Polybrominated diphenyl ether in the East Asian environment: a critical review

Polybrominated diphenyl ethers (PBDEs) have been extensively used as flame retardants in consumer goods. Sufficient evidence shows that PBDEs have been rapidly accumulating in the environment worldwide. In Asia, deca-bromodiphenyl ether has been produced and used in large quantities, while penta-BDE has largely ceased in the mid-1990s. This paper summarizes and critically reviews the status of PBDE pollution in East Asia, with emphases on the comparisons with Europe and North America and the interpretation of the differences. In general, the concentrations of PBDEs in atmosphere, sludge, human and biological samples of East Asia are comparable to or lower than those in Europe and North America. However, in the sediments of waters near densely populated and heavily industrialized areas, PBDE levels are among the highest ever reported in the literature. In Japan and China, concentrations of PBDEs in sediment cores showed an increasing trend for the past 20-30 years. Also, PBDEs levels in human breast milk in Japan increased about 10-fold in the past 20 years. The presence of PBDEs in fur seal has increased about 150-fold in 1994 than that in 1972. Regional and inter-continental transport cannot be confirmed due to insufficient information. However, the detection of a number of PBDE congeners in a pristine lake on the Qinghai-Tibet Plateau may be an evidence of their long-range transport.     

Changes of AhR-mediated activity of humic substances after irradiation

Humic substances (HS) and natural organic matter (NOM) are natural organic compounds ubiquitous in the environment. However, some studies indicate that both HS and NOM can act as xenobiotics, e.g. induce hormone-like effects in fish, amphibians and invertebrates. Molecules of these substances contain a number of aromatic rings and conjugated double bonds--the so called chromophores. Irradiation of dissolved HS and NOM can lead to a series of photochemical reactions which can act on these substances itself, or on other substances present in aquatic environment along with HS and NOM such as e.g. xenobiotics. In our previous study, we have found significant interactions of five humic acids (HA) with cytosolic aryl hydrocarbon receptor (AhR) in an in vitro bioassay based on H4IIE-luc cells. In the present study, we have studied the changes in AhR-mediated activities both of HS and NOM after irradiation that simulated natural solar light. Nine different HS and two NOM samples were irradiated in Pyrex tubes with a medium-pressure mercury lamp for a duration of 0 to 52 h (which corresponds to 0-52 d natural solar radiation). Original concentrations of the samples were 50 mg L(-1), and the greatest concentration of HS and NOM photoproducts subsequently tested in the bioassay was 17 mg L(-1), which is an environmentally relevant concentration. After irradiation the absorbances of all the samples were less than the original materials. The AhR-mediated activity of the HA-Fluka and HA Sodium Salt were partially decreased by irradiation. The activities of other HS and NOM, that were either AhR-active or -inactive were not changed by irradiation. The results of the study demonstrate that AhR-mediated activities of two active HA is caused by both photo-stable and photo-labile AhR activators, while the other three active HA contain only photo-stable AhR activators. Potential mechanisms of the observed irradiation-induced changes in AhR-mediated activities are discussed.     

Analysis of radiocaesium in the Lebanese soil one decade after the Chernobyl accident

Fallout from the Chernobyl reactor accident due to the transport of a radioactive cloud over Lebanon in the beginning of May 1986 was studied 12 years after the accident for determining the level of (137)Cs concentration in soil. Gamma spectroscopy measurements were performed by using coaxial high sensitivity HPGe detectors. More than 90 soil samples were collected from points uniformly distributed throughout the land of Lebanon in order to evaluate their radioactivity. The data obtained showed a relatively high (137)Cs activity per surface area contamination, up to 6545Bqm(-2) in the top soil layer 0-3cm. The average activity of (137)Cs in the top soil layer 0-3cm in depth was 59.7Bqkg(-1) dry soil ranging from 15 to 119Bqkg(-1) dry soil. The horizontal variability was found to be about 45% between the sampling sites. The depth distribution of total (137)Cs activity in soil showed an exponential decrease. Estimation of the annual effective dose due to external radiation from (137)Cs contaminated soil for selected sites gave values ranging from 19.3 to 91.6 micro Svy(-1).     

Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes

Aiming to determine the plutonium amount as well as its isotopic composition, in particular, in swipe samples for safeguards purposes, an analytical method was developed with a plutonium separation step based on extraction chromatography using 2 cm TEVA columns and detection with quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with membrane desolvation system. The method was successfully applied to New Brunswick plutonium certified reference materials as well as to Lawrence Livermore National Laboratory round robin samples, based on the round robin samples provided by the Institute for Reference Materials and Measurements (Belgium), as part of the Regular European Interlaboratory Measurement Evaluation Programme (REIMEP), campaign 16 (isotopic abundances of plutonium in plutonium nitrate samples), with a total plutonium amount between 1 and 0.25 ng per sample. After the introduction of an additional separation step, it was also possible to carry out precise and accurate total plutonium, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu atom ratios determination in sediment sample showing its applicability to environmental samples in general, reaching a detection limit equivalent to 5 mBq(239)Pu kg(-1).     

Generic approaches to transfer

A review of methods which have been used to describe and predict transfer of radionuclides in biota was undertaken. The intent was to identify approaches that might prove useful in extending predictive estimates to other organisms and environments. Empirical approaches, such as found in the use of transfer factors, were examined. Kinetic methodologies were also presented. Allometric functions, with their ability to make broad generalizations, were also discussed. Data from several earlier radioecological assessments were tested for their potential utility in developing allometric relationships, with the result implying that such an approach might prove useful.     

