Kegg Pathway: Biphenyl degradation

KEGG ID: 00621

Reference Diagram

KEGG Diagram for Biphenyl degradation

Rat

There are 0 IPI Records from this pathway found in Rattus norvegicus.

Location of Biphenyl degradation proteins on Rat Genome

IPI Record Position

Mouse

There are 0 IPI Records from this pathway found in Mus musculus.

Location of Biphenyl degradation proteins on Mouse Genome

IPI Record Position

Human

There are 0 IPI Records from this pathway found in Homo sapiens.

Location of Biphenyl degradation proteins on Human Genome

IPI Record Position

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Recent Literature

Involvement of independent mechanism upon poly(ADP-ribose) polymerase (PARP) activation in methylmercury cytotoxicity in rat cerebellar granule cell culture.

J Neurosci Res. 2008 Jul 14;
Sakaue M, Mori N, Okazaki M, Ishii M, Inagaki Y, Iino Y, Miyahara K, Yamamoto M, Kumagai T, Hara S, Yamamoto M, Arishima K

Poly(ADP-ribose) polymerase (PARP) activation plays a role in repairing injured DNA, while its overactivation is involved in various diseases, including neuronal degradation. In the present study, we investigated the use of a PARP inhibitor, 3,4-dihydro-5-[4-(1-piperidinyl)butoxy]-1(2H)-isoquinolinone (DPQ), whether methylmercury-induced cell death in the primary culture of cerebellar granule cells involved PARP activation. DPQ decreased the methylmercury-induced cell death in a dose-dependent manner. Unexpectedly, this protective effect was DPQ specific; none of the other PARP inhibitors-1,5-dihydroxyisoquinoline, 3-aminobenzamide, or PJ34-affected neuronal cell death. Methylmercury-induced cell death involves the decrease of glutathione (GSH) and production of reactive oxygen species. Therefore, to understand the mechanism by which DPQ inhibits cytotoxicity, we first studied the effect of DPQ on buthionine sulfoximine- or diethyl maleate-induced death of primary cultured cells and human neuroblastoma IMR-32 cells, both of which are mediated by GSH depletion. DPQ inhibited the cell death of both cultured cells, but it did not restore the decrease of cellular GSH by buthionine sulfoximine to the control level. Second, we evaluated the antioxidant activity of PARP inhibitors by methods with ABTS (2-2'-azinobis(3-ethylbenzothiazoline 6-sulfonate) or DPPH (1,1-diphenyl-2-picrylhydrazyl) used as a radical because antioxidants also efficiently suppress methylmercury-induced cell death. The antioxidant activity of DPQ was the lowest among the tested PARP inhibitors. Taken together, our results indicate that DPQ effectively protects cells against methylmercury- and GSH depletion-induced death. Furthermore, they suggest that DPQ exerts its protective effect through a mechanism other than PARP inhibition and direct antioxidation, and that PARP activation is not involved in methylmercury-induced neuronal cell death. (c) 2008 Wiley-Liss, Inc.

degradation of fluoroBiphenyl by Pseudomonas pseudoalcaligenes KF707.

FEMS Microbiol Lett. 2008 Jun 20;
Murphy CD, Quirke S, Balogun O

The Biphenyl-degrading bacterium Pseudomonas pseudoalcaligenes KF707 can use 2- and 4-fluoroBiphenyl as sole carbon and energy sources. Accumulation of fluorinated catabolites was determined by fluorine-19 nuclear magnetic spectroscopy ((19)F NMR) and revealed that growth on 4-fluoroBiphenyl yielded 4-fluorobenzoate and 4-fluoro-1,2-dihydro-1,2-dihydroxybenzoate as major fluorometabolites; 2-fluorobenzoate and 2-fluoromuconic acid were observed in 2-fluoroBiphenyl-grown cultures. Pseudomonas pseudoalcaligenes KF707 was not able to use either 2- or 4-fluorobenzoate as a growth substrate. Thus, fluoroBiphenyl is probably degraded via the classical Bph pathway to fluorobenzoate, which is partially transformed via the enzymes of benzoate catabolism. This is the first report of investigations on the growth of bacteria on fluorinated Biphenyls and demonstrates that as with chloroBiphenyl degradation, mineralization of the compounds depends upon the bacterium's ability to effectively catabolize the halobenzoate intermediate.

