The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers’ approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.

Both dissolved organic matters (DOM) and natural biofilms are important substances in controlling the behavior of trace metals in natural aquatic environments. In this study, ethylenediaminetetraacetic acid (EDTA) was selected as a typical DOM to investigate the effect of DOM on the adsorption of trace metals to the biofilms in natural waters. The adsorption of Cd to biofilms, including adsorption isotherm at a fixed pH (pH = 6.0) and pH-edge adsorption (pH ranging from 4.3 to 9.0) with different adsorption sequences, was determined without EDTA and in the presence of EDTA ([EDTA] = 0.5 μmol/L for isotherms measurement and [EDTA] = 0.5 and 2.0 μmol/L for pH-dependent adsorption). The presence of EDTA generally decreased the adsorption of Cd, and the effect was determined by solution pH, concentration of EDTA, and adsorption sequence. Higher concentration or higher pH usually resulted in a more significant decrease. The influence of adsorption sequence on the effect of EDTA was insignificant in lower pH range, while the adsorption usually decreased in the order of Cd only adsorption > Cd first adsorption > EDTA first adsorption ≈ simultaneous adsorption in higher pH range. The effect of EDTA could be attributed to the conversion of Cd speciation, the competition with the biofilms for Cd, and the dissolution of Mn oxides from the biofilms. EDTA affected the adsorption of Cd to natural biofilms, and the effect could be fairly significant. The role of Mn oxides in determining the behavior of trace metals might be underestimated.

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Markušovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite > pyrite > tetrahedrite > arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu > Sb > Hg > As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.

PURPOSE: The main goals of this study were to investigate (1) the behavior of microbial communities in response to low-dose bioavailable anthracene addition in lightly contaminated sediment from Bizerte Lagoon and (2) the effects of bioremediation treatments on microbial biomass, activity, and community structure. METHODS: Sediment microcosms amended with 1 ppm anthracene were incubated in triplicate during 30 days. Biostimulation (addition of nitrogen and phosphorus fertilizer) and bioaugmentation (inoculation of a hydrocarbonoclastic bacterium) were used as bioremediation treatments. Bacterial biomass was estimated using flow cytometry. Sediment oxygen consumption was measured with oxygen microelectrodes. Bacterial community structure was assessed by molecular fingerprints (terminal restriction fragment length polymorphism; T-RFLP) analysis. RESULTS: Anthracene contamination resulted in a significant reduction of bacterial abundance with an impact on cell integrity. Concomitantly, sediment oxygen consumption was strongly inhibited. Correspondence analysis on T-RFLP data indicated that bacterial community structures from anthracene-contaminated microcosms were different from that of the control. Interestingly, the changes observed in microbial biomass, structure, and activities as a result of anthracene contamination were not alleviated even with the use of biostimulation and combination of biostimulation and bioaugmentation strategy for anthracene bioremediation. Nevertheless, both treatment methods resulted in different community structures relative to the contaminated and control microcosms with the appearance of distinct populations. CONCLUSION: Anthracene spiking severely affected microbial communities, suggesting dominance of nontolerant populations in this lightly-contaminated sediment. Although biostimulation and/or bioaugmentation treatments did not alleviate the anthracene toxic effects, the changes observed in microbial population and structure suggest that the proposed treatments might be promising to promote bacterial growth. Further works are still required to propose a more efficient strategy to stimulate biodegradation that takes into account the complex interactions between species for resource access.

Losses of phosphorus (P) from soil and slurry during episodic rainfall events can contribute to eutrophication of surface water. However, chemical amendments have the potential to decrease P and suspended solids (SS) losses from land application of slurry. Current legislation attempts to avoid losses to a water body by prohibiting slurry spreading when heavy rainfall is forecast within 48 h. Therefore, in some climatic regions, slurry spreading opportunities may be limited. The current study examined the impact of three time intervals (TIs; 12, 24 and 48 h) between pig slurry application and simulated rainfall with an intensity of 11.0 ± 0.59 mm h-1. Intact grassed soil samples, 1 m long, 0.225 m wide and 0.05 m deep, were placed in runoff boxes and pig slurry or amended pig slurry was applied to the soil surface. The amendments examined were: (1) commercial-grade liquid alum (8 % Al2O3) applied at a rate of 0.88:1 [Al/ total phosphorus (TP)], (2) commercial-grade liquid ferric chloride (38 % FeCl3) applied at a rate of 0.89:1 [Fe/TP] and (3) commercial-grade liquid poly-aluminium chloride (10 % Al2O3) applied at a rate of 0.72:1 [Al/TP]. Results showed that an increased TI between slurry application and rainfall led to decreased P and SS losses in runoff, confirming that the prohibition of land-spreading slurry if heavy rain is forecast in the next 48 h is justified. Averaged over the three TIs, the addition of amendment reduced all types of P losses to concentrations significantly different (p < 0.05) to those from unamended slurry, with no significant difference between treatments. Losses from amended slurry with a TI of 12 h were less than from unamended slurry with a TI of 48 h, indicating that chemical amendment of slurry may be more effective at ameliorating P loss in runoff than current TI-based legislation. Due to the high cost of amendments, their incorporation into existing management practices can only be justified on a targeted basis where inherent soil characteristics deem their usage suitable to receive amended slurry. © 2013 Springer-Verlag Berlin Heidelberg.

