3-Chlorocarbazole, 3,6-dichlorocarbazole, dibromocarbazole, and 1,3,6,8-tetrabromocarbazole are emerging environmental contaminants which have been detected recently in water, sediment, and soil samples. However, their sources and occurrence have not been explained. Here, we report an enzymatic synthesis of bromo- and chlorocarbazoles by chloroperoxidase from Caldariomyces fumago in water. Density functional theory (DFT) method was used to predict the most stable products. Carbazole and chloroperoxidase were assayed in vitro in the presence of hydrogen peroxide, bromide, and chloride ions in different substrate ratio treatments against constant and varying enzyme concentrations. Halogenated carbazoles formed were identified by high-resolution gas chromatography coupled to mass spectrometry. In all treatments, bromination and chlorination took place, but the composition and concentration of compounds formed varied from one treatment to another. Mono-, di-, tri-, and tetra-substituted bromo- and chlorocarbazoles which include the reported environmental contaminants were synthesized. 3-Substituted and 3,6-substituted congeners were relatively higher in concentration. Enzyme concentration did not favor preferential formation of any of the compounds synthesized. However, their synthesis was influenced by halide concentration. Congeners with bromine and chlorine at position of C-3, C-3,6, C-1,3,6, and C-1,3,6,8 were calculated as the stable intermediate sigma complexes by DFT method. Regioselectivity in halogenation is discussed and hypothesis of the likely stable products in the environment explained. This study provides evidence that bromo- and chlorocarbazoles reported previously can be formed enzymatically in the environment, demonstrating the need to consider aromatic pollutants transformation and their potential toxicity enhancements in the management of water pollution and contaminated sites.

The occurrence and fate of eight PPCPs was studied in river waters from upstream to downstream of the three rivers in the Pearl River Delta, China. The correlations of PPCP levels and water quality parameters were also investigated. The analytes of the highest concentrations were caffeine, acetaminophen, and ciprofloxacin. Carbamazepine and erythromycin-H2O were detected at the lowest concentrations. The highest concentrations of PPCPs were found in the Shijing River, with 865 ng/L caffeine, 339 ng/L acetaminophen, and 304 ng/L ciprofloxacin. In general, the levels of PPCPs in the Zhujiang River were higher at sites where the metropolitan city Guangzhou is located and decreased from the epicenter along the river. Low levels of PPCPs were generally found in the Beijiang River. Positive correlations were found between PPCP levels, total nitrogen, ammonium nitrogen, and cumulative fluorescence excitation-emission matrix (EEM) volume. Among the four PPCPs evaluated (caffeine, acetaminophen, ciprofloxacin, and sulfamethoxazole), caffeine had the best correlations with the correlation coefficients ranging from 0.62 to 0.98. The prediction of PPCP concentrations at specified locations can be substantially simplified.

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton–Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.

Estuarine areas represent complex and highly changing environments at the interface between freshwater and marine aquatic ecosystems. Therefore, the aquatic organisms living in estuaries have to face highly variable environmental conditions. The aim of this work was to study the influence of environmental changes from either natural or anthropogenic origins on the physiological responses of Mytilus edulis. Mussels were collected in the Vilaine estuary during early summer because this season represents a critical period of active reproduction in mussels and of increased anthropogenic inputs from agricultural and boating activities into the estuary. The physiological status of the mussel M. edulis was evaluated through measurements of a suite of biomarkers related to: oxidative stress (catalase, malondialdehyde), detoxication (benzopyrene hydroxylase, carboxylesterase), neurotoxicity (acetylcholinesterase), reproductive cycle (vitelline, condition index, maturation stages), immunotoxicity (hemocyte concentration, granulocyte percentage, phagocytosis, reactive oxygen species production, oxidative burst), and general physiological stress (lysosomal stability). A selection of relevant organic contaminant (pesticides, (polycyclic aromatic hydrocarbons, polychlorobiphenyls) was measured as well as environmental parameters (water temperature, salinity, total suspended solids, turbidity, chlorophyll a, pheopigments) and mussel phycotoxin contamination. Two locations differently exposed to the plume of the Vilaine River were compared. Both temporal and inter-site variations of these biomarkers were studied. Our results show that reproduction cycle and environmental parameters such as temperature, organic ontaminants, and algal blooms could strongly influence the biomarker responses. These observations highlight the necessity to conduct integrated environmental approaches in order to better understand the causes of biomarker variations.