First evidence of polybrominated diphenyl ether (flame retardants) effects in feral barbel from the Ebro River basin (NE, Spain).

Chemosphere. 2008 Jun 30;
Raldúa D, Padrós F, Solé M, Eljarrat E, Barceló D, Riva MC, Barata C

Polybrominated diphenyl ethers (PBDEs) are chemicals of environmental concern due to their lipophilic, persistent and bioaccumulable characteristics as well as for their potential endocrine disrupting role. Former studies carried out in a tributary of the Cinca river (Ebro basin, NE Spain) revealed high levels of PBDEs in fish due to the discharges of effluents rich in PBDEs coming from a nearby industrial park in Barbastro. In this study, several biomarkers of pollutants exposure were measured in barbel, Barbus graellsii, before (upstream) and after (downstream) the main industrial site (Barbastro) in the Vero river. The results evidenced an enhanced hepatic phase I and II metabolism (measured as reductases, glutathione S transferase and uridinediphospho-glucuronosyltransferase), and of the antioxidant enzyme glutathione peroxidase. Conversely, fishes collected from downstream reaches had their phase I CYP1A dependent ethoxyresorufin O-deethylase, antioxidant diaphorase and brain cholinesterase activities depleted. In addition, the histological study of the liver and kidney of these fish evidenced an increase of the number and size of macrophage aggregates in most individuals collected downstream. Bivariate correlated analyses showed that the above mentioned biomarkers were correlated to measured PBDE congeners, thus indicating that the observed biological effects were unlikely to be related to other environmental factors than PBDEs. Overall, the measured biochemical and histological markers provide new evidence that in field exposed fish, PBDEs levels were associated with high activities of phase I and II metabolic enzymes, oxidative stress in liver, neurotoxicity in brain and histopathological effects in both liver and kidney.

Conjugated autoxidizable triene (CAT) assay: A novel spectrophotometric method for determination of antioxidant capacity using triacylglycerol as ultraviolet probe.

Anal Biochem. 2008 Jun 10;
Laguerre M, López-Giraldo LJ, Lecomte J, Baréa B, Cambon E, Tchobo PF, Barouh N, Villeneuve P

Described here is a novel spectrophotometric method for estimating antioxidant capacity in a 96-well microplate using as UV probes the conjugated triene triacylglycerols (TAGs) naturally present in tung oil. The TAGs of this commercially available oil contain around 86% eleostearic acid, an octadecatrienoic acid with conjugated trienes exhibiting strong UV absorption at 273nm. In an oil-in-water emulsion at 37 degrees C, the azo initiator 2,2'-azobis(2-amidinopropane) dihydrochloride generated a constant flux of peroxy radicals, which destroyed the conjugated trienes. The absorbance decay at 273nm, related to oxidative degradation of conjugated triene TAGs, was monitored in the absence and presence of various concentrations of antioxidants. To validate this new method, the antioxidant capacity of four phenolic compounds (gallic acid, (-)-epicatechin, chlorogenic acid, and rosmarinic acid) was measured using an area-under-the-curve calculation and expressed as Trolox equivalents, the value for Trolox being taken as reference. The order of efficacy was found to be rosmarinic acid>chlorogenic acid approximately epicatechin>Trolox>gallic acid, which can be partially explained by the number of catecholic moieties and the polarity of these antioxidants. Moreover, the conjugated autoxidizable triene (CAT) assay provided good insight into antioxidant behavior (i.e., retarder or chain breaker). The same molecules were then analyzed in 2,2-diphenyl-1-picrylhydrazyl and fluorescein-based oxygen radical absorbance capacity assays, and the results are discussed critically with respect to those obtained with the CAT assay. This new method may constitute an easy-to-use, sensitive, and high-throughput in vitro protocol for evaluation of the antioxidant capacity of pure molecules and natural extracts in lipid oxidation.

Biodegradation of Fluoranthene by Basidiomycetes Fungal Isolate Pleurotus Ostreatus HP-1.

