Accumulation features and temporal trends of PCDDs, PCDFs and PCBs in Baikal seals (Pusa sibirica)

This study investigated the accumulation features and temporal trends of PCDD/Fs, dioxin-like PCBs (DL-PCBs) and non-dioxin-like PCBs (NDL-PCBs) in the blubber of Baikal seals collected in 1992 and 2005. DL-PCBs (480-3600 ng/g) and NDL-PCBs (980-35,000 ng/g) were dominant contaminants. Concentrations of PCDDs and PCBs in males were significantly higher than in females. In males, age-dependent accumulation was observed for PCDDs, mono-ortho PCBs and NDL-PCBs. PCDFs and non-ortho PCBs showed no such trends, implying that exposure of seals to these contaminants has been decreasing in recent years. No decreasing temporal trend was observed for PCDDs, mono-ortho PCBs and NDL-PCBs, suggesting that Baikal seals are still exposed to PCDDs and PCBs. TEQs of PCDDs and mono-ortho PCBs in seals collected in 2005 accounted for 62-77% of total TEQs. The TEQ levels in 40% of the specimens exceeded the threshold level for immunosuppression observed in harbor seals (209 pg/g).     

Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.     

Tissue distribution of polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) in harbour porpoises (Phocoena phocoena) from Swedish waters

Polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) were analysed in blubber, nuchal fat, liver, muscle, kidney and brain of three male harbour porpoises (Phocoena phocoena) from the west coast of Sweden. To estimate spatial variation, PCNs and non-ortho CBs were analysed in six blubber samples collected at different anatomical sites of each animal. Highest wet weight concentrations of ΣPCNs were detected in the lipid rich tissues (blubber and nuchal fat) and liver (520–730 and 520 pg/g, respectively) and lowest in brain (22 pg/g). TetraCNs were most abundant in muscle, kidney and brain, while the hexaCNs were most abundant in the lipid rich tissues and liver. The highest lipid weight concentration recorded (11 ng/g) was for the hexaCN congeners no. 66/67 in liver. These coeluting hexaCN congeners accounted for 80–100% of total hexaCNs in all tissues examined.Concentrations of Σnon-ortho CBs were highest in lipid rich tissues (220–280 pg/g wet weight). Non-ortho CB no. 77 and 169 constituted between 62–86% and 4.9–9.3%, respectively, of total Σnon-ortho CBs. No major variation of Σnon-ortho CB concentrations was found between the six different blubber sites but higher ΣPCN concentrations (wet weight) were found dorsally at the peduncle. Toxic equivalent concentrations (TEQs) showed that non-ortho CB no. 126 was the main contributor to total TEQs in all tissues, except liver in which hexaCN congener nos. 66/67 contributed to about 50% of total TEQs.     

Polybrominated diphenyl ethers,polychlorinated dibenzo-dioxins,-furans,and-biphenyls in three species of antarctic penguins