The value of Seasonal Correction Factors in assessing the health risk from domestic radon: a case study in Northamptonshire, UK

Following an intensive survey of domestic radon levels in the United Kingdom (UK), the former National Radiological Protection Board (NRPB), now the Radiation Protection Division of the Health Protection Agency (HPA-RPD), established a measurement protocol and promulgated Seasonal Correction Factors applicable to the country as a whole. Radon levels in the domestic built environment are assumed to vary systematically and repeatably during the year, being generally higher in winter. The Seasonal Correction Factors therefore comprise a series of numerical multipliers, which convert a 1-month or 3-month radon concentration measurement, commencing in any month of the year, to an effective annual mean radon concentration. In a recent project undertaken to assess the utility of short-term exposures in quantifying domestic radon levels, a comparative assessment of a number of integrating detector types was undertaken, with radon levels in 34 houses on common geology monitored over a 12-month period using dose-integrating track-etch detectors exposed in pairs (one upstairs, one downstairs) at 1-month and 3-month resolution. Seasonal variability of radon concentrations departed significantly from that expected on the basis of the HPA-RPD Seasonal Correction Factor set, with year-end discontinuities at both 1-month and 3-month measurement resolutions. Following this study, monitoring with electrets was continued in four properties, with weekly radon concentration data now available for a total duration in excess of three and a half years. Analysis of this data has permitted the derivation of reliable local Seasonal Correction Factors. Overall, these are significantly lower than those recommended by HPA-RPD, but are comparable with other results from the UK and from abroad, particularly those that recognise geological diversity and are consequently prepared on a regional rather than a national basis. This finding calls into question the validity of using nationally aggregated Seasonal Correction Factors, especially for shorter exposures, and the universal applicability of these corrections is discussed in detail.     

Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

Impact of dredging in a shallow coastal lagoon: Microtox Basic Solid-Phase Test, trace metals and Corophium bioassay

The aim of this work was to measure survival of the amphipod Corophium insidiosum and luminescence inhibition in the marine bacterium Vibrio fisheri on surface sediment samples collected from a shallow coastal lagoon (Pialassa Baiona, northern Adriatic Italian coast) before execution of dredging operations to deepen the main inner channel of the lagoon and restore the water circulation. Trace metal (Cd, Cu, Cr, Hg, Ni, Pb) concentrations, grain size and organic carbon matter content as loss of ignition were also measured. Toxicity testing with V. fisheri was carried out according to the Microtox Basic Solid-Phase Test (BSPT) protocol. The preliminary outcomes of this work show that: (a) the investigated area can be categorised as moderately degraded; (b) there is no evident spatial pattern in sediment toxicity and trace metal concentrations; (c) Microtox responses are not biased by sediment characteristics such as silt, clay and organic matter content.     

Transport and fate of mercury under different hydrologic regimes in polluted stream in mining area

Seepage from Hg mine wastes and calcines contains high concentrations of mercury (Hg). Hg pollution is a major environmental problem in areas with abandoned mercury mines and retorting units. This study evaluates factors, especially the hydrological and sedimentary variables, governing temporal and spatial variation in levels and state of mercury in streams impacted by Hg contaminated runo . Samples were taken during di erent flow regimes in theWanshan Hg mining area in Guizhou Province, China. In its headwaters the sampled streams/rivers pass by several mine wastes and calcines with high concentration of Hg. Seepage causes serious Hg contamination to the downstream area. Concentrations of Hg in water samples showed significant seasonal variations. Periods of higher flow showed high concentrations of total Hg (THg) in water due to more particles being re-suspended and transported. The concentrations of major anions (e.g., Cl??, F??, NO3?? and SO4 2??) were lower during higher flow due to dilution. Due to both sedimentation of particles and dilution from tributaries the concentration of THg decreased from 2100 ng/L to background levels (< 50 ng/L) within 10 km distance downstream. Sedimentation is the main reason for the fast decrease of the concentration, it accounts for 69% and 60% for higher flow and lower flow regimes respectively in the upper part of the stream. Speciation calculation of the dissolved Hg fraction (DHg) (using Visual MINTEQ) showed that Hg(OH)2 associated with dissolved organic matter is the main form of Hg in dissolved phase in surface waters in Wanshan (over 95%).     

Efficacy of natural biocide on control of microbial induced corrosion in oil pipelines mediated by Desulfovibrio vulgaris and Desulfovibrio gigas

We compared the efficacy of a natural biocide with four chemical tetrakishydroxymethyl phosphonium sulfonate, benzyl trimethyl ammonium chloride, and formaldehyde, glutaraldehyde, to control microbial induced corrosion in oil pipelines. The efficacy of biocides were monitored against Desulfovibrio vulgaris and Desulfovibrio gigas in experimental pipes by measuring cell counts, H2S production, Fe(II) production, production of extracellular polymeric substances and structure of biofilm. The treatment with cow urine had minimum planktonic cell counts of 3 102 CFU/mL as well as biofilm cell counts of 9 101 CFU/mL as compared with tetrakishydroxyl methyl phosphonium sulfonate, benzyl trimethyl ammonium chloride, formaldehyde and glutaraldehyde. Sulfide production was the lowest with cow urine (0.08 mmol/L), followed by tetrakishydroxymethyl phosphonium sulfonate 0.72 mmol/L. On day 90 of treatment, Fe(II) production was also found to be the lowest with cow urine. The scanning electron microscopic studies indicated that the biofilm bacteria were killed by cow urine. These results demonstrate the cow urine mediated control of microbially induced corrosion, and this is indicative of its potential as a viable substitute of toxic biocides. To the best of our knowledge, this seems to be the first report which screens possible biocidal activity by cow urine as compared to the most common biocides which oil industry is currently using.