Tributyltin partitioning in sediments: effect of aging

The effect of aging on the solid/pore-water partitioning and desorption behaviour of tributyltin (TBT) in sediments was examined. Three sediment samples with contrasting physical and chemical properties were spiked with 10 mg/kg TBT and aged under sterile conditions for periods of time ranging from 1 to 84 days. Aging had a negligible effect on partitioning and desorption behaviour in a sandy sample with very low organic carbon content (0.2% w/w). In contrast, for samples with larger amounts of organic carbon (2.6% and 4.8% w/w), aging caused substantial increases in TBT sorption. For these samples, apparent distribution coefficients (KD,app) obtained from sequential 2 h desorption experiments also exhibited a twofold increase between spiked sediments subjected to aging for 1 day and 84 days. This study demonstrates that aging effects may be an important aspect of TBT fate in contaminated sediments.     

Effect of chromium on the fatty acid composition of two strains of Euglena gracilis

The effect of hexavalent chromium on fatty acid composition was studied in two strains of Euglena gracilis; UTEX 753 (from the Culture Collection of Algae of Texas University, USA) and MAT (isolated from a highly polluted River). Both were grown in photoauxotrophic and photoheterotrophic conditions and exposed to two metal concentrations, one below and one above IC50. The high malondialdehyde (MDA) levels (3 to 7-fold) obtained with chromium concentration above IC50, suggested the existence of metal-induced lipid peroxidation. Total lipid content increased only with concentration below IC50, whereas it was inhibited by higher metal concentration. Photoheterotrophic control strains exhibited a significantly higher proportion of saturated and polyunsaturated fatty acids. Polyunsaturated acids were most affected by chromium, especially those related to chloroplast structures. Ultra-structure studies showed clear thylakoid disorganization in all treated cells. The results indicate that hexavalent chromium affects levels of fatty acids, especially those related to photosynthetic activity.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.     

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.     

Effect of pH control at the anode for the electrokinetic removal of phenanthrene from kaolin soil

Polycyclic aromatic hydrocarbon (PAH)-contaminated soils exist at numerous sites, and these sites may threaten public health and the environment because many PAH compounds are toxic, mutagenic, and/or carcinogenic. PAHs are also hydrophobic and persistent, so conventional remediation methods are often costly or inefficient, especially when the contaminants are present in low permeability and/or organic soils. An innovative technique, electrokinetically enhanced in situ flushing, has the potential to increase soil-solution-contaminant interaction and PAH removal efficiency for low permeability soils; however, the electrolysis reaction at the anode may adversely affect the remediation of low acid buffering capacity soils, such as kaolin. Therefore, the objective of this study was to improve the remediation of low acid buffering soils by controlling the pH at the anode to counteract the electrolysis reaction. Six bench-scale electrokinetic experiments were conducted, where each test employed one of three different flushing solutions, deionized water, a surfactant, or a cosolvent. For each of these solutions, tests were performed with and without a 0.01 M NaOH solution at the anode to control the pH. The test using deionized water with pH control generated a higher electroosmotic flow than the equivalent test performed without pH control, but the electroosmotic flow difference between the surfactant and cosolvent tests with and without pH control was minor compared to that observed with the deionized water tests. Controlling the pH was beneficial for increasing contaminant solubilization and migration from the soil region adjacent to the anode, but the high contaminant concentrations that resulted in the middle or cathode soil regions indicates that subsequent changes in the soil and/or solution chemistry caused contaminant deposition and low overall contaminant removal efficiency.     

Congener-specific accumulation of polychlorinated biphenyls in ovarian follicular wall follows repeated exposure to PCB 126 and PCB 153. Comparison of tissue levels of PCB and biological changes

OBJECTIVE: Small (SF), medium (MF) and large (LF) preovulatory porcine follicles were isolated and incubated in an Erlenmeyer flask containing 5 ml of medium with addition of PCB 126 or PCB 153 to test differences in their accumulation in the follicular wall. METHODS; The follicles were incubated in M199 medium at 37 degrees C with constant shaking at 70 rpm, for 6 days. The media were changed every day and repeated dose 25 pg/ml of PCB 126 or 25 ng/ml of PCB 153 was added each day till 6 days of culture. Media were collected every day and frozen for steroid analysis by RIA. 24 h after the last treatment follicles were frozen for further polychlorinated biphenyls (PCB) content analysis. PCB concentrations in the follicular wall were analysed by mass spectrometry. RESULTS: 3.3%; 3.6% and 5.6% of total PCB 126 dose, and 71%; 71.4% and 30.4% of total PCB 153 dose accumulated in SF, MF and LF follicles, respectively. The accumulative effect of PCB was manifested by the disruption of estradiol (E2) secretion. In SF antiestrogenic action of PCB 126 was observed during the whole time of exposure while PCB 153 decreased E2 till 4 days of culture and then estrogenic action was observed. In MF, both these congeners decreased E2 till 5 days of exposure and then estrogenic actions were noted with the highest magnification in the case of PCB 126. In LF both PCB studied increased E2 till 3 days of exposure with the highest magnification of PCB 126, then antiestrogenic action was noted. Testosterone secretion was generally affected in a pattern oposite to that of E2 suggesting action on P450arom activity. CONCLUSION: The results of these studies demonstrated that disruption of aromatization process in the follicles following repeated exposure to both congeners is not directly correlated with the bioaccumulation or amount of PCB within the follicular wall.     

