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.

Field studies were conducted to investigate arsenic (As), copper (Cu), and zinc (Zn) contamination in agricultural soils and wheat crops at two areas in Huaibei, China. Area A is in the proximity of Shuoli coal mine. In area B, three coal mines and a coal cleaning plant were distributed. The potential health risk of As, Cu, and Zn exposure to the local inhabitants through consumption of wheat grains was also estimated. The results showed that significantly higher (p < 0.05) concentrations of As, Cu, and Zn were found in soils collected from area B than in those from area A. Arsenic concentrations in wheat sampled from area A were negatively correlated with the distance from the coal mine (p < 0.001). Concentrations of Cu and Zn in wheat seedlings and grains collected from area B were significantly higher (p < 0.05) than in those collected from area A, with the exception of Zn in wheat seedlings. Concentrations of Cu and Zn in most wheat grain samples were above the permissible limits of Cu and Zn in edible plants set by the Food and Agriculture Organization/World Health Organization. The hazard index of aggregate risk through consumption of wheat grains was 2.3-2.4 for rural inhabitants and 1.4-1.5 for urban inhabitants. The average intake of inorganic As for rural inhabitants in Huaibei was above 10 μg day(-1). These findings indicated that the inhabitants around the coal mine are experiencing a significant potential health risk due to the consumption of locally grown wheat.

Pharmaceutical compounds were increasingly detected in environmental matrices but little is known whether these compounds would transport to coastal zones via watersheds. Three typical tidal rivers in southeastern China were selected and 15 surface sediment samples (0-10 cm) were collected along a 50-km tidal section of each river. Surface sediment samples were frozen-drying and then extracted for pharmaceutical compounds by an accelerated solvent extraction system. The pharmaceutical compounds in extracts were scanned using a high-performance liquid chromatography/tandern mass spectrometry (HPLC-MS/MS). Three hundred and thirty compounds from nine pharmaceutical groups were detected with signal-to-noise above three (detectable level) in the surface sediments, of which 186 compounds were with a signal-to-noise above ten (measurable level). Of all, 291 and 80 compounds were detectable and measurable in all the three rivers, respectively. The Jiulong River showed a high load of pharmaceutical compounds in surface sediment than other two rivers. Of the nine pharmaceutical groups, the antihistamines and detoxification group and anti-infective drug group contributed five dominant compounds in the surface sediments in all the three rivers. Natures of pharmaceutical compounds rather than the sediment properties (pH, EC, and total carbon content) might influence their residues. The incredible number and intensity of pharmaceutical residues were detected in tidal surface sediments of the three rivers indicating that the pharmaceutical contamination should be strongly considered in China. Source identification and eco-toxicity assessment should be taken into account in the future study. Therapeutic medicine managements need to be strictly improved at a watershed scale to reduce loads of pharmaceuticals into aquatic ecosystems.

Instead of direct current power supply, a series of electrokinetic remediation experiments driven by solar energy on fluorine-contaminated soil were conducted in a self-made electrolyzer, in order to reduce energy expenditure of electrokinetic remediation. After the 12-day electrokinetic remediation driven by solar energy, the removal efficiency of fluorine was 22.3 %, and electrokinetic treatment had an impact on changes in partitioning of fluorine in soil. It proved that the combination of electrokinetics and solar energy was feasible and effective to some extent for the remediation of fluorine-contaminated soil. Meanwhile, the experimental results also indicated that the electromigration was a more dominant transport mechanism for the removal of fluorine from contaminated soil than electroosmosis, and the weather condition was the important factor in affecting the removal efficiency.

Residues of pesticides in fish farming productions from barrage ponds are seldom studied in spite of increasing health questionings and environmental concerns. The purpose of this study is to establish the pesticide contamination profiles of sediments and edible fish from five ponds in Northeastern France. Multi-residues method and liquid chromatography–tandem mass spectrometry analysis were used to quantify 13 pesticides (azoxystrobin, carbendazim, clomazone, diflufenican, dimethachlor, fluroxypyr, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl). Ten sediments and 143 muscles samples were analysed, corresponding to two successive fishing campaigns (first fishing date and second fishing date (P2), about 1 year later) on five sites (noted C-0, C-25, C-45, C-75 and C-85 to express the increasing gradient of crop area). Isoproturon was present in all sediments samples (1.8–56.4 μg/kg dry weight). During P2 period, carbendazim was quantified in the fish of site C-0 (0.09 ± 0.02, 0.2 ± 0.1 and 0.17 ± 0.06 μg/kg wet weight (ww) for roach, carp and perch, respectively). Metazachlor was only quantified in perch of the site C-25 (0.13 ± 0.02 μg/kg ww). Concentrations of isoproturon were similar for the sites C-45 and C-75 with 0.4 ± 0.1 and 0.75 ± 0.06 μg/kg ww for carp and perch, respectively. Contamination of fish reflected generally concentrations in surroundings. Isoproturon was the most concentrated and its main source was water for perch while carp was exposed through both water and sediments, highlighting their life strategies in pond.