Appl Biochem Biotechnol. 2008 Jun 24;
Patel H, Gupte A, Gupte S

The biodegradation of fluoranthene, a high molecular weight polycyclic aromatic hydrocarbon (PAH), was investigated in submerged culture using the wood decaying fungus isolated from forest locality in Gujarat, India. The basidiomycete fungal isolate was found to have an ability to grow on sabaroud dextrose agar containing 50 mgl(-1) of each naphthalene, anthracene, acenaphthene, benzo (a) anthracene, pyrene, flouranthene, carbazole, and Biphenyl. The involvement of extracellular fungal peroxidases such as manganese peroxidase (MnP) and laccase (Phenol oxidase) in the degradation of fluoranthene was studied. On the eighth day of incubation 54.09% of 70 mg l(-1) fluoranthene was removed. There after no PAHs removal was observed till the 20th day of the incubation period. The isolate was identified as Pleurotus ostreatus by 18S rRNA, 5.8S rRNA, and partial 28S rRNA gene sequencing. To the best of our knowledge this is the first time Pleurotus ostreatus have been reported to degrade such a high concentration of fluoranthene within much lower time period of incubation. Depletion in the residual fluoranthene in the culture medium was determined by HPLC. Attempts were made to identify the degradation product in the culture medium with the help of FT-IR, NMR, and HPTLC analysis. In the present study positive correlation between fluoranthene degradation and the ligninolytic enzyme (MnP and laccase) production is observed, thus this isolate can play an effective role for bioremediation of PAHs contaminated sites.

Extensive biodegradation of polychlorinated Biphenyls in Aroclor 1242 and electrical transformer fluid (Askarel) by natural strains of microorganisms indigenous to contaminated African systems.

Chemosphere. 2008 Jun 11;
Adebusoye SA, Ilori MO, Picardal FW, Amund OO

Evidence for substantial aerobic degradation of Aroclor 1242 and Askarel fluid by newly characterized bacterial strains belonging to the Enterobacter, Ralstonia and Pseudomonas genera is presented. The organisms exhibited degradative activity in terms of total PCB/Askarel degradation, degradation of individual congeners and diversity of congeners attacked. Maximal degradation by the various isolates of Askarel ranged from 69% to 86% whereas, Aroclor 1242, with the exception of Ralstonia sp. SA-4 (9.7%), was degraded by 37% to 91%. PCB analysis showed that at least 45 of the representative congeners in Aroclor 1242 were extensively transformed by benzoate-grown cells without the need for Biphenyl as an inducer of the upper degradation pathway. In incubations with Aroclor 1242, no clear correlation was observed between percentage of congener transformed and the degree of chlorination, regardless of the presence or absence of Biphenyl. Recovery of significant but nonstoichiometric amounts of chloride from the culture media showed partial dechlorination of congeners and suggested production of partial degradation products. Addition of Biphenyl evidently enhanced dechlorination of the mixture by some isolates. With the exception of Ralstonia sp. SA-5, chloride released ranged from 24% to 60% in the presence of Biphenyl versus 0.35% to 15% without Biphenyl.

RV09, a novel resveratrol analogue, inhibits NO and TNF-alpha production by LPS-activated microglia.

Int Immunopharmacol. 2008 Aug; 8(8): 1074-82
Meng XL, Yang JY, Chen GL, Zhang LJ, Wang LH, Li J, Wang JM, Wu CF

Excessive activation of microglial cells has been implicated in various neurodegenerative diseases. Resveratrol, a polyphenolic compound found in grapes and wine, has been reported to reduce the activation of microglia. In the present study, 5-[2-(4-bromothiophen-2-yl)vinyl]benzene-1,3-diol (RV09), a novel resveratrol analogue, was found to suppress NO production by LPS-activated N9 microglial cell line and/or cultured rat cortical microglia. RV09 appeared to have a slight NO-scavenging activity in sodium nitroprusside (SNP) solution. The inhibition of iNOS was also observed, suggesting the blockage of transcriptional levels. Moreover, RV09 attenuated the expression of mRNA and protein of tumor necrosis factor-alpha (TNF-alpha) in a concentration-dependent manner. Further studies revealed that RV09 blocked IkappaBalpha phosphorylation and degradation, as well as reactive oxygen species (ROS) production in N9 microglial cells. It was also found that RV09 is a effective scavenger for 2,2-diphenyl-1-picrylhydrazyl (DPPH) used as a general free radical model. In the summary, these data suggest that, by blocking IkappaBalpha phosphorylation and degradation, RV09 acts to suppress the LPS-induced NO and TNF-alpha production in microglia, and this effect was mediated, at least in part, by inhibiting the generation of ROS. Our results suggested that RV09 is a novel anti-inflammatory agent which can inhibit proinflammatory responses of microglia.

