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IL-33 represents a potential link between the airway epithelium and induction of a Th2-type inflammatory response in asthma. However, the association with markers of eosinophilic airway inflammation has not previously been reported in patients with steroid-free asthma.To describe the relationship between airway IL-33 and markers of eosinophilic airway inflammation, as well potential triggers of IL-33, in mild, steroid-free asthma.IL-33 mRNA expression and IL-33 immunoreactivity were measured in bronchial biopsies from patients with asthma untreated with inhaled steroids and healthy individuals. Furthermore, fractional exhaled nitric oxide (FeNO) and eosinophils in sputum and BAL were measured, as well as airway hyperresponsiveness to mannitol and methacholine. Epithelial integrity was assessed by computerized image analysis on haematoxylin-stained sections, and TLR mRNA expression by PCR.A total of 23 patients with asthma and 10 healthy individuals were examined (age: 24 years (20-40); females: 53%). The level of IL-33 mRNA expression was significantly higher in patients with asthma compared to healthy individuals (Median (IQR) 1.12 (0.78) vs. 0.86, P = 0.04). There was a positive correlation between IL-33 mRNA expression and the level of FeNO (r = 0.56, P = 0.01), whereas there was no association with airway or blood eosinophils. IL-33 expression was unrelated to loss of epithelial integrity, but correlated with an increased expression of TLR2 and TLR4 (TLR2: r = 0.47, P = 0.04; TLR4: 0.68, P 0.001), as well allergy to house dust mites (HDMs).In mild untreated asthma, the expression of IL-33 mRNA in bronchial mucosa is related to innate immune activation and allergic sensitization to HDM, rather than epithelial damage, and correlates with FeNO. These findings suggest that in mild allergic asthma, IL-33 may represent a link between innate immune activation and FeNO production.

The efficiency of a biologically activated carbon system for treating wastewater polluted with petroleum products was examined and the effects of process parameters on its efficacy were evaluated. In each experiment 17 alkylated and 19 non-alkylated polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPHs, C(10)-C(40)) were extracted using semipermeable membrane devices from wastewater before and after treatment. The acquired data during experiments were analyzed using principal component analysis (PCA). The treatment system robustly removed dissolved PAHs across the studied ranges of the process parameters, providing overall removal efficiencies of 96.9-99.7% for the sum of 36 PAHs. However, the major contributor to their removal was sorption rather than biodegradation, and despite the general efficiency of the process there was up to a 9-fold range in the sums of quantified PAHs in the effluents between experiments. Combinations of long process contact time (24 h) with high temperature (24 degrees C) and moderate oxygen concentration (6-7 mg O(2) L(-1)) resulted in good removal of bioavailable PAHs. The removal of TPHs was more dependent on biological activities during the wastewater treatment, and consequently more dependent on the process parameters. In addition, small but significant proportions of PAHs were volatilized and released during the wastewater treatment.

A chemical and ecotoxicological assessment of treatment of wastewater that had been polluted with petroleum products using only Activated Sludge (AS) and four biologically activated sorbents (BASs), consisting of activated sludge plus: coal-based activated carbon (-C1), coconut shell-based activated carbon (-C2), zeolite (-Z), and anthracite (-A) were conducted. The efficiency and robustness of the four wastewater treatment systems were evaluated by calculating the reduced total petroleum hydrocarbon (TPH) and polycyclic aromatic hydrocarbon (PAH) contents and the acute ecotoxicity of the effluents. The chemical analysis showed that the combined treatment systems were very effective for reducing the total petroleum hydrocarbon and readily bioavailable PAH contents. The most efficient systems were the BAS-C1 and -C2, which removed 60–88% and 99.5–99.6% of TPH and PAH, respectively. The activated sludge-only treatment was the least effective for purifying the wastewater. Chemical oxygen demand was reduced by >90% by all carbon-based BASs (BAS-C1, BAS-C2 and BAS-A). Shifts in the relative composition of the individual PAHs were identified in samples taken before and after treatment. Algal and bacterial bioassays showed that the toxicities of effluents following treatment by all four systems (except AS for algae) were reduced by more than 80% and 90%, respectively. However, crustacean tests indicated that the carbon-based BASs reduced the toxicity [Vtox(50)] only by 19–67%. Our results indicated that the combination of sorption and biodegradation processes have great potential in the treatment of petroleum products polluted wastewater and is less sensitive for inhibitors of the biological process than treatments in which activated sludge alone is used. The assessment of chemical and ecotoxicological endpoints provided valuable information, but contrasting results for one of the assays indicates that further analysis on the capacity of the different treatment systems is warranted.

Semipermeable membrane devices (SPMDs) were exposed at ten sampling points, each representing a different stage in the treatment process, in a municipal sewage treatment plant. Differences in SPMD uptake kinetics of polycyclic aromatic hydrocarbons (PAHs) due to variations in conditions at the sampling sites were evaluated by using five performance reference compounds (PRCs) with log K(ow) values of 4.20 to 6.34. PRC release rate constants (k(e,PRC) values) were calculated for PRCs for which 50-98% of the initial amounts were lost during the sampling period. The k(e,PRC) values were high, ranging from 0.08 to 0.11 day(-1) for the studied PRCs, at sampling site W1 (raw sewage), the only sampling site where significant amounts of the PRCs with log K(ow) values5 were released from the SPMDs. At the other sampling sites, only PRCs with log K(ow) values between 4.20 and 4.50 were released in significant amounts. The release rates at these sites were lowest (0.04 day(-1)) at sampling site W9 (the secondary clarifier) and highest (0.18 day(-1)) at W8 (the active sludge aeration basin). Differences between sampling rates (R(s)) obtained using published laboratory-calibrated data and PRC-corrected R(s) values were visualized by principal component analysis (PCA). The water concentrations of 24 studied PAHs fell substantially during the course of the sewage treatment process. However, low molecular weight PAHs were more effectively removed than high molecular weight PAHs. Significant deviations between actual and estimated water concentrations may arise unless PRC-corrected R(s) values are applied.

