Technical note monitoring native vegetation on a dumpsite of PCB-contaminated soil

Composition of native vegetation on a polychlorinated biphenyls (PCB)-contaminated soil dumpsite at Lhenice, South Bohemia (Czech Republic), was determined and species variability in the accumulation of PCBs in plant biomass was investigated. Soil stripping contaminated by PCBs originated at a factory producing electrical transformers that mostly used the commercial PCB mixture Delor 103 and 106. The PCB content of soil in the most contaminated part of the dumpsite reached 153 mg kg(-1) dry soil. Low diversity of plant species was found on the dumpsite. Results showed three grass species, Festuca arundinacea Schreb., Phalaroides arundinacea (L.) Rauschert., and Calamagrostis epigeios (L.) Roth., to be the major components of the vegetation and confirmed their high tolerance toward PCB contamination. The highest content of PCB in plant biomass--813.2 microg kg(-1) dry biomass--was determined in Festuca aboveground biomass. For phytoextraction purposes especially, Festuca can be recommended due to its high biomass yield, but its bioconcentration factor was very low (0.006). Tripleurospermum maritimum (L.) Sch. Bip. and Cirsium arvense (L.) Scop. grew mainly at the margins of the most contaminated part of the dumpsite. The PCB content determined in their aboveground biomass-278.7 and 289.5 microg kg(-1) dry biomass, respectively--was nonsignificantly lower compared to grass species Phalaroides and Calamagrostis. Salix (Salix viminalis L. and Salix caprea L.) was monitored among plant species composition at this site as a representative of woody species.     

Dehalogenation of chlorinated aromatic compounds using a hybrid bioinorganic catalyst on cells of <Emphasis Type="Italic">Desulfovibrio desulfuricans</Emphasis>

A novel bioinorganic catalyst was obtained via reduction of Pd(II) to Pd⁰ on to the surface of cells of Desulfovibrio desulfuricans at the expense of H₂. Palladised biomass, supplied with formate or H₂ as an electron donor, catalysed the dehalogenation of 2-chlorophenol and polychlorinated biphenyls. In the example of 2,3,4,5-tetrachlorobiphenyl, the bioinorganic catalyst promoted a rate of chloride release of 9.33 ± 0.17 nmol min^–1 mg ^–1and only ~5% of this value was obtained using chemically reduced or commercially available Pd ⁰. In the case of 2,2,4,4,6,6-hexachlorobiphenyl the rate was more than four orders of magnitude faster than the degradation reported using a sulfidogenic culture. Negligible chloride release occurred from any of the chloroaromatic compounds using biomass alone, or from palladised biomass challenged with hexane carrier solvent only. Analysis of the spent solution showed that in addition to catalysis of reductive dehalogenation the new material was able to remove very effectively the organic residua, with neither any PCB nor any breakdown products identifiable by GC/MS.Revisions requested 8 September 2004; Revisions received 21 October 2004;     

Identification of sex-specific DNA methylation changes driven by specific chemicals in cord blood in a Faroese birth cohort

Faroe islanders consume marine foods contaminated with methylmercury (MeHg), polychlorinated biphenyls (PCBs), and other toxicants associated with chronic disease risks. Differential DNA methylation at specific CpG sites in cord blood may serve as a surrogate biomarker of health impacts from chemical exposures. We aimed to identify key environmental chemicals in cord blood associated with DNA methylation changes in a population with elevated exposure to chemical mixtures. We studied 72 participants of a Faroese birth cohort recruited between 1986 and 1987 and followed until adulthood. The cord blood DNA methylome was profiled using Infinium HumanMethylation450 BeadChips. We determined the associations of CpG site changes with concentrations of MeHg, major PCBs, other organochlorine compounds [hexachlorobenzene (HCB), p,p’-dichlorodiphenyldichloroethylene (p,p’-DDE) and p,p’-dichlorodiphenyltrichloroethane], and perfluoroalkyl substances. In a combined sex analysis, among the 16 chemicals studied, PCB congener 105 (CB-105) exposure was associated with the majority of differentially methylated CpG sites (214 out of a total of 250). In female-only analysis, only 73 CB-105 associated CpG sites were detected, 44 of which were mapped to genes in the ELAV1-associated cancer network. In males-only, methylation changes were seen for perfluorooctane sulfonate, HCB, and p,p’-DDE in 10,598, 1,238, and 1,473 CpG sites, respectively, 15% of which were enriched in cytobands of the X-chromosome associated with neurological disorders. In this multiple-pollutant and genome-wide study, we identified key epigenetic toxicants. The significant enrichment of specific X-chromosome sites in males implies potential sex-specific epigenome responses to prenatal chemical exposures.     