Many best management practices have been developed and implemented to treat the nonpoint source pollution of the aquatic environment in Korea's four major river basins. The performance and cost of these facilities were evaluated and compared using broad categories, including grassed swales, constructed wetlands, vegetated filter strips, hydrodynamic separators, media filters, and infiltration trenches, based on the monitoring and maintenance work undertaken between 2005 and 2012. Constructed wetlands, media filters, and infiltration trenches generally performed better in removing pollutants than other types of facilities, while media filters were the most expensive factor in terms of construction and operational costs. In addition, constructed wetlands incurred the least operational cost, as well as helping to control the quantity of runoff. This illustrates that a high cost facility does not necessarily give a better performance. A slightly more expensive facility, such as wetland, could prove to be a reasonably effective treatment. The selection of the most appropriate treatment for stormwater runoff should be based on an overall analysis of performance and cost.

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.

Phthalic acid esters (PAEs) pollution in agricultural soils caused by widely employed plastic products is becoming more and more widespread in China. PAEs polluted soil can lead to phytotoxicity in higher plants and potential health risks to human being. We evaluated the individual toxicity of di-n-butyl phthalate (DnBP) and bis(2-ethylhexyl) phthalate (DEHP), two representative PAEs, to sown rape (Brassica chinensis L.) seeds within 72 h (as germination stage) and seedlings after germination for 14 days by monitoring responses and trends of different biological parameters. No significant effects of six concentrations of PAE ranging from 0 (not treated/NT) to 500 mg kg(-1) on germination rate in soil were observed. However, root length, shoot length, and biomass (fresh weight) were inhibited by both pollutants (except root length and biomass under DEHP). Stimulatory effects of both target pollutants on malondialdehyde (MDA) content, superoxide dismutase (SODase) activity, ascorbate peroxidase (APXase) content, and polyphenoloxidase (PPOase) activity in shoots and roots (SODase activity in shoots excluded) were in the same trend with the promotion of proline (Pro) but differed with acetylcholinesterase activity (except in shoots under DnBP) for analyzed samples treated for 72 h and 14 days. Responses of representative storage compounds free amino acids (FAA) and total soluble sugar (TSS) under both PAEs were raised. Sensitivity of APXase and Pro in roots demonstrates their possibility in estimation of PAE phytotoxicity and the higher toxicity of DnBP, which has also been approved by the morphological photos of seedlings at day 14. Higher sensitivity of the roots was also observed. The recommended soil allowable concentration is 5 mg DnBP kg(-1) soil for the development of rape. We still need to know the phytotoxicity of DEHP at whole seedling stage for both the growing and development; on the other hand, soil criteria for PAE compounds are urgently required in China.

Polycyclic aromatic hydrocarbons (PAHs) are widespread fused-ring contaminants formed during incomplete combustion of almost all kind of organic materials from both natural and anthropogenic sources. Some PAHs have been shown to be carcinogenic to humans, and a wide range of PAHs are found in wildlife all around the globe including avian species. The purpose of this project was to assess the effects of a standard mixture of 16 PAHs (United States Environmental Protection Agency) on the hepatic fatty acid β-oxidation in chicken embryos (Gallus gallus domesticus) exposed in ovo. The hepatic β-oxidation was measured using a tritium release assay with [9,10-³H]-palmitic acid (16:0) as substrate. Treated groups were divided into groups of 0.05, 0.1, 0.3, 0.5, and 0.8 mg PAHs/kg egg weight. The hepatic β-oxidation was reduced after exposure in ovo to the 16 PAHs mixture compared to control. The mechanisms causing reduced fatty acid oxidation in the present study are unclear, however may be due to deficient membrane structure, the functionality of enzymes controlling the rate of fatty acid entering into the mitochondria, or complex pathways connected to endocrine disruption. To the best of our knowledge, this is the first time a PAH-caused reduction of hepatic β-oxidation of fatty acids in avian embryos has been observed. The implication of this finding on risk assessment of PAH exposure in avian wildlife remains to be determined.

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007-2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.