Linear alkylbenzene sulfonate (LAS) is a synthetic anionic surfactant widely present in the environment due to its intensive production and use in the detergency field. Admitting that current procedure of risk assessment has limits in providing realistic risk assessment data and predicting the cumulative effect of the toxicant mixtures, the incorporation of information regarding the mode of action and cell response mechanism seems to be a potential solution to overcome these limits. In this regard, we investigated in this study the LAS cytotoxicity on human intestinal Caco-2 cells, trying to unveil the protein actors implicated in the cell response using proteomics approach in order to give a better understanding of the toxicological effect and allow the identification of appropriate biomarkers reflecting the mode of action associated with LAS. As results, we demonstrated that LAS induces a time- and dose-dependent cytotoxicity in Caco-2 cells accompanied by an induction of oxidative stress followed by an excessive increase of intracellular calcium level. Proteomics approach helped in discovering three informative biomarkers of effect associated with LAS cytotoxic effect, reported for the first time: calreticulin, thioredoxin, and heat shock cognate 71 (HSP7C), confirmed by real-time PCR and western blot analysis. These biomarkers could serve for more reliable future risk assessment studies that consider the toxicants mode of action in order to help in the prediction of potential cumulative effects of environmentally coexisting contaminants.

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.

A new inorganic-organic hybrid material zirconium-glycine complex (ZGC) was firstly used as a coagulant in a coagulation process to treat Pearl River raw water. Its coagulation performance was compared with commonly used aluminum (Al) coagulants such as aluminum sulfate (Al₂(SO₄)₃) and polyaluminum chloride (PAC), in terms of water quality parameters and floc properties. ZGC coagulation achieved higher removal of turbidity (93.8 %) than other traditional coagulants. Charge neutralization was proven to act as a dominant mechanism during ZGC coagulation. The aggregated flocs with ZGC showed the fastest growth rate and good recovery ability compared with the other coagulants and achieved the largest floc size within 5 min. The ZGC coagulant can decrease the hydraulic retention time and increase removal efficiency.

We determined the distribution of polychlorinated biphenyls (PCBs), pentachlorobenzene (PeCBz), hexachlorobenzene (HxCBz), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in surface sediments at 21 sites inside and outside Muroran Port, Japan. The concentration ranges and geometric means of PCBs (Σ209PCB), PeCBz, HxCBz, and PCDD/Fs and toxicity equivalence quantity (total TEQ) of dioxins inside Muroran Port were 1,100–65,000 (mean, 17,000) pg/g dw, 37–220 (100) pg/g dw, 31–810 (84) pg/g dw, 69–410 (170) pg/g dw, and 0.51–6.2 (2.3) pg TEQ/g dw, respectively. Their corresponding inventories inside Muroran Port were estimated to be 76, 0.31, 0.32, 0.55, and 7.8 g TEQ, respectively. The amounts of these pollutants were higher inside the port than outside the port and especially large in the inner part of the port. Most PCBs were homologues and congeners of penta- to hepta-chlorinated compounds, and the PCBs around Muroran Port were derived from technical PCBs, especially KC500 and KC600. As for PCDD/Fs, the influence of pentachlorophenol was significant, although pollution due to chloronitrofen and combustion was detected. The congeners of PCDD/Fs predominantly contributed to total TEQ. The concentration distributions of PeCBz, HxCBz, and PCDD/Fs and total TEQ were highly correlated with one another. This indicates that they are derived from the same combustion process.

The removal and mechanism of Cu²⁺and Cd²⁺from aqueous single-metal solutions were investigated by using a novel biosorbent from waste-activated sludge. A series of adsorption experiments was designed to disclose the effects of the key factors on the adsorption capacity of the biosorbent for the metal ions. The mass ratio of the biosorbent to metal ion was optimized as 2 to balance the adsorption capacity and the removal efficiency. A right shaking speed (150 r/min) not only ensured enough contact frequency between the sorbent and the adsorbate but also reduced the mass transfer resistance. The natural pH value (about 5.5) of the metal solutions benefited a high adsorption capacity of the biosorbent and avoided the consumption of acid or base for pH adjustment. The adsorption reactions belonged to the endothermic process between 15 and 45 °C. As the scanning electron microscopy (SEM) images showed, the meshy structure with long chains and many branches was ideal for the biosorbent to quickly capture the metal ions. The energy-dispersive X-ray (EDX) spectra confirmed that the adsorbed metal ions lay in the precipitates of the adsorption reactions. According to the FTIR analyses, the functional groups responsible for Cu²⁺adsorption majorly consisted of O–H, N–H, COOH, CONH₂, and the groups containing sulfur and phosphorus, while those for Cd²⁺adsorption contained O–H, N–H, COOH, and CONH₂. The differences in the responsible functional groups explained the phenomenon that the adsorption capacity of the biosorbent for Cu²⁺was higher than that for Cd²⁺.

