Total gaseous mercury (TGM) fluxes from the forest floor and a boreal wetland were measured by a flux chamber technique coupled with an automatic mercury vapour analyser. The fluxes were measured at three sampling sites in southern Finland, 61°14′ N, 25°04′ E in summer 2007, with additionally in situ TGM concentrations in the air at one of the sites and mercury bulk deposition at another. Most of the flux data were collected during the daytime. At one of the sites, diurnal flux behaviour was studied, and a clear cycle with an afternoon maximum and a night minimum was observed. The highest emissions (up to 3.5 ng m−2 h−1) were observed at the forest floor site having a moss and grass cover. At the wetland and litter-rich forest floor sites, the emissions were below 1 ng m−2 h−1 and sometimes negative (down to −1.0 ng m−2 h−1), indicating mercury uptake. The measured average fluxes in August were 0.9 ± 1.1 and 0.2 ± 0.3 ng m−2 h−1 for the forest floor sites and wetland sites, respectively. The flux data were compared with the mercury bulk deposition, which proved to be of the same magnitude, but opposite in sign. At the mossy forest floor site, the extrapolated TGM emissions were 130% of the Hg deposition in August 2007. Comparison with other studies showed that the fluxes in background areas are relatively uniform, regardless of measurement site location and method used. Airborne TGM remained at the background level during the study, with an average value of 1.3 ± 0.2 ng m−3; it frequently showed a diurnal cycle pattern.

This study assessed the efficiency of sewage treatment plants (STPs) in removing sterols based on chemical analyses of both influents and effluents. Samples from 3s and three tertiary plants were collected and analyzed by gas chromatography mass spectrometry for 23 individual sterols including mestranol, norethindrone, equol, estrone, equilin, norgestrel, 17α-ethinylestradiol, 17α-estradiol, 17β-estradiol, estriol, dihydrocholesterol (cholestanol), coprostanol, epicoprostanol, cholesterol, desmosterol, campesterol, stigmasterol, β-sitosterol, coprostanone, cholestanone, epicholestanol, stigmastanol, and 24-ethylcoprostanol. The percentage of sterols remaining in effluent samples (compared to influent samples) ranged from 0% to 80% and varied among sterol compounds and with STP location and treatment type. Differences in the efficiency of sterol removal for secondary and tertiary STPs were statistically significant. Although the concentration of sterol compounds differed between influents and effluents, sterol abundances remained the same. The most abundant sterol detected was cholesterol, followed by the fecal sterol coprostanol, and the plant sterols 24-ethylcoprostanol and β-sitosterol. For three STPs, the hormone estrone was detected in effluents at concentrations of 0.03–0.05 μg L−1. Ten sterol ratios specific for human fecal contamination and eight sterol ratios for differentiating among multiple sources of fecal contamination were calculated and showed that 12 ratios for influent and nine ratios for effluent were successful for human fecal source tracking. Based on sterol ratio values in this study, new criteria for identification of human fecal contamination were suggested.

This study investigated the encapsulation and photocatalysis of chlorophenol compounds in water using porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer. The chloride ions generated during photocatalytic process were identified and quantified. 2,4,6-Trichlorophenol, pentachlorophenol, and 2,4-dichlorophenol were satisfactorily decomposed in the photoreactor using porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer, with removal efficiencies of 2,454, 498, and 760 mg/g of porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer. The half-life times reached around 30 min, with the exception of that for 2,4-dichlorophenol. The star polymer-impregnated porphyrin is a promising photocatalyst for the removal of chlorophenols.

A simple spectrophotometric method was developed to quantify chlorophenol (CP) concentrations after reaction with potassium permanganate and quenching with sodium sulfite. Other quenching agents (peroxide, sodium thiosulfate and hydroxylamine hydrochloride) were found to create absorbance in the spectral range required for CP quantification. Analysis at pH 12 gave greater absorption and sensitivity for the method compared with pH 5.6. The calibration curves of the proposed methods were linear in the concentration ranges 0.0061–0.61 and 0.0078–0.78 mM with detection limit of 0.0006 and 0.0008 mM for dichlorophenols and monochlorophenols, respectively. The oxidation kinetics of five chlorophenols in aqueous solution with excess potassium permanganate were evaluated using the analytical method. The pseudo-first-order reaction rates were found to be relatively rapid 1.42 × 10−3 to 0.024 s−1 and followed the sequence 2-chlorophenol (2-CP) > 2,6-dichlorophenol (2,6-DCP) > 4-chlorophenol (4-CP) > 2,4-dichlorophenol (2, 4-DCP) > 3-chlorophenol (3-CP). The apparent second-order rate constant was calculated from the measured pseudo-first-order rate constant with respect to CP with initial KMnO4 concentration (1.5 mM) and follows the same sequence of pseudo-first-order rate constant. This shows that chlorine atoms in the structure of chlorophenol had a significant influence on the oxidation of chlorophenols by potassium permanganate. Permanganate can be used for the treatment of chlorophenol-contaminated soil and groundwater.

