Retention and mobility of atmospheric particle-associated organic pollutant PCDD/Fs and PAHs in maize leaves

The fate of polychlorinated dibenzo- p -dioxins and dibenzofurans and polycyclic aromatic hydrocarbons deposited to maize leaves under ambient conditions was investigated, with focus on those compounds that are primarily associated with particles in the atmosphere. Leaf samples collected from mature maize plants over an 8-wk period were subjected to four extraction procedures: (1) rinsing with distilled water; (2) shaking in aqueous EDTA solution; (3) immersion in chloroform/methanol; (4) soxhlet extraction with toluene. Of the compounds deposited primarily in association with particles, > 20% of the total leaf contamination was present in the first two aqueous extracts, indicating that only a small portion of these substances was subject to ready erosion from the leaf surfaces. Some 50–60% of the chemical was present in the third extract, while 20–40% was found in the final extract. The chemical in the final extract was no longer associated with particles, since these had been removed with the first three extractions. This chemical must have desorbed from the particles with which it was originally deposited, and migrated through the epicuticular waxes. Model calculations indicated that 15–35% of the chemical in the third extract had also desorbed from the particles, and there was evidence that polychlorinated dibenzo- p -dioxins and dibenzofurans desorb more readily than polycyclic aromatic hydrocarbons. It is concluded that desorption of chemical from particles and subsequent transport through the cuticle is an important process determining plant accumulation of organic contaminants associated with atmospheric particles.     

Dioxin-like Polychlorinated Biphenyls Contamination and Distribution in Soils from the Modern Yellow River Delta,China

The concentrations of 12 dioxin-like Polychlorinated Biphenyls (dl-PCBs) were determined from 37 soil samples collected from the modern Yellow River Delta (China) in March 2006. The PCB concentrations were determined by dual capillary GC-ECD. The total dl-PCBs concentrations were in the range of 108.7 to 2153 ng/kg with an average of 800.5 ng/kg. The toxic equivalency (TEQ) in this area varies from 2.3 × 10^{? 5} to 9.5 × 10^{? 5} ng-TEQ/kg, so the delta is slightly polluted by PCBs. PCB118, the main congener, accounted for 46.7% of the total dl-PCB. More than 60% dl-PCBs were penta-PCBs. The spatial distribution of the dl-PCBs is discussed in detail. The distribution of the PCBs suggests that water runoff is the main source of the total contaminant burden in the delta, and that atmospheric precipitation plays an important role.     

Ecotoxicological Risk Assessment of Polychlorinated Biphenyls (PCBs) in Bank Sediments from along the Yamuna River in Delhi,India

The River Yamuna originates from the Yamunotri glacier of the Himalayas and travels 22 km in the Delhi region. The river is used for various purposes in Delhi including drinking water supply. Twenty-eight polychlorinated biphenyls (PCBs) congeners were measured in bank sediments along the river, and their ecotoxicological risk was evaluated. Concentrations of ∑28PCBs varied from 0.20–21.16 ng g^?1 (dry wt.) with mean and median values of 6.63 ng g^?1 and 5.84 ng g^?1 (±0.69 ng g^?1), respectively. The concentration of 12 dl-PCBs concentrations varied from 0.04–2.86 ng g^?1 with a mean of 1.04 ± 0.11 ng g^?1, and their toxic equivalency ranged between <0.01–28.67 pg WHO-TEQ g^?1 with a mean of 10.77 ± 1.06 pg WHO-TEQ g^?1. CB-37, CB-44, CB-114, and CB-118 congeners were dominant among all PCBs congeners. The tri-PCBs (49%) were the main contributors to the PCB homolog followed by tetra-PCBs (35%), and penta-PCB (14%). Because there are no environmental guidelines in India for PCBs in river and marine sediments, concentrations of PCBs and their toxic equivalents were compared in a screening-level assessment with established freshwater sediment quality guidelines and found lower than those guideline values, which suggests no adverse ecotoxicological effect.     

