The Duisburg birth cohort study: influence of the prenatal exposure to PCDD/Fs and dioxin-like PCBs on thyroid hormone status in newborns and neurodevelopment of infants until the age of 24 months

Prenatal exposure to polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can affect neurobehavioral development of infants and children. This effect may be mediated through disruption of thyroid hormone homeostasis. However, epidemiological studies reveal no consistent influence of PCDD/Fs and PCBs on thyroid status and neurodevelopment at environmental background levels. The effects may resolve with time of further decreasing exposure to these compounds. The aim of this study was to find out if there are still effects related to prenatal PCDD/F and PCB observable at the meanwhile decreased levels of exposure by using the same methods which have been applied in similar studies during the last 10 years in Europe. The birth cohort study was initiated in the year 2000 in the industrialized city of Duisburg, Germany. 232 healthy mother-infant pairs were recruited between 2000 and 2002. Dioxins, dioxin-like PCBs and six indicator PCBs were analyzed in maternal blood during pregnancy and in maternal milk following extraction and sample clean-up by HRGC/HRMS. Thyroid stimulating hormone (TSH), total thyroxine (T4), total triiodothyronine (T3), free thyroxine (FT4) and free triiodothyronine (FT3) were measured in serum samples of the pregnant women and in cord serum samples by chemiluminescent immunometric assay. Neurological examinations were performed at ages 2 weeks and 18 months using the neurological optimality score (NOS), mental and motor development were assessed using the Bayley Scales of Infant Development (BSID) at ages 12 and 24 months. Multiple linear regression analysis was used to describe the association of PCDD/F and PCB in maternal blood or milk with the outcome measurements after adjustment for confounding. Blood levels (n=182) of WHO 2005 toxic equivalents (TEQ) (PCDD/F+PCB) were in the range of 3.8-58.4 pg/glipid base (median: 19.3 pg/glipid base). The corresponding data for human milk (n=149) were 2.6-52.4 pg/glipid base (median: 19.7 pg/glipid base). Multiple regression analysis showed no decrease of thyroid hormones related to WHO 2005 TEQ in blood and milk of mothers and their newborns. Furthermore, no associations between exposure and neurological and developmental measures were observed. This study supports the view that the current decreased exposure to PCDD/Fs and PCBs does not impair thyroid function of newborns and neurodevelopment of infants until the age of 24 months.     

Naturally Occurring Ah-Receptor Agonists in Foods: Implications Regarding Dietary Dioxin Exposure and Health Risk

The human diet contains numerous naturally-occurring compounds that are aryl hydrocarbon receptor (AhR) agonists. This analysis compares the dietary TCDD-equivalent (TEQ) dose from specific vegetable indoles vs. the AhR-active PCDD/Fs. Daily dietary doses of indole-3-carbinole (I3C) and its condensation product indolo [3,2-b]carbazole (ICZ) were derived from the published literature. Relative estimate of potency (REP) values were developed for I3C (8.7 × 10^?7) and ICZ (0.5). The TEQ doses of I3C and ICZ together comprised >99% of the total daily TEQ dose; the daily ICZ TEQ dose (1.4 × 10⁶ pg TEQ/day) was approximately 45,000-fold greater than the current dietary PCDD/F TEQ dose (32 pg TEQ/day). When 30-year accumulated body burden and area-under-the curve doses were calculated, I3C/ICZ still comprised a significant fraction (up to 95 and 96%, respectively) of the total TEQ dose. Further, reduction or elimination of meat and dairy products yielded a minimal (less than 4%) decrease in total TEQ dose. These findings indicate that reducing the intake of animal products (the primary source of dietary PCDD/Fs) might not achieve a significant reduction in total “dietary dioxin TEQ” dose; the comparisons also suggest that trace levels of PCDD/Fs in the human diet are unlikely to pose a significant health risk.     