The mining exploitation of metallic sulphides, together with the activities associated to the mineral treatment and smelting, when maintained through centuries due to the wealth of the ores, generate important accumulations of wastes in structures of different kind of tailing dams and ponds, for instance. When no previous corrective steps are taken, as usually happens in old exploitations, this means a serious risk of environmental pollution, due to the mobilisation of heavy metals. The present study has been carried out in a mining district, actively exploited during the last two millennia, that was the first world’s producer of lead during some periods (Linares-La Carolina, southern Spain). In this district, the mining activity was associated to a philonian network of metallic sulphurs and ended by the 1980s of the past century. The ancient mining operations, mostly subterranean, have generated large accumulations of residues without any prior corrective action. Therefore, this work intends to characterise these mining dams and determine the influence of these mining wastes on the quality of surface and ground waters. With this goal, three structures that store the mining refuse of different mineralogical origin have been selected. First, a geochemical characterisation of the soil was performed in the area surrounding each of the structures. In all cases, high levels of trace elements (including Pb, Zn, Cu, Cd, Mn, As, Sb and Ba) were observed. A hydrochemical study revealed the mobilisation through the aqueous medium of certain contaminants from the leachate of these ancient accumulations; these contaminants will flow to the streams that drain the area or to the aquifers of the sector. The internal characterisation of these structures was performed with geophysical techniques, specifically electrical resistivity imaging (ERI). The six generated resistivity models have allowed the identification of the morphology of the structures, variations in the vertical and horizontal distribution of the deposited material, fracture zones, water content and reload–unload zones and the contact of the mining wastes with the substrate. Thus, the ERI study confirms the lack of impermeabilisation measures for the terrain in the spill zones in all three cases, which indicates a high risk of contamination of the soil and waters. The obtained images also permit the identification of the ideal positions to conduct future borehole controls.

This review addresses the quantification of anthropogenic pollutants in lacustrine sediments by multidisciplinary analyses including: chronostratigraphy using radioisotopes (¹³⁷Cs) and radiocarbon dates (¹⁴C), trace metal analysis, faecal indicator analysis, as well as antibiotic-resistant genes by molecular analysis. Sediment cores from lakes Lucerne and Geneva that are located at a distance of 150 km from each other reveal a synchronous increase in anthropogenic trace metals (Pb, Cu, Zn, and Mn) following the industrial revolution in Europe about 1850. In both lakes, the peak of water pollution by toxic metals due to discharge of industrial wastewaters was reached in the middle of the twentieth century. During the second part of the twentieth century, both sites show a decrease in metal pollution following the implementation of wastewater treatment plants. On the contrary, the Vidy Bay of Lake Geneva where the treated wastewaters from the city of Lausanne are released since 1964 points out a dramatic increase in trace metal deposition. Later, a high increase in organic matter deposition, in bacteria (Escherichia coli and Enterococcus faecalis) activity as well as antibiotic-resistant genes and bacteria occurred into the bay, simultaneously with the eutrophication of the large and deep perialpine lakes in the 1970s due to excessive external nutrient loading.

The high hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) is the main limiting factor for the remediation of soils and aquifers. Surfactants are amphiphilic substances which encourage the transfer of hydrophobic compounds from the solid to the liquid phase. While the interaction between organic matter and surfactants has been widely studied, there is a lack of knowledge concerning the relationship between surfactant efficiency and the granulometry of soil and/or geologic material. In this paper, three non-ionic surfactants (Tween 80, Gold Crew, and BS-400) were used to study the desorption of pyrene, chosen as a representative PAH, in soils with different grain size proportions (1%, 5%, 10%, and 20% of clay and silt) and no organic matter (<0.1%). The best quantity of surfactant to apply is closely related to the proportion of fine materials. Tween 80 gave better maximum desorption than Gold Crew and BS-400 (89%, 40%, and 36%, respectively). As an important proportion of aquifers show fine material above 1%, the effective critical micellar concentration obtained when applying surfactants to this type of geologic materials has to be higher than 150 mg L−1 for Tween 80, and higher than 65 mg L−1, and 100 mg L−1 for Golf Crew and BS 400, respectively. Furthermore, results indicate that carrying out simple laboratory tests before the use of surfactants on a field scale is necessary to improve the efficiency and minimize the financial and environmental impact of its application.

