Polybrominated diphenyl ether exposure to electronics recycling workers--a follow up study

Workers at an electronics recycling plant have previously been shown to have elevated serum levels of polybrominated diphenyl ethers (PBDEs) compared to referents without occupational PBDE exposure. Subsequent structural changes and industrial hygiene measures at the plant were applied to improve the work environment. The present study aims to assess the impact of these work environment changes on the occupational exposure to PBDEs.

Blood were drawn from the workers and analyzed at two different laboratories, and serum concentrations of several PBDE congeners were determined by GC/MS or GC/HRMS. Cross-sectional studies were performed prior to (in 1997; N = 19) and after (in 2000; N = 27) workplace improvements. Longitudinal studies were performed on twelve of the workers that were sampled at both occasions.

Even though the amount of processed goods had doubled in 2000 as compared to 1997, there was a significant decrease in the serum levels of BDE-183 and BDE-209. For BDE-209 the levels observed in year 2000 were even lower than in referents with no occupational exposure. In contrast to the decrease of higher brominated diphenyl ethers, the concentrations of BDE-47 did not significantly change. For BDE-153, the cross-sectional study indicated no change, whereas the longitudinal follow up indicated a significant increase.

This study shows that the industrial hygiene improvements clearly reduced the occupational exposure to BDE-183 and BDE-209 at the plant. Still, the levels of hexa- to nonaBDEs but not BDE-209 were elevated, compared to referents with no occupational exposure.     

Temporal trend of bis(4-chlorophenyl) sulfone, methylsulfonyl-DDE and -PCBs in Baltic guillemot (Uria aalge) egg 1971-2001--a comparison to 4,4'-DDE and PCB trends

The dynamics of organohalogen contaminants and their metabolites are best studied over time by analysis of biota at high trophic levels. In this study, time trends, 1971-2001, of bis(4-chlorophenyl) sulfone (BCPS) and of methylsulfonyl-substituted metabolites of PCBs and 4,4'-DDE, were investigated in eggs of guillemot (Uria aalge) hatching in the Baltic Proper. Temporal trends of PCBs, trans-nonachlor, beta-HCH, 4,4'-DDT, and 4,4'-DDE were also assessed. Tris(4-chlorophenyl) methane (TCPMe), a 4,4'-DDT by-product, was detected in the eggs. The concentration of BCPS ranged between 2.6-0.76 microg/g on a lipid weight basis over the three decades and showed a significant 1.6% annual decrease. Three metabolites of PCBs, i.e. 3'-MeSO2-CB101, 4'-MeSO2-CB101 and 4-MeSO2-CB149, were quantified in all samples over time and showed an annual decrease of approximately 3% compared to MeSO2-DDE with a decrease of 8.9%. The methylsulfonyl-PCB and -DDE metabolites are eliminated more slowly than the persistent PCB congeners and 4,4'-DDE. Trans-nonachlor decreases by 16% compared to 19% and 9% for 4,4'-DDT and beta-HCH, respectively. The concentration of TCPMe in guillemot decreased by 8.2% per year. A linear relationship was found between TCPMe and 4,4'-DDE concentrations which supports the theory that TCPMe has an origin as a contaminant in commercial 4,4'-DDT products. The very slow decrease in BCPS concentrations is notable and remains to be explained. BCPS is still present at rather high concentrations in the guillemot eggs. The enantiomeric fraction varied between 0.27 and 0.67 which indicates less of a specific retention of the chiral MeSO2-PCBs in guillemot eggs than in grey seal tissues, for example. Independent of meta- or para-substitution of the sulfone group, the most accumulative atropisomer of each of four MeSO2-PCB pairs has been assigned an absolute R structure.     

Multiple biomarker responses in caged benthic gastropods <Emphasis Type="Italic">Bellamya aeruginosa</Emphasis> after in situ exposure to Taihu Lake in China

Background

Freshwater sediments have been recognized as a long-term sink and potential source for environmental pollutants released into the aquatic ecosystems. In this study, the sediment quality of Taihu Lake, which is susceptible to anthropogenic contamination, was assessed by a combination of chemical analytical and biological end points. Specifically, the snail Bellamya aeruginosa was caged in situ at two locations representing different pollution levels for different exposure times (7, 14 and 21 days). At each of these time points, biochemical parameters, i.e., phase I biotransformation enzymes ethoxyresorufin-O-deethylase (EROD), the antioxidant enzymes superoxide dismutase and catalase, reactive oxygen species, protein carbonyl content and lipid peroxidation, were evaluated in the hepatopancreas of snails. In addition, surface sediments were collected for analysis of contaminants of concern, including inorganic pollutants, organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers.

