An As-contaminated perched aquifer under an urban area affected by mining was studied over a year to determine the contamination source species and the mechanism of As mobilization. Results show that the dissolution of calcium arsenates in residues disposed on an inactive smelter has caused high levels of As pollution in the adjoining downgradient 6-km perched aquifer, reaching up to 158 mg/L of dissolved As, and releasing a total of ca. 7.5 tons of As in a year. Furthermore, free calcium ion availability was found to control As mobility in the aquifer through the diagenetic precipitation of calcium arsenates (Ca5H2(AsO4)4·cH2O) preventing further mobilization of As. Results shown here represent a model for understanding a highly underreported mechanism of retention of arsenate species likely to dominate in calcium-rich environments, such as those in calcareous sediments and soils, where the commonly reported mechanism of adsorption to iron(III) oxyhydroxides is not the dominant process.

Arsenic contamination of floodplain soils is extensive and additional fresh arsenic inputs to the pedosphere from human activities are ongoing.We investigate the cumulative effects of repetitive soil redox cycles, which occur naturally during flooding and draining, on a calcareous fluvisol, the native microbial community and arsenic mobility following a simulated contamination event.We show through bioreactor experiments, spectroscopic techniques and modelling that repetitive redox cycling can decrease arsenic mobility during reducing conditions by up to 45%. Phylogenetic and functional analyses of the microbial community indicate that iron cycling is a key driver of observed changes to solution chemistry. We discuss probable mechanisms responsible for the arsenic immobilisation observed in-situ. The proposed mechanisms include, decreased heterotrophic iron reduction due to the depletion of labile particulate organic matter (POM), increases to the proportion of co-precipitated vs. aqueous or sorbed arsenic with α-FeOOH/Fe(OH)3 and potential precipitation of amorphous ferric arsenate.

The performance of Cytisus striatus in association with different microbial inoculant treatments on the dissipation of the insecticide hexachlorocyclohexane (HCH) was studied. Two soils with different organic matter (A and B soil) content were spiked with 0 or 65 mg HCH kg−1. Plants were either not inoculated (NI), or inoculated with the endophyte Rhodococcus erythropolis ET54b and the HCH-degrader Sphingomonas sp. D4 separately or in combination (ET, D4 and ETD4). Unplanted pots were also established. HCH phytotoxicity was more pronounced in the B soil. Soil HCH concentrations in unplanted pots were similar to initial concentrations, whereas concentrations were reduced after plant growth: by 20% and 8% in A and B soil, respectively. Microbial inoculants also modified HCH dissipation, although effects were soil-dependent. Inoculation with the combination of strains (ETD4) led to a significant enhancement in HCH dissipation: up to 53% in the A soil and 43% in the B soil.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg−1 to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.

A field investigation was carried out to determine PBDE concentrations over a one-year period in agricultural soils onto which 80 tonnes biosolids/hectare had been applied. The PBDE concentrations increased from 80 to 300 pg/g dry weight basis to 300 × 103–600 × 103 pg/g dw due to biosolids application, and PBDEs migrated downwards to depths of at least 0.85 m. Concentrations decreased non-uniformly with depth. PBDE levels decreased exponentially in the topmost biosolids-amended soils layer, while increasing in the next underlying soil layer over the one-year period. The rate of decrease of total PBDE mass in the top 0.00–0.05 m layer was almost two orders of magnitude greater than the rates of increase in total PBDE mass in the lower layers, indicating that effects such as photodegradation and/or volatilization likely were to have been significant in the surface layer.

Isosteric heats (ΔH) of sorption/desorption of phenanthrene were determined for carbonaceous materials (Pahokee peat, lignite, and high-volatile bituminous coal) and two soils based on reported equilibrium sorption/desorption isotherms at four different temperatures (4, 20, 46 and 77 °C). In addition, ΔH for desorption of native phenanthrene was determined to elucidate the “aging” effect by equilibrating samples with water at six temperatures (20, 40, 53, 61, 73, and 86 °C). Isosteric heats decreased with increasing solute concentration and were in a range of 19–35 kJ mol−1. Values higher than the heat of octanol–water phase transfer for phenanthrene (19 kJ mol−1) imply that both partitioning and adsorption processes are involved for these materials, where the sorptive contributions from both processes were estimated based on the phenanthrene thermodynamic data. Moreover, on the basis of ΔH values of desorption, release of native and spiked phenanthrene from our samples was similar.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-p-furans (PCDD/Fs) were analysed in soil from a Swedish sawmill site where chlorophenols (CPs) had been used more than 40 years ago. The most contaminated area at the site was the preservation subarea where the PCDD/F WHO2005-TEQ level was 3450 times higher than the current Swedish guideline value of 200 ng TEQ/kg soil for land for industrial use. It was also shown that a fire which destroyed the sawmill might have affected the congener distribution at the concerned areas. To get a broader picture of the contamination both GIS (spatial interpolation analysis) and multivariate data analysis (PCA) were applied to visualize and compare PCDD/F levels as well as congener distributions at different areas at the site. It is shown that GIS and PCA are powerful tools in decisions on future investigations, risk assessments and remediation of contaminated sites.

An original combined organic geochemistry and soil science approach was used to elucidate PAH availability controlling factors in a multi-contaminated industrial soil. Water granulodensimetric fractionation was applied to obtain five water-stable material fractions. These were characterized by elemental, molecular and mineral analysis, and microscopic observations. Among the different fractions, fine silts distinguished themselves by higher carbon and nitrogen contents, lower C/N ratio, an enrichment in total PAH and especially high molecular weight compounds, a coal tar signature and the lowest PAH availability. This fine silt fraction seemed to play a protective role for PAH that might be explained by its size and/or its specific reactivity. The mineral phases present in this fraction were proposed to explain the protection of organic matter. This led to a specific molecular signature of OM, having higher sorption properties both processes (sorption and mineral-bound protection) resulting in a lower PAH availability.

This study addressed the relative importance of particle coating, sewage sludge amendment, and aging on aggregation and dissolution of manufactured Ag nanoparticles (Ag MNPs) in soil pore water. Ag MNPs with citrate (CIT) or polyvinylpyrrolidone (PVP) coatings were incubated with soil or municipal sewage sludge which was then amended to soil (1% or 3% sludge (w/w)). Pore waters were extracted after 1 week and 2 and 6 months and analyzed for chemical speciation, aggregation state and dissolution. Ag MNP coating had profound effects on aggregation state and partitioning to pore water in the absence of sewage sludge, but pre-incubation with sewage sludge negated these effects. This suggests that Ag MNP coating does not need to be taken into account to understand fate of AgMNPs applied to soil through biosolids amendment. Aging of soil also had profound effects that depended on Ag MNP coating and sludge amendment.

MicroResp™ is a miniaturised method for measuring substrate induced respiration (SIR) in soil. We modified the MicroResp™ method to develop a rapid tool for quantifying the ecotoxicological impact of contaminants. The method is based on reduction in SIR across a gradient of contaminant, allowing for determination of dose–response curves EC-values. Contaminants are mixed into soil samples at a range of concentrations; each sample is then dispensed into a column of eight wells in 96 well format (deep) plates. Moisture and glucose are added to the samples at levels to provide maximum response. Released CO2 from the soils is then measured using colorimetric gel-traps, following the standard MicroResp™ methodology. Examination revealed that this method works over a range of soil types and is insensitive to minor variations in assay length (2–7 h), alteration of moisture content (±20 μL from optimum), and soil storage conditions (4 °C versus fresh).