Biodegradation of pentachlorophenol in natural soil by inoculatedRhodococcus chlorophenolicus

Rhodococcus chlorophenolicus PCP-1, a mineralizer of polychlorinated phenols, was inoculated into natural sandy loam and peaty soils with pentachlorophenol (PCP) at concentrations usually found at lightly and heavily polluted industrial sites (30 to 600 mg PCP/kg). A single inoculum of 10⁵ to 10⁸ cells per g of peat soil and as little as 500 cells/g sandy soil initiated mineralization of¹⁴C-PCP. The mineralization rates of PCP were 130 to 250 mg mineralized per kg soil in 4 months in the heavily (600 mg/kg) polluted soils and 13 to 18 mg/kg in the lightly (30 mg/kg) polluted soils. There were no detectable PCP mineralizing organisms in the soils prior to inoculation, and also there was no significant adaptation of the indigenous microbial population to degrade PCP during 4 months observation in the uninoculated soils. The inoculum-induced mineralization continued for longer than 4 months after a single inoculation. Uninoculated, lightly polluted soils (30 mg PCP/kg) also showed loss of PCP, but some of this reappeared as pentachloroanisol and other organic chlorine compounds (EOX). Such products did not accumulate in theR. chlorophenolicus-inoculated soils, where instead EOX was mineralized 90 to 98%.R. chlorophenolicus mineralized PCP unhindered by the substrate competition offered by the PCP-methylating bacteria indigenously occurring in the soils or by simultaneously inoculated O-methylatingR. rhodochrous.     

Seasonal microbial community dynamics in a flowerpot-using personal composting system for disposal of household biowaste

Microbial community dynamics in a flowerpot-using solid biowaste composting (FUSBIC) process were monitored seasonally by quinone profiling and conventional microbiological methods. The FUSBIC system, which consisted of three flowerpots (14 L or 20 L capacity) with 5-6 kg each of a soil-compost mixture (SCM) as the primary reactors, was loaded daily with household biowaste from November 1998 to October 1999. The monthly average waste reduction rate was 88.2% for the 14-L system and 92.5% for the 20-L system on a wet weight basis. The direct total microbial count detected in the 14-L primary reactors ranged from 4.5 to 9.6x10(11) cells.g(-1) of dry wt of SCM, and the viable count of aerobic heterotrophic bacteria recovered on agar plates at 28 degrees C varied from 1.9 to 5.7x10(11) CFU.g(-1) of dry wt. The quinone content of SCM samples from the 14-L and 20-L systems ranged from 160 to 353 nmol.g(-1) of dry SCM. Ubiquinones, unsaturated menaquinones, and partially saturated menaquinones constituted 15.0-36.4, 14.8-22.0, and 41.8-61.6 mol% of the total content, respectively. The major quinone types detected were usually MK-8(H(2)), MK-9(H(2)), and Q-10. Variations in quinone profiles were evaluated numerically by using two parameters, the dissimilarity index (D) and microbial divergence index (MD(q)). The upper limit of seasonal changes in the microbial community structure was about 30% as expressed by D values. The MD(q) values calculated ranged from 18 to 22. A significant positive correlation was found between seasonal temperature and bacterial populations containing partially saturated menaquinones. These results indicated that the FUSBIC system contained highly diverse microbial populations that fluctuated to some extent depending on seasonal temperature. Members of the Actinobacteria were suggested to be the major constituents of the total population present.     

Phylogenetic characterization of a polychlorinated-dioxin- dechlorinating microbial community by use of microcosm studies

Microcosms capable of reductive dechlorination of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were constructed in glass bottles by seeding them with a polluted river sediment and incubating them anaerobically with an organic medium. All of the PCDD/F congeners detected were equally reduced without the accumulation of significant amounts of less-chlorinated congeners as the intermediate or end products. Alternatively, large amounts of catechol and salicylic acid were produced in the upper aqueous phase. Thus, the dechlorination of PCDD/Fs and the oxidative degradation of the dechlorinated products seemed to take place simultaneously in the microcosm. Denaturing gel gradient electrophoresis and clone library analyses of PCR-amplified 16S rRNA genes from the microcosm showed that members of the phyla Firmicutes, Proteobacteria, and Bacteroidetes predominated. A significant number of Chloroflexi clones were also detected. Quantitative real-time PCR with specific primer sets showed that the 16S rRNA genes of a putative dechlorinator, "Dehalococcoides," and its relatives accounted for 0.1% of the total rRNA gene copies of the microcosm. Most of the clones thus obtained formed a cluster distinct from the typical "Dehalococcoides" group. Quinone profiling indicated that ubiquinones accounted for 18 to 25% of the total quinone content, suggesting the coexistence and activity of ubiquinone-containing aerobic bacteria. These results suggest that the apparent complete dechlorination of PCDD/Fs found in the microcosm was due to a combination of the dechlorinating activity of the "Dehalococcoides"-like organisms and the oxidative degradation of the dechlorinated products by aerobic bacteria with aromatic hydrocarbon dioxygenases.     