Effect of chlorobenzoates on the degradation of polychlorinated biphenyls (PCB) by Pseudomonas stutzeri

Chlorobenzoic acids (CBA) are frequently dead-end products of partial aerobic biodegradation of polychlorinated biphenyls (PCB). When CBA produced from PCB accumulate in the growth medium, they can inhibit the bacterial growth and consequently, slow down PCB biodegradation. In this study, the effects of seven mono- and dichlorinated CBA on growth of Pseudomonas stutzeri on different substrates and on the PCB degradation by this strain in a liquid mineral medium were tested. 3-CBA was the strongest growth inhibitor for P. stutzeri growing on glucose, benzoate and biphenyl. It was found to inhibit heavily the elimination of some di- and trichlorinated biphenyls. In contrast, its influence on the elimination of more chlorinated congeners was much less significant.The authors are with the Department of Biochemical Technology, Faculty of Chemical Technology, Slovak Technical University, 812 37 Bratislava, Slovakia.     

High-rate continuous biodegradation of concentrated chlorinated aliphatics by a durable enrichment of methanogenic origin under carrier-dependent conditions

The simultaneous biodegradation of toxic compounds in mixtures is a major current concern. To bioremediate a toxic mixture, we designed a strategy combining an ad-sorbent carrier with an ecological and nutritional system which allowed work close to heavily polluted conditions in nature. Starting from a methanogenic community, we developed a microbial consortium acclimated to a mixture of about 30 chlorinated aliphatics in a fixed-film stationary-bed bioreactor. Prior to the establishment of a durable period of dechlorination, an interval of progressive dechlorination of the toxic mixture was observed during which the excess of the toxic compounds was stored on the carrier. The latter, consisting of activated carbon in a polyurethane foam, allowed us to work at concentrations far above the solubility of the toxic compounds (apparent concentrations of about 10 g/L). The complete disappearance of hexachloroethane as well as its lower homologues, penta-, tetra-, and trichloroethane, present in the toxic mixture, was observed. Additionally, octachlorocyclopentene, carbon tetrachloride, trichloro-ethylene, tetrachloroethylene, and hexachloro-1,3-butadiene also completely disappeared. For the four latter compounds, from mass balances in the bioreactor, degradation rates around 10 mumol/L per day were determined with total dechlorination. The enrichment culture thus developed exhibited high degradation performances similar to those reported in the literature for pure or enriched anaerobic microbial cultures in contact with a single toxic compound. The results demonstrate the possibility of concurrent high-rate degradation of several highly chlorinated toxic compounds, under conditions approximating field situations.(c) 1995 John Wiley & Sons, Inc.     

红球菌R04联苯/多氯联苯代谢相关调控蛋白RHOGL007659的生理功能

【目的】研究红球菌(Rhodococcus sp.)R04调控蛋白RHOGL007659的生理功能及其缺陷菌株的代谢特性,初步探究红球菌R04降解联苯的调控机制。【方法】通过基因同源重组敲除红球菌R04联苯代谢相关基因RHOGL007659。比较红球菌R04(野生型)和缺陷型菌株R04Δ7659(基因RHOGL007659缺陷型的R04)在不同碳源培养下的生长情况,HPLC分析R04和R04Δ7659转化联苯的能力。提取R04和R04Δ7659的总RNA,实时荧光定量PCR检测联苯降解关键基因的转录表达。纯化Bph B(联苯降解脱氢酶)和Bph D(联苯降解水解酶),制备多克隆抗体。Western blot分析Bph B和Bph D蛋白在R04和R04Δ7659中的表达水平。【结果】获得了RHOGL007659基因的缺陷型菌株R04Δ7659,与R04相比,R04Δ7659在联苯培养条件下的生物量趋近于零。HPLC分析表明,RHOGL007659基因的缺失使红球菌R04丧失转化联苯的能力。实时荧光定量PCR结果表明,在联苯培养条件下,缺失RHOGL007659后的R04,其联苯降解关键基因均有不同程度的下调表达。Western blot分析显示RHOGL007659缺失后,联苯降解关键酶Bph B和Bph D表达量均降低,这与实时荧光定量PCR结果相一致。【结论】RHOGL007659是红球菌R04联苯降解关键基因簇的调控蛋白,该蛋白对红球菌R04代谢联苯过程具有正调控作用。     