Background, Aims and Scope Fish-eating seabirds are recognized to be at risk of accumulating toxic contaminants due to their high position in the trophic web and to their low ability to metabolize xenobiotic compounds. Penguins are widely distributed in Antarctica and represent an important fraction of the Antarctic biomass. They feed mainly on krill and, depending on krill availability, also on fish. It has been reported that predators may be a sink for volatile and toxic chemicals and this may pose a serious environmental problem. Polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-dioxins (PCDDs),-furans (PCDFs), and-biphenyls (PCBs), including non-ortho congeners, hexachlorobenzene (HCB) and p,p′-DDE, were quantified in three species of Antarctic Pygoscelids in order to evaluate their accumulation patterns. The potential toxicity of twenty-two dioxin-like congeners was assessed and expressed as 2,3,7,8-tetraCDD equivalents (TEQs). Differences between males and females were investigated. Methods Blood samples of the Adélie penguin Pygoscelis adeliae, Chinstrap penguin Pygoscelis antarctica and Gentoo penguin Pygoscelis papua were collected at Admiralty Bay, King George Is (62°10′39″ S, 58°26′46″ W) in February 2004. Halogenated hydrocarbons were identified and quantified using gas chromatography coupled with gas chromatography mass spectrometry analyses. Results are expressed on a wet weight basis. Results and Discussion HCB, p,p′-DDE and ΣPCBs were higher in Adélie penguins (6.7±6.1, 8.2±3.3 and 9.8±3.8 ng/g, respectively) than in Chinstrap and Gentoo penguins, both of which showed values in the same order of magnitude, but approximately 40% lower than Adélie penguins. Hexa-CBs ranged 35–45% of the residue. Low-chlorinated PCBs (nos. 70+76+95+56+60+101) accounted for 40–60% in the three species. PCB101 made up 15% of the residue in Adélie penguins. PBDEs were 291±477, 107±104 and 116±108 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively; the most abundant congeners were BDE47 in Adélie and Chinstrap penguins and BDE17 in Gentoo penguins. PCDDs were 22±32, 6.5±7.4 and 18±23 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively. PCDFs were higher in Adélie penguins and lower in Chinstrap penguins. PCDDs/Fs and PBDEs were higher in males than in females of Gentoo and Chinstrap penguins; differences in concentrations were likely related to the partial detoxification that occurs in females during egg formation. Of the four non-ortho PCBs measured, PCB126 occurred at the highest concentrations and contributed the majority of the non-ortho PCB-TEQ in Gentoo and Chinstrap penguins. The highest TEQs were found in the Gentoo penguin and due mainly to PCDDs and non-ortho PCBs. Conclusions POP concentrations in penguins were lower than those found in seabird species from other areas of the world. Different chemical accumulation patterns were observed in relation to species and sex; the Adélie penguin showed the highest POP levels. Dissimilar ecological or metabolic features may be involved; the diverse timing of reproduction steps can be responsible for those differences; moreover, Adélie penguins feed on krill (a fatty resource) more abundantly than the other two species during the rearing period. Recommendation and Outlook The South Shetland Islands might be subjected to a higher chemical impact with respect to the rest of Antarctica, due to their being near South America. Because penguins are fish-eating birds showing low detoxifying capacities and key-species in Antarctic ecosystems, further studies on their xenobiotic metabolism should be carried out.     

Mechanochemical removal of organo-chlorinated compounds by inorganic components of soil

The purpose of this work is to evaluate the catalytic efficiency of two metal oxides, ferrihydrite and birnessite and of a ferruginous smectite, towards organic molecules such as 4-chloroaniline (4-CA), pentachlorophenol (PCP), and five polychlorinated biphenyls (PCBs) characterised by different number and position of chlorine atoms. Mechanochemical dry contacts with light grinding between catalytic surfaces and pollutants have been carried out.

The efficiency of the mechanochemical removal was compared with batch experiments for the soluble compounds (PCP and 4-CA). The removal of 4-CA and PCP by the mechanochemical procedure resulted more effective than by batch contact in the presence of birnessite and ferrihydrite, particularly at higher pH (100% removal of 4-CA by birnessite in 30 min at pH 8.6 after the mechanochemical contact compared to 20% removal using the batch interaction at the same pH).

The mechanochemical contact of PCBs and birnessite produced a removal of pollutant that was a function of the number of chlorine atoms (complete removal of 2,2^′-dichlorobiphenyl in 10 days and a removal of 30% and 20% of 2^′,3,4-trichlorobiphenyl and 3,3^′,4,4^′-tetrachlorobiphenyl, respectively in 90 days) and of the position of chlorine atoms about the biphenyl rings (100% of 2,2^′-dichlorobiphenyl in 10 days, 84% of 3,3^′-dichlorobiphenyl in 15 days and 40% of 4,4^′-dichlorobiphenyl in 27 days).     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0-23 (mean: 13, median: 14) and 2.7-20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16-326 (mean: 107, median: 100) and 12-252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

