Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl₂ ⁰ to monodentate complex –C–O–HgCl and then bidentate complex –C–O–Hg–O–C– with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

Polyethylene passive samplers (PE) were deployed in Narragansett Bay, RI, to examine freely dissolved concentrations of polybrominated diphenyl ethers (PBDEs) in surface, bottom, and sediment porewater. PBDE congeners in the water column and porewater were below 3 pg L⁻¹. In the surface water, only PBDE congeners containing up to 5 bromines were detected, while in the deeper water congeners 153 and 154 (6 bromines) were also detected. Activity ratios of surface-bottom water and porewater-bottom water suggested that lower brominated (di-tetra) congeners reached Narragansett Bay from surface waters and sediments. PBDEs in the surface water probably originated from a combination of air–water exchange, freshwater runoff, rivers, and wastewater treatment plants. It is suggested that deep water was the source of higher brominated PBDEs to the Bay implying that the more hydrophobic PBDEs reached depth on particles and/or that these congeners were degraded in sediments. On-going sources supply PBDEs to Narragansett Bay.

Polycyclic aromatic hydrocarbon (PAH) diagnostic ratios have recently come into common use as a tool for identifying and assessing pollution emission sources. Some diagnostic ratios are based on parent PAHs, others on the proportions of alkyl-substituted to non-substituted molecules. The ratios are applicable to PAHs determined in different environmental media: air (gas + particle phase), water, sediment, soil, as well as biomonitor organisms such as leaves or coniferous needles, and mussels. These ratios distinguish PAH pollution originating from petroleum products, petroleum combustion and biomass or coal burning. The compounds involved in each ratio have the same molar mass, so it is assumed they have similar physicochemical properties. Numerous studies show that diagnostic ratios change in value to different extents during phase transfers and environmental degradation. The paper reviews applications of diagnostic ratios, comments on their use and specifies their limitations.

Atmospheric deposition of Hg is the predominant pathway for Hg to reach sensitive ecosystems, but the importance of emissions on near-field deposition remains unclear. To better understand spatial variability in Hg deposition, mercury concentrations were analyzed in sediment cores from 12 lakes with undeveloped watersheds near to (<50 km) and remote from (>150 km) several major urban areas in the United States. Background and focusing corrected Hg fluxes and flux ratios (modern to background) in the near-urban lakes (68 ± 6.9 μg m⁻² yr⁻¹ and 9.8 ± 4.8, respectively) greatly exceed those in the remote lakes (14 ± 9.3 μg m⁻² yr⁻¹ and 3.5 ± 1.0) and the fluxes are strongly related to distance from the nearest major urban area (r² = 0.87) and to population and Hg emissions within 50–100 km of the lakes. Comparison to monitored wet deposition suggests that dry deposition is a major contributor of Hg to lakes near major urban areas.

This study was set up to relate lead (Pb) bioavailability with its toxicity to plants in soils. Tomato and barley seedlings were grown in six different PbCl₂ spiked soils (pH: 4.7–7.4; eCEC: 4.2–41.7 cmolc/kg). Soils were leached and pH corrected after spiking to exclude confounding factors. Plant growth was halved at 1600–6500 mg Pb/kg soil for tomato and at 1900–8300 mg Pb/kg soil for barley. These soil Pb threshold were unrelated to soil pH, organic carbon, texture or eCEC and neither soil solution Pb nor Pb²⁺ ion activity adequately explained Pb toxicity among soils. Shoot phosphorus (P) concentrations significantly decreased with increasing soil Pb concentrations. Tomato grown in hydroponics at either varying P supply or at increasing Pb (equal initial P) illustrated that shoot P explained growth response in both scenarios. The results suggest that Pb toxicity is partially related to Pb induced P deficiency, likely due to lead phosphate precipitation.

We investigated the effects of ozone and leaf senescence on steady-state stomatal conductance and stomatal response to light variation. Measurements were carried out in a free-air ozone exposure experiment on a representative deciduous broadleaved tree species in Japan (Fagus crenata). Both steady-state and dynamic stomatal response to light variation varied intrinsically with season due to leaf senescence. Ozone induced the decrease in steady-state leaf gas exchange and the sluggish stomatal closure progressively. These findings suggest that ozone reduces the ability of plants to adapt to a fluctuating light environment under natural conditions, and therefore impairs plant growth and ability to control water loss.