The aim of present study was for the vermiremediation of dyeing sludge from textile mill into nutrient-rich vermicompost using earthworm Eisenia fetida. The dyeing sludge was mixed with cattle dung in different ratios, i.e., 0:100 (D₀), 25:75 (D₂₅), 50:50 (D₅₀), 75:25 (D₇₅), and 100:0 (D₁₀₀) with earthworms, and 0:100 (S₀), 25:75 (S₂₅), 50:50 (S₅₀), 75:25 (S₇₅), and 100:0 (S₁₀₀) without earthworms. Minimum mortality and maximum population build-up were observed in a 25:75 mixture. Nitrogen, phosphorus, sodium, and pH increased from the initial to the final products with earthworms, while electrical conductivity, C/N ratio, organic carbon, and potassium declined in all the feed mixtures. Vermicomposting with E. fetida was better for composting to change this sludge into nutrient-rich manure.

Revegetation in the water-level-fluctuation zone (WLFZ) could stabilize riverbanks, maintain local biodiversity, and improve reservoir water quality in the Three Gorges Reservoir Region (TGRR). However, submergence and cadmium (Cd) may seriously affect the survival of transplantations. Bermuda grass (Cynodon dactylon) is a stoloniferous and rhizomatous prostrate weed displaying high growth rate. A previous study has demonstrated that Bermuda grass can tolerate deep submergence and Cd stress, respectively. In the present study, we further analyzed physiological responses of Bermuda grass induced by Cd-and-submergence stress. The ultimate goal was to explore the possibility of using Bermuda grass for revegetation in the WLFZ of China's TGRR and other riparian areas. The Cd-and-submergence-treated plants had higher malondialdehyde contents and peroxidase than control, and both increased with the Cd concentration increase. All treated plants catalase activity increased with the experimental duration increases, and their superoxide dismutase also gradually increased with the Cd concentration from 1 day to 15 days. Total biomass of the same Cd-and-submergence plants increased along the experimental duration as well. Plants exposed to Cd-and-submergence stress showed shoot elongation. The heights of all treated plants were taller than those of the control. Leaf chlorophyll contents, maximum leaf length, and soluble sugars contents of all the Cd-and-submergence-treated plants were more than those of the untreated control. Although Cd inhibits plants growth, decreases chlorophyll and biomass content, and with the submergence induced the leaf and shoot elongation, more part of the Cd-and-submergence stress plants appeared in the air, exhibited fast growth with maintenance of leaf color, which guaranteed the plants' photosynthesis, and ensured the total biomass and carbohydrate sustainability, further promoting Cd-and-submergence tolerance. The results imply that the negative effects of cadmium on Bermuda grass growth might be offset by submergence.

While the World Health Organization 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalency factors are useful estimates of relative potencies of mixtures when conducting risk assessments, they are not useful when comparing the results of bioassays such as the H4IIE-luc to concentrations of TCDD equivalents calculated from instrumental analyses. Since there are thousands of dioxin-like compounds (DLCs), one use of screening assays is to determine if all of the aryl hydrocarbon receptor (AhR) active DLCs in a mixture have been accounted for in instrumental analyses. For this purpose, bioassay-specific relative potency (ReP) values are needed. RePs of 21 polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls that exhibit effects mediated through the AhR were determined by use of the H4IIE-luc assay. Different values of RePs are derived, depending on the statistical, curve-fitting methods used to derive them from the dose–response relationships. Here, we discuss the various methods for deriving RePs from in vitro data and their assumptions and effects on values of RePs. Full dose–response curves of 2,3,7,8-TCDD and other representative DLCs were used to estimate effective concentrations at multiple points (e.g., EC20-50-80), which were then used to estimate ReP of each DLC to 2,3,7,8-TCDD.

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Kožuf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).

Wild pigs (Sus scrofa) are widespread across many landscapes throughout the world and are considered to be an invasive pest to agriculture and the environment, or conversely a native or desired game species and resource for hunting. Wild pig population monitoring is often required for a variety of management or research objectives, and many methods and analyses for monitoring abundance are available. Here, we describe monitoring methods that have proven or potential applications to wild pig management. We describe the advantages and disadvantages of methods so that potential users can efficiently consider and identify the option(s) best suited to their combination of objectives, circumstances, and resources. This paper offers guidance to wildlife managers, researchers, and stakeholders considering population monitoring of wild pigs and will help ensure that they can fulfill their monitoring objectives while optimizing their use of resources.