Enantioselective bioaccumulation of hexabromocyclododecane and congener-specific accumulation of brominated diphenyl ethers in an eastern Canadian Arctic marine food web.

Environ Sci Technol. 2008 May 15; 42(10): 3634-9
Tomy GT, Pleskach K, Oswald T, Halldorson T, Helm PA, MacInnis G, Marvin CH

The extent of trophic transfer of the three diastereoisomers of hexabromocyclododecane (HBCD) and seven brominated diphenyl ether (BDE) congeners was examined in components of an Arctic marine food web from eastern Canada. Alpha and gamma-HBCD diastereoisomers were detected in all species and total (sigma) HBCD concentrations ranged from 0.6 +/- 0.2 pg/g (geometric mean +/- 1 x standard error (SE), lipid weight (lw)) in arctic cod to 3.9 +/- 0.9 ng/g (lw) in narwhal. beta-HBCD was below method detection limits in all the samples. Mean sigmaBDE (sum of seven congeners) concentrations ranged from 0.4 +/- 0.2 ng/g (lw) in walrus to 73 +/- 10 ng/g (lw) in zooplankton. The relative trophic status of biota was determined by nitrogen stable isotopes (delta15N), and results indicated clear differences in HBCD isomer and BDE congener profiles with trophic level (TL). Trophic magnification was observed for the alpha-diastereoisomer and BDE-47 as concentrations increased with increasing TL in the food web, whereas there was trophic dilution of gamma-HBCD and BDE-209 through the food web. Only the (-)alpha-enantiomer showed a strong positive relationship between concentration and TL (p < 0.01) with a trophic magnification factor (TMF) value of 2.2. A small but significant increase in the enantiomeric fraction value of the alpha-enantiomers with TL was also observed (r2 = 0.22, p < 0.005), implying that there is an overall preferential enrichment of the (-)alpha-enantiomer relative to the (+)alpha-enantiomer likely due to the greater bioaccumulation potential of the (-)alpha-enantiomer and/or to the greater susceptibility of the (+)alpha-enantiomer to metabolism.

Protection of ionizing radiation-induced cytogenetic damage by hydroalcoholic extract of Cynodon dactylon in Chinese hamster lung fibroblast cells and human peripheral blood lymphocytes.

J Environ Pathol Toxicol Oncol. 2008; 27(2): 101-12
Rao BS, Upadhya D, Adiga SK

The radiomodulatory potential of hydroalcoholic extract of a medicinal plant Cynodon dactylon (family: Poaceae) against radiation-induced cytogenetic damage was analyzed using Chinese hamster lung fibroblast (V79) cells and human peripheral blood lymphocytes (HPBLs) growing in vitro. Induction of micronuclei was used as an index of cytogenetic damage, evaluated in cytokinesis blocked binucleate cells. The hydroalcoholic Cynodon dactylon extract (CDE) rendered protection against the radiation-induced DNA damage, as evidenced by the significant (p<0.001) reduction in micronucleated binucleate cells (MNBNC%) after various doses of CDE treatment in V79 cells and HPBLs. The optimum dose of CDE (40 and 50 microg/ml in HPBLs and V79 cells, respectively) with the greatest reduction in micronuclei was further used in combination with various doses of gamma radiation (0.5, 1, 2, 3, and 4 Gy) exposed 1 h after CDE treatment. A linear dose-dependent MNBNC% increase in radiation alone group was observed, while 40/50 microg/ml CDE significantly resulted in the reduction of MNBNC%, compared to the respective radiation alone groups. CDE resulted in a dose-dependent increase in free radical scavenging ability against various free radicals, viz., 2, 2-diphenyl-2-picryl-hydrazyl (DPPH); 2, 2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS); superoxide anion (O2*-); hydroxyl radical (OH*) and nitric oxide radical (NO*) generated in vitro. Also, an excellent (70%) inhibition of lipid peroxidation in vitro was observed at a dose of 300 microg/ml CDE, attaining the saturation point at higher doses. The present findings demonstrated the radioprotective effect of CDE, also rendering protection against radiation-induced genomic instability and DNA damage. The observed radioprotective effect may be partly attributed to the free radical scavenging and antilipid peroxidative potential of CDE.

Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

J Chromatogr A. 2008 May 28;
Kierkegaard A, Sellström U, McLachlan MS

Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

Effect of ozonation on polychlorinated Biphenyl degradation and on soil physico-chemical properties.

