The effects of permethrin (PER) on a panel of antoxidant enzymes; superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST) and indices of protein oxidation status (carbonylation and free thiols) were determined in digestive gland and gills of the clam Ruditapes decussatus. Animals were exposed to 100 ppb PER for 2 days. These enzyme activities increased significantly in digestive gland (p < 0.05) after PER treatment and oxidative modification of proteins was detected in both gill and digestive gland extracts using redox proteomics. PER exposure significantly reduced the amount of protein free thiol groups in digestive gland rather than in gill, when compared to controls. Conversely, digestive gland showed significantly higher levels of carbonylated proteins than gill after PER exposure. Some proteins were successfully identified by mass spectrometry of tryptic peptides. Our data suggest that digestive gland of R. decussatus can be used as a model tissue for investigating environmental risk of PER contamination.

In this report, we refer to pharmaceuticals that are widespread in the urban aquatic environment and that mainly originate from wastewater treatment plants or non-point source sewage as “wastewater-marking pharmaceuticals” (WWMPs). To some extent, they reflect the condition or trend of water contamination and also contribute to aquatic environmental risk assessment. The method reported here for screening typical WWMPs was proposed based on academic concerns about them and their concentrations present in the urban aquatic environment, as well as their properties of accumulation, persistence, eco-toxicity and related environmental risks caused by them. The screening system consisted of an initial screening system and a further screening system. In the former, pharmaceuticals were categorised into different evaluation levels, and in the latter, each pharmaceutical was given a normalised final evaluation score, which was the sum of every score for its properties of accumulation, persistence, eco-toxicity and environmental risk in the aquatic environment. The system was applied to 126 pharmaceuticals frequently detected in the aquatic environment. In the initial screening procedure, five pharmaceuticals were classified into the “high” category, 16 pharmaceuticals into the “medium” category, 15 pharmaceuticals into the “low” category and 90 pharmaceuticals into the “very low” category. Subsequently, further screening were conducted on 36 pharmaceuticals considered as being of “high”, “medium” and “low” categories in the former system. We identified 7 pharmaceuticals with final evaluation scores of 1–10, 10 pharmaceuticals with scores of 11–15, 15 pharmaceuticals with scores from 16 to 20 and 4 pharmaceuticals with scores above 21. The results showed that this screening system could contribute to the effective selection of target WWMPs, which would be important for spatial-temporal dynamics, transference and pollution control of pharmaceuticals in the urban aquatic environment. However, there remains a number of pharmaceutical parameters with measured data gaps, such as organic carbon adsorption coefficients and bioconcentration factors, which, if filled, would improve the accuracy of the screening system.

A large-scale sampling program was conducted to simultaneously collect surface water, overlying water, pore water, and sediment samples at monthly intervals between March and December 2010 from Baiyangdian Lake, North China to assess the distribution of DDTs and determine the net direction of sediment–water exchange. Total DDT concentrations ranged 2.36–22.4 ng/L, 0.72–21.9 ng/L, 2.25–33.7 ng/L, and 4.42–7.29 ng/g in surface water, overlying water, pore water, and sediments, respectively, which were at the intermediate levels compared to those of other area around the world. Seasonal variations of DDTs were featured by higher concentration in summer. This was likely associated with (a) the increase of land runoff in the summer and (b) application of dicofol and DDT-containing antifouling paints for ships in summer. Sediment–water fugacity ratios of the DDT isomers were used to predict the direction of the sediment–water exchange of these isomers. The sediment–surface water, sediment–overlying water, and sediment–pore water fugacity ratios of DDT isomers averaged 0.34, 0.44, and 0.1, which are significantly lower than the equilibrium status (1.0), suggesting that the net flux direction were from the water to sediment and the sediment acted as a sink for the DDTs. The difference of DDT concentrations between sediment and water samples was found to be an important factor affecting the diffusion of DDT from the water to sediment.

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99 ‰ for the δ⁶⁵Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in ⁶⁵Cu compared to the soil. As a result of the same trial, the δ⁵⁶Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal–organic complexation and weathering can modify particular isotopic signatures.

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2 × 15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.

We developed a semiquantitative job exposure matrix (JEM) for workers exposed to polychlorinated biphenyls (PCBs) at a capacitor manufacturing plant from 1946 to 1977. In a recently updated mortality study, mortality of prostate and stomach cancer increased with increasing levels of cumulative exposure estimated with this JEM (trend p values = 0.003 and 0.04, respectively). Capacitor manufacturing began with winding bales of foil and paper film, which were placed in a metal capacitor box (pre-assembly), and placed in a vacuum chamber for flood-filling (impregnation) with dielectric fluid (PCBs). Capacitors dripping with PCB residues were then transported to sealing stations where ports were soldered shut before degreasing, leak testing, and painting. Using a systematic approach, all 509 unique jobs identified in the work histories were rated by predetermined process- and plant-specific exposure determinants; then categorized based on the jobs’ similarities (combination of exposure determinants) into 35 job exposure categories. The job exposure categories were ranked followed by a qualitative PCB exposure rating (baseline, low, medium, and high) for inhalation and dermal intensity. Category differences in other chemical exposures (solvents, etc.) prevented further combining of categories. The mean of all available PCB concentrations (1975 and 1977) for jobs within each intensity rating was regarded as a representative value for that intensity level. Inhalation (in microgram per cubic milligram) and dermal (unitless) exposures were regarded as equally important. Intensity was frequency adjusted for jobs with continuous or intermittent PCB exposures. Era-modifying factors were applied to the earlier time periods (1946–1974) because exposures were considered to have been greater than in later eras (1975–1977). Such interpolations, extrapolations, and modifying factors may introduce non-differential misclassification; however, we do believe our rigorous method minimized misclassification, as shown by the significant exposure–response trends in the epidemiologic analysis.

