), and Mo (MoO₄²⁻) was examined in excessively limed lakes. In-situ dialysis (MWCO 1 kDa) was performed in the surface and bottom waters of two excessively limed lakes (pH 7.1-7.7) and one acidic lake (pH ∼ 5.4). The dialysable metal concentrations were compared to the equilibrium distribution of species as calculated with the geochemical code Visual MINTEQ incorporating the CD-MUSIC and Stockholm Humic models for complexation onto colloidal ferrihydrite and dissolved organic matter. Arsenic and molybdenum in the excessively limed lakes were to a large extent present in the dialysable fraction (> 79% and > 92% respectively). They were calculated to exist as free or adsorbed oxyanions. Most of the Al was observed to reside in the colloidal fraction (51-82%). In agreement with this, model predictions indicated aluminium to be present mostly as colloids or bound to dissolved organic matter. Only a small fraction was modelled as Al(OH)₄⁻ ions. In most cases, modelled values were in agreement with the dialysis results. The free concentrations of the three oxyanions were mostly low compared to toxic levels.     

The problem of arsenic interference in the analysis of soils for cadmium by inductively coupled plasma-optical emission spectrometry

Cadmium determination in soils that contain arsenic may be subject to interference. When this problem is not appreciated spurious results may be accepted as correct. Spectrometric methods for the quantitative determination of cadmium in the presence of arsenic were compared. Data are given for each method to demonstrate the problem of arsenic interference. Cadmium determination by Flame Atomic Absorption Spectrometry was free from arsenic interference. Cadmium determination by Inductively Coupled Plasma Spectrometry and Graphite Furnace Flame Atomic Absorption Spectrometry were subject to interference at arsenic concentrations greater than 50 microg l-1 and 10 mg l-1, respectively. A strategy for cadmium determination in arsenic contaminated soils is suggested.     

Uranium contents and (235)U/(238)U atom ratios in soil and earthworms in western Kosovo after the 1999 war

The uranium content and (235)U/(238)U atom ratio were determined in soils and earthworms of an area of Kosovo (Djakovica garrison), heavily shelled with depleted uranium (DU) ammunition during the 1999 war. The aim of the study was to reconstruct the small-scale distribution of uranium and assess the influence of the DU added to the surface environment. The total uranium concentration and the (235)U/(238)U ratio of topsoils showed great variability and were inversely correlated. The highest uranium levels (up to 31.47 mg kg(-1)) and lowest (235)U/(238)U ratios (minimum 0.002147) were measured in topsoils collected inside, or very close to, the clusters of DU penetrator holes. Regarding the fractionation of uranium in the surface soils, the uranium concentrations in the soluble and exchangeable fractions increased as the total uranium concentration of the topsoils increased. High and rather uniform percentage contents of uranium (24-36%) were associated with the poorly crystalline iron oxide phases of soils. In the U-enriched soils the elevated levels of the element were probably due to the presence of very small, unevenly distributed oxidized DU particles. The total uranium concentration in earthworms was in the range 0.142-0.656 mg kg(-1), with the highest concentrations in Lumbricus terrestris. The juveniles of all three studied species seemed to accumulate uranium more than adults, probably due to age-related differences in metabolism. The (235)U/(238)U ratio in the earthworms was variable (0.005241-0.007266) and independent of both the total uranium contents in soils and the absolute uranium levels in the animals. Bioconcentration was greater at lower U concentrations in soil, probably due to an increasing rate of elimination of uranium by the earthworms as the soil contents of the element increase. The results of this study clearly indicate that DU was added to the soil of the study area. Nevertheless, the phenomenon was very limited spatially and the total uranium concentrations fell within the natural range of the element in soils. Moreover, the absolute uranium concentrations indicate that there was no contamination of the earthworm species studied.     

Freshwater DOM quantity and quality from a two-component model of UV absorbance

We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOC L⁻¹). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r² = 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC] was satisfactory for 9 of 11 independent data sets (181 of 213 individual samples).     

Colloidal organic matter from wastewater treatment plant effluents: Characterization and role in metal distribution

Colloidal organic matter from wastewater treatment plants was characterized and examined with respect to its role in metal distribution by using tangential flow ultrafiltration, liquid chromatography coupled with organic carbon and UV detectors, and an asymmetrical flow field-flow fractionation (AFlFFF) multidetection platform. Results revealed that a humic-like fraction of low aromaticity with an average molar mass ranging from 1600 to 2600 Da was the main colloidal component. High molar mass fractions (HMM), with molar mass ranges between 20 and 200 kDa, were present in lower proportions. Ag, Cd, Cu, Cr, Mn and Zn were found mainly in the dissolved phase (<0.45 μm) and their distribution between colloidal and truly dissolved fractions was strongly influenced by the distribution of dissolved organic carbon. AFlFFF coupled to ICP-MS showed that Ag, Cd, Cu, Cr, Mn and Zn associate to the low molar mass fraction of the colloidal pool, whereas Al, Fe and Pb were equally bound to low and high molar mass fractions.     