Water quality degradation is often a severe consequence of rapid economic expansion in developing countries. Methods to assess spatial-temporal patterns and trends in water quality are essential for guiding adaptive management efforts aimed at water quality remediation. Temporal and spatial patterns of surface water quality were investigated for 54 monitoring sites in the Wen-Rui Tang River watershed of eastern China to identify such patterns in water quality occurring across a rural-suburban-urban interface. Twenty physical and chemical water quality parameters were analyzed in surface waters collected once every 4–8 weeks from 2000 to 2010. Temporal and spatial variations among water quality parameters were assessed between seasons (wet/dry) and among major land use zones (urban/suburban/rural). Factor analysis was used to identify parameters that were important in assessing seasonal and spatial variations in water quality. Results revealed that parameters related to organic pollutants (dissolved oxygen (DO), chemical oxygen demand (manganese) (CODMₙ), and 5-day biochemical oxygen demand (BOD₅)), nutrients (ammonia nitrogen (NH₄⁺-N), total nitrogen (TN), total phosphorus (TP)), and salt concentration (electrical conductivity (EC)) were the most important parameters contributing to water quality variation. Collectively, they explained 70.9 % of the total variance. A trend study using the seasonal Kendall test revealed reductions in CODMₙ, BOD₅, NH₄⁺-N, petrol, V-phen, and EC concentrations over the 11-year study period. Cluster analysis was employed to evaluate variation among 14 sampling sites representative of dominant land use categories and indicated three, three, and four clusters based on organic, nutrient, and salt water quality characteristics, respectively. Factors that are typically responsible for water quality degradation (including population, topography, and land use) showed no strong correlation with water quality trends implying considerable point source inputs in the watershed. The results of this study help inform ongoing water quality remediation efforts by documenting trends in water quality across various land use zones.

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L⁻¹and 0.002–0.828/(0.006–2.758) μg L⁻¹, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L⁻¹and 0.01–22.61 μg L⁻¹, respectively, while for phenols were in the range of 0.03–102.54 μg L⁻¹and 0.02–10.84 μg L⁻¹, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.

In this paper, degradation of a mixture of three azo dyes was studied by the photo-assisted electrochemical process using an O₂-diffusion cathode containing carbon nanotubes and boron-doped diamond (BDD) anode. The concentration of three textile dyes (C.I. Acid Orange 8 (AO8), C.I. Acid Orange 10 (AO10), and C.I. Acid Orange 12 (AO12)) was determined simultaneously despite the severe overlap of their spectra. For this purpose, partial least square (PLS), as a multivariate calibration method, was utilized based on recording UV–Vis spectra during the decolorization process. Moreover, the central composite design was used for the modeling of photo-assisted electrochemical decolorization of the aqueous solutions containing three dyes. The investigated parameters were the initial concentration of three dyes, applied current and reaction time. Analysis of variance (ANOVA) revealed that the obtained regression models match the experimental results well with R (Khataee et al. 2010, Clean-Soil Air Water 38 (1):96–103, 2010) of 0.972, 0.971, and 0.957 for AO8, AO10, and AO12, respectively. Three-dimensional surface and contour plots were applied to describe the relation between experimental conditions and the observed response. The results of TOC analysis confirmed good ability of proposed photo-assisted electrochemical process for degradation and mineralization of textile industry wastewater.

To investigate the effect of organic matter evolution on heavy metal sorption, fluorescence excitation–emission matrix (EEM) spectra combined with parallel factor (PARAFAC) analysis were employed to characterize the evolution and metal-complexing potential of fluorescent water-extractable organic matter (WEOM) from composted municipal solid wastes (MSWs). The WEOMs examined comprised humic-, fulvic-, tryptophan-, and tyrosine-like substances. Composting treatment increased the content of humic- and fulvic-like matter, and changed the existence pattern of tryptophan- and tyrosine-like substances (i.e., the tryptophan- and tyrosine-like substances from uncomposted MSWs were mainly bound in protein-like matter, whereas those from composted MSWs were primarily bound in humic- and fulvic-like substances). Furthermore, composting treatment increased the polar functional group, aromaticity, and humification degree of the WEOMs, but decreased the aliphatic and hydroxyl group. These evolutions decreased the Cu(II) affinities of fulvic- and humic-like substances and the Pb(II) affinities and complexing capacities of fulvic-like substances, but increased the Cu(II) complexing capacities of fulvic- and humic-like substances. These results reveal that mature composts from the MSWs can be used for the remediation of Cu- and Pb-contaminated soils in situ, whereas immature composts can enhance the metal transferability from soil to plant.

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as QT(J g⁻¹soil), ∆Hₘₑₜ(kJ mol⁻¹), JQ/S(J g⁻¹ h⁻¹), k (h⁻¹), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution QT(expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. QTfor IMI increases at 0.0–20 μg g⁻¹and then decreases at 20–80 μg g⁻¹, possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC₅₀) of IMI and ACE are 95.7 and 77.2 μg g⁻¹, respectively. ACE displays slightly higher toxicity than IMI. Plots of k and QTagainst microbial biomass-C indicate that the k and QTare growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.