Semipermeable membrane devices (SPMDs) are previous termanext term widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics ...

Semipermeable membrane devices (SPMD) represent a passive sampling technology that is becoming widely used for monitoring of surface waters pollution. While "classic" procedures employ dialysis to recover target compounds from exposed SPMDs, in the present study analytes were isolated from cut membrane together with sequestering medium (triolein) using hexane as an extraction solvent. This approach allowed us to reduce the time needed for accomplishment of isolation step from 48 h to only 1 h. Automated gel permeation chromatography (GPC) clean-up is employed in the following step to separate triolein from analytes fraction. Musk compounds (MCs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and several other persistent organochlorine compounds (OCs) were determined in the respective fraction by GC method employing selective detectors (MSD, ECD). As shown in a series of analyses of SPMDs deployed in various aquatic ecosystems, high recoveries and good repeatability of results together with a possibility to obtain the information on the pollution of sampling site at the day of sample arrival to laboratory make this newly implemented procedure an interesting alternative to time consuming dialysis.

The bactericide triclosan and methyl triclosan, an environmental transformation product thereof, have been previously detected in lakes and a river in Switzerland. Both compounds are emitted via wastewater treatment plants (WWTPs), with methyl triclosan probably being formed by biological methylation. Passive sampling with semi-permeable membrane devices (SPMDs) showed the presence of methyl triclosan in some lakes, suggesting some potential for bioaccumulation of the compound. In this study, we report the presence of methyl triclosan in fish (white fish, Coregonus sp.; roach, Rutilus rutilus) from various lakes in Switzerland receiving inputs from WWTPs. Identification of the compound was based on mass spectral (MS) evidence including MS/MS data. The concentrations of methyl triclosan in the fish were up to 35 ng g(-1) on a wet weight basis and up to 365 ng g(-1) on a lipid basis with concentrations in a relatively narrow range for fish from the same lake (Thunersee, 4-6 ng g(-1); Zurichsee, 32-62 ng g(-1); Pfaffikersee, 43-56 ng g(-1); Greifensee, 165-365 ng g(-1), lipid basis). No methyl triclosan (

Spatial and temporal variation of vapor- and particle-phase polycyclic aromatic hydrocarbons (PAHs) was determined in six urban and sub-urban locations in Kaunas, Lithuania during heating and non heating seasons. Two different sampling methodologies were used: passive (based on semipermeable membrane device, SPMD) and active (based on collection on filter and sorption). Sixteen priority PAHs as well as methylated PAHs were quantified in the collected samples. The sampled total amount of 16 PAHs investigated in SPMDs ranged from 10–138 ng/day outdoors, from 5–59 ng/day indoors during the winter sampling campaign. In summer these amounts varied from 11–19 ng/day outdoors and from 19–27 ng/day indoors. The total concentrations of vapor and particle-phase PAH in winter in actively taken samples varied from 49–286 ng/m3 outdoors and from 28–83 ng/m3 indoors. Seasonal differences as well as the influence of the fuel burning for domestic heating purposes on the PAH concentration outdoors were well reflected by the data obtained using the SPMD methodology.

The bactericide triclosan and methyl triclosan, an environmental transformation product thereof, were detected in lakes and in a river in Switzerland at concentrations of up to 74 and 2 ng L(-1), respectively. Both compounds were emitted via wastewater treatment plants (WWTPs), with methyl triclosan probably being formed by biological methylation. A regional mass balance for a lake (Greifensee) indicated significant removal of triclosan by processes other than flushing. Laboratory experiments showed that triclosan in the dissociated form was rapidly decomposed in lake water when exposed to sunlight (half-life less than 1 h in August at 47 degrees latitude). Methyl triclosan and nondissociated triclosan, however, were relatively stable toward photodegradation. Modeling these experimental data for the situation of lake Greifensee indicated that photodegradation can account for the elimination of triclosan from the lake and suggested a seasonal dependence of the concentrations (lower in summer, higher in winter), consistent with observed concentrations. Although emissions of methyl triclosan from WWTPs were only approximately 2% relative to those of triclosan, its predicted concentration relative to triclosan in the epilimnion of the lake increases to 30% in summer. Passive sampling with semipermeable membrane devices (SPMDs) indicated the presence of methyl triclosan in lakes with inputs from anthropogenic sources but not in a remote mountain lake. Surprisingly, no parent triclosan was observed in the SPMDs from these lakes. Methyl triclosan appears to be preferentially accumulated in SPMDs under the conditions in these lakes, leading to concentrations comparable to those of persistent chlorinated organic pollutants.

To assess the short-term trend of pollution by hexachlorobenzene (HCB), chlorophenols, and polychlorinated biphenyls (PCB) emitted to a marine environment, existing and former loads were estimated based on pollutant concentrations in water, blue mussels, and sediment, using partitioning calculations. The study included chemical analyses of organochlorines in sediment samples, caged mussels, and semipermeable membrane devices (SPMD) incubated in the water column and in the outflow from an adjacent plant in order to find out whether the high pollutant concentrations found in the superficial sediment corresponded to former or existing discharges. A comparison was made of hypothetical water concentrations calculated from values determined in SPMDs, mussels, and sediment, assuming equilibrium in the distribution of the pollutants between mussels and water or sediment and water. Sediment-derived water concentrations of HCB in the vicinity of the outlet were much higher than the water concentrations calculated from SPMDs or mussels, indicating that the discharges of HCB from a local source were strongly reduced during the past decade. It is concluded that partitioning calculations applied on analytical data from mussels and superficial sediment, when combined with SPMD data, make possible the detection of short-term changes of environmental loads of hydrophobic pollutants.

