Streamwater chemistry in three contrasting monolithologic Czech catchments

Hydrochemical patterns resulting from differing bedrock geochemistry were ascertained by concurrent streamwater sampling in three small catchments, each underlain by geochemically contrasting silicate rock types in the western Czech Republic, Central Europe in 2001–2010. The catchments are situated 5–7 km apart in the Slavkov Forest and are occupied by Norway spruce (Picea abies) plantations. They have similar altitude, area, topography, mean annual air temperature, and atmospheric deposition fluxes. The amount of base cations oxides (Ca + Mg + Na + K) is markedly different among the three studied rocks (leucogranite 8%, amphibolite 22%, serpentinite 36%). The leucogranite contains a very small amount of MgO, while the serpentinite contains extremely large amounts of MgO. The amphibolite contains an intermediate amount of MgO and elevated CaO. The Lysina, on leucogranite, exhibited very small concentrations of Mg (median 0.4 mg L⁻¹) in streamwater; Pluh?v Bor, on serpentinite, contained extremely high concentrations of streamwater Mg (18 mg L⁻¹). Streamwater in the Na Zeleném catchment, on amphibolite, contained an intermediate amount of Mg and an elevated Ca. Very low pH (4.2), negative alkalinity (−60 μeq L⁻¹) and high inorganic monomeric Al concentrations (0.3 mg L⁻¹) were found in the stream draining leucogranite. Serpentinite streamwater exhibited the highest pH (7.6), alkalinity (+940 μeq L⁻¹) and Ni concentrations (100 μg L⁻¹). Aquatic chemistry reflected the composition of the underlying rocks within the studied catchments. Contrasting streamwater compositions of the studied catchments were generated according to the MAGIC model simulations mainly by differences in chemical weathering rates of base cations (65 meq m⁻² a⁻¹ at Lysina, 198 meq m⁻² a⁻¹ at Na Zeleném, and 241 meq m⁻² a⁻¹ at Pluh?v Bor).     

Mobility of metals in nickel mine spoil materials

An understanding of the biogeochemical behaviour of metals in mine spoil materials is a prerequisite to rehabilitate Ni mining sites. The objective of this study was to characterize the fate of metals in different Ni ore spoil materials as influenced by hydrological conditions and fertilisation practices. In tropical ultramafic complexes, the different stages of lateritic weathering lead to two types of ores, and therefore, to two spoil types. They are mainly either a clay-rich saprolite, so-called “garnierite”, enriched in phyllosilicates, or a limonitic material, enriched in Fe oxides. Lysimeter columns were designed to monitor leaching waters through both spoil materials. The garnieritic spoil released higher concentrations of Mg (mean = 2.25 mg L⁻¹), Ni (0.39 mg L⁻¹) and Cr (1.19 mg L⁻¹) than the limonitic spoil (Mg = 0.5 mg L⁻¹; Ni = 0.03 mg L⁻¹ and Cr = 0.25 mg L⁻¹). Chromium was mainly in an anionic form in leaching solutions. As exchangeable pools of Cr(VI) in limonite (980 mg kg⁻¹ of KH₂PO₄-extractable Cr) are considerable its release in water may still occur in the case of a pH increase. In mixed spoil, metal concentrations were almost as low as in the limonitic one. The effect of mineral-N fertilisation was a strong release of cations (Ni, Mg) into the leachate. Phosphate amendment did not affect the soil solution composition under experimental conditions.     

Rhizosphere and flooding regime as key factors for the mobilisation of arsenic and potentially harmful metals in basic,mining-polluted salt marsh soils

The occurrence of mining areas in the vicinities of salt marshes may affect their ecological functions and facilitate the transfer of pollutants into the food chain. The mobilisation of metals in salt marsh soils is controlled by abiotic (pH, redox potential) and biotic (influence of rhizosphere) factors. The effect of the rhizosphere of two plant species (Sarcocornia fruticosa and Phragmites australis) and different flooding regimes on potentially harmful metals and As mobilisation from salt marsh soil polluted by mining activities were investigated (total concentrations: 536 mg kg⁻¹ As, 37 mg kg⁻¹ Cd, 6746 mg kg⁻¹ Pb, 15,320 mg kg⁻¹ Zn). The results show that the changes in redox conditions (from 300 mV to −100 mV) and pH after flooding and rewetting periods may mobilise the contaminant elements into soil solution (e.g., 100 μg L⁻¹ Cd, 30 μg L⁻¹ Pb, 7 mg L⁻¹ Zn), where they are available for plants or may be leached from the soil. Drying periods generated peaks of concentrations in the soil solution (up to 120 μg L⁻¹ Cd and 50 μg L⁻¹ Pb). The risk assessment of As and metal-polluted salt marshes should take into account flood dynamics in order to prevent metal(loid) mobilisation.     