J Hazard Mater. 2008 Apr 24;
Javorská H, Tlustoš P, Komárek M, Leštan D, Kaliszová R, Száková J

The objectives of this study were to investigate the effectiveness of ozone treatment on degradation of polychlorinated Biphenyl (PCB) contaminated soils and to observe the subsequent changes in soil physico-chemical properties. Furthermore, the ability of plants to grow on the ozone-treated soils was evaluated. Soils with different physico-chemical characteristics spiked with seven PCB congeners in two different time periods were chosen. Ozonation was more efficient for PCB degradation in freshly spiked soils and the removal efficiency increased with increasing ozonation time. The highest decrease was found in the soil with a lower soil organic matter (SOM) content and a coarser soil structure indicating the substantial effect of soil characteristics on the efficiency of ozonation. The composition of individual PCB congeners changed in all treatments in terms of higher accumulation rate of highly chlorinated Biphenyls with a higher ozonation time. Increased mobility of several elements, changes in SOM content and in soil pH were detected after ozonation. Vulnerability of plants to these modifications was documented on rape seedlings. No inhibition in growth during any treatment and predominantly higher concentration of PCB in non-ozonated treatments were observed. Results suggest that this method can present a promising environmental friendly remediation technology for PCB contaminated soils.

Structural determination and DPPH radical-scavenging activity of two acylated flavonoid tetraglycosides in oolong tea (Camellia sinensis).

Chem Pharm Bull (Tokyo). 2008 Jun; 56(6): 851-3
Lee VS, Chen CR, Liao YW, Tzen JT, Chang CI

Two major acylated flavonoid tetraglycosides were isolated from the methanol extract of oolong tea. Their structures were elucidated by spectroscopic methods as quercetin 3-O-[2(G)-(E)-coumaroyl-3(G)-O-beta-D-glucosyl-3(R)-O-beta-D-glucosylrutinoside] (1) and kaempferol 3-O-[2(G)-(E)-coumaroyl-3(G)-O-beta-D-glucosyl-3(R)-O-beta-D-glucosylrutinoside] (2). Compounds 1 and 2 exhibited scavenging activity against DPPH radical with EC(50) values of 30.5 and 487.2 microM, respectively.

A mass budget of polybrominated diphenyl ethers in San Francisco Bay, CA.

Environ Int. 2008 May 30;
Oram JJ, McKee LJ, Werme CE, Connor MS, Oros DR, Grace R, Rodigari F

A mass budget of polybrominated diphenyl ethers (PBDEs) in San Francisco Bay is developed as a first step towards understanding the local sources and transport processes controlling PBDE fate in a highly urbanized estuary. Extensive monitoring of PBDEs in estuarine water and sediment, freshwater tributaries, air, and wastewater effluents and sludges were integrated with a mass budget model to provide a synthetic view of these emerging contaminants. The Bay inventories of BDE 47 and BDE 209 in 2006 were estimated to be 33+/-3 kg and 153+/-45 kg, respectively. Empirically derived estimates of annual inputs of BDE 47 and BDE 209 from all quantifiable external sources ranged from 11 to 28 kg/y and 22 to 24 kg/y, respectively. BDE 47 loads were dominated by wastewater while runoff from local tributaries represented the largest contributor to BDE 209 loads. Model results suggest the Bay PBDE inventory is highly sensitive to changes in external loads, with degradation and outflow being the major processes governing PBDE fate. The mass budget presented provides a framework for integrating future monitoring and modeling efforts.

Comparative absorption and bioaccumulation of polybrominated diphenyl ethers following ingestion via dust and oil in male rats.

Environ Sci Technol. 2008 Apr 1; 42(7): 2694-700
Huwe JK, Hakk H, Smith DJ, Diliberto JJ, Richardson V, Stapleton HM, Birnbaum LS