Surface sediment, amphipods (Monoporeia affinis), isopods (Saduria entomon) and fourhorn sculpins (Oncocottus quadricornis) were collected at two coastal stations in the Gulf of Bothnia, one in the Bothnian Bay and the other in the Bothnian Sea. The objective was to study the concentrations, composition profiles, bioaccumulation features and spatial differences of organochlorine compounds such as hexachlorocyclohexanes (HCHs), DDTs, hexachlorobenzene (HCBz), chlordanes (CHLs), dieldrin, Mirex and polychlorinated biphenyls (PCBs). All groups of compounds were found in every sample investigated, with the exception of Mirex that was not detected in the sediment samples. The concentrations for e.g. PCBs and CHLs ranged from 700 to 2400 and 70 to 400 ng/g lipid in the specimens. For the corresponding sediments the results were 9.0-9.3 ng/g dw for PCBs and 0.54-0.57 ng/g dw for CHLs, respectively. Bioaccumulation differences between the species with regard to both degree of and type of compound were observed. The highest accumulation potential was found for the cyclodiene compounds including CHLs and Mirex in isopod. Finally, there were only small concentration and bioaccumulation differences between the two stations.

A bleached sulfate integrated pulp and paper mill producing printing and writing paper from mixed tropical hardwood and bamboo was studied. The mill uses a "conventional bleaching sequence," C-E-H1-H2, with an average molecular chlorine consumption of 50 kg per ton of air-dried pulp (ADP). The content of polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs) in the bleaching filtrate in terms of the nordic toxicity equivalent (N-TEQ) was 33.5, 1.15, 0.56, and 0.014 pg/L for the E, C, H1, and H2 bleaching stages, respectively. The corresponding PCDFs and PCDDs loads in ng/t ADP were in the same ranking, i.e., 670, 69, 11.2, and 0.28, respectively. The congener and isomeric pattern of PCDFs and PCDDs of the bleaching filtrate and the bleached pulp was found to be typical for the chlorine bleaching plant effluent. The obtained dioxin load formed in the mill is in agreement with Western studies for the given multiple chlorine of 0.21-0.23. The load is, however, lower than reported discharges from Scandinavian mills using 1980s bleaching technologies, but substantially higher than the discharges from mills with modern bleaching technologies. Modifications in the bleaching plant to reduce molecular chlorine use are necessary to reduce dioxin formation.http://link.springer-ny.com/link/service/journals/00244/bibs/37n3p303.html

During January 1995, a severe flooding event in central and western Europe caused a significant outflow of contaminated freshwater into the Northern Sea and to Skagerrak. This water reached the Swedish west coast in mid-March. During this time, SPMD (semipermeable membrane device) sampling was performed directly in the plume. Depending on the salinity, this contaminated water was found at a depth of 22−25 m in Skagerrak. Two SPMD sampling sites were placed in this area at a depth of 24 m, and the SPMDs were changed every 12−16 days during the 12-week study. In the meantime, water temperature increased from 4 to 8 °C at the 24 m depth. PCBs, DDTs, chlordane, hexachlorobenzene, α-HCH, γ-HCH (lindane), dieldrin, and other organochlorine compounds were detected in the SPMD samples. A time trend with elevated concentrations during the floodwater arrival, followed by decreasing concentrations, could be seen for most of the compounds studied. The highest levels of organochlorine compounds were found for PCBs and...

Recent insights into the early events in Sindbis virus RNA replication suggest a requirement for either the P123 or P23 polyprotein, as well as mature nsP4, the RNA-dependent RNA polymerase, for initiation of minus-strand RNA synthesis. Based on this observation, we have succeeded in reconstituting an in vitro system for template-dependent initiation of SIN RNA replication. Extracts were isolated from cells infected with vaccinia virus recombinants expressing various SIN proteins and assayed by the addition of exogenous template RNAs. Extracts from cells expressing P123 C>S , a protease-defective P123 polyprotein, and nsP4 synthesized a genome-length minus-sense RNA product. Replicase activity was dependent upon addition of exogenous RNA and was specific for alphavirus plus-strand RNA templates. RNA synthesis was also obtained by coexpression of nsP1, P23 C>S , and nsP4. However, extracts from cells expressing nsP4 and P123, a cleavage-competent P123 polyprotein, had much less replicase activity. In addition, a P123 polyprotein containing a mutation in the nsP2 protease which increased the efficiency of processing exhibited very little, if any, replicase activity. These results provide further evidence that processing of the polyprotein inactivates the minus-strand initiation complex. Finally, RNA synthesis was detected when soluble nsP4 was added to a membrane fraction containing P123 C>S , thus providing a functional assay for purification of the nsP4 RNA polymerase.

Sediment trap sampling of settling particulate matter (SPM) was carried out in remote coastal and offshore stations in the Bothnian Bay (BB) and the Bothnian Sea (BS) located in the northern Baltic Sea. This was done to investigate occurrence, composition profiles, sedimentation, and spatial differences of PCBs, HCHs, hexachlorobenzene, DDTs, chlordane compounds, and dieldrin. The contamination load at the coastal stations was compared to that of surface bottom sediments. At one coastal station, sediment samples were collected in two different seasons (autumn and spring) in order to compare seasonal variations. All compound groups were found in the SPM and sediment samples analyzed. The contaminant concentrations in SPM at the coastal stations ranged, on dry weight basis, from 0.41 to 8.6 ng/g for chlordanes and HCHs and at the offshore stations from 3.2 to 31 ng/g for hexachlorobenzene and PCBs. The levels in SPM at the offshore stations were 10 times higher (on the average) than the coastal stations, li...