活的但非可培养功能菌群对多氯联苯降解的探索进展

活的但非可培养(“viable but non-culturable”,简称VBNC)状态是微生物应对各种环境压力的一种生存机制.面对日益严重的异生质污染问题,研究污染胁迫下VBNC状态菌的潜在环境功能具有重要意义.该文阐述了VBNC状态菌的研究现状,针对多氯联苯微生物降解存在的问题,重点介绍环境中潜在VBNC功能菌群的复苏培养.提出利用藤黄球菌(Micrococcus luteus)复苏促进因子(resuscitation-promoting factor,简称Rpf)探索具有潜在多氯联苯降解功能的VBNC状态菌群,为多氯联苯高效降解菌群的筛选提供新思路.同时,结合VBNC状态菌絮凝、硝化除臭等方面的探索研究,对VBNC状态菌的潜在环境功能进行了展望.     

Toxicological biomarkers of 2,3,4,7,8-pentachlorodibenzofuran in proteins secreted by HepG2 cells

Using a proteomic approach, a study was conducted for determination of the effects of 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PCDF) on proteins secreted by HepG2 cells. Briefly, HepG2 cells were exposed to various concentrations of 2,3,4,7,8-PCDF for 24 or 48 h. MTT and comet assays were then conducted for determination of cytotoxicity and genotoxicity, respectively. Results of an MTT assay showed that 1 nM of 2,3,4,7,8-PCDF was the maximum concentration that did not cause cell death. In addition, a dose- and time dependent increase of DNA damage was observed in HepG2 cells exposed to 2,3,4,7,8-PCDF. Therefore, two different concentrations of 2,3,4,7,8-PCDF, 1 and 5 nM, were selected for further analysis of proteomic biomarkers using two different pI ranges (4-7 and 6-9) and large two dimensional gel electrophoresis. Results showed identification of 32 proteins ( 29 up- and 3 down-regulated) by nano-LC-ESI-MS/MS and nano-ESI on a Q-TOF2 MS. Among these, the identities of pyridoxine-5'-phosphate oxidase, UDP-glucose 6-dehydrogenase, plasminogen activator inhibitor I precursor, plasminogen activator inhibitor-3, proteasome activator complex subunit 1, isoform 1 of 14-3-3 protein sigma, peptidyl-prolyl cis-trans isomerase A, 14-3-3 protein gamma, protein DJ-1, and nucleoside diphosphate kinase A were confirmed by western blot analysis. The differential expression of protein DJ-1, proteasome activator complex subunit 1 and plasminogen activator inhibitor-3 was further validated in plasma proteins from rats exposed to 2,3,4,7,8-PCDF. These proteins could be used as potential toxicological biomarkers of 2,3,4,7,8-PCDF.     

Degradation of Polychlorinated Biphenyls by UV-Catalyzed Photolysis

Photolysis of five polychlorinated biphenyl (PCB) congeners [2,4,4′-trichlorobiphenyl (PCB 28), 2,2′,5,′5-tetrachlorobiphenyl (PCB 52), 2,2′,4,5,5′-pentachlorobiphenyl (PCB 101), 2,2′,4,4′,5,′5-hexachlorobiphenyl (PCB 153) and 2,2′,3,4,4′,5,′5-heptachlorobiphenyl (PCB 180)] individually and in combination were carried out in the solvents methanol, ethanol, and 2-propanol. The disappearance of parent congener generally increased with UV intensity. The solvents had significant or limited effect on the removal of PCBs depending on the congener used. Because 2-propanol was highly toxic and methoxylated products were formed when methanol was used, ethanol was selected as the optimum solvent. The results of photolysis of the PCB mixture showed that PCB 52 was formed and accumulated after 4 h of photolysis. The addition of sodium hydroxide increased the rate of photolysis of the PCB mixture. One hundred percent removal can be obtained of the PCB in mixture in 90 min under optimized conditions. Gas chromatography–mass spectrometry was used to determine the intermediates of the photolysis of PCBs under optimized conditions. For the PCB congeners and mixture studied, the major photolytic intermediates were less chlorinated congeners, and biphenyl was the major product with minor amounts of hydroxylated PCBs, ethylated, dimethylated, and methylated biphenyls. Biphenyl could be further degraded by a prolonged photolysis. Toxicity of the PCB mixture during photolysis was monitored by the Microtox^® test. It was found that the toxicity increased at the early stage of photolysis, and gradually decreased as the reaction proceeded. After 90 min, the EC₅₀ of the reaction mixture was similar to that of the untreated sample.     