Oral Bioavailability of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans in Industrial Soils

In this study, the oral bioavailabilities of numerous 2,3,7,8-PCDD/F congeners were evaluated in soil samples from an industrial site. The purpose of this study is several-fold: (1) to compare the soil bioavailability results of the different PCDD/F congeners; (2) to evaluate the consistency of the bioavailability results with those obtained in an in vitro bioaccessibility study with simulated GI tract fluids; and (3) to develop quantitative bioavailability measurements that are appropriate for use in a health risk assessment for this site. Soil samples containing PCDD/F toxic equivalent (TEQ) concentrations ranging from 0.53–45.2 ng/g were administered to female Sprague Dawley rats via oral gavage. Reference formulations of PCDD/Fs were administered intravenously or by oral gavage. The overall relative bioavailability of PCDD/Fs in the soil samples on a TEQ basis ranged from 17 to 51%, with a mean of 38%. The results of the in vitro bioaccessibility study were consistent with the bioavailability results (mean extracted TEQ of 22%). Because of the clear relationship between increasing chlorination and decreasing bioavailability and bioaccessibility observed in this study, we suggest that simply extrapolating results from one congener to another may be associated with a high degree of uncertainty.     

Monitoring PCDD/Fs in Soil and Herbage Samples Collected Near a Hazardous Waste Incinerator: Health Risks for the Population Living Nearby

In 1998, we started a wide environmental surveillance program focused on evaluating the environmental impact of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) emitted by a new hazardous waste incinerator (HWI) (Tarragona County, Catalonia, Spain) and assessing the potential health risks for the population living nearby. The HWI began regular operations in 1999. Since then, periodical surveys have been performed. We report here the results concerning PCDD/F levels in 40 soil and 40 herbage samples collected in years 2004 and 2005, respectively, in the vicinity of the HWI. The human health risks derived from exposure to PCDD/Fs were also assessed. PCDD/F concentrations in soils ranged from 0.06 to 12.60 ng I-TEQ/kg, with median and mean values of 0.65 and 1.14 ng I-TEQ/kg, respectively. In herbage, PCDD/F concentrations ranged from 0.03 to 1.57 ng I-TEQ/kg, with median and mean values of 0.31 and 0.40 ng I-TEQ/kg, respectively. A comparison of these results with those from the baseline survey shows that, after six years of regular operation, the HWI did not significantly increase PCDD/F levels in soils and herbage in the surrounding environment. Moreover, PCDD/F emissions from the HWI do not mean additional significant risks for the health of the individuals living in the vicinity of the facility. The results of the current study together with those of recent investigations in municipal waste incinerators indicate that, when adequately controlled for PCDD/F emissions, modern waste incinerators should not portend any special concern for the populations living nearby.     

Phylogenetic Characterization of a Polychlorinated-Dioxin- Dechlorinating Microbial Community by Use of Microcosm Studies

Microcosms capable of reductive dechlorination of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were constructed in glass bottles by seeding them with a polluted river sediment and incubating them anaerobically with an organic medium. All of the PCDD/F congeners detected were equally reduced without the accumulation of significant amounts of less-chlorinated congeners as the intermediate or end products. Alternatively, large amounts of catechol and salicylic acid were produced in the upper aqueous phase. Thus, the dechlorination of PCDD/Fs and the oxidative degradation of the dechlorinated products seemed to take place simultaneously in the microcosm. Denaturing gel gradient electrophoresis and clone library analyses of PCR-amplified 16S rRNA genes from the microcosm showed that members of the phyla Firmicutes, Proteobacteria, and Bacteroidetes predominated. A significant number of Chloroflexi clones were also detected. Quantitative real-time PCR with specific primer sets showed that the 16S rRNA genes of a putative dechlorinator, “Dehalococcoides,” and its relatives accounted for 0.1% of the total rRNA gene copies of the microcosm. Most of the clones thus obtained formed a cluster distinct from the typical “Dehalococcoides” group. Quinone profiling indicated that ubiquinones accounted for 18 to 25% of the total quinone content, suggesting the coexistence and activity of ubiquinone-containing aerobic bacteria. These results suggest that the apparent complete dechlorination of PCDD/Fs found in the microcosm was due to a combination of the dechlorinating activity of the “Dehalococcoides”-like organisms and the oxidative degradation of the dechlorinated products by aerobic bacteria with aromatic hydrocarbon dioxygenases.     