The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite

The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 × 10⁻⁵ M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II)_EQBM) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II)_EQBM level of 10⁻⁷ M without Fe(II) competition, the reactive transport calculations using a constant K_d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II)_EQBM (10⁻⁵ M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K_d approach.When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the two competing sorbates and their respective concentrations. At background Fe(II) concentrations of 5.3 × 10⁻⁵ M, and a Ni(II)_EQBM level of 10⁻⁷ M, the Ni(II) breakthrough time was ∼15 times earlier than in the absence of competition. At such Fe(II) concentrations the Ni(II) breakthrough curves at all source concentrations less than 3.5 × 10⁻⁵ M (fixed by the NiCO_3,S solubility limit) are the same i.e. Ni(II) exhibits linear (low) sorption.Competitive sorption effects can have significant influences on the transport of radionuclides through compacted bentonite i.e. reduce the migration rates. Since, for the case considered here, the Fe(II) concentration in the near field of a high-level radioactive waste repository may change in time and space, the transport of bivalent transition metal radionuclides can only be properly modelled using a multi-species reactive transport code which includes a sorption model.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH₄) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH₄ was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH₄ with depth (5500 μmol L⁻¹ DIC, 500 μmol L⁻¹ CH₄). Highest DIC and CH₄ production rates occurred close to the water table (decomposition constant k_d ∼ 10⁻³-10⁻⁴ a⁻¹) or in some distinct zones at depth (k_d ∼ 10⁻⁴ a⁻¹). Deeper into the peat, decomposition proceeded very slowly at about k_d = 10⁻⁷ a⁻¹. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol⁻¹ CH₄). The methanogenic precursor acetate also accumulated (150 μmol L⁻¹). In line with these findings, CH₄ was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol⁻¹ CH₄. This was indicated by an isotopic fractionation α_CO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol⁻¹ substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH₄ may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.     

Anion exclusion effects in compacted bentonites: Towards a better understanding of anion diffusion

Diffusion of ³⁶Cl⁻ in compacted bentonite was studied using through-diffusion, out-diffusion and profile analysis techniques. Both the bulk dry density of the bentonite and the composition of the external solution were varied. Increasing the bulk dry density of the bentonite resulted in a decrease of both the effective diffusion coefficient and the Cl-accessible porosity. Increasing the ionic strength of the external solutions resulted in an increase of both the effective diffusion coefficient and the Cl-accessible porosity. This can be explained by anion exclusion effects (Donnan exclusion). At high ionic strength values (I ? 1 M NaCl) the Cl-accessible porosity approaches the interparticle porosity. This interparticle porosity is the difference between the total and interlayer porosity of the bentonite. The interlayer porosity was found to depend on the degree of compaction. Up to a bulk dry density of 1300 kg m⁻³ the interlayer is built up of 3 water layers. Between 1300 and 1800 kg m⁻³ the interlayer water is reduced from 3 to 2 layers of water. Above 1800 kg m⁻³ evidence for a further decrease to 1 layer of water was found. These findings are in agreement with X-ray data found in the literature showing a decrease of the basal spacing of montmorillonite (the main clay mineral in bentonite) with increasing degree of compaction. The relationship between the effective diffusion coefficient of Cl⁻ and the diffusion-accessible porosity can be described by an empirical relationship analogous to Archie’s law. To predict the effective diffusion coefficient of Cl⁻ in compacted bentonite, the diffusion coefficient of Cl⁻ in water, the bulk dry density and the ionic strength of the pore water have to be known.     

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L⁻¹ within the Sacramento River to 39.9 mg L⁻¹ at the outfall from an island drain (median 3.0 mg L⁻¹), while lignin concentrations ranged from 3.0 μg L⁻¹ within the Sacramento River to 111 μg L⁻¹ at the outfall from an island drain (median 11.6 μg L⁻¹). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC)⁻¹ at an island drain to 0.84 mg (100 mg OC)⁻¹ for a wetland (median 0.36 mg (100 mg OC)⁻¹), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.     