Potential for phytoremediation of polychlorinated biphenyl-(PCB-)contaminated soil

Weathered soils contaminated with commercial-grade Aroclor 1260 from three sites in Canada were used to investigate the polychlorinated biphenyl (PCB) phytoextraction potential of nine plant species (Festuca arundinacea, Glycine max, Medicago sativa, Phalaris arundinacea, Lolium multiflorum, Carex normalis, and three varieties of Cucurbita pepo ssp. pepo) under controlled greenhouse conditions. The soils used varied in PCB concentration (90-4200 microg/g) and total organic content (0.06-2.02%). Greenhouse experiments controlled for PCB volatilization through the use of a vented enclosure and by isolating the contaminated soils with parafilm. After 8 wks, PCB concentrations of 47-6700 microg/g were observed in root tissues. Although PCB concentrations in shoot tissues were lower (< 1-470 microg/g), the absolute amounts of PCBs observed in shoot tissue were significant (1.7-290 microg) once shoot biomass was accounted for. Congener signatures indicated that tetra- to hexa-chlorobiphenyls contributed the largest proportions to shoot tissues, but hepta-to nona-chorobiphenyls were also present in measurable amounts. Overall, the results indicate that varieties of C. pepo were more effective at extracting PCBs from soil than other plants screened The evidence suggests that this was mainly due to root uptake of PCBs and tranlocation to the shoots, rather than volatilization of PCBs from soil. All plants screened showed signs of stress in the most highly contaminated soil (4200 microg/g), but not in the two lower PCB contaminated soils (250 and 90 microg/g, respectively). No detectable decreases in soil PCB concentrations were observed in these short-term greenhouse experiments, but the results suggest that this may be achievable through multiple plantings.     