Microbial community succession and lignocellulose degradation during agricultural waste composting

The changes of microbial community during agricultural waste composting were successfully studied by quinone profiles. Mesophilic bacteria indicated by MK-7 and mesophilic fungi containing Q-9 as major quinone were predominant and seemed to be important during the initial stage of composting. Actinobacteria indicated by a series of partially saturated and long-chain menaquinones were preponderant during the thermophilic period. While Actinobacteria, fungi and some bacteria, especially those microbes containing MK-7(H4) found in Gram-positive bacteria with a low G+C content or Actinobacteria were found cooperate during the latter maturating period. Since lignocellulsoe is abundant in the agricultural wastes and its degradation is essential for the operation of composting, it’s important to establish the correlation between the quinone profiles changes and lignocellulose degradation. The microbes containing Q-9 or Q-10(H2) as major quinone were found to be the most important hemicellulose and cellulose degrading microorganisms during composting. While the microorganisms containing Q-9(H2) as major quinone and many thermophilic Actinobacteria were believed to be responsible for lignin degradation during agricultural waste composting.     

Influence of Low-Level Prenatal Exposure to PCDD/Fs and PCBs on Empathizing,Systemizing and Autistic Traits: Results from the Duisburg Birth Cohort Study

Background

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) are assumed to act as endocrine disruptor chemicals. Prenatal exposure to these pollutants might influence fetal steroid hormone levels, which are thought to be related to sex-typical development and autistic traits.

Objectives

We examined associations of prenatal levels of PCDD/Fs and PCBs with autism traits and sex-typical behaviour in childhood.

Methods

We measured levels of PCDD/Fs and PCBs in maternal blood samples during pregnancy using gas chromatography/high-resolution mass spectrometry. Sex-typical behaviour was assessed at 9 years of age (n = 96) and autistic traits at 10 years of age using the Social Responsiveness Scale (SRS; n = 100). Multiple regression analyses were conducted to estimate the associations between prenatal exposure and outcome variables.

Results

Blood concentrations (WHO₂₀₀₅-TEq) of ƩPCDD/Fs ranged from 2.93–46.45 pg/g _{lipid base} (median = 12.91 pg/g _{lipid base}) and concentrations of ƩPCBs were in the range of 1.24–25.47 pg/g _{lipid base} (median = 6.85 pg/g _{lipid base}) which is within the range of German background exposure. We found significant negative associations between PCDD/F levels in maternal blood and SRS scores in the whole group (β = -6.66, p < .05), in girls (β = -10.98, p < .05) and, in one SRS subscale, in boys (β = -6.86, p < .05). For PCB levels, associations with one SRS subscale were significant for the whole study group as were associations with two subscales in girls. We did not find significant associations between PCDD/F or PCB levels and sex-typical behaviour for either sex.

Conclusions

In an earlier part of this study, prenatal exposure to PCDD/Fs and PCBs was found to be associated with lower testosterone levels, therefore, our findings are consistent with the idea that autism spectrum conditions are related to fetal androgen levels. Several possible mechanisms, through which PCDD/Fs and PCBs might influence autistic behaviour, are discussed.     