Operational discharges from oceangoing vessels, including discharges of bilgewater, release oil into marine ecosystems that can potentially damage marine life, terrestrial life, human health, and the environment. Bilgewater is a mix of oily fluids and other pollutants from a variety of sources onboard a vessel. If bilgewater cannot be retained onboard, it must be treated by an oily water separator before discharge for larger ocean-going vessels. We evaluated the effectiveness of bilgewater treatment systems by analyzing land-based type approval data, collecting and analyzing shipboard bilgewater effluent data, assessing bilgewater effluent concentrations compared to regulatory standards, evaluating the accuracy of shipboard oil content monitors relative to analytical results, and assessing additional pollution reduction benefits of treatment systems. Land-based type approval data were gathered for 20 treatment systems. Additionally, multiple samples of influent and effluent from operational bilgewater treatment systems onboard three vessels were collected and analyzed, and compared to the land-based type approval data. Based on type approval data, 15 treatment systems were performing below 5 ppm oil. Shipboard performance measurements verified land-based type approval data for the three systems that were sampled. However, oil content monitor readings were more variable than actual oil concentration measurements from effluent samples, resulting in false negatives and positives. The treatment systems sampled onboard for this study generally reduced the majority of other potentially harmful pollutants, which are not currently regulated, with the exception of some heavy metal analytes.

Cadmium (Cd) stress responses in seedlings of two Indian rice cultivars, MTU 7029 and MO 16 were investigated under ammonium-based fertilizer amendment. Cd translocation was reduced by fertilizer treatment. An increase in the production of organic acids as well as nitrogenous compounds and maintenance of nutrient status were implicated for decrease in Cd translocation which in turn promoted shoot growth. Fertilizer treatment increased photosynthetic pigments and activity of antioxidant enzymes that ensured steady photosynthetic rate during Cd stress. MO 16 showed Cd exclusion characteristics when compared with MTU 7029. Photosynthesis performance of MO 16 was not affected by Cd treatments. These findings suggest that photosynthesis influenced decrease in Cd translocation enhanced shoot growth of seedlings during ammonium phosphate–sulfur fertilizer supplementation.

Organic matter (OM) plays a key role in microbial response to soil metal contamination, yet little is known about how the composition of the OM affects this response in Mediterranean calcareous agricultural soils. A set of Mediterranean soils, with different contents and compositions of OM and carbonate and fine mineral fractions, was spiked with a mixture of Cd, Cu, Pb, and Zn and incubated for 12 months for aging. Microbial (Biolog Ecoplates) and enzyme activities (dehydrogenase, DHA; β-galactosidase, BGAL; phosphatase, PHOS; and urease, URE) were assessed and related to metal availability and soil physicochemical parameters. All enzyme activities decreased significantly with metal contamination: 36–68 % (DHA), 24–85 % (BGAL), 22–72 % (PHOS), and 14–84 % (URE) inhibitions. Similarly, catabolic activity was negatively affected, especially phenol catabolism (∼86 % compared to 25–55 % inhibition for the rest of the substrates). Catabolic and DHA activities were negatively correlated with ethylenediaminetetraacetic acid (EDTA)-extractable Cd and Pb, but positively with CaCl₂, NaNO₃, and DTPA-extractable Cu and Zn. Soluble OM (water- and hot-water-soluble organic C) was positively related to enzyme and catabolic activities. Recalcitrant OM and fine mineral fractions were positively related to BGAL and PHOS. Conversely, catabolic activity was negatively related to clay and positively to silt and labile OM. Results indicate that the microbial response to metal contamination is highly affected by texture and OM composition.

Although polychlorinated biphenyls (PCBs) have been banned in many countries for more than three decades, exposures to PCBs continue to be of concern due to their long half-lives and carcinogenic effects. In National Institute for Occupational Safety and Health studies, we are using semiquantitative plant-specific job exposure matrices (JEMs) to estimate historical PCB exposures for workers (n = 24,865) exposed to PCBs from 1938 to 1978 at three capacitor manufacturing plants. A subcohort of these workers (n = 410) employed in two of these plants had serum PCB concentrations measured at up to four times between 1976 and 1989. Our objectives were to evaluate the strength of association between an individual worker’s measured serum PCB levels and the same worker’s cumulative exposure estimated through 1977 with the (1) JEM and (2) duration of employment, and to calculate the explained variance the JEM provides for serum PCB levels using (3) simple linear regression. Consistent strong and statistically significant associations were observed between the cumulative exposures estimated with the JEM and serum PCB concentrations for all years. The strength of association between duration of employment and serum PCBs was good for highly chlorinated (Aroclor 1254/HPCB) but not less chlorinated (Aroclor 1242/LPCB) PCBs. In the simple regression models, cumulative occupational exposure estimated using the JEMs explained 14–24 % of the variance of the Aroclor 1242/LPCB and 22–39 % for Aroclor 1254/HPCB serum concentrations. We regard the cumulative exposure estimated with the JEM as a better estimate of PCB body burdens than serum concentrations quantified as Aroclor 1242/LPCB and Aroclor 1254/HPCB.