Polychlorinated biphenyls and dibenzofurans retained in the tissues of a deceased patient with Yucheng in Taiwan

Various tissues from a deceased Yucheng (oil disease) patient were analyzed for individual polychlorinated biphenyl (PCB) and dibenzofuran (PCDF) congeners. With a few exceptions, PCBs with 5 or less chlorine atoms were almost completely excreted from the patient's tissues about two years after the ingestion of the toxic oil. In contrast, most PCB congeners with 6 or more chlorine atoms were retained in the tissues. The intestinal fat contains the highest level of PCBs while the liver contains the highest concentration of PCDFs. The major PCDF congeners retained in the tissues were 1,2,3,4,7,8-hexaCDF, 2,3,4,7,8-pentaCDF, and 1,2,4,7,8-pentaCDF. The former two congeners, especially 2,3,4,7,8-pentaCDF, are very toxic PCDFs; they may play important roles in the etiology of Yucheng.     

Concentrations of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans,and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City,Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0–23 (mean: 13, median: 14) and 2.7–20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16–326 (mean: 107, median: 100) and 12–252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Sources of polychlorinated biphenyl blank contamination and their impact on fingerprinting

Abstract

The development of high-resolution mass spectrometry methods for the measurement of polychlorinated biphenyls (PCBs) in environmental samples has dramatically reduced detection limits, leading to problems obtaining clean blanks. When PCBs are detected in samples at concentrations similar to the blanks, blank contamination must be addressed before fingerprinting and source apportionment through positive matrix factorization (PMF) can be successful. We tested a variety of blank correction methods using data from a study of water column concentrations of PCBs in the Spokane River, where concentrations of Σ₂₀₉PCBs in whole water samples averaged 171?pg/L without blank correction and Σ₂₀₉PCBs in the blanks averaged 88?pg/L. The results suggest that subtracting blank masses from sample masses can lead to erroneous results. Instead, censoring at one times the batch-specific blank level is a better approach. The sources of PCBs in field and method blanks were investigated by examining their congener profiles via PMF. The results suggest that commercial PCB formulations (in the US, Aroclors) continue to be the primary source of PCBs in blanks forty years after PCB production and use were banned in the United States. Other sources of PCBs to blanks include PCB 11 from pigments; PCBs 44?+?47?+?65, 45?+?51, and 68 arising from polymers cured using bis(2,4-dichlorobenzoyl) peroxide; and PCBs 1, 2, 3, 4, 8, 15 and others arising from silicone products derived from phenylsiloxanes, such as silicone-based adhesives.     

臭氧-氯联合灭活饮用水中枯草芽孢杆菌芽孢的研究

以枯草芽孢杆菌芽孢为模型微生物,研究了实际水体中单独氯消毒、单独臭氧消毒和臭氧-自由氯联合作用的灭菌效果.结果表明,枯草芽孢杆菌芽孢对单独氯消毒的抗性很大,6 mg/L氯作用240 min后灭活率仅为0.84个对数级;臭氧对枯草芽孢杆菌芽孢有较好的灭活效果,臭氧作用5 min,对其有4.68个对数级的灭活率.与单独氯消...     

Sources and toxicities of phenolic polychlorinated biphenyls (OH-PCBs)