Anaerobic reductive dehalogenation of polychlorinated dioxins

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) are among the most harmful environmental contaminants. Their widespread distribution due to unintentional or unknown release coincides with environmental persistence, acute and chronic toxicity to living organisms, and long-term effects due to the compounds’ tendency for bioaccumulation and biomagnification. While microbial aerobic degradation of PCDD/Fs is mainly reported for the turnover of low chlorinated congeners, this review focuses on anaerobic reductive dehalogenation, which may constitute a potential remediation strategy for polychlorinated compounds in soils and sediments. Microorganisms in sediments and in microcosms or enrichment cultures have been shown to be involved in the reductive dechlorination of dioxins. Bacteria related to the genus Dehalococcoides are capable of the reductive transformation of dioxins leading to lower chlorinated dioxins including di- and monochlorinated congeners. Thus, reductive dehalogenation might be one of the very few mechanisms able to mediate the turnover of polychlorinated dioxins by reducing their toxicity and paving the way for a subsequent breakdown of the carbon skeleton.     

Risk Assessment of Some PCDDs,PCDFs, Dioxin-Like PCBs,and PCBs in Contaminated Dairy Products: An Egyptian Pilot Case Study

Samples of butter, cream, and white cheese were collected from the city of Ismailia, Egypt, and analyzed for polychloro dibenzo-p-dioxins, pentachloro dibenzo-p-furans, and dioxin-like polychlorinated biphenyl, PCBs. Butter samples had the highest mean content of PCDD/F and dioxin-like PCBs. Butter samples were the most contaminated samples in all dairy products analyzed in this study, whereas white cheese samples were the least contaminated. The spectrum of congeners detected in butter and cream were similar, with all congeners at detectable levels, whereas the spectrum of congeners detected in white cheese differed, with some congeners, namely 1,2,3,4,7,8-Hexa CDD, 1,2,3,4,6,7,8-Hepta CDD, and 1,2,3,7,8,9-Hexa CDD below WHO TE toxicity levels. 1,2,3,7,7-PeCDD, with its high concentration, was the principal contributor to the TEQ intake in both cream and butter samples. Similarly, the high concentration of 2,3,4,7,8-PeCDF in cream, butter, and white cheese samples was the main factor contributing to their TEQ intake. Estimated intakes of PCDDs/Fs were 129.2, 115.8, and 51.25 pg WHO-TEQ/day for butter, cream, and white cheese, respectively. Taking into account the sum of PCDDs/Fs and dioxin-like PCBs, estimated intakes were, 171.7, 155.8, and 68 pg WHO-TEQ/day, for butter, cream, and white cheese, respectively. Assuming an average bodyweight of 60 kg (WHO-TEQ/kg), these levels correspond to bodyweight-normalized intake levels of .15, 2.92 and 0.95 pg WHO-TEQ/kg/day.     

The influence of the Cucurbitaceae on mitigating the phytotoxicity and PCDD/PCDF content of soil amended with sewage sludge

The study evaluates the impact of sewage sludge on OECD - Organization for Economic Cooperation and Development and vegetable soil phytotoxicity, measured using three test species: Lepidium sativum, Sinapis alba and Sorghum saccharatum, and total and TEQ PCDD/PCDF (toxic equivalency polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans) soil concentration, measured using HRGC/HRMS - High Resolution Gas Chromatography/High Resolution Mass Spectrometry. It also evaluates the effect of zucchini and cucumber cultivation during 5-weeks period on mitigating these parameters. The application of 3, 9 and 18 t/ha of sewage sludge gradually increases the phytotoxicity of both OECD and vegetable soil. In the case of OECD soil, the highest roots growth inhibitions were observed for S. alba (73%, 86% and 87%, respectively) and the lowest for S. saccharatum (7%, 59% and 70%), while in vegetable soil inhibitions were averagely 25% lower. Sludge application also led to a 38% (3 t/ha), 169% (9 t/ha) and 506% (18 t/ha) increase in PCDD/PCDF concentration, and the TEQs were augmented by 15%, 159% and 251%. Both soil phytotoxicity and total and TEQ PCDD/PCDF concentrations were diminished as a result of zucchini and cucumber cultivation. The maximum reduction of soil phytotoxicity (83%) was observed as an effect of cucumber cultivation, while zucchini was 11% less effective. Zucchini, in turn, was more efficient in PCDD/PCDF removal (37% reduction), followed by cucumber (24%). Such differences were not observed in the case of TEQ reductions (68% and 66% for zucchini and cucumber cultivation, respectively).     