南极食物链顶端海鸟卵中PCBs和OCPs积累水平及其全球意义

采用气相色谱-电子捕获检测器(GC-ECD)内标法定量测定了南极乔治王岛世袭栖息地海鸟(棕贼鸥、灰贼鸥、巨海燕、白眉企鹅)卵样中持久性有机氯污染物多氯联苯(PCBs)和有机氯农药(OCPs)残留量,研究探讨南极海洋食物链顶级生物体有机毒物积累水平探讨其环境意义。结果显示,卵样中有机毒物积累水平依次为:多氯联苯>滴滴涕>氯代苯>六六六。贼鸥卵样多氯联苯含量范围在91.9~515.5ng/g,滴滴涕56.6~304.4ng/g,氯代苯6.5~70.5ng/g,六六六<0.5~2.0ng/g;企鹅卵样多氯联苯含量范围在0.4~0.9ng/g,滴滴涕2.4~10.3ng/g,氯代苯6.0~10.2ng/g,六六六0.1~0.4ng/g;巨海燕卵样多氯联苯含量范围在38.1~81.7ng/g,滴滴涕12.7~53.7ng/g,氯代苯4.2~8.8ng/g,六六六0.5~1.5ng/g。研究结果还显示,不同种类海鸟卵样检出多氯联苯和有机氯农药均以七氯、六氯联苯、滴滴涕同系物(P,P′-DDE)和氯代苯化合物为主体。贼鸥、巨海燕卵样检出9种多氯联苯同系物(大小依次为PCB-180>PCB-153>PCB-194>PCB-138>PCB-118>PCB-170>PCB-101>PCB163>PCB-149)。贼鸥卵样七氯、六氯取代物的多氯联苯同系物含量在17.5~205.5ng/g占其总多氯联苯的62%;巨海燕卵样在14.5~30.5ng/g,占其总多氯联苯的69%;企鹅卵样检出5种多氯联苯同系物相对积蓄较低,其卵样之间变化相对稳定。对不同种类海鸟卵样的有机污染物数据进行统计分析,结果显示不同鸟种有机毒物积累水平的差异取决于不同鸟种的生态习性,如活动范围、迁徒距离、觅食习性以及巢址选择等,最主要是海鸟在海洋生态食物链中的位置,其食谱的宽窄,同时表明海鸟体内PCBs和OCPs积累通过食物链逐级加强的结果。有机毒物最高积累水平出现在棕贼鸥卵样中,灰贼鸥和巨海燕次之,企鹅最低。因为贼鸥不仅食性杂食谱宽,而且贼鸥与企鹅及其他小型海鸟之间存在着一定的捕食与被捕食的关系。南极海鸟卵样多氯联苯和有机氯农药的检出,是全球性有机氯污染又一新的重要证据。南极海鸟卵样中有机毒物的检出,揭示了人造有机污染物在南极鸟类代间转移的存在,它们在南大洋生态系统中的消除将会需要较长的时间过程,表明人类活动对南极生物圈与南极海洋环境的持久影响,南极是全球唯一无污染地区的价值正在丧失。     

ortho-substituted PCB95 alters intracellular calcium signaling and causes cellular acidification in PC12 cells by an immunophilin-dependent mechanism

ortho-Substituted PCBs mobilize Ca2+ from isolated brain microsomes by interaction with FKBP12/RyR complexes. Investigation into the cellular importance of this mechanism was undertaken using PC12 cells by fluoroimaging the actions of specific PCB congeners on [Ca2+]i and pH. RyR and IP3R share a common intracellular Ca2+ store in PC12 cells. Perfusion of nM to low microM PCB95 caused a transient rise of [Ca2+]i that was not completely dependent on extracellular Ca2+. Pre-incubation of the cells with ryanodine or FK506 completely eliminated PCB95 responses, suggesting a primary action on the FKPP12/RyR-sensitive store. PCB95, but not PCB126, induced a gradual decrease in cytosolic pH that could be completely eliminated by FK506 pre-incubation of the cells. Direct respiration measurement using isolated brain mitochondria demonstrated that neither of the PCBs directly altered any stage of mitochondrial respiration. These results revealed that PCB95 disrupts intracellular Ca2+ signaling in PC12 cells by interaction with the FKBP12/RyR complex that in turn accelerated cellular metabolism, possibly affecting signaling between ER and mitochondria. Since ortho-substituted PCBs have been shown to be neurotoxic and may affect neurodevelopment, studies on the molecular mechanism by which they alter cellular signaling may provide valuable information on the physiological roles of FKPB12 and RyR on neuronal functions.     

Metabolism of polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins by cytochrome P450 BM-3 and its mutant

The metabolism of polychlorinated dibenzo-p-dioxins by cytochrome P450 BM-3 from Bacillus megaterium and a mutant enzyme of it (AL₄V; Ala74Gly, Phe87Val, Leu188Gln triple mutant) was examined. Both purified enzymes metabolized 1-monochloro-, 2,3-dichloro-, and 2,3,7-trichloro-dibenzo-p-dioxin, but not 2,3,7,8-tetrachloro-dibenzo-p-dioxin. The mutant AL ₄V had 2–12 times higher activity than the wild-type P450 BM-3 towards polychlorinated dibenzo-p-dioxins. The products were hydroxylated at an unsubstituted position and/or showing migration of the chloride and were less toxic derivatives with lower than 10% toxicity of the original compounds.Revisions requested 26 August 2004; Revisions received 15 October 2004