Polychlorinated biphenyls (PCBs), a group of 209 congeners that differ in the number and position of chlorines on the biphenyl ring, are anthropogenic chemicals that belong to the persistent organic pollutants (POPs). For many years, PCBs have been a topic of interest because of their biomagnification in the food chain and their environmental persistence. PCBs with fewer chlorine atoms, however, are less persistent and more susceptible to metabolic attack, giving rise to chemicals characterized by the addition of one or more hydroxyl groups to the chlorinated biphenyl skeleton, collectively known as hydroxylated PCBs (OH-PCBs). In animals and plants, this biotransformation of PCBs to OH-PCBs is primarily carried out by cytochrome P-450-dependent monooxygenases. One of the reasons for infrequent detection of lower chlorinated PCBs in serum and other biological matrices is their shorter half-lives, and their metabolic transformation, resulting in OH-PCBs or their conjugates, such as sulfates and glucuronides, or macromolecule adducts. Recent biomonitoring studies have reported the presence of OH-PCBs in human serum. The occurrence of OH-PCBs, the size of this group (there are 837 mono-hydroxyl PCBs alone), and their wide spectra of physical characteristics (pKa’s and log P’s ranging over 5 to 6 orders of magnitude) give rise to a multiplicity of biological effects. Among those are bioactivation to electrophilic metabolites that can form covalent adducts with DNA and other macromolecules, interference with hormonal signaling, inhibition of enzymes that regulate cellular concentrations of active hormones, and interference with the transport of hormones. This new information creates an urgent need for a new perspective on these often overlooked metabolites.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

Comparative distribution, sourcing, and chemical behavior of PCDD/Fs and PCBs in an estuary environment

PCDD/F and PCB field data (1041 samples) in five media (dissolved, suspended sediment, bed sediment, catfish, and blue crab) were studied to explore dual contaminant patterns in the Houston Ship Channel, Texas, USA. PCDD/Fs showed greater concentration than PCBs in suspended sediments while PCBs were higher in apparent dissolved (truly dissolved + DOC-associated), fish, and crab. PCDD/Fs at nearly all locations contributed more strongly to dioxin-like toxicity. The fraction of PCB TEQ was, however, enriched in biotic over abiotic media due in large part to the presence of PCB 126, which was mostly undetected in water and sediment and yet exhibited a BAF three times greater than 2,3,7,8-TCDD. Dissolved-suspended sediment and suspended-bed sediment relationships showed that (1) observed apparent dissolved concentration differences (as fraction of total water were mean 10% PCDD/Fs and 63% PCBs) can reasonably be explained by a four-phase partition model (truly dissolved, DOC-associated, suspended OC, and suspended BC) for PCBs but not for PCDD/Fs and (2) the contaminants behaved similarly in bed to suspended sediment concentration ratios (C_bed/C_susp) upstream of a major confluence but not downstream. PCA-cluster analysis pointed to the possibility that suspended sediment PCB contamination originates from resuspended bed sediment while PCDD/Fs in suspended sediment originates more probably from other sediment sources such as upstream wash load or air deposition. Finally, examinations of a congener marker ratio (PCB 209/206) seemed to indicate that a source of pure PCB 209 may exist in bed sediment near Patrick Bayou though the source was not completely localized.     

PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Performance of a Semi-Industrial Scale Gasification Process for the Destruction of Polychlorinated Biphenyls

Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO₂ 18%, and CH₄ 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10^?7 mg/m³ (at 298 K, 1 atm, dry basis, 7% O₂). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10^?6 ng-toxic equivalent (TEQ)/m³ and 7.1 × 10^?6 ng-TEQ/m³ (at 298 K, 1 atm, dry basis, 7% O₂) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH₄).     

Distribution characteristics of PCBs in the sediments of the lower Nakdong River, Korea

The objective of this study is to investigate the distribution characteristics of polychlorinated biphenyl (PCB) congeners in sediments of the lower Nakdong River of Korea. The sediments were collected using a grab sampler in May 1999. PCBs were extracted in the Soxhlet extractor and cleaned by using adsorption chromatographic techniques and concentrated sulfuric acid. A HP6890 gas chromatograph equipped with an electron capture detector was used for quantification. The results of congener specific analysis showed that the total concentration is ranged over 1.1-141 ng/g dry weight. The levels of PCB congeners are significantly correlated with the total organic carbons (TOC) in the sediments. The major fractions of PCBs in these sediments are congeners containing 4, 5 or 6 chlorine atoms per biphenyl molecule.