Results

Chemical analyses revealed that sediments from Taihu Lake were contaminated with trace elements and organic pollutants. Concentrations of trace elements (Cu, Ni and As) and organochlorinated pesticides (4,4′-DDE) exceeded their corresponding threshold effect level according to the sediment quality assessment values for freshwater ecosystems in Canada, indicating that adverse biological effects may occur. All biomarkers, except EROD activity, were induced in snails during all exposure times. The integrated biomarker response index (IBR) indicated that during the initial exposure phase (7 days), B. aeruginosa were subjected to significant environmental stress, which diminished during later sampling time points.

Conclusions

Results showed that IBR correlated well with the levels of environmental contaminants, demonstrating the applicability of this biomonitoring approach to complex environmental exposure scenarios.

     

Bis(4-chlorophenyl) sulfone (BCPS) in Swedish marine and fresh water wildlife-a screening study

Bis(4-chlorophenyl) sulfone (BCPS) is a high production volume chemical (HPVC) applied in thermostable polymers. BCPS has been detected as an environmental contaminant both in Europe and in North America but it is still not a commonly studied pollutant. In this study, three Baltic Sea fish species; herring (Clupea harengus), salmon (Salmo salar) and perch (Perca fluviatilis) from the Swedish coast, and one inland fish species, arctic char (Salvelinus alpinus), were analysed to screen for the occurrence and distribution of BCPS. Salmon and arctic char, were sampled in the early 1970s as well as the late 1990s. Fish eating grey seal (Halichoerus gryphus) and guillemot (Uria aalge) from the Baltic Sea were included to screen for whether BCPS biomagnify or not. The representativeness of the analysed samples for studying bioaccumulation of environmental pollutants was compared through analysis of two well known persistent and bioaccumulating compounds, 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153), and 4,4'-DDE. Pooled muscle and blubber samples based on 4-10 individuals were used for analysis, as well as individual samples of grey seal blubber. 2,4,4'-Trichlorodiphenyl sulfone, was synthesised and applied as an internal standard. BCPS was detected in all marine samples but in only one of the fresh water fish samples. The highest BCPS concentrations detected, 1600 and 1900 ng/g lipid weighet (l.w.), were found in muscle from Baltic guillemot. The results indicate that BCPS is bioaccumulated in both grey seal and guillemot, and that the guillemot has higher concentrations of BCPS than the grey seal (50-500 ng/g l.w.). The concentrations found in different species of fish from the Baltic Sea ranged between 15-37 ng/g l.w. and lower concentrations were found in freshwater species (n.d.-1.8 ng/g l.w.). The present study shows that BCPS is found in all investigated species of wildlife but, in most species, still at low concentrations. However, the guillemot has levels in the low ppm range indicating a considerable biomagnification of BCPS in this species.     

Synthesis of polychlorinated [14C]alkanes (PCA) of high specific activity

The synthesis of certain ¹⁴C-labelled polychlorinated alkanes is described. The compounds used as starting material were [1-¹⁴C]lauric acid, [1-¹⁴C]hexadecane and [U-¹⁴C]palmitic acid. The carboxylic acids were reduced with lithium aluminium hydride. The alcohol obtained was treated with triphenylphosphine dichloride which gave the corresponding 1-chloroalkane. The chlorination of the alkanes was performed in tetrachloromethane by use of sulphuryl chloride with benzoyl peroxide or UV-light as initiators. Three mixtures of polychlorinated dodecanes (45.9%, 55.9% and 68.5% chlorine) and two polychlorinated hexadecanes (34.1% and 69% chlorine) were synthesized. The products of higher chlorine content prepared were only available via the photoinduced chlorination.     

EVAPOTRANSPIRATION MEASUREMENT AND ESTIMATION OF THREE WETLAND ENVIRONMENTS IN THE UPPER ST. JOHNS RIVER BASIN,FLORIDA1

ABSTRACT: Accurate estimates of evapotranspiration from areas dominated by wetland vegetation are needed in the water budget of the Upper St. Johns River Basin. However, local data on evapotranspiration rates, especially in wetland environments, were lacking in the project area. In response to this need, the St. Johns River Water Management District collected evapotranspiration field data in Fort Drum Marsh Conservation Area over the period 1996 through 1999. Three large lysimeters were installed to measure the evapotranspiration from different wetland environments: sawgrass (Cladium jamaicense), cattail (Typha domingensis), and open water. In addition, pan evaporation was measured with a standard class “A” pan. Concurrently, meteorological data including rainfall, solar radiation, wind speed, relative humidity, air temperature, and atmospheric pressure were collected. By comparing computed evapotranspiration rates with those measured in the lysimeters, parameters in the Penman‐Monteith, the Priestley‐Taylor, and Reference‐ET methods, and evaporation pan coefficients were estimated for monthly and seasonal cycles. The results from the data collected in this study show that mean monthly evapotranspiration rates, computed by the different methods, are relatively close. From a practical point of view, results indicate that the evaporation pan can be used equally well as the more complex and data‐intensive methods. This paper presents the measured evapotranspiration rates, evaporation pan coefficients, and the estimated parameter values for three different methods to compute evapotranspiration in the project area. Since local data on evaporation are often scarce or lacking, this information may be useful to watershed hydrologists for practical application in other project regions.     