Quinones of phototrophic purple bacteria

Abstract The quinone composition of the recognized species of the phototrophic purple nonsulfur bacteria, the Ectothiorhodospiraceae, and some Chromatiaceae species has been determined. Altogether more than 50 strains of 33 species have been investigated. Some of the purple nonsulfur bacteria have Q-10 as sole quinone component, while others have Q-10, Q-9, or Q-8, respectively, together with menaquinones of the same isoprenoid chain length as the major components. Rhodoquinone is present in Rhodospirillum rubrum and Rhodospirillum photometricum . The Ectothiorhodospira species have either Q-8 and MK-8, like the Chromatiaceae species, or Q-7 and MK-7 as the major components.     

Levels of Polychlorinated Dibenzo-P-Dioxins (PCDDs) and Polychlorinated Dibenzo-P-Furans (PCDFs) in the Atmosphere (PM10) of a Coastal Area of West Bengal,India

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzo-p-furans (PCDDs/Fs) were analyzed in the coastal air of West Bengal, India. Total PCDD/Fs ranged from 4–2491 fg m^–3 with a mean of 355 fg m^–3 and their I-TEQ values ranged between 1 to 62.6 fg I-TEQ m^–3, with an average of 17.1 fg I-TEQ m^–3. The dominant congeners were OCDD (46%) OCDF (14%) 1,2,3,4,6,7,8-HpCDF (11%) and 1,2,3,4,6,7,8-HpCDD (10%) and accounted for >80% to the total PCDDs/Fs. TCDD (29%) > PeCDF (28%) > HxCDF (16%) > PeCDD (13%) were the dominant TEQ contributors. Rough estimates of tolerable daily intake (TDI) show a low health risk of exposure to PCDD/Fs measured in the ambient air of a rural coastal area of West Bengal, India.     

Quinone profiles in lake sediments: Implications for microbial diversity and community structures

Microbial quinone compositions of sediment mud samples from five different lakes in Japan were studied by spectrochromatography and mass spectrometry. The total quinone content of these samples ranged from 1.97 to 18.0 nmol/g dry weight of sediment, of which a combined fraction of ubiquinones and menaquinones accounted for 42 to 74%. The remaining fraction (26 to 58%) consisted of the photosynthetic quinones, plastoquinones and phylloquinone. The sediment samples produced PQ-9 or Q-8 as the most abundant quinone type regardless of their geographic locations and depths. These results indicate that oxygenic phototrophic microorganisms and Q-8-containing proteobacteria constituted major parts of microbial populations in the lake sediment. In the surface water of the same sampling sites, plastoquinones and phylloquinone occurred in much higher proportions. These findings suggested that the high abundance of oxygenic phototrophs in the sediment muds resulted from their constant movement or sedimentation from the surface water. Numerical analyses of the quinone profiles showed that the microbial communities of the sediment were diverse and different in different lakes but similar to each other in the diversity of bioenergetic modes. Three physiological groups of microbes showing ubiquinone-mediated aerobic respiration, oxygenic photosynthesis, and menaquinone-associated respiration were suggested to inhabit the lake sediments in balance.     

Recent developments in microbial biotransformation and biodegradation of dioxins

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), commonly known as dioxins (PCDD/Fs), are toxic environmental pollutants formed from various sources. Elimination of these pollutants from the environment is a difficult task due to their persistent and ubiquitous nature. Removal of dioxins by biological degradation (biodegradation) is considered a feasible method as an alternative to other expensive physicochemical approaches. Biodegradation of dioxins has been extensively studied in several microorganisms, and details concerning biodiversity, biodegradation, biochemistry and molecular biology of this process have accumulated during the last three decades. There are several microbial mechanisms responsible for biodegradation of dioxins, including oxidative degradation by dioxygenase-containing aerobic bacteria, bacterial and fungal cytochrome P-450, fungal lignolytic enzymes, reductive dechlorination by anaerobic bacteria, and direct ether ring cleavage by fungi containing etherase-like enzymes. Many attempts have been made to bioremediate PCDD/Fs using this basic knowledge of microbial dioxin degradation. This review emphasizes the present knowledge and recent advancements in the microbial biotransformation, biodegradation and bioremediation of dioxins.     