Household dust has been implicated as a major source of polybrominated diphenyl ether (PBDE) exposure in humans. This finding has important implications for young children, who tend to ingest more dust than adults and may be more susceptible to some of the putative developmental effects of PBDEs. Absorption parameters of PBDEs from ingested dust are unknown; therefore, the objectives of this study were to determine and to compare the uptake of PBDEs from either household dust (NIST Standard Reference Material 2585) or a corn oil solution. Male rats were administered dust or corn oil doses at 1 or 6 microg of PBDEs kg(-1) body wt in the diet for 21 days (n = 4 rats per group). The concentrations of 15 PBDEs were measured in adipose tissue and liver from each treatment group and showed that bioconcentration was congener dependent, but for the majority of congeners, the concentrations did not differ with either dose level or dose vehicle. Hepatic Cyp2b1 and 2b2 mRNA expression increased in rats receiving the higher PBDE doses, suggesting potential effects on metabolic activity. Retention of PBDEs in tissues ranged from <5% of the dose for BDE-209 to 70% for BDEs-47, 100, and 153 but generally did not differ between the high dust and high oil treatment groups. Excretion via the feces was significantly lower in the high oil dosed rats suggesting differences in absorption, excretion, and/or metabolism. The present study shows that PBDEs in dust are readily bioavailable and are biologically active, as indicated by increased transcription of hepatic enzymes.

Multivariate data analyses of persistent organic pollutants in maternal adipose tissue in Singapore.

Environ Sci Technol. 2008 Apr 1; 42(7): 2681-7
Tan J, Li QQ, Loganath A, Chong YS, Xiao M, Obbard JP

Persistent organic pollutants (POPs) were detected in 88 maternal adipose tissue samples collected during year 2004 to 2006, in Singapore. Organochlorine pesticides (OCPs) were the most dominant followed by polychlorinated Biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Multivariate data analyses (MVA) including principal component analysis (PCA), partial least-squares regression (PLSR), and partial least-squares discriminant analysis (PLS-DA) were applied to elucidate the relationship between concentrations of POPs in adipose tissues and donors' characteristics. Food consumption played the most significant role in accounting for levels of POPs in adipose tissue. Fish and poultry consumption was the route of PCBs and PBDEs in mothers in Singapore, while beta-HCH came mainly from vegetables. An age-dependent accumulation of POPs was found for beta-HCH and PCB congeners, and lactation and gestation functioned as a decontamination processes for PCBs in adipose tissue. Gestational diabetes mellitus (GDM) may change the profile of POPs in adipose tissue, probably due to an alteration in lipid metabolism. POPs investigated here may not be the cause of antenatal complication in pregnant women, and baby gender was not related to the pattern of contaminants in maternal adipose tissue.

Analysis of polybrominated diphenyl ethers (PBDEs) by liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS): application to house dust.

Anal Bioanal Chem. 2008 Jul; 391(6): 2249-56
Lagalante AF, Oswald TD

Eight polybrominated diphenyl ether (PBDE) congeners of primary interest to the US EPA were separated using reverse-phase liquid chromatography on an octadecylsilane column. BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209 were baseline-resolved under isocratic conditions in 92:8 methanol/water (v/v). Negative-ion atmospheric pressure photoionization (NI-APPI) with a toluene dopant produced precursor ions corresponding to [M-Br+O](-) for the eight congeners studied. Each congener was quantified by tandem mass spectrometry through a unique multiple reaction monitoring (MRM) transition. On-column limits of detection were between 2.4 and 27.8 pg for the eight congeners studied, with an intra-day method precision of 9%. The LC/NI-APPI/MS/MS method was validated for the analysis of the eight PBDE congeners in NIST SRM 2585 (Organics in House Dust). Pressurized liquid extraction (PLE) with subsequent LC/NI-APPI/MS/MS analysis afforded quantitative recovery for all eight PBDE congeners with recoveries ranging from 92.7 to 113%. The liquid-phase separation of the LC/NI-APPI/MS/MS method is not prone to the thermal degradation issues that plague splitless GC based analyses of highly brominated PBDEs such as BDE-209.

Bioaccumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated Biphenyls (PCBs) in wild aquatic species from an electronic waste (e-waste) recycling site in South China.

Environ Int. 2008 May 24;
Wu JP, Luo XJ, Zhang Y, Luo Y, Chen SJ, Mai BX, Yang ZY

