Solubilization of particulate Cu by different solutions, mimicking digestive fluids of deposit-feeders, was quantified in stable isotope ⁶⁵Cu-spiked sediments (with 3 days-2 months Cu-sediment contact time or aging). Copper solubilization generally decreased with prolonged aging. However, such decrease became less evident after 1 month and equilibrium of Cu in sediments could be reached after 2 months. Aging effects on Cu solubilization can be explained by the changes in Cu geochemical fractionation with aging: Cu generally transferred from more mobile phases (carbonate and Fe–Mn associated) to more refractory phases (organic associated and residual phase). Besides Cu geochemical fractionation, digestive fluid composition and different Cu solubilization pathways involved, as well as sedimentary organic content, could all affect the digestive solubilization of Cu and its change with aging. Our results emphasize the necessity of considering Cu aging in laboratory sediment toxicity experiments, and in risk assessment of Cu contaminated sediments.

Molecular weight (MW) is a fundamental property of dissolved organic matter (DOM), which potentially affects the binding behavior between DOM and metals. Here, a combined approach of ultrafiltration fractionation, fluorescence excitation-emission matrix quenching and parallel factor analysis (PARAFAC) was employed to elucidate fluorescent characteristics and metal binding properties of individual MW fractions of DOM in landfill leachate. Four humic-like and two protein-like components were identified by PARAFAC. Among them, a fulvic acid-like component was found to be responsible for Cd(II) binding while Cu(II) inclined to complex with humic-like components rather than protein-like ones. Apart from that, MW was found to exert less influence on metal binding than that of specific metals or components. Key components distributed within various fractions of DOM were the main influence on the impact of MW on metal binding.

Understanding the complex biotic and abiotic interactions invoked by the rice root system in oxygen-depleted soil is an important step in screening genotypes for low toxic metal or metalloid accumulation. A hydroponic and a rhizobox experiment have been conducted to explore the effects of varying root oxygen release on chemical changes, As fractionation in rhizosphere soil and Fe plaque formation, As uptake and tolerance by different rice genotypes. The results showed that rice genotypes with higher rates of radial oxygen loss (ROL) and at the bolting stage, tended to have greater effects on rhizosphere Eh, pH, Fe³⁺/Fe²⁺ quotients, As fractionation and mobility and also on Fe plaque formation compared to those with lower ROL and at the tillering stage. Genotypes with higher ROL have a strong ability to reduce As accumulation in shoots and increase As tolerance by reducing As mobilization in the rhizosphere and by limiting As translocation.

Aided phytostabilization using a combination of compost, zerovalent iron grit and coal fly ash (CZA) amendments and revegetation effectively promoted the biological recovery of mining spoils generated at a gold mine in Portugal. Selective dissolution of spoil samples in combination with solid phase characterization using microbeam X-ray absorption near edge structure (μXANES) spectroscopy and microbeam X-ray fluorescence (μXRF) mapping were used to assess As associations in spoils ten years after CZA treatment. The results show that As preferentially associates with poorly crystalline Fe-oxyhydroxides as opposed to crystalline Fe-(oxyhydr)oxide phases. The crystalline Fe(III)-phases dominated in the treated spoil and exceeded those of the untreated spoil three-fold, but only 2.6–6.8% of total As was associated with this fraction. Correlation maps of As:Fe reveal that As in the CZA-treated spoils is primarily contained in surface coatings as precipitates and sorbates. Arsenic binding with poorly crystalline Fe-oxyhydroxides did not inhibit As uptake by plants.

Total metal concentrations (Cr, Ni, Cu, Zn, and Pb), acid volatile sulfide and simultaneously extracted metals (AVS–SEM), and heavy metal fractionation were used to assess the heavy metals contamination status and ecological risk in the sediments of the Pearl River Estuary (PRE) and adjacent shelf. Elevated concentrations at estuarine sites and lower concentrations at adjacent shelf sites are observed, especially for Cu and Zn. Within the PRE, the concentration of heavy metals in the western shore was mostly higher than that in the middle shore. The metals from anthropogenic sources mainly occur in the labile fraction and may be taken up by organisms as the environmental parameters change. A combination of total metal concentrations, metal contamination index and sequential extraction analysis is necessary to get the comprehensive information on the baseline, anthropogenic discharge and bioavailability of heavy metals.

Surface sediments from intertidal Bohai Bay were sampled for the geochemical and environmental assessment of six trace metals (Cd, Cr, Cu, Ni, Pb and Zn). Results indicate that sediment grain size plays an important role in controlling the distribution and fractionation of them. Metal concentrations in clayey silt sediments are all clearly higher than in sand and silty sand ones. Cd and Pb in clayey silt sediments are more mobile than in sand and silty sand ones. Two sediment quality guidelines and two geochemical normalization methods (index of geoaccumulation and enrichment factor) were used to judge the potential risk and accumulation of metals. According to the mean probable effects level quotient, the combination of studied metals may have a 21% probability of being toxic. The sediments with high fraction of clay and silt have been contaminated by trace metals to various degrees, among which Cr contributes the most to contamination.