The biogeochemistry of atmospherically derived Pb in the boreal forest of Sweden

The use of stable Pb isotopes for tracing Pb contamination within the environment has strongly increased our understanding of the fate of airborne Pb contaminants within the boreal forest. This paper presents new stable Pb isotope (²⁰⁶Pb/²⁰⁷Pb ratio) measurements of solid soil samples, stream water (from a mire outlet and a stream draining a forest dominated catchment) and components of Picea abies (roots, needles and stemwood), and synthesizes some of the authors’ recent findings regarding the biogeochemistry of Pb within the boreal forest. The data clearly indicate that the biogeochemical cycling of Pb in the present-day boreal forest ecosystem is dominated by pollution Pb from atmospheric deposition. The ²⁰⁶Pb/²⁰⁷Pb ratios of the mor layer (O-horizon), forest plants and stream water (mainly between 1.14 and 1.20) are similar to atmospheric Pb pollution (1.14–1.19), while the local geogenic Pb of the mineral soil (C-horizon) has high ratios (>1.30). Roots and basal stemwood of the analyzed forest trees have higher ²⁰⁶Pb/²⁰⁷Pb ratios (1.15–1.30) than needles and apical stemwood (1.14–1.18), which indicate that the latter components are more dominated by pollution derived Pb. The low ²⁰⁶Pb/²⁰⁷Pb ratios of the mor layer suggest that the upward transport of Pb as a result of plant uptake is small (<0.04 mg m⁻² a⁻¹) in comparison to atmospheric inputs (∼0.5 mg m⁻² a⁻¹) and annual losses with percolating soil-water (∼2 mg m⁻² a⁻¹); consequently, the Pb levels in the mor layer are now decreasing while the pool of Pb in the mineral soil is increasing. Streams draining mires appear more strongly affected by pollution Pb than streams from forested catchments, as indicated by Pb concentrations about three times higher and lower ²⁰⁶Pb/²⁰⁷Pb ratios (1.16 ± 0.01 in comparison to 1.18 ± 0.02). To what extent stream water Pb levels will respond to the build-up of Pb in deeper mineral soil layers remains uncertain.     

Methane microseepage from different sectors of the Yakela condensed gas field in Tarim Basin,Xinjiang, China

Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH₄ source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH₄ fluxes are pervasive in all sectors and therefore, only part of the CH₄ migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH₄ fluxes, up to ∼14 mg m⁻² d⁻¹ (mean of 7.55 mg m⁻² d⁻¹) with higher spatial variability (standard deviation, σ: 2.58 mg m⁻² d⁻¹), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m⁻² d⁻¹) and the external area (mean of 1.55 mg m⁻² d⁻¹), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m⁻² d⁻¹). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of ¹³C, from δ¹³C₁ of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH₄ exhaled from the Yakela field is in the order of 10² tonnes a⁻¹.     

A surface structural model for ferrihydrite I: Sites related to primary charge, molar mass, and mass density

A multisite surface complexation (MUSIC) model for ferrihydrite (Fh) has been developed. The surface structure and composition of Fh nanoparticles are described in relation to ion binding and surface charge development. The site densities of the various reactive surface groups, the molar mass, the mass density, the specific surface area, and the particle size are quantified. As derived theoretically, molecular mass and mass density of nanoparticles will depend on the types of surface groups and the corresponding site densities and will vary with particle size and surface area because of a relatively large contribution of the surface groups in comparison to the mineral core of nanoparticles. The nano-sized (∼2.6 nm) particles of freshly prepared 2-line Fh as a whole have an increased molar mass of M ∼ 101 ± 2 g/mol Fe, a reduced mass density of ∼3.5 ± 0.1 g/cm³, both relatively to the mineral core. The specific surface area is ∼650 m²/g. Six-line Fh (5-6 nm) has a molar mass of M ∼ 94 ± 2 g/mol, a mass density of ∼3.9 ± 0.1 g/cm³, and a surface area of ∼280 ± 30 m²/g. Data analysis shows that the mineral core of Fh has an average chemical composition very close to FeOOH with M ∼ 89 g/mol. The mineral core has a mass density around ∼4.15 ± 0.1 g/cm³, which is between that of feroxyhyte, goethite, and lepidocrocite. These results can be used to constrain structural models for Fh. Singly-coordinated surface groups dominate the surface of ferrihydrite (∼6.0 ± 0.5 nm⁻²). These groups can be present in two structural configurations. In pairs, the groups either form the edge of a single Fe-octahedron (∼2.5 nm⁻²) or are present at a single corner (∼3.5 nm⁻²) of two adjacent Fe octahedra. These configurations can form bidentate surface complexes by edge- and double-corner sharing, respectively, and may therefore respond differently to the binding of ions such as uranyl, carbonate, arsenite, phosphate, and others. The relatively low PZC of ferrihydrite can be rationalized based on the estimated proton affinity constant for singly-coordinated surface groups. Nanoparticles have an enhanced surface charge. The charging behavior of Fh nanoparticles can be described satisfactory using the capacitance of a spherical Stern layer condenser in combination with a diffuse double layer for flat plates.     