Effect of cow slurry amendment on atrazine dissipation and bacterial community structure in an agricultural Andisol

Atrazine is a commonly used herbicide for maize production in Chile, but it has recently been shown to be ineffective in soils that receive applications of cow slurries generated from the dairy industry. This effect may be caused either by the sorption of the pesticide to organic matter or more rapid degradation in slurry-amended soils. The objectives of this study were to evaluate the effects of cow slurry on atrazine dissipation, the formation of atrazine metabolites and the modification of bacterial community in Andisol. The cow slurry was applied at doses of 100,000-300,000 L ha^− 1. After 4 weeks, atrazine was applied to the slurry-amended soils at concentrations of 1-3 mg kg^− 1. The amounts of atrazine and its metabolites were determined by high performance liquid chromatography (HPLC). The soil microbial community was monitored by measurement of CO₂ evolution and changes in bacterial community using PCR-DGGE of 16S rRNA genes. The results show that cow slurry applications had no effect on atrazine dissipation, which had a half-life of 15-19 days. The atrazine metabolites were detected after 20 days and were significantly higher in soils amended with the slurry at both 20 and 40 days after application of the herbicide. Respiration rates were elevated after 10 days in all soils with atrazine addition. Both the atrazine and slurry amendments altered the bacterial community structures, indicated by the appearance of specific bands in the DGGE gels after 10 days. Cloning and sequencing of the 16S rRNA genes from the DGGE gels showed that the bands represented various genera of β-proteobacteria that appeared in response to atrazine. According to our results, further field studies are required to explain the lower effectiveness of atrazine in weed control. These studies may include the effect of dissolved organic carbon on the atrazine mobility.     

EXAFS speciation and phytoavailability of Pb in a contaminated soil amended with compost and gypsum

Due to unregulated uses of lead pellets for hunting purposes in Japan, soils and sediments in some river basins and wetlands have become highly contaminated with Pb. Deterioration of natural vegetation has occurred sporadically in these areas, and therefore revegetation is needed for ecological restoration. The objectives of the present study were to assess the effects of surface applications of compost and gypsum amendments on Pb availability to a watercress plant (Nasturtium officinale W.T. Aiton) and molecular-scale speciation of Pb in soil solid phases. The compost and gypsum amendments significantly decreased dissolved Pb and Sb in pore water. The concentration of Pb in aboveground plant tissues was 190 mg kg^− 1 in the control soil and was reduced to < 20 mg kg^− 1 in the compost and gypsum-amended soils. The concentration of Sb in plants grown in the control soil was 13 mg kg^− 1, whereas that in the soils receiving compost and gypsum decreased below detectable levels. Redox potential was higher in vegetated soils (ave. 349 mV) than in the unvegetated soils (ave. 99 mV) due to oxygen introduced by plant roots. Extended X-ray absorption fine structure (EXAFS) spectroscopy illustrated that Pb occurred as Pb sorbed on birnessite and/or ferrihydrite (Pb-Mn/Fe, ~ 60%) and Pb sorbed on organic matter (Pb-org, ~ 15%), and galena (PbS, ~ 10%) in the vegetated and unvegetated control soils. The compost amendment increased the proportion of Pb-org by 2-fold than in the control soils. The amended soils with plant growth decreased the proportion of Pb-Mn/Fe phases by half of that without plant growth. Galena and anglesite (PbSO₄) were not detected in compost-amended soils and even in gypsum-amended soils since a significant soil reduction to anoxic levels did not occur in the entire soil. The present study indicated that, under flooded conditions, surface applications of compost and gypsum amendments reduced plant Pb uptake from the Pb contaminated soil.     