Rare earth elements (REE) were analyzed in surface sediments from the Guadiana Estuary (SW Iberian Pyrite Belt). NASC (North American Shale Composite) normalized REE patterns show clearly convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE, indicating acid-mixing processes between fluvial waters affected by acid mine drainage (AMD) and seawater. However, REE distributions in the mouth (closer to the coastal area) show slightly LREE-enriched and flat patterns, indicating saline-mixing processes typical of the coastal zone. NASC-normalized ratios (La/Gd and La/Yb) do not discriminate between both mixing processes in the estuary. Instead, a new parameter (EMREE) has been applied to measure the curvature in the MREE segment. The values of EMREE>0 are indicative of acid signatures and their spatial distribution reveal the existence of two decantation zones from flocculation processes related to drought periods and flood events. Studying REE fractionation through the EMREE may serve as a good proxy for AMD-pollution in estuarine environments in relation to the traditional methods.

Studies were conducted to examine the effect of flue gas carbon dioxide (CO₂) on solubility and availability of different metals in fly ash of Powder River Basin (PRB) coal, Wyoming, USA. Initial fly ash (control) was alkaline and contains large amounts of water-soluble and exchangeable metals. Reaction of flue gas CO₂ with alkaline fly ash resulted in the formation of carbonates which minimized the solubility of metals. Results for metal fractionation studies also supported this fact. The present study also suggested that most of the water-soluble and exchangeable metals present in the control (untreated) fly ash samples decreased in the flue gas-treated samples. This may be due to the transfer of the above two forms to more resistant forms like carbonate bound (CBD), oxide bound (OXD), and residual (RS). Geochemical modeling (Visual MINTEQ) of water solubility data suggested that the saturation index (SI) values of dolomite (CaMg(CO₃)₂) and calcite (CaCO₃) were oversaturated, which has potential to mineralize atmospheric CO₂ and thereby reduce leaching of toxic metals from fly ash. Results from this study also showed that the reaction of flue gas CO₂ with alkaline fly ash not only control the solubility of toxic metals but also form carbonate minerals which have the potential to fix CO₂.

In this study, we test whether the δ¹³C and δ¹⁵N in a peat profile are, respectively, linked to the recent dilution of atmospheric δ¹³CO₂ caused by increased fossil fuel combustion and changes in atmospheric δ¹⁵N deposition. We analysed bulk peat and Sphagnum fuscum branch C and N concentrations and bulk peat, S. fuscum branch and Andromeda polifolia leaf δ¹³C and δ¹⁵N from a 30-cm hummock-like peat profile from an Aapa mire in northern Finland. Statistically significant correlations were found between the dilution of atmospheric δ¹³CO₂ and bulk peat δ¹³C, as well as between historically increasing wet N deposition and bulk peat δ¹⁵N. However, these correlations may be affected by early stage kinetic fractionation during decomposition and possibly other processes. We conclude that bulk peat stable carbon and nitrogen isotope ratios may reflect the dilution of atmospheric δ¹³CO₂ and the changes in δ¹⁵N deposition, but probably also reflect the effects of early stage kinetic fractionation during diagenesis. This needs to be taken into account when interpreting palaeodata. There is a need for further studies of δ¹⁵N profiles in sufficiently old dated cores from sites with different rates of decomposition: These would facilitate more reliable separation of depositional δ¹⁵N from patterns caused by other processes.

Biocovers are an alternative for mitigating fugitive and residual emissions of methane from landfills. In this study, we evaluated the performance of two experimental passive methane oxidation biocovers (PMOBs) constructed within the existing final cover of the St-Nicéphore landfill (Quebec, Canada). The biocovers were fed in a controlled manner with raw biogas and surface fluxes were obtained using static chambers. This enabled calculating mass balances of CH₄ and oxidation efficiencies (f ₒ_MB). Most of the time, f ₒ_MB ≥ 92 % were obtained for loadings as high as 818 g CH₄ m⁻² day⁻¹ (PMOB-2) and 290 g CH₄ m⁻² day⁻¹ (PMOB-3B). The lowest efficiencies (f ₒ_MB = 45.5 % and 34.0 %, respectively) were obtained during cold days (air temperature ~0 °C). Efficiencies were also calculated using stable isotopes (f ₒ_SI); the highest f ₒ_SI were 66.4 % for PMOB-2 and 87.3 % for PMOB-3B; whereas the lowest were 18.8 % and 23.1 %, respectively. However, f ₒ_SI values reflect CH₄ oxidation up to a depth of 0.10 m, which may partly explain the difference in regards to mass balance-derived efficiencies. Indeed, it is expected that a significant fraction of the total CH₄ oxidation occurs within the zone near the surface, where there is greater O₂ availability. The influence of the values of fractionation factors α ₒₓ and α ₜᵣₐₙₛ were also evaluated in this paper.