Twelve chlordane (CHLs) components and their metabolites (heptachlor, heptachlor epoxide, U82, MC4, trans-chlordane, MC5, cis-chlordane, MC7, oxychlordane, MC6, trans- and cis-nonachlor) and aldrin, dieldrin, endrin, isodrin, endosulfan 1, endosulfan 2, and mirex were quantified in mixed subsurface phyto- and zooplankton collected at four spatially distant sites in the southern part of the Baltic Sea. The CHLs concentrations in plankton were low, i.e. 5.3, 8.7, 9.2 and 8.7 ng/g lipid in Gdansk Depth, Gotland Basin, Bornholm Basin and Pomeranian Bay, respectively. Chlordane compounds showed similar distributions and patterns in plankton at all four sampling sites. The trans-nonachlor to cis-chlordane ratio (N:C ratio) in plankton was between 0.76 and 1.0 which clearly indicates pollution from distant sources due to long-range aerial transport. The relatively high concentrations of heptachlor epoxide seem to be related to local sources of pollution around of the Baltic Sea. Dieldrin was the major cyclodiene pesticide quantified and its concentration was uniformly distributed in the plankton sampled and ranged from 23 to 42 ng/g lipid, while aldrin, endrin, isodrin, endosulfan 1, endosulfan 2 and mirex were undetected.

The effect of nutrient enrichment on the distribution of polychlorinated biphenyl's (PCBs) in the microbial food web and the residence time of PCBs in seawater was studied in an experimental mesoco ...

Semipermeable membrane devices (SPMDs) are polymeric membranes enclosing a thin film (1 mL) of a synthetic lipid. Herein, SPMDs are used to sample bioavailable persistent organochlorine contaminants, viz. PCBs, DDTs, chlordanes, lindane, chlorobenzenes, and dieldrin, in composts. The study comprises three different indoor household composts and one fortified compost. The contaminant levels in the composts range between 0.2 and 444 ng/g of dry weight. SPMDs were applied inside the compost (S/solid) and above the surface inside a closed container (S/air). After a sampling time of 28 days, the amount of PCBs accumulated from the natural household composts were 440-11000 and 72-470 ng/SPMD for S/solid and S/air, respectively. The concentration of the pesticides ranged between 4 and 300 ng/SPMD for both sample types. The amount accumulated in the S/solid correlates with the results obtained in a traditional compost analysis. Furthermore, the S/air analysis reveals the fugitive properties of the technical mixtures and individual congeners, evaporating from the compost surfaces. Thus, the SPMDs provide a simple and efficient way to sample, and clean up, pollutants in compost, as well as substances evaporating from the soil surface. The SPMD methodology will be a useful tool, although of semiquantitative character, for soil and solid surface monitoring studies and for studies aiming at the fate of organochlorine contaminants.

Blue mussel, flounder, perch and lamprey from the Gulf of Gdansk accumulate many tetra- through hepta-CNs. Highest concentrations in fishes and lamprey are PCN congeners such as nos. 42, 52, 60, 61 and 69, which do not have vicinal (adjacent) carbon atoms unsubstituted with chlorine (NVC-Cl PCNs) and seem to be relatively resistant in the marine environment. In mussel, chloronaphthalenes such as nos. 3840, 33/34/37, 2843 and 47 dominate, i.e. the congeners, which have two or three vicinal carbon atoms unsubstituted with chlorine (DVC-Cl and TVC-Cl PCNs). PCNs with two vicinal carbon atoms unsubstituted with chlorine (DVC-Cl PCNs) are less abundant in fish and lamprey than NVC-Cl members, while those congeners with three (TVC-Cl PCNs) or four (QVC-Cl PCNs) vicinal carbon atoms unsubstituted are present as only minor compounds or are absent. Congener-specific data obtained using a non-destructive sample extraction and clean-up method coupled to HRGC-HRMS can be useful to explain potential species- or site-specific differences of the pollution pattern with PCNs. Most of the hexa-CNs, both hepta-CNs and some penta- and tetra-CNs show their high potency for bioaccumulation in flounder when related to mussel as their food.

To identify potential sources and accumulation features concentrations, profiles, and patterns of polychlorinated naphthalene (PCN) residues were determined in sediment, mussel, crab, plankton, and...

Forty-four congeners of higher chlorinated naphthalenes were identified and quantified in the breast muscles, liver and adipose fat of a few specimens of white-tailed sea eagle collected from the Baltic coastal and inland breeding areas in Poland in 1991–1992. Many of the identified chloronaphthalenes (CNs) were well resolved as single peaks on the Rtx-5 HRGC-MS/EI-SIR chromatograms; but still some of them coeluted in pairs (four tetra-, two penta- and six hexa-CNs) or triplicate (six tetra-CNs) on the chromatograms. All tetra-, penta-, hexa- and hepta-CNs present in Halowax 1014, a technical mixture of CNs, were found in the tissues of white-tailed sea eagles indicating a high persistency of these ubiquitous environmental contaminants. The profile and pattern of chloronaphthalenes found in sea eagles differed largely from that of Halowax 1014, suggesting a selective and structure-related metabolism of many CN congeners. Among the most persistent and highly bioaccumulating CNs in tissues of the sea eagles were congeners such as 1,3,5,7-T4CN (CA' no. 42), 1,2,4.6-/1,2,4,7-/1,2,5,7-T4CN (CN nos. 33/34/37) and 1,4,6,7-T4CN (CN no. 47); 1,2,3,5,7-/1.2,4,6,7-P5CN (CNnos. 52/60) and 1,2,4,6,8-P5CN (CN no. 61), and 1,2,3,4,6,7-/1,2,3,5.6,7-H6CN. Differences in the metabolic potency of some of the most persistent tetra- and penta-CNs were observed between juvenile and adult white-tailed sea eagles. The CN congener no. 54 (1,2,3,6,7-P5CN) also is present in tissues of white-tailed sea eagles. It is formed during combustion processes and has not been found in the technical mixtures of PCNs of the Halowax series.