Impact of dissolved organic matter on colloid transport in the vadose zone: deterministic approximation of transport deposition coefficients from polymeric coating characteristics

Although numerous studies have been conducted to discern colloid transport and stability processes, the mechanistic understanding of how dissolved organic matter (DOM) affects colloid fate in unsaturated soils (i.e., the vadose zone) remains unclear. This study aims to bridge the gap between the physicochemical responses of colloid complexes and porous media interfaces to solution chemistry, and the effect these changes have on colloid transport and fate. Measurements of adsorbed layer thickness, density, and charge of DOM-colloid complexes and transport experiments with tandem internal process visualization were conducted for key constituents of DOM, humic (HA) and fulvic acids (FA), at acidic, neutral and basic pH and two CaCl₂ concentrations. Polymeric characteristics reveal that, of the two tested DOM constituents, only HA electrosterically stabilizes colloids. This stabilization is highly dependent on solution pH which controls DOM polymer adsorption affinity, and on the presence of Ca⁺² which promotes charge neutralization and inter-particle bridging. Transport experiments indicate that HA improved colloid transport significantly, while FA only marginally affected transport despite having a large effect on particle charge. A transport model with deposition and pore-exclusion parameters fit experimental breakthrough curves well. Trends in deposition coefficients are correlated to the changes in colloid surface potential for bare colloids, but must include adsorbed layer thickness and density for sterically stabilized colloids. Additionally, internal process observations with bright field microscopy reveal that, under optimal conditions for retention, experiments with FA or no DOM promoted colloid retention at solid-water interfaces, while experiments with HA enhanced colloid retention at air-water interfaces, presumably due to partitioning of HA at the air-water interface and/or increased hydrophobic characteristics of HA-colloid complexes.     

Arsenic accumulation in irrigated agricultural soils in Northern Greece

The accumulation of arsenic in soils and food crops due to the use of arsenic contaminated groundwater for irrigation has created worldwide concern. In the Chalkidiki prefecture in Northern Greece, groundwater As reach levels above 1000 μg/L within the Nea Triglia geothermal area. While this groundwater is no longer used for drinking, it represents the sole source for irrigation.This paper provides a first assessment of the spatial extent of As accumulation and of As mobility during rainfall and irrigation periods. Arsenic content in sampled soils ranged from 20 to 513 mg/kg inside to 5-66 mg/kg outside the geothermal area. Around irrigation sprinklers, high As concentrations extended horizontally to distances of at least 1.5 m, and to 50 cm in depth. During simulated rain events in soil columns (pH = 5, 0 μg As/L), accumulated As was quite mobile, resulting in porewater As concentrations of 500-1500 μg/L and exposing plant roots to high As(V) concentrations. In experiments with irrigation water (pH = 7.5, 1500 μg As/L), As was strongly retained (50.5-99.5%) by the majority of the soils. Uncontaminated soils (< 30 mg As/kg) kept soil porewater As concentrations to below 50 μg/L. An estimated retardation factor R_f = 434 for weakly contaminated soil (< 100 mg/kg) indicates good ability to reduce As mobility. Highly contaminated soils (> 500 mg/kg) could not retain any of the added As. Invoked mechanisms affecting As mobility in those soils were adsorption on solid phases such as Fe/Mn-phases and As co-precipitation with Ca. Low As accumulation was found in collected olives (0.3-25 μg/kg in flesh and 0.3-5.6 μg/kg in pits). However, soil arsenic concentrations are frequently elevated to far above recommended levels and arsenic uptake in faster growing plants has to be assessed.     

Ozonation effect on natural organic matter adsorption and biodegradation - Application to a membrane bioreactor containing activated carbon for drinking water production

More stringent legislation on dissolved organic matter (DOM) urges the drinking water industry to improve in DOM removal, especially when applied to water with high dissolved organic carbon (DOC) contents and low turbidity. To improve conventional processes currently used in drinking water treatment plants (DWTPs), the performances of a hybrid membrane bioreactor containing fluidised activated carbon were investigated at the DWTP of Rennes. Preliminary results showed that the residual DOC was the major part of the non-biodegradable fraction. In order to increase the global efficiency, an upstream oxidation step was added to the process. Ozone was chosen to break large molecules and increase their biodegradability. The first step consisted of carrying out lab-scale experiments in order to optimise the necessary ozone dose by measuring the process yield, in terms of biodegradable dissolved organic carbon (BDOC). Secondly, activated carbon adsorption of the DOC present in ozonated water was quantified. The whole process was tested in a pilot unit under field conditions at the DWTP of Rennes (France). Lab-scale experiments confirmed that ozonation increases the BDOC fraction, reduces the aromaticity of the DOC and produces small size organic compounds. Adsorption tests led to the conclusion that activated carbon unexpectedly removes BDOC first. Finally, the pilot unit results revealed an additional BDOC removal (from 0.10 to 0.15 mg L⁻¹) of dissolved organic carbon from the raw water considered.     

