Possible involvement of frontier (π) electrons in the metabolism of poly-chlorinated biphenyls (PCBs)

The electron density, at each carbon atom, of the highest occupied π orbital of thirteen polychlorinated biphenyl (PCB) and one polychlorinated dibenzofuran (PCDF) molecules were calculated and the result was compared with their in vitro and/or in vivo metabolism. We noted that 1. the carbon position at which the frontier electron density was highest was most readily hydroxylated or sulfonated, 2. if the carbon with the highest frontier (π) electrons was occupied by chlorine, either a replacement occurred or the carbon with the next highest electron density was activated for metabolism, 3. due to steric hinderance ‘ortho’ carbons in PCBs were least preferred for such reactions inspite of possessing favorable electron density, 4. this was applicable to both phenobarbitol (PB) - type and 3-methyl cholanthrene (3 MC) - type PCB inducers. Frontier (π) electron density could be an easy guide for understanding the metabolic products of persistent and toxic environmental pollutants in vitro or in vivo and in understanding their environmental fate.     

Phosphate solubilizing actinomycetes in the estuarine environment: an inventory.

Sediment samples were collected from different stations of the Vellar estuary for isolation of total actinomycetes and phosphate solubilizing actinomycetes. Phosphatase activity in the sediments was also investigated Consistently a higher number of actinomycetes, phosphate solubilizing actinomycetes and phosphatase activity were recorded from the clay sediments than the sandy sediments at all the stations. In all, 7 strains showed positive phosphatase activity. Among them, one strain PS-3 exhibited good activity and was further investigated for optimum phosphorus solubilization at different pH (6, 6.5, 7, 7.5 and 8) and incubation (1st day to 20th day) periods. The solubilizing activity was maximum at the pH 7 and an incubation period of 13 days was required for an appreciable quantity of phosphorus to be leached into the medium. Based on the chemotaxonomical and conventional methods of identification, the strain PS-3 has been tentatively identified as Streptomyces galbus. The present study indicates that phosphatase enzyme and S. galbus along with other actinomycetes species would play a major role in solubilizing the phosphate in the estuarine ecosystem and increasing the soluble phosphate concentration thereby enhancing the productivity     

Characterization of trace organic contaminants in marine sediment from Yeongil Bay, Korea: 2. Dioxin-like and estrogenic activities

This study employed mechanism-specific in vitro bioassays to help characterize the occurrence and distribution of dioxin-like and estrogenic contaminants in sediment from Yeongil Bay, Korea. Approximately 85% of the sediments tested induced significant dioxin-like activity in the H4IIE-luc bioassay, while approximately 50% induced significant estrogenic activity in the MVLN bioassay. Instrumentally-derived estimates of 2,3,7,8-tetrachlorodibenzo-p-dioxin and 17beta-estradiol equivalents tended to underestimate the magnitude of response observed in the bioassays, suggesting that compounds detected by chemical analysis did not account for all the activity associated with Yeongil Bay sediments, or that non-additive interactions were occurring. The greatest dioxin-like and estrogenic activity was associated with the mid-polarity Florisil fractions (F2) expected to contain polycyclic aromatic hydrocarbons (PAHs) as well as chlorinated dioxins and furans. As in previous studies of Korean coastal sediment, more polar fractions (F3) generated more modest responses both in terms of magnitude and the number of samples responding.     

Residues of phosphamidon in rice fields

Thirty-day-old seedlings of rice plants (IR-20 variety) from the nursery were transplanted into experimental plots and after 52 days were sprayed with phosphamidon (Dimecron 85% EC) at two dose-rates (0.38 kg a.i. ha(-1) and 0.76 kg a.i. ha(-1)). Residues of phosphamidon in the plant, soil and water were analysed by GLC, at various time intervals, and were found to decrease steadily up to 15 days. A second application of the pesticide was made on day 113 and grains harvested on day 138. The residue level in the plants was 0.12 microg g(-1) and in the grains 0.04 microg g(-1) with the high dose. This is slightly below the EPA prescribed tolerance level of 0.05 microg g(-1). The residues in both soil and water were very low, 24 h after spraying.     

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.     

Dyes removal from water using polymeric nanocomposites: a review

Environmental Chemistry Letters - Most dyes are pollutants that should be removed from waters due to their mutagenic and carcinogenic properties, requiring advanced adsorption methods. Here, we...     