Sexually mature male mosquitofish (Gambusia holbrooki) were collected from various sites around Melbourne in 2009 to evaluate the performance of gonopodial indices as a biomarker for endocrine disruption in Melbourne's waterways. The mosquitofish indices assessed were body length (BL), gonopodial length (GL)/BL ratio, ray 4:6 ratio and the absence or presence of hooks and serrae, and these varied between sites. The study was complemented by measurements of estrogenic, retinoid, thyroid and aryl hydrocarbon (AhR) receptor activities of the water. Male mosquitofish were 16.3–21.5 mm in length, and although there was a statistically significant positive relationship showing that bigger fish had longer gonopodia than small fish (r2 = 0.52, p < 0.001), there were few significant differences in GL/BL ratio of fish between sites. Measured estrogenic activity was mostly in the range 0.1–1.7 ng/L EEQ, with one site having much higher levels (~12 ng/L EEQ). Aryl hydrocarbon (AhR) receptor activity was observed in all water samples (7–180 ng/L βNF EQ), although there was no consistent pattern in the level of AhR activity observed, i.e., ‘clean’ sites were as likely to return a high AhR activity response as urban or wastewater treatment plant (WWTP)-impacted sites. There was no correlation between measurements of receptor actvity and gonopodial length (GL):BL ratio and BL. We conclude that the mosquitofish gonopodia only fulfills part of the criteria for biomarker selection for screening. The mosquitofish indices assessed were cheap and easy-to-perform procedures; however, there is no baseline data from the selected sites to evaluate whether differences in the morpholical indices observed at a site were a result of natural selection in the population or due to estrogenic exposure.

General assessments of orebody types and associated mine wastes with regard to their environmental signature and human health hazards are needed to help in managing present and historical mine waste facilities. Bioaccessibility tests and mineralogical analysis were carried out on mine waste from a systematic sampling of mine sites from the Central Wales orefield, UK. The bioaccessible Pb widely ranged from 270 to 20,300 mg/kg (mean 7,250 mg/kg, median 4,890 mg/kg), and the bioaccessible fraction from 4.53 to >100 % (mean 33.2 %, median 32.2 %), with significant (p = 0.001) differences among the mine sites. This implies sensitivity of bioaccessibility to site-specific conditions and suggests caution in the use of models to assess human health impacts generalised on the basis of the mineral deposit type. Mineralogical similarities of the oxidation products of primary galena provided a better control over the observed Pb bioaccessibility range. The higher Pb bioaccessibility (%) was related to samples containing cerussite, irrespective of the presence of other Pb minerals in the mineral assemblage; lower Pb bioaccessibility resulted where anglesite was the main Pb mineral phase and cerussite was absent. A solubility diagram for the various Pb minerals in the waste was derived using PHREEQC model, and the experimental Pb concentrations, measured in the simulated gastric solution, were compared with the equilibrium modelling results. For samples containing cerussite, the model well predicted the soluble Pb concentrations measured in the gastric solution, indicative of the carbonate mineral phase control on the Pb in solution for these samples and little kinetic control on the dissolution of cerussite. On the contrary, most mine waste samples containing dominant anglesite and or plumbojarosite (no cerussite) had lower solution Pb values, falling at or below the anglesite and plumbojarosite solubility equilibrium concentrations, implying kinetic or textural factors hindering the dissolution.

The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of "a Baltic Sea with life undisturbed by hazardous substances". One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8-14, 8.0-640 and 320-1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9-15 ng/l) followed by PFOS (3.8-20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77 %). In the target industry, PFOS concentrations varied between 1,400 and 18,000 μg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 μg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.

Atmospheric pollutants may cause damage to monuments and historical buildings. Besides air contaminants, soluble salts are also responsible for stone deterioration and decay in outdoor and indoor monuments. The problem of how to conserve works of arts thus requires a deep knowledge of contaminants' concentration and distribution inside buildings. In this work, water-soluble ions inside St. Mark's Basilica in Venice were studied, with the aim of understanding their principal source and distribution inside the building. With the aid of Fourier transform infrared spectroscopy and scanning electron microscopy analysis, the interaction between ions and surface's material was also investigated. Ion chromatographic analysis of depositions highlighted a large amount of “deteriorating agents” such as sulphates and chlorides. A possible source in the innermost area of the basilica has been found for formates and nitrates. On the contrary, a decrease of chloride, from the entrance to the innermost area, has been found, which indicates that the source is outside the building. It is emphasized that different contaminants behave differently on different material, and the effect of pollution inside churches and monuments is not easy to predict. Wood and brick seem to react differently than stone and mortar to the damaging action of salts and pollutants. The present work should be considered a useful tool for the future preservation of St. Mark's Basilica in Venice.

The photocatalytic degradations of 4-chlorophenol (CP), 4-chloro-2-methylphenol (CMP), 4-chloro-3,5-dimethylphenol (CDMP) and 4-chloro-2-isopropyl-5-methylphenol (CIMP) were investigated in water and in simulated soil washing wastes containing Brij 35 (polyoxyethylene(23)dodecyl ether) in the presence of TiO₂ dispersions. A neat inhibition of substrate decomposition proportional to their growing hydrophobicity was observed in the washing wastes for CP, CMP and CDMP, whereas CIMP showed a different behaviour. The mineralization of the organic chlorine of CP and CIMP was relatively fast and complete, whereas it was much slower for CMP and CDMP. Micellar solubilization and substrate adsorption onto the semiconductor play opposite roles on the degradation kinetics, and a breakpoint between the corresponding induced effects was evidenced when the pollutants become completely bound to the micellar aggregates.