The effect of different humic fractions on polychlorinated biphenyl (PCB) contamination in soils was tested in the field by means of 53 soil samples from a high-altitude grassland plateau in the Italian Alps. Three humic fractions (humin, humic acids, and fulvic acids) were characterized in parallel by quantifying 12 PCB congeners to establish a direct relationship between PCB levels and humic fraction concentrations. Humin (the most hydrophobic fraction) appears to be the most closely correlated with the amount of PCBs in soil (R ²â€‰= 0.83), while fulvic acid shows the lowest correlation (R ²â€‰= 0.49). The idea of preferential sorption of hydrophobic compounds in the humin fraction is discussed, and the humin carbon content (f ₕᵤₘᵢₙC) is proposed as an improved parameter for evaluating the potential for POP accumulation in soils, replacing total organic carbon (f ₒc). Congener studies revealed that penta- and hexa-substituted-CBs show the optimal combination of physicochemical properties for equilibrating with the humin content in soil. Moreover, f ₕᵤₘᵢₙC/f ₒc is conceptually equivalent to the empirical coefficients used in predictive K ₛₐ equations. In our samples, the f ₕᵤₘᵢₙC/f ₒc was 0.55, a value in between the empirical coefficients proposed in the literature. In predictive equations, the use of f ₕᵤₘᵢₙC instead f ₒc avoids the necessity of using an empirical parameter for a ‘generic’ condition by introducing an experimental parameter (f ₕᵤₘᵢₙC) that takes into account local conditions (organic matter composition).

Arsenic occurs in the earth's crust in various chemical forms as a result of both natural and anthropogenic sources. Soil chemical extractions may help understand As availability, as well as the possibility of As entry into the food chain. Phytoextraction has been proposed as a technology for remediation of As-contaminated soils. The study was carried out to assess the bioavailability of As by extractants and to compare the performance of castor bean and sunflower for As removal from soils. Two soils were contaminated with Na2HAsO4.7H2O adding 35 and 150 mg As dm−3 soil. Arsenic availability was assessed using the following extractants: tri-distilled water, ammonium sulfate, ammonium phosphate, ammonium oxalate + oxalic acid, organic acids mixture, Mehlich-1, and United States Environmental Protection Agency 3051. The roots and shoots of 35-day-old plants were collected and dry matter yield as well as As concentration were determined. The accumulation of As in shoot was also calculated in order to evaluate the plants potential for As phytoextraction. The extractants tested were efficient to assess the concentration of available As in soil. Addition of As to the soils did not cause severe toxicity in plants, although the dose 150 mg As dm−3 soil decreased shoot and root yield in both species. Castor bean was less sensitive to As than sunflower, but none of the species had hyperaccumulation characteristics. These species can be used for revegetation of areas contaminated with As up to safe limit of 150 mg As dm−3 soil, as proposed by CONAMA for industrial areas in Brazil.

Leachable chromium in the incineration fly ash and wastewater sludge has been thermally stabilized by plasma melting at the temperature of 1,773 K. To better understand how chromium is stabilized with the high-temperature treatment, chemical structure of the slags sampled at temperature zones of 1,100–1,700 K has been studied by synchrotron X-ray absorption spectroscopy. The component-fitted X-ray absorption near edge structure spectra of chromium indicate that the main chromium compounds in the sludge and fly ash are Cr(OH)₃, Cr₂O₃, and CrCl₃. A small amount of toxic CrO₃ is also observed in the fly ash. In the plasma melting chamber under the reducing environment, the high-oxidation state chromium is not found. The slags in the plasma melting chamber have much less leachable chromium, which is due to chemical interactions between chromium and SiO₂ in the slags. The existence of the interconnected Cr-O-Si species is observed by refined extended X-ray absorption fine structure spectroscopy. In the Cr₂O₃ phase of the slags, their bond distances, and coordination numbers for the first (Cr-O) and second (Cr-(O)-Cr) shells have insignificant perturbation when experienced with different melting temperatures between 1,300 and 1,700 K. It seems that Cr₂O₃ and chromium encapsulated in the silicate matrix of the slags have relatively much lower leachability. With this concept, to obtain a low chromium leachability slag from the plasma melting process, the residence time of the melting chamber may be decreased, and the slag discharge temperatures may be increased to 1,300 K. This work also exemplifies utilization of molecule-scale data obtained from synchrotron X-ray absorption spectroscopy to reveal how chromium is thermally stabilized in a commercial scale plasma melting process.