Assessment of deep aquifer groundwater quality in a geographically unique climatic region of Southern Western Ghats,India using water quality indices

Water quality index (WQI) models are generally used in hydrochemical studies to simplify complex data into single values to reflect the overall quality. In this study, deep groundwater quality in the Chittur and Palakkad Taluks of the Bharathapuzha river basin of Kerala, India, was assessed by employing the WQI method developed by the Canadian Council of Ministers of the Environment (CCME). The assessment of overall water quality is indispensable due to the specific characteristics of the study area, such as geography, climate, over-drafting, and prevalent agricultural practices. Forty representative samples were collected from the study area for monsoon (MON) and pre-monsoon (PRM) seasons. The results showed a general increase of contents from MON to PRM. The major cations were spread in the order Ca²⁺>Na+>Mg²⁺>K⁺ and the anions HCO₃⁻>Cl⁻>CO₃²⁻ based on their relative abundance. Among various parameters analysed, alkalinity and bicarbonate levels during MON were comparatively high, which is indicative of carbonate weathering, and 90% of the samples failed to meet the World Health Organization (WHO, 2017)/Bureau of Indian Standards (BIS, 2012) drinking water guidelines. The CCME WQI analysis revealed that nearly 50% of the samples during each season represented good and excellent categories. The samples in the poor category comprised 10% in MON and 15% in PRM. The overall WQI exhibited 15% of poor category samples as well. The spatial depiction of CCME WQI classes helped to expose zones of degraded quality in the centre to eastward parts. The spatial and temporal variations of CCME WQI classes and different physicochemical attributes indicated the influence of common factors attributing to the deep groundwater quality. The study also revealed inland salinity at Kolluparamba and Peruvamba stations, where agricultural activities were rampant with poor surface water irrigation.     

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.     

A database of avian blood spot examinations for exposure of wild birds to environmental toxicants: the DABSE biomonitoring project

DABSE, a database for avian blood spot examination for exposure to toxicants, is a new biomonitoring project in wild birds that has the goal of providing reference values of harmful agents, as measured in whole blood stored as dried blood spots. Once these "normal" values have been established, the diagnosis of environmental contaminant-mediated ill-health (such as manifestations of sickness, increased mortality, a reduction in population, poor breeding success, abnormal behavior) in an individual bird or in a population could be facilitated by comparing exposure values in the investigation to reference values of the same species in the database. One might then identify the cause and pave the way for a mitigating response. The toxicant component of DABSE is being examined at the low ng ml(-1) level in 200 μl of whole blood. As these analyses are invariably very costly, an effort has been made to lower these costs and so enable more testing by quantitating representative compounds as markers for the whole group. These markers are invariably found in birds' blood at the highest concentration of all the constituents in that group. The toxicant groups comprise:- (a) elements-arsenic, cadmium, lead, mercury and selenium; (b) organochlorine pesticides, markers being p,p'-DDT, p,p'-DDE, β-HCH, HCB and oxychlordane; (c) polychlorinated biphenyls (PCBs), the marker being congener 153; (d) polybrominated diphenyl esters (PBDEs), the marker being congener 47; (e) perfluorinated compounds (PFCs), the markers being perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). DABSE will be expanded to determine exposure to infectious diseases and perhaps acute toxicoses.     

Concentrations and accumulation profiles of PCDDs, PCDFs and dioxin-like PCBs in adipose fat tissues of Korean women

Reports on residue levels and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in human adipose tissue are scarce in Korea. In this study, concentrations and accumulation features of PCDD/Fs and DL-PCBs were determined in the samples of adipose tissue collected from Korean women in 2007-2008. The total dioxin-like toxic equivalent (TEQ) concentrations (3.4-42 pg g(-1) lipid wt) in Korean adipose tissues were similar to those reported in European and other Asian countries. The relative contributions of individual compounds to total TEQs were as follows: non-ortho PCBs (mean: 45%) > PCDFs (28%) > PCDDs (24%) > mono-ortho PCBs (3%), a pattern similar to those reported for seafoods in Korea. The dominant PCDD/F congeners found in adipose tissues were OCDD and 2,3,4,7,8-PeCDF and dominant PCBs were 118, 156 and 105. No correlation was found between subject's age and concentrations of dioxin-like contaminants. Body mass index was not correlated with concentrations of PCDD/Fs and was negatively (p < 0.001) correlated with concentrations of DL-PCBs. The results of this study provide baseline information on PCDD/Fs and DL-PCBs in adipose tissues of the general population in Korea.