Three-spined sticklebacks were exposed to 20 polychlorinated biphenyls (PCBs) through gastrointestinal intake. The PCBs, viz. 2,2{prime},3,4-TeCB, 2,2{prime},4,6{prime}-TeCB, 2,3,3{prime},5{prime}-TeCB, 2,3,4,4{prime}-TeCB, 2,3{prime},4,5{prime}-TeCB, 3,3{prime},4,5-TeCB, 2,2{prime},3,4{prime},6-PeCB, 2,2{prime},4,4{prime},5-PeCB, 2,2{prime},4,6,6{prime}-PeCB, 2,3,3{prime},5,6-PeCB, 2,3,4,4{prime},6-PeCB, 3,3{prime}4,4{prime}5-PeCB, 2,2{prime},3,4,5,6{prime}-HxCB, 2,2{prime},4,4{prime},5,5{prime}-HxCB, 3,3{prime},4,4{prime},5,5{prime}-HxCB, 2,2{prime},3,3{prime},4,5,6-HpCB, 2,2{prime},3,4,4{prime},6,6{prime}-HpCB, 2,2{prime},3,4{prime},5,6,6{prime}-HpCB, 2,3,3{prime},4,4{prime},5,6-HpCB, and 2,3,3{prime},4{prime},5,5{prime},6-HpCB, were selected by means of a full factorial design in combination with principal component analyses based on several physicochemical properties of tetra- through hepta-PCBs. After exposure to the training set, pooled samples of the sticklebacks were analyzed by GC-MS after lipid determination and cleanup using Florisil open-column chromatography. Bioaccumulation factors (BAFs) were calculated on a lipid basis by dividing the PCB concentrations in the fish by the respective concentrations in the feed. Higher chlorinated PCBs showed, in general, higher bioaccumulation than the lower chlorinated congeners. Polychlorinated biphenyls with vicinal hydrogens in the meta- and para-positions exhibited low bioaccumulation. Finally, 18 of the 20 measured BAFs were used to calculate a multivariate quantitative structure-activity relationship (QSAR) by means of partial least squares fitting to latent structures. By applying this QSAR, the bioaccumulation potentials of 136 nontested tetra- through hepta-PCB congeners were predicted.

Okadaic at low concentrations specifically inhibits protein phosphatase 2A. Treatment of cells with this inhibitor leads to growth arrest and cell injury within 1 to 2 days. After testing several different types of cells we found that mouse 3T6 cells and insect Sf9 cells responded to okadaic acid by apoptosis, as defined by changes in morphology and degradation of chromatin to fragments of nucleosome size. Infection of insect cells by baculovirus prevented the okadaic acid-induced apoptosis. Analysis of phosphoprotein synthesis by polyacrylamide gel electrophoresis showed that okadaic acid treatment resulted in hyperphosphorylation of some cellular proteins, including histone H1. Concomitant baculovirus infection of the cells did not change the overall phosphorylation pattern, but appeared to mitigate the okadaic acid-induced hyperphosphorylation of histone H1.

In 1974, abnormally high mortality was recorded among yolk-sac fry of Baltic salmon (Salmo salar) originating from feral females manually stripped and fertilized with milt from feral males. The cause of this mortality, designated M74, is unknown. The hypothesis is that xenobiotic compounds responsible for reproduction failure in higher vertebrates in the Baltic Sea also interfere with reproduction in Baltic salmon. The significance of M74 should not be underestimated, because the syndrome has caused up to 75% yearly mortality of developing Baltic salmon yolk-sac larvae in a fish hatchery dedicated to production of smolt during the last two decades. The author cannot exclude the possibility that only a relatively low number of naturally spawned eggs develop normally because of M74. No individual pollutant has been shown to be responsible for the development of M74 syndrome. However, a higher total body burden of organochlorine substances may be responsible for the M74 syndrome. The presence of induced hepatic cytochrome P450 enzymes in both yolk-sac fry suffering from M74 and adult feral females producing offspring affected by M74 supports this hypothesis. In addition, the P450 enzyme activity in offspring from feral fish is higher than the activity in yolk-sac fry from hatchery-raised fish,more » suggesting that feral Baltic salmon are influenced by organic xenobiotics.« less

During a 2-year experimental period female baltic salmon (Salmo salar) were fed pellets impregnated with oil extracted from Baltic herring (Clupea harengus). This extract contained lipid-soluble xenobiotics present in Baltic herring, which constitute a major part of the natural diet of Baltic salmon. The fish were examined at the time of ovulation in November each year. After 2 years of feeding, the load of polychlorinated dibenzo-paradioxins and furans in the exposed group was about twice that in the control group, but still low compared with concentrations in feral Baltic salmon. In spite of the relatively low exposure level, several vital biochemical functions were disturbed in the treated fish. Organic skeletal variables were affected indicating that the bone metabolism had been altered. Furthermore, the activities of enzymes involved in steroid biosynthesis were affected, which could lead to disturbances in reproductive functions. Splenocytes from exposed fish sampled in November 1990 showed a reduced mitogenic response, indicating that their immune system was suppressed. Feeding the salmon with pollutant-impregnated pellets also resulted in an induction of the hepatic ethoxyresorufin-O-deethylase (EROD) activity after only 6 weeks of exposure. Likewise, morphological abnormalities, i.e. hypertrophic hepatocytes and various stages of hepatic degeneration, were already apparent after 6 weeks of exposure. However, no EROD induction or morphological responses were recorded at the second and third sampling event, i.e. after one and 2 years of exposure, respectively. this could indicate that some physiological functions may adapt to a restricted xenobiotic load.