Trace element distribution and 235U/238U ratios in Euphrates waters and in soils and tree barks of Dhi Qar province (southern Iraq)

To assess the quality of the environment in southern Iraq after the Gulf War II, a geochemical survey was carried out. The survey provided data on the chemistry of Euphrates waters, as well as the trace element contents, U and Pb isotopic composition, and PAH levels in soil and tree bark samples. The trace element concentrations and the ²³⁵U/²³⁸U ratio values in the Euphrates waters were within the usual natural range, except for the high contents of Sr due to a widespread presence of gypsum in soils of this area. The trace element contents in soils agreed with the common geochemistry of soils from floodplain sediments. Some exceptions were the high contents of Co, Cr and Ni, which had a natural origin related to ophiolitic outcrops in the upper sector of the Euphrates basin. The high concentrations of S and Sr were linked to the abundance of gypsum in soils. A marked geochemical homogeneity of soil samples was suggested by the similar distribution pattern of rare earth elements, while the ²³⁵U/²³⁸U ratio was also fairly homogeneous and within the natural range. The chemistry of the tree bark samples closely reflected that of the soils, with some notable exceptions. Unlike the soils, some tree bark samples had anomalous values of the ²³⁵U/²³⁸U ratio due to mixing of depleted uranium (DU) with the natural uranium pool. Moreover, the distribution of some trace elements (such as REEs, Th and Zr) and the isotopic composition of Pb in barks clearly differed from those of the nearby soils. The overall results suggested that significant external inputs occurred implying that once formed the DU-enriched particles could travel over long distances. The polycyclic aromatic hydrocarbon concentrations in tree bark samples showed that phenanthrene, fluoranthene and pyrene were the most abundant components, indicating an important role of automotive traffic.     

Potential impact of former Zn ore extraction activities on dissolved uranium distribution in the Riou-Mort watershed (France)

The industrial basin of Decazeville (Riou-Mort watershed, South-West France) is well known for its heavy metal pollution and its subsequent environmental effects on the Lot-Garonne River system. The source of this pollution is the Riou-Mort River, which drains smelting waste areas. A first survey after remediation works has revealed elevated dissolved uranium (U(D)) concentrations in the outlet of the Riou-Mort River. The objective of this research is to identify the origin of U(D) in the Riou-Mort watershed and to evaluate the impact of industrial activities on this element. Uranium was measured at 10 water sampling sites, located upstream and downstream the industrial basin, and in three smelting waste deposits. Uranium concentrations in the smelting waste deposits reach up to 14.4 mg kg(-1) and (234U/238U) activity ratios (AR) are near unity. Dissolved U concentrations in the Riou-Mort River and its main tributaries ranges over two orders of magnitude from 0.02 to 6.1 microg L(-1). The highest levels were measured in a site with no anthropogenic pollution, upstream from the industrial area. This observation suggests that U(D) is mainly linked to weathering; the elevated U concentrations originate from the naturally occurring radioactive materials (NORM) located in the Permian bedrock and no significant U pollution exists, at present, in the Riou-Mort watershed. This work demonstrates that spatial monitoring coupled with a long time-series are an essential prerequisite in assessment of spatiotemporal variations of U(D), prior to a diagnostic of pollution in a small watershed.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Arsenic retention and release in ombrotrophic peatlands

Organic matter can play an important role in the mobility and fate of As in the environment, but there is a lack of data on As biogeochemistry in ombrotrophic peatlands. The aim of this study was to investigate As retention and release in atmospherically contaminated ombrotrophic peat soils in the Peak District National Park (UK). Solid phase As concentrations in the peat soils exceed 25 mg kg^− 1. Solid phase As and Fe concentrations are closely correlated at sites where the peat is subjected to drying and oxic conditions. In a wetter zone of the bog, solid phase As and Fe distributions are decoupled, suggesting that As retention in these systems is not solely controlled by the presence of Fe oxides. Comparison of solid phase As and Pb distributions reveals that As has been subjected to post-depositional mobility in areas of water table fluctuation. Conversely, at permanently waterlogged locations As is immobile. Detailed stream water sampling reveals that As is released from the organic-rich uplands soils into the fluvial system. Dissolved As concentrations are highly variable, with values ranging from 0.20 to 7.28 μg l^− 1. Stream water As concentrations are elevated during late summer stormflow periods when there has been re-wetting of the peat after significant water table draw-down. Dissolved As is strongly correlated to dissolved organic carbon under stormflow and baseflow. The results of this study suggest that organic matter plays an important role in As dynamics in ombrotrophic peatlands, but further work is needed to identify the exact As binding and release mechanisms. Drying and re-wetting of ombrotrophic peat soils and associated changes in redox status has the potential to lead to increased As mobility. Further work is needed to provide information on how predicted climate change will influence As cycling at sites containing a legacy of atmospheric contamination.