Enantioseparation and identification for the rationalization of the environmental impact of 4 polychlorinated biphenyls

Polychlorinated biphenyls (PCBs) are harmful and persistent organic pollutants that have long been used in industrial manufacturing. Their persistence leads to accumulation in the food chain causing potential toxic effects. As 19 out of 78 of the chiral congeners have stable atropisomers at ambient temperature, we studied some typical enantiomers: PCB45, PCB95, PCB136, and PCB149. The chiral stationary phases OD‐H and OJ‐H were used for separation in analytic high‐performance liquid chromatography (HPLC), as well as for collection in semi‐preparative HPLC. The resolution was optimized with respect to n‐hexane–based mobile phases, temperature, and flow rate. All pure enantiomers were recovered from semi‐preparative HPLC within 15 minutes for practical purpose. Characterization of the absolute configurations were conducted with a combination of theoretical and experimental electronic circular dichroism measurements. The enantiomers of PCB45, PCB95, PCB136, and PCB149 proved to be eluted as R > S, S > R, R > S, and S > R, respectively. Molecular structures (eg, substituent groups) and properties (eg, bond lengths, bond angles, and dipole moments) were quantitatively analyzed to understand the toxicity effect of PCBs. In summary, we have developed a well‐established methodology of collection and configuration identification for analogous PCB derivatives.     

Root exudates and plant secondary metabolites of different plants enhance polychlorinated biphenyl degradation by rhizobacteria

Polychlorinated biphenyls (PCBs) are toxic and persistent compounds that are difficult to break down and biodegrade. Plant secondary metabolites (PSMs) on root exudates can act as inducers of the biphenyl catabolic pathway, enhancing PCB biodegradation. In this study, the authors evaluated the effect of root exudates and PSMs obtained from Avena sativa, Brachiaria decumbens, Medicago sativa, and Brassica juncea on the biodegradation of PCB 44, PCB 66, PCB 118, PCB 138, PCB 153, PCB 170, and PCB 180 by a microbial consortium isolated from the rhizosphere of plants grown on soil contaminated with Aroclor 1260. Microorganisms were identified as Pseudomonas sp. and Stenotrophomonas sp. based on their 16S rRNA sequence. The plant root exudates increased the degradation percentage of PCB 44, PCB 66, and PCB 118, which were used as carbon source by the microorganisms. Flavanone, flavone, isoflavone, 7-hydroxyflavanone, 7-hydroxyflavone, and 6-hydroxyflavone were the PSMs identified in the root exudates, which increased the degradation percentage of all seven PCB congeners; they were also used as growth substrates by microbial consortium. These results showed the importance of the interaction between plants and microorganisms for achieving the removal of persistent pollutants such as PCBs from soil.     

Determination of the rotational barriers of atropisomeric polychlorinated biphenyls (PCBs) by a novel stopped-flow multidimensional gas chromatographic technique

The rotational barriers ΔG^‡ (T) of the four atropisomeric polychlorinated biphenyls (PCBs) 2,2′,3,5′,6-pentachlorobiphenyl (PCB 95), 2,2′3,3′,4,6′-hexachlorobiphenyl (PCB 132), 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136), and 2,2′,3,4′,5′,6-hexachlorobiphenyl (PCB 149) were determined via on-line enantiomerization kinetics by a new stopped-flow multidimensional gas chromatographic technique (stopped-flow MDGC) employing Chirasil-Dex as chiral stationary phase for enantiomer separation. The calculated rotational barriers ΔG^‡ (T) of the trichloro-ortho-substituted atropisomers are 184 ± 2 kJ/mol for PCB 95, 189 ± 4 kJ/mol for PCB 132, and 184 ± 1 kJ/mol for PCB 149 at 300°C. The rotational barrier ΔG^‡ (T) of tetrachloro-ortho-substituted PCB 136 is at least (or higher than) 210 kJ/mol at 320°C. Chirality 10:316–320, 1998. © 1998 Wiley-Liss, Inc.