Dioxins and dibenzofurans are suspected to be quite toxic. They are fat soluble, and therefore, accumulate in fat-rich tissues (e.g., fish liver) and in products like milk. They have been detected in a large amount of food raw materials. Therefore it is urgent to find ways to purify such materials. Supercritical carbon dioxide has been tested for its ability to extract these dioxins from cod liver oil containing different concentrations of free fatty acids. The efficiency depends on the applied pressure and on other conditions, such as free fatty acid content and entrainer added to the carbon dioxide. The dioxins are best extracted with no ethanol added. In a semi-continuous mode, a reasonable separation of dioxins takes place at 150 bar and 40 °C, better than at higher pressures. About 25% of dioxins can be found in the first 10% of the oil extracted.

Semipermeable membrane devices (SPMDs) are passive monitors that are being increasingly used by monitoring agencies and wastewater dischargers to measure the contents of lipophilic organic chemical ...

Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log KOA values > 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control. SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.

Semipermeable membrane devices (SPMDs) are passive samplers used to measure the vapor phase of organic pollutants in air. This study tested whether extremely high wind-speeds during a 21-day sampling increased the sampling rates of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), and whether the release of performance reference compounds (PRCs) was related to the uptakes at different wind-speeds. Five samplers were deployed in an indoor, unheated, and dark wind tunnel with different wind-speeds at each site (6-50 m s(-1)). In addition, one sampler was deployed outside the wind tunnel and one outside the building. To test whether a sampler, designed to reduce the wind-speeds, decreased the uptake and release rates, each sampler in the wind tunnel included two SPMDs positioned inside a protective device and one unprotected SPMD outside the device. The highest amounts of PAHs and PCBs were found in the SPMDs exposed to the assumed highest wind-speeds. Thus, the SPMD sampling rates increased with increasing wind-speeds, indicating that the uptake was largely controlled by the boundary layer at the membrane-air interface. The coefficient of variance (introduced by the 21-day sampling and the chemical analysis) for the air concentrations of three PAHs and three PCBs, calculated using the PRC data, was 28-46%. Thus, the PRCs had a high ability to predict site effects of wind and assess the actual sampling situation. Comparison between protected and unprotected SPMDs showed that the sampler design reduced the wind-speed inside the devices and thereby the uptake and release rates.

Although the hepatitis C virus (HCV) genome is synthesized by the virus-encoded RNA-dependent RNA polymerase NS5B, other viral and cellular factors are assumed to be required for template-specific initiation and regulation of RNA-synthesis. The cellular protein La, which normally associates with RNA polymerase III transcripts, also interacts with the 5'- and 3'-untranslated regions of several RNA viruses, including HCV. To investigate whether other viral gene products may be involved in this interaction, we constructed an HCV cDNA expression library in bacteriophage T7 allowing portions of the HCV polyprotein to be displayed on the phage surface. Screening of the phage library against La resulted in selection of clones displaying the N-terminal region of HCV NS5A. Co-precipitation of full-length and truncated forms of recombinant NS5A with La revealed that the N-terminal region of NS5A was both necessary and sufficient for binding to La. Although this region of NS5A is essential for HCV replication, the role of the NS5A-La interaction in the infected cell remains to be established.

Consumer care products often contain UV filters, organic compounds which absorb ultraviolet light. These compounds may enter surface waters directly (when released from the skin during swimming and bathing) or indirectly via wastewater treatment plants (when released during showering or washed from textiles). Predicted and measured UV filter concentrations were compared in a regional mass balance study for two Swiss lakes: Lake Zurich, a typical midland lake which is also an important drinking water resource, and Hüttnersee, a small bathing lake. Both lakes are extensively used for recreational activities and considerable direct input of UV filters is thus expected. This input was estimated from the number of visitors at swimming areas around the lakes and a survey of the usage of sunscreen products among these visitors. Possible additional indirect input via wastewater treatment plants was not considered in this study. The quantitatively most important UV filters, as indicated by the survey data, ethylhexyl methoxycinnamate, octocrylene, 4-methylbenzylidene camphor, butyl methoxydibenzoylmethane, and benzophenone-3, all lipophilic compounds, were selected for analysis by gas chromatography-mass spectrometry. Concentrations of individual UV filters in water from Lake Zurich were low, ranging from2 ng l(-1) (detection limit) to 29 ng l(-1), and somewhat higher at Hüttnersee, ranging from2 to 125 ng l(-1), with the highest concentrations found in summer, consistent with direct inputs to the lakes during this time. The concentrations were clearly lower than predicted from input estimates based on the surveys. This may be in part due to (i) an overestimation of these inputs (e.g. less than the 50% wash-off of UV filters assumed to occur during swimming), and (ii) some removal of these compounds from the lakes by degradation and/or sorption/sedimentation. UV filters were also detected in semipermeable membrane devices (SPMDs) deployed at Lake Zurich and Greifensee, another midland lake, at concentrations of 80-950 ng SPMD(-1), confirming the presence of the compounds in surface waters and indicating a certain potential for bioaccumulation. SPMD-derived water concentrations were in the range of 1-10 ng l(-1) and thus corresponded well with those determined in water directly. No UV filters were detected above blank levels in SPMDs deployed at a remote mountain lake used for background measurements.