A mixture of common Southern Piedmont (USA) grassland species (Lolium arundinacea, Paspalum dilatatum, Cynodon dactylon and Trifolium repens) was exposed to O₃ [ambient (non-filtered; NF) and twice-ambient (2X) concentrations] and fed to individually caged New Zealand white rabbits (Oryctolagus cuniculus) in a digestibility experiment. Forages and feed refusals were analyzed for concentrations of total cell wall constituents, lignin, crude protein, and soluble and hydrolyzable phenolic fractions. Neutral detergent fiber and acid detergent fiber digestibility by rabbits were significantly lower for 2X than NF forage. Decreased digestibility could not be attributed to lignin concentrations, but was associated with increased concentrations of acid-hydrolyzable and saponifiable phenolics. Exposure of forage to elevated O₃ resulted in decreased digestible dry matter intake by rabbits. Elevated O₃ concentrations could be expected to have a negative impact on forage quality, resulting in decreased nutrient utilization by mammalian herbivores in Southern Piedmont grasslands under projected future climate scenarios.

Oxidative damage has been proposed as an important mechanism linking pesticide exposure to health effects. A study of 268 young Shanghai children was conducted to examine the relationship between organophosphate pesticide (OP) exposure and a biomarker of oxidative DNA damage. Urine samples were analyzed for five nonspecific dialkyl phosphate (DAP) metabolites [dimethyl phosphates (DMs) and diethyl phosphates (DEs)] and 8-hydroxy-2′-deoxyguanosine (8-OHdG). The creatinine-adjusted median of 8-OHdG in urine samples was 3.99ng/mg. Increased exposure to OPs was associated with greater levels of urinary 8-OHdG [total DAPs: ß (adjusted)=0.46 per log₁₀ unit increase, 95% confidence interval (CI)=0.40–0.53, p=0.000; DMs: ß (adjusted)=0.34, 95% CI=0.28–0.41, p=0.000; DEs: ß (adjusted)=0.48, 95% CI=0.42–0.54, p=0.000]. Thus, the 8-OHdG biomarker is useful for increasing our understanding of the link between childhood exposure to OPs and health outcomes.

Chlorinated paraffins (CPs) were found in the biodegradable fraction of source separated waste from Uppsala, Sweden. We identified and quantified the CPs by multivariate evaluation of gas chromatography-electron capture detection chromatograms. Using principal component analyses (PCA) we identified different types of CP-formulations and also obtain quantitative data. PCA yielded better identifications of individual CP-formulations than visual comparison of chromatograms. Partial least squares regression gave good calibration curves of the standards, but did not work for the waste samples. No source of CPs could be identified in the waste collection chain, and as the waste samples seemed to contain at least two different CP-formulations the source was probably to be found in the waste material itself. The method was used to determine CPs in additional environmental samples, demonstrating that multivariate methods may be developed into a powerful tool for identification and quantification of complex mixture.

The Effects of silicon (Si) on the distribution of cadmium (Cd) compartmentation in root tips of Kandelia obovata (S., L.) Yong were investigated by pot experiments. Cd concentrations in the apoplastic saps and symplastic fractions of the root tips of K. obovata seedlings were decreased at both Si-supplied treatments. Si addition reduced the concentrations of BaCl₂₋extractable cell-wall-Cd in root tips, but increased the concentrations of Na₃citrate-extractable cell-wall-Cd and HCl-extractable cell-wall-Cd in root tips. The total root-tip contents of Cd were mainly distributed in the apoplast and most of the Cd in the apoplast was bound to the cell wall. Our experiment found that Si increased the ratio of apoplast Cd (>87.08%) and reduced the ratio of Cd in the symplast (<12.92%). This suggested that Si enhanced binding of Cd to the cell walls and restricted the apoplastic transport of Cd.