The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

Co-injection of air and steam for the prevention of the downward migration of DNAPLs during steam enhanced extraction: an experimental evaluation of optimum injection ratio predictions

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant, the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In a previous work, a theoretical model was developed to predict the optimum injection ratio of air to steam that would eliminate accumulation of DNAPL ahead of the temperature front and thus minimize the potential for downward migration. In this work, the theoretical model is summarized, and an experiment is presented in order to evaluate the optimum injection ratio prediction. In the experiment, a two-dimensional water saturated sand pack is contaminated with a known mass of TCE (DNAPL). The system is then remediated by co-injecting air and steam at the predicted optimum injection ratio, calculated based on the average contaminant soil concentration in the sand pack. Results for the co-injection of air and steam are compared to results for the injection of pure steam or pure air. Injection at the predicted optimum injection ratio for a volumetric average NAPL saturation, reduced accumulation of the contaminant ahead of the condensation front by over 90%, as compared to steam injection alone. This indicates that the optimum injection ratio prediction is a valuable tool for limiting the spreading of DNAPL during steam-enhanced extraction. Injection at the optimum injection ratio resulted in earlier recovery of contaminant than for steam injection alone. Co-injection of steam and air is also shown to result in much higher recovery rates than air injection alone.     

Cytotoxicity and DNA damage of five organophosphorus pesticides mediated by oxidative stress in PC12 cells and protection by vitamin E

Previous studies have demonstrated that pesticides could induce cytotoxicity and genotoxicity in vivo and in vitro, and that oxidative stress may be an important factor involved. However, investigations comparing the capability of different organophosphorous (OP) compounds to induce cytotoxicity, genotoxicity and oxidative stress are limited. Hence, the aim of this paper was to access the cytotoxic and genotoxic effects of five OPs or metabolites, Acephate (ACE), Methamidophos (MET), Chloramidophos (CHL), Malathion (MAT) and Malaoxon (MAO), and to clarify the role of oxidative stress, using PC12 cells. The results demonstrated that MET, MAT and MAO caused significant inhibition of cell viability and increased DNA damage in PC12 cells at 40 mg L^?1. MAO was more toxic than the other OPs. ACE, MET, MAT and MAO increased the levels of intracellular reactive oxygen species (ROS) and malondialdehyde (MDA), and decreased the activity of superoxide dismutase (SOD), catalase (CAT) and glutathione (GSH) at 20 mg L^?1 and 40 mg L^?1 to different degrees. Pre-treatment with vitamin E(600 μM)caused a significant attenuation in the cytotoxic and genotoxic effect; pre-treatment reversed subsequent OP-induced elevation of peroxidation products and the decline of anti-oxidant enzyme activities. These results indicate that oxidative damage is likely to be an initiating event that contributes to the OP-induced cytotoxicity.     

Polycyclic aromatic hydrocarbons, black carbon, and molecular markers in soils of Switzerland

Polycyclic aromatic hydrocarbons (PAH) were analysed in 23 soil samples (0–10 cm layer) from the Swiss soil monitoring network (NABO) together with total organic carbon (TOC) and black carbon (BC) concentration, as well as some PAH source diagnostic ratios and molecular markers. The concentrations of the sum of 16 EPA priority PAHs ranged from 50 to 619 μg/kg dw. Concentrations increased from arable, permanent and pasture grassland, forest, to urban soils and were 21–89% lower than median numbers reported in the literature for similar Swiss and European soils. NABO soils contained BC in concentrations from 0.4 to 1.8 mg/g dw, except for two sites with markedly higher levels. These numbers corresponded to 1–6% of TOC and were comparable to the limited published BC data in soil and sediments obtained with comparable analytical methods. The various PAH ratios and molecular markers pointed to a domination of pyrogenically formed PAHs in Swiss soils. In concert, the gathered data suggest the following major findings: (1) gas phase PAHs (naphthalene to fluorene) were long-range transported, cold-condensated at higher altitudes, and approaching equilibrium with soil organic matter (OM); (2) (partially) particle-bound PAHs (phenanthrene to benzo[ghi]perylene) were mostly deposited regionally in urban areas, and not equilibrated with soil OM; (3) Diesel combustion appeared to be a major emission source of PAH and BC in urban areas; and (4) wood combustion might have contributed significantly to PAH burdens in some soils of remote/alpine (forest) sites.     

Improvements of nano-SiO2 on sludge/fly ash mortar

Sewage sludge ash has been widely applied to cementitious materials. In this study, in order to determine effects of nano-SiO(2) additives on properties of sludge/fly ash mortar, different amounts of nano-SiO(2) were added to sludge/fly ash mortar specimens to investigate their physical properties and micro-structures. A water-binding ratio of 0.7 was assigned to the mix. Substitution amounts of 0%, 10%, 20%, and 30% of sludge/fly ash (1:1 ratio) were proposed. Moreover, 0%, 1%, 2%, and 3% of nano-SiO(2) was added to the mix. Tests, including SEM and compressive strength, were carried out on mortar specimens cured at 3, 7, and 28 days. Results showed that sludge/fly ash can make the crystals of cement hydration product finer. Moreover, crystals increased after nano-SiO(2) was added. Hence, nano-SiO(2) can improve the effects of sludge/fly ash on the hydration of mortar. Further, due to the low pozzolanic reaction active index of sludge ash, early compressive strengths of sludge/fly ash mortar were decreased. Yet, nano-SiO(2) could help produce hydration crystals, which implies that the addition of nano-SiO(2) to mortar can improve the influence of sludge/fly ash on the development of the early strength of the mortar.     

Simultaneous treatment of PVC and oyster-shell wastes by mechanochemical means

This work presents a new process for dechlorinating poly-vinyl chloride (PVC) by the use of oyster-shell waste. The process consists of milling of PVC waste with oyster-shell waste, followed by washing the milled sample with water. The milling of PVC and oyster-shell mixture results in size reduction and rupture in bonds, leading to mechanically induced reactions between the two to form CaCl2 and hydrocarbon with C=C bonds. Washing the milled mixtures with water at room temperature allows complete removal of chlorine from the milled sample. More than 95% of chlorine in PVC was removed when 2h grinding is conducted for the mixture. The present process could offer a potential route to the handling and disposal of oyster-shell and PVC wastes.