Effects of dry density and exchangeable cations on the diffusion process of sodium ions in compacted montmorillonite

As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na⁺ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na⁺ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na⁺ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol^− 1 as the dry density increased from 0.9 to 1.0 Mg m^− 3, whereas it increased to 24.7 kJ mol^− 1 as the dry density increased to 1.8 Mg m^− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol^− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m^− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m^− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.     

Activation energy for diffusion of helium in water-saturated, compacted Na-montmorillonite

It is important to clarify the migration behavior of hydrogen gas dissolved in water-saturated, compacted bentonite, which is a promising material for geologic disposal of high-level waste and TRU waste disposal. The diffusion coefficients of helium, which can be detected under extremely low background conditions, in water-saturated, compacted Na-montmorillonite were determined as a function of temperature by a transient diffusion method. The activation energies for diffusion of helium were then obtained. The activation energies were from 6.9 ± 4.8 to 19 ± 2.8 kJ mol^− 1 and were regarded to be independent of dry density. The activation energies of helium in water-saturated Na-montmorillonite were roughly equal to those in bulk water, 14.9 kJ mol^− 1, and in ice, from 11 to 13 kJ mol^− 1. It is possible that helium diffuses not only in pore water but also in interlayer water.     

Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Monomethylmercury sources in a tropical artificial reservoir

The distribution and speciation of mercury (Hg) in the water column, the inputs (wet deposition and tributaries) and the outputs (atmospheric evasion and outlet) of an artificial partially anoxic tropical lake (Petit-Saut reservoir, French Guiana) were investigated on a seasonal basis in order to appraise the cycling and transformations of this metal. The total mercury (HgT) concentrations in the oxygenated epilimnetic waters averaged 5 ± 3 pmol L⁻¹ in the unfiltered samples (HgT_UNF) and 4 ± 2 pmol L⁻¹ in the dissolved (HgT_D) phase (<0.45 μm). On average, the monomethylmercury (MMHg) constituted 8%, 40% and 18% of the HgT in the dissolved phase, the particulate suspended matter and in the unfiltered samples, respectively. Covariant elevated concentrations of particulate MMHg and chlorophyll a in the epilimnion suggest that phytoplankton is an active component for the MMHg transfer in the lake. In the anoxic hypolimnion the HgT_UNF averages 13 ± 6 pmol L⁻¹ and the HgT_D 8 ± 4 pmol L⁻¹. The averages of MMHg_P and MMHg_D in hypolimnetic waters were two and three times the corresponding values of the epilimnion, 170 ± 90 pmol g⁻¹ and 0.9 ± 0.5 pmol L⁻¹, respectively. In the long dry and wet seasons, at the flooded forest and upstream dam sampling stations, the vertical profiles of MMHg_D concentrations accounted for two distinct maxima: one just below the oxycline and the other near the benthic interface. Direct wet atmospheric deposition accounted for 14 moles yr⁻¹ HgT_UNF, with 0.7 moles yr⁻¹ as MMHg_UNF, while circa 76 moles yr⁻¹ of HgT_UNF, with 4.7 moles yr⁻¹ as MMHg_UNF, coming from tributaries. Circa 78 moles (∼17% as MMHg) are annually exported through the dam, while 23 moles yr⁻¹ of Hg⁰ evolve in the atmosphere. A mass balance calculation suggests that the endogenic production of MMHg_UNF attained 8.1 moles yr⁻¹, corresponding to a methylation rate of 0.06% d⁻¹. As a result, the Petit-Saut reservoir is a large man-made reactor that has extensively altered mercury speciation in favor of methylated species.     