Twentieth century overview of heavy metals in the Galician Rias (NW Iberian Peninsula)

The 18 Galician Rias, comprising 25% of the Iberian Peninsula coastline, form a unique system within the European continental Atlantic coast and provide a useful reference area for studies of metals. These rias are sensitive to anthropogenic influence due to the socioeconomic importance generated in these areas by industry, aquaculture, port activities, fishing, tourism and, accordingly, several islands lying within close proximity to the rias have recently been declared natural parks. Aquaculture in the Galician Rias is a growth industry and in 2000 the rias supported 3386 mussel rafts producing 2.5 x 10(8) kg year(-1), i.e. 40% of European Union total seafood production. The Galician Rias are partially stratified estuaries with positive residual circulation with fresh (runoff lower than 100 m3 s(-1) and salt water mixing inside the basins. This behaviour has direct consequences on metal fluxes whereby the rias behave as a barrier and accumulate metals in the sediments. Metals tend to deposit close to point sources and remobilization occurs inside the ria, leading to a seaward decrease in metal concentration. With the exception of the Ulla (Arosa Ria) and Eume (Ares-Betanzos Ria) head rivers and the Lagares river (Vigo Ria) the available data suggest that riverine freshwater inputs are not the main source of contamination. Metal studies reported in the literature mainly relate to Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, and to a lesser extent Hg and Sn. Studies of other harmful metals such as Ag, Se and As are notably lacking. In addition, the studies have been localized and mainly restricted to the surface sediment. Data of heavy metals in the dissolved phase, suspended particulate matter and biota is scarce in the mainstream literature and should be considered in the future research. From the entire Galician coast, data from seven rias of socio-economic importance form the bulk of the published work. There is an urgent need to standardize procedures, employ 'clean' procedures to avoid contamination of samples and regular assessment of analytical accuracy with CRMs in order that results can be compared among the scientific community and produce reliable results. The continuation of coastal environmental studies requires an enlargement of the sampling locations as well as systematic and periodic analysis of known pollution sources in order to decide whether coastal regeneration action is needed. Studies dedicated to metals in the water column are lacking and need more attention in future research. The majority of the available data correspond to the fluvial front (30%) at ria head and, to a lesser extent, to the oceanic front (3%), under summer upwelling events. Current awareness of the rias suggests that they are not contaminated although there is some evidence of important localized anthropogenically induced enrichments at the outflow of the Lagares River (Pb, Zn), the San Simón inlet (Pb) and near to the harbor (Pb, Zn, Cu) in the Vigo Ria, the inner part (Cu, Zn, Hg, Pb) of the Pontevedra Ria, the Ulla River estuary (Cu, Cr, Mn, Ni; Zn) in the Arosa Ria, the inner zone (Cu, Pb, Zn) of the Coru?a Ria, the Ferrol Ria (Zn) and the Eume Estuary (Zn, Mn, Ni, Co) in the Ares-Betanzos Ria. In addition, TBT enrichment has been found along the Galician coast, being highest in the industrial bays (Vigo, Coru?a and Ferrol). Nevertheless, it is important to point out the lack of information concerning the relationship between metal concentrations in different fractions of sediments and/or water and their bioavailability and toxicity on biota in order to confirm metal contamination dangers. The present paper reviews all the information published on metals in the rias up to the year 2000 and takes a biogeochemical standpoint, i.e. metal presence in the ria reservoirs: water column, suspended particulate matter, sediments and biota, as well as the fluvial and oceanic frontiers.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

A mini review of bisphenol A (BPA) effects on cancer-related cellular signaling pathways

Environmental Science and Pollution Research - Bisphenol A (BPA) is a plasticizer used widely in many industrial products and is now well established as an endocrine-disrupting chemical (EDC). BPA...     

Predicting logP of pesticides using different software

We compared experimental and calculated logP values using a data set of 235 pesticides and experimental values from four different sources: The Pesticide Manual, Hansch Manual, ANPA and KowWin databases. LogP were calculated with four softwares: HyperChem, Pallas, KowWin and TOPKAT. Crossed comparison of the experimental and calculated values proved useful, especially for pesticides. These are harder to study than simpler organic compounds. Structurally they are complex, heterogeneous and similar to drugs from a chemical point of view. They offer an interesting way to verify the goodness of the different methods. Other studies compared several logP predictors using a single set of experimental values taken as a reference. Here we discuss the utility of the different logP predictors, with reference to experimental data found in different databases. This offers three advantages: (1) it avoids bias due to the assumption that one single data set is correct; (2) a given predictor can be developed on the same data set used for evaluation; (3) it takes account of experimental variability and can compare it with the predictor's variability. In our study Pallas and KowWin gave the best results for prediction, followed by TOPKAT.