铜川煤矿区重金属污染对土壤微生物群落代谢和酶活性的影响

研究了陕西省铜川煤矿矿区的重金属污染状况以及不同程度的重金属污染对土壤微生物代谢、微生物群落功能以及土壤酶活性的影响.结果表明： 铜川矿区土壤中重金属Cu、Zn、Cd、Pb全量及有效量均显著高于非矿区土壤,其中Cd污染最为严重.采用Biolog方法结合主成分分析和聚类分析发现,随着污染程度的增加,不同土壤微生物群落间的代谢特征发生显著变化,而且这种变化主要体现在糖类和氨基酸类碳源的利用差异.在轻度、中度污染情况下,土壤微生物群落对碳源的利用表现出激活效应;而在重度污染的情况下,土壤微生物群落对碳源的利用表现出抑制效应.随着污染程度的增加,脲酶、蛋白酶、碱性磷酸酶和过氧化氢酶的活性均呈现降低的趋势,矿区土壤脲酶、蛋白酶、碱性磷酸酶和过氧化氢酶活性分别是非矿区土壤中相应酶活性的50.5%～65.1%、19.1%～57.1%、87.2%～97.5%、77.3%～86.0%;蔗糖酶和纤维素酶在中等污染程度以下的土壤中表现为激活效应,而在重度污染的土壤中表现为抑制效应.     

Dairy ruminant exposure to persistent organic pollutants and excretion to milk

Human activities produce polluting compounds such as persistent organic pollutants (POPs), which may interact with agriculture. These molecules have raised concern about the risk of transfer through the food chain via the animal product. POPs are characterised by a strong persistence in the environment, a high volatility and a lipophilicity, which lead to their accumulation in fat tissues. These compounds are listed in international conventions to organise the information about their potential toxicity for humans and the environment. The aim of this paper is to synthesise current information on dairy ruminant exposure to POPs and the risk of their transfer to milk. Three major groups of POPs have been considered: the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), the polychlorobiphenyls (PCBs) and the polycyclic aromatic hydrocarbons (PAHs). The results show that contamination of fodder and soil by these compounds is observed when they are exposed to emission sources (steelworks, cementworks, waste incinerators or motorways) compared with remote areas. In general, soil contamination is considered higher than plant contamination. Highest concentrations of POPs in soil may be close to 1000 ng/kg dry matter (DM) for PCDD/Fs, to 10 000 mg/kg DM for PAHs and 100 μg/kg DM for PCBs. The contamination of milk by POPs depends on environmental factors, factors related to the rearing system (fodder and potentially contaminated soil, stage of lactation, medical state of the herd) and of the characteristics of the contaminants. Transfer rates to milk have been established: for PCBs the rate of transfer varies from 5% to 90%, for PCDD/Fs from 1% to 40% and for PAHs from 0.5% to 8%. The differential transfer of the compounds towards milk is related to the hydrophobicity of the pollutants as well as to the metabolic susceptibility of the compounds.     

On the isolation of polychlorinated dibenzo-p-dioxins and furans from serum samples using immunoaffinity chromatography prior to high-resolution gas chromatography–mass spectrometry

Immunoaffinity chromatography (IAC) for the purification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from biological samples was explored as a means to simplify the cleanup procedure and thereby decrease the time and cost of dioxin analysis. A monoclonal antibody (DD3) was used to produce IAC columns and to isolate the PCDD/Fs from serum. Native and ¹³C-labeled PCDD/Fs were spiked at the ppq to ppt range into serum. Quantitation of the PCDD/Fs was performed by a standard dioxin analytical method, i.e. high-resolution gas chromatography–mass spectrometry (GC–MS), which was easily compatible with IAC. Five of the most toxic PCDD/Fs consistently showed acceptable recoveries (>25%) and were reliably quantitated. The congeners specifically recovered by this method represent almost 80% of the toxic equivalency of dioxins and furans present in the serum samples. Dioxin-like polychlorinated biphenyls (PCBs) were not recognized by this antibody column. Compared to conventional dioxin cleanup methods, IAC decreased solvent usage by 1.5 l/sample and took only 2 h to process a sample for analysis.