Semipermeable membrane devices (SPMDs) were deployed at six sites in the Bangkok region, Thailand, to investigate spatial variations in atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). Sampling sites affected by various levels of traffic intensity were studied. In addition, PAH levels were determined in a common human food plant (water spinach) harvested from canals and ponds in the sampling areas. Significant differences in atmospheric PAH concentrations between sites were found, with 10 times higher PAH levels in the urban areas compared to the rural areas. Increasing concentrations of 1-methylphenanthrene relative to phenanthrene were found in the urban air close to the city center, indicating that traffic probably contributed to the higher PAH concentrations detected. Due to SPMD's passive sampling technique, their long-term operation and high ability to detect spatial differences, they proved to be suitable for semiquantitative field studies of PAHs. The PAH compounds sampled with SPMDs were mainly associated with gaseous PAHs, while both gas phase and particle-bound PAHs were detected in the plant samples. The relative abundance ratios of some PAHs in the plants were not well correlated with the ratios detected in the SPMDs, indicating that gas-phase exposure made low contribution to the PAH concentrations in the plants. However, similarities in the profiles of 3-ring PAHs between the SPMD and plant samples indicate that gas-phase exchange occurs between the atmosphere and the plants.

Four species of harbour porpoise (Phocoena phocoena) and one herring ( Clupea harengus ) sample from the southern Baltic Sea were analysed in an attent to study the concentration and biomagnification of 17 chlordane related compounds (CHLs) including 12 components present in technical chlordane, the toxic metabolites oxychlordane and cis-heptachlorepoxide and the photoconversion products photoheptachlor and two photo-cis-chlordanes. The concentration and biomagnification ability of CHLs were also compared to other organochlorines such as HCHs (hexachlorocyclohexanes), hexachlorobenzene, DDTs, dieldrin, mirex and PCBs (polychlorinated biphenyls). Of the CHLs analysed, 16 were detected in porpoise and 15 in herring including the photoconversion products. In both species the highest concentrations were found for PCBs and DDTs. The concentration of PCBs and CHLs in porpoise varied from 5700–16000 and 470–1250 ng/g lipid, and in herring from 1300 and 49 ng/g lipid, respectively. The biomagnification factor (BMF: concentration in organism/concentration in food; all lipid normalized) in porpoise was found to be high for CHLs followed by dieldrin and lowest for HCHs. Among the CHLs, a big variation of BMF (BMF range ∼1–150) was found e.g. the nonachlorinated compounds biomagnified to the highest degree followed by cis -heptachlorepoxide, photoheptachlor and oxychlordane.

Zooplankton, mysis (Mysis sp.) and herring (Clupea harengus) were collected at two pelagic locations in the northern part of the Baltic Sea, one in Bothnian Bay (BB) and the other in the Bothnian Sea (BS), in order to investigate concentrations, composition profiles, biomagnification features and spatial differences of organochlorine contaminants. Compounds included in this study are hexachlorocyclohexanes (HCHs), DDTs, hexachlorobenzene (HCBz), chlordanes (CHLs), dieldrin, mirex and polychlorinated biphenyls (PCBs). All groups of compound were detected in every sample investigated, with the exception of mirex that was detected only in the herring samples. The concentrations of organochlorine compounds in all samples ranged, e.g. from 250 to 1500 ng/g lipid for PCBs and from 6 to 150 ng/g lipid for CHLs. The biomagnification factor (BMF) is calculated as the concentration of the compounds in the organism divided by the concentration in food normalised to lipids. In the zooplankton-mysis-herring food web, large variations in BMFs between the different compound groups were observed. The highest BMFs were obtained for the CHLs followed by the DDTs and the lowest for the HCHs. Nonachlorinated CHLs had the highest BMFs within the group of CHLs and for the DDTs p,p'-DDT had a higher biomagnification potential than its metabolites p,p'-DDE and p,p'-DDD. Finally, concentration and biomagnification differences between the two stations were observed. The herring in the southernmost station (BS) displayed approximately two- to sixfold higher biomagnification than the herring from the north (BB).

Herring (Clupea harengus) and perch (Perca fluviatilis) were collected in the northern and southern Baltic Sea and analyzed for the presence of the cyclodiene pesticides chlordane (CHL), heptachlor, aldrin, dieldrin, endrin, isodrin, endosulfan and mirex, as well as other organochlorine contaminants, hexachlorocyclohexanes (HCHs), DDTs, hexachlorobenzene (HCBz) and polychlorinated biphenyls (PCBs) in order to investigate concentrations, accumulation and differences in geographical distribution. In the northern part of the Baltic Sea, Gulf of Bothnia, herring were collected at two pelagic stations, one in the Bothnian Bay (BB) and the other in the Bothnian Sea (BS), respectively; perch were collected at four coastal locations along the Swedish coast. All these locations were selected to represent background areas except one in the vicinity of an industrialised and contaminated area. Both specimens were also caught in the southern part of the Baltic Sea, in the Gulf of Gdansk (GG), Poland, a potentially highly polluted area. From the eight cyclodiene pesticides analyzed, three were detected in herring and perch samples, including 12 different CHL-related compounds, dieldrin and mirex. To our knowledge, it is the first time that mirex has been detected in samples from the Baltic Sea. Neither heptachlor, aldrin, endrin, isodrin nor endosulfan were found. However, HCHs, DDTs, HCBz and PCBs were found in every sample investigated, and the concentrations ranged e.g. for the cyclodiene chemicals dieldrin and CHL-related compounds from 30 to 170 ng/g lipid and for PCBs from 360 to 5400 ng/g lipid, both fish species included. Differences in contamination burden between the sites can be seen, e.g. for herring the BB and GG locals were similar, and generally lower than BS for all chemicals except that of DDT where GG was the highest. For the perch samples the industrialised location had markedly higher concentrations of HCBz and PCBs than the other locations. This species also identifies GG as the most DDT contaminated site among the three studied areas.