KALMAN FILTER ESTIMATION AND PREDICTION OF DAILY STREAM FLOWS: II. APPLICATION TO THE POTOMAC RIVER1

Results are reported from an application of the state space formulation and the Kalman filter to real-time forecasting of daily river flows. It is shown that the application of filtering techniques improves the overall forecasting performance of the model. As is true for most hydrologic systems, the model is not completely known. Therefore, the procedures pertaining to on-line parameter and noise statistics estimation, as presented in the first paper, are implemented. The example in this paper shows that these techniques also perform satisfactorily when applied to a real-world situation.     

A new structure-affinity relationship for TCDD receptor binding

We have investigated the capacity of various indoles to inhibit specific binding of [1,6-³H]2,3,7,8-tetrachlorodibenzo- -dioxin ([³H]TCDD) in rat liver cytosol, as analyzed by electrofocusing in polyacrylamide gels. Of these indoles, indolo[3,2- ]carbazole was the most active. The IC₅₀ value for TCDD receptor binding of indolo[3,2- ]carbazole as well as for 2,3,7,8-tetrachlorodibenzofuran was 3.6 nM. We have also studied the influence on binding exerted by introduction of some substituents on indolo[3,2- ]carbazole. Substitution with methyl groups at the 5 and 11 positions resulted in an increased affinity (IC₅₀ 1.2 nM) for the TCDD receptor as compared to the parent compound. Computer-supported molecular structure studies indicated that if the van der Waals radii of atoms are included, a rectangle of 6.8 × 13.7 Å may account for the binding of high-affinity ligands to the TCDD receptor.     

Porous organoclay composite for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Complex mixtures of hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs) in contaminated soil and groundwater can have severe and long-lasting effects on health. The evidence that these contaminants can cause adverse health effects in animals and humans is rapidly expanding. The frequent and wide-spread occurrence of PAHs in groundwater makes appropriate intervention strategies for their remediation highly desirable. The core objective of this research was to assess the ability of a clay-based composite to sorb and remove toxic contaminants from groundwater at a wood-preserving chemical waste site. Treatment efficiencies were evaluated using either effluent from an oil-water separator (OWS) or a bioreactor (B2). The effluent water from these units was passed through fixed bed columns containing either an organoclay composite or granular activated carbon. The sorbent columns were placed in-line using existing sampling ports at the effluent of the OWS or B2. Individual one-liter samples of treated and untreated effluent were collected in Kimax bottles over the course of 78 h (total of 50 samples). Subsequently each sample was extracted by solid phase extraction methodology, and pentachlorophenol (PCP) and PAH concentrations were quantitated via GC/MS. Columns containing porous organoclay composite, i.e. sand-immobilized cetylpyridinium-exchanged low-pH montmorillonite clay (CP/LPHM), were shown to reduce the contaminant load from the OWS effluent stream by 97%. The concentrations of benzo[a]pyrene (BaP) and PCP were considerably reduced (i.e. >99%). An effluent stream from the bioreactor was also filtered through columns packed with composite or an equivalent amount of GAC. Although the composite reduced the majority of contaminants (including BaP and PCP), it was less effective in diminishing the levels of lower ring versus higher ring PAHs. Conversely, GAC was more effective in removing the lower ring PAHs, except for naphthalene and PCP. The effectiveness of sorption of PCP from the OWS effluent by the composite was confirmed using a PCP-sensitive adult hydra bioassay previously described in our laboratory. The findings of this initial study have delineated differences between CP/LPHM and GAC for groundwater remediation, and suggest that GAC (instead of sand) as the solid support for organoclay may be more effective for the treatment of contaminated groundwater under field conditions than GAC or CP/LPHM alone. Further work is ongoing to confirm this conclusion.     

Biodegradation of 4-nonylphenol in seawater and sediment

Biodegradation of 14C-labelled nonylphenol at the concentration 11 microg litre (-1) in seawater has been estimated by collection and quantification of the formed labelled carbon dioxide. Initially degradation was very slow but when the microorganisms had become adapted, after four weeks at 11 degrees C, the degradation rate increased rapidly and after 58 days about 50% of 14C from NP was found in the CO2 fraction. In the presence of sediment the initial degradation rate was high and did not increase after longer incubation. Lack of oxygen reduced the degradation rate by half in the presence of sediment.