Aeration to degas CO2, increase pH,and increase iron oxidation rates for efficient treatment of net alkaline mine drainage

Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering “hybrid” systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m⁻² day⁻¹ and Fe loading from field data, 3.6 × 10³ and 3.0 × 10⁴ m² oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO₂, increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Both net-alkaline discharges were suboxic with a pH of ≈5.7, Fe(II) concentration of ≈16 mg L⁻¹, and low Mn and Al concentrations. Flow rates were ≈4000 L min⁻¹ at Site 21 and 15,000 L min⁻¹ at Packer 5. Three-h aeration experiments with flow rates scaled to a 14-L reactor resulted in pH increases from 5.7 to greater than 7, temperature increases from 12 to 22 °C, dissolved O₂ increases to saturation with respect to the atmosphere, and Fe(II) concentration decreases from 16 to <0.05 mg L⁻¹. A 17,000-L pilot-scale reactor at Site 21 produced similar results although aeration was not as complete as in the smaller reactor. Two non-aerated experiments at Site 21 with 13 and 25-h run times resulted in pH changes of ?0.2 and Fe(II) concentration decreases of less than 3 mg L⁻¹.     

Particulate-associated potentially harmful elements in urban road dusts in Xi’an,China

Sixty five urban road dust samples were collected from different land use areas of ∼240 km² in Xi’an, China. The concentrations of Ag, As, Cr, Cu, Hg, Pb, Sb and Zn were determined to investigate potentially harmful element (PHE) contamination, distribution and possible sources. In addition, the concentrations in different size fractions were measured to assess their potential impact on human health. The highest concentrations were found in the fraction with particle diameters between 80 μm and 101 μm, the finest particles (<63 μm) were not the most important carriers for Ag, As, Cd, Cr, Cu, Hg, Pb and Zn. The percentages of these elements in particles with diameters less than 63 μm (PM₆₃) and less than 101 μm (PM₁₀₁) were in the range of 7–15%, and 30–55%, respectively. Three main factors influencing element distributions have been identified: (a) industrial activities; (b) prior agricultural land use; and (c) other activities commonly found in urban areas, such as traffic, coal combustion, waste dumping, and building construction/renovation. The highest concentrations were found in industrial areas for As (20 mg kg⁻¹), Cr (853 mg kg⁻¹), Cu (1071 mg kg⁻¹), Pb (3060 mg kg⁻¹) and Zn (2112 mg kg⁻¹), and in previous agricultural areas for Ag and Hg, indicating significant contributions from industrial activities and prior agricultural activities.     

Two-dimensional pH distributions and dynamics in bioturbated marine sediments

The seafloor is the site of intense biogeochemical and mineral dissolution-precipitation reactions which generate strong gradients in pH near the sediment-overlying water interface. These gradients are usually measured in one-dimension vertically with depth. Two-dimensional pH distributions in marine sediments were examined at high resolution (65 × 65 μm pixel) and analytical precision over areas of ∼150 to 225 cm² using a newly developed pH planar fluorosensor. Dramatic three-dimensional gradients, complex heterogeneity, and dynamic changes of pH occur in the surficial zone of deposits inhabited by macrofauna. pH can vary by ±2 units horizontally as well as vertically over millimeter scales. pH minima zones often form in association with redoxclines within a few millimeters of inner burrow walls, and become more pronounced with time if burrows remain stable and irrigated for extended periods. Microenvironmental pH minima also form locally around decaying biomass and relict burrow tracks, and dissipate with time (∼5 d). H⁺ concentrations and fluxes in sandy mud show complex acid-base reaction distributions with net H⁺ fluxes around burrows up to ∼12 nmol cm⁻² d⁻¹ and maximum net reaction rates varying between −90 (consumption) to 120 (production) μM d⁻¹ (∼90 nmol cm⁻¹ d⁻¹ burrow length). Acid producing zones that surround irrigated burrows are largely balanced by acid titration zones along inner burrow walls and outer radial boundaries. The geometry and scaling of pH microenvironments are functions of diagenetic reaction rates and three-dimensional transport patterns determined by sediment properties, such as diffusive tortuosity, and by benthic community characteristics such as the abundance, mobility, and size of infauna. Previously, undocumented biogeochemical phenomena such as low pH regions associated with in-filled relict biogenic structures and burrowing tracks are readily demonstrated by two-dimensional and time-dependent images of pH and sedimentary structure.