Herein is a procedure described using a semipermeable membrane (SPM) for enrichment of organic chemicals from lipid-containing samples. Dialysis with SPMs in an organic solvent can separate organochlorine contaminants such as non-, mono-, and di-o-PCBs, PCDDs, PCDFs, PCDTs, PCNs, pesticides, and PAHs from lipids. The method is nondestructive and more than 20 g of lipid can be dialyzed in a single membrane with acceptable recoveries of the internal standards, nearly independent of amount and type of lipid dialyzed. The lipid removal process shows good consistency between subsamples, and the lipid content can be reduced by 90-99%, depending on species and amount lipid. Neither triglycerides nor phospholipids were obtained in the dialysate fraction. The utility and reliability of the method is displayed by good precision for 72 PCBs and 27 organochlorine pesticides in the concentration range 0.05-50 micrograms/sample for triplicate subsamples, by the consistency in PCDD/F levels compared to a classic analytical procedure, and by the analysis of the above listed chemicals in approximately 200 biological samples of a wide variety of types. This technique can also be used as an enrichment device for contaminants when huge amounts of lipids are extracted for toxicological studies. Moreover, it is possible to use SPM to cleanup other samples from molecules with relatively high masses, e.g. sediments, soil, compost, and tar materials.

Black cormorants, Phalacrocorax carbo sinensis (the breast muscles and liver) originating from the colony near Katy Rybackie on the south coast of the Gulf of Gdansk, Baltic Sea, were collected in 1992 and analysed for polychlorinated naphthalenes. PCNs were determined employing a multi-residue procedure including a non-destructive wide-bore open-tube extraction step, cleanup using semipermeable polyethylene membrane, HPLC fractionation of planar compounds on activated carbon column and final separation and identification and quantification with HRGC/HRMS. Tetra- to hepta-CNs were found in all samples examined, and penta- and next tetra-CNs were dominating homologue groups. Dominating members in the fingerprint of PCNs in black cormorants were 1,3,5,7-T4CN (no. 42); 1,2,3,5,7-/1,2,4,6,7-P5CN (no. 52/60); 1,2,4,6,8-P5CN (no. 61); 1,2,3,4,6,7-/1,2,3,5,6,7-H6CN (no. 66/67); 1,2,4,6-/1,2,4,7-/1,2,5,7-T4CN (no. 33/34); 1,2,4,5,7-P5CN (no. 58); and 1,2,4,7,8-P5CN (no. 62). When related to potential food items, black cormorants biomagnify in their body many PCNs and the congeners no. 42 and 66/67 show highest biomagnification factor (BMF) values.

Three indoor, household composts and the earthworms living in them were analyzed for their congener-specific content of polychlorinated biphenyls (PCBs) and organochlorine pesticides, including DDTs, chlordanes, dieldrin, and penta- and hexachlorobenzene. The concentrations of the chlordanes were 0.01 to 0.2 ng/g dry weight (dw) in compost and 0.03 to 0.06 ng/g wet weight (ww) in the worms. Of all the pesticides, the DDTs and chlorobenzenes were found in the highest concentrations. The levels of PCBs found in the composts were 32 to 440 ng sum PCB/g dw and 23 to 290 ng/g ww in the worms. These observations are in strong agreement with reported data from studies of outdoor composts. The PCB congener pattern was similar to that of commercial technical mixtures (dominated by tetrachlorinated PCBs) in contrast with data reported from outdoor composts.

The high-resolution gas chromatographic-mass spectrometric analysis of 25 Great Lakes fish extracts confirmed the identities of several 2,3,7,8-tetrasubstituted polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs). The dominant congener in extracts from Lake Michigan, Lake Erie, Lake St. Clair, Lake Huron, and Lake Superior fish was 2,3,7,8-tetrachlorodibenzofuran (TCDF). The fish extracts from Lake Ontario showed significant levels of 2,3,7,8-tetrachlorobenzo-p-dioxin (TCDD) besides containing considerable amounts of PCDFs. The 2,3,7,8-TCDD equivalents in these extracts were determined by their activities as inducers of aryl hydrocarbon hydroxylase (AHH) and ethoxyresorufin O-deethylase (EROD) in rat hepatoma H-4-II E cells in culture. For most of these samples, there was less than a 2-fold difference in the bioassay-estimated 2,3,7,8-TCDD equivalents and the total PCDDs plus PCDFs as determined by GC-MS. The bioassay-derived values were significantly (>2-fold) higher for the Lake Erie and Lake Ontario fish extracts. This difference may be due to several factors including synergistic interactive effects of the congeners in the bioassay induction response or the presence of bioassay-active components that are not detected by GC-MS analysis.

A series of polychlorinated biphenyl (PCB) fires and explosion in PCB-filled capacitors and transformers is discussed. A sampling program followed by isomer specific determination of trace levels of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) is described. Data from a series of Swedish PCB accidents are given. In addition to PCDFs and PCDDs, we have also found a series of polychlorinated biphenylenes (PCBPs). Cleaning of contaminated areas was done by vacuum cleaning followed by high pressure washing. Images FIGURE 14.

Fires, explosions and other accidents in polychlorinated biphenyl (PCB)-filled equipment can result in possible exposure of firemen, cleaning personnel and regular workers. Inhalation, dermal exposure and ingestion are the possible routes of exposure. An indirect assessment of the exposure can be made by analyses of wipes, air and water samples and clothes. A direct assessment of exposure can be made by analyses of blood samples, adipose and other tissue samples, feces and bile.