Water and several wild aquatic species including Chinese mysterysnail, prawn, fish, and water snake were collected from a reservoir surrounded by several e-waste recycling workshops in South China. The samples were examined to investigate the levels and bioaccumulation extent of polybrominated diphenyl ethers (PBDEs) and polychlorinated Biphenyls (PCBs) released from electronic waste (e-waste) which was processed by crude recycling method. Elevated levels of PBDEs [52.7 to 1702 ng/g wet weight (ww)] and PCBs (20.2-25958 ng/g ww) were found in the collected biota species compared to that in the reference samples (13.0-20.5 ng/g ww for PBDEs and 75.4-82.8 ng/g ww for PCBs). log BAF (bioaccumulation factor) ranged from 2.9 to 5.3 for PBDEs and from 1.2 to 8.4 for PCBs, depending on congeners and species. The relationship between log BAFs and log K(OW) (octanol-water partition coefficient) can be adequately described by species-specific parabolic models wherein log BAFs generally increased at log K(OW)<7 then decreased with further increasing log K(OW) both for PBDEs and PCBs. The exceptions were for Chinese mysterysnail and prawn, in which the log BAFs showed a positive linear correlation with log K(OW) for PBDEs. Some PBDE and PCB congeners showed BAF values declining from the general trend predicted by K(OW), largely attributing to metabolism of these congeners in species sampled.

Photodegradation study of decabromodiphenyl ether by UV spectrophotometry and a hybrid hard- and soft-modelling approach.

Anal Chim Acta. 2008 Jun 16; 618(1): 18-28
Mas S, de Juan A, Lacorte S, Tauler R

This work presents an exploratory study of the photochemical degradation process of decabromodiphenyl ether (decaBDE) and gives an interpretation of the kinetic pathway, species and effects of the key factors involved in the degradation process. Use of lowly brominated diphenyl ethers (PBDE) has been banned by the EU and there seems to be evidence of the photolytic degradation of highly brominated PBDEs into lowly brominated congeners. Hence, the importance of knowing the photodegradation process of decaBDE. The photodegradation was investigated under UV light by UV-spectrophotometric monitoring. A novel hybrid data analysis approach, based on the combination of hard- and soft-spectrophotometric multivariate curve resolution, was applied to elucidate the mechanism of the degradation process, to resolve kinetic profiles and pure spectra of the photodegradation products and to evaluate the rate constants. The photodegradation process could be described with a kinetic model based on three consecutive first-order reactions and a decrease of the degradation process was observed as solvent polarity increased. Complementary identification of photodegradation products by gas chromatography coupled to mass spectrometry using negative chemical ionization (GC-NCI-MS) is attempted. This work presents a novel attempt of describing in a comprehensive way the photochemical degradation process of decaBDE, with all successive steps and related rate constants. This study proves also the potential of the proposed hybrid data analysis methodology as a general strategy to interpret the evolution of these photochemical reactions.

Blood levels of organochlorine pesticide residues and risk of reproductive tract cancer among women from Jaipur, India.

Adv Exp Med Biol. 2008; 617: 387-94
Mathur V, John PJ, Soni I, Bhatnagar P

Residues of organochlorine pesticides are integral part of our environment. Because of their strong lipophilic and non-biodegradable nature, organisms at higher trophic levels in the food chain tend to accumulate them. The aim of the present study was to assess the influence of organochlorine pesticides upon the occurrence of reproductive tract cancers in women from Jaipur, India. Blood samples were collected from 150 females. In that group, 100 females suffered from reproductive tract cancers like cervical, uterine, vaginal and ovarian cancers, while the rest did not suffer from cancers or any other major disease and were treated as control group. The collected blood samples were subjected to pesticide extraction and analyzed with the help of gas chromatography. The pesticides detected were benzene hexa chlororide and its isomers, dieldrin, heptachlor, dichloro diphenyl trichloro ethane and its metabolites. The data obtained indicate that the organochlorine pesticide residue levels were significantly higher in all the cancer patients as compared with the control group.

Hepatic cytochrome P450 activity and pollutant concentrations in paradise shelducks and southern black-backed gulls in the South Island of New Zealand.

Ecotoxicology. 2008 May 13;
Numata M, Fawcett JP, Saville DJ, Rosengren RJ

Cytochrome P450 (CYP) enzymes catalyse the oxidative metabolism of various xenobiotics including environmental pollutants. We investigated liver microsomal CYP marker activities in 60 paradise shelducks (Tadorna variegata; herbivore) and 77 southern black-backed gulls (Larus dominicanus; omnivore) collected at three sites with putatively different levels of pollution in the South Island of New Zealand. Ethoxyresorufin O-deethylase (EROD) activity was high in birds at an urban landfill site compared to those at a relatively pristine and an agricultural site. Analysis of p-nitrophenol hydroxylase and erythromycin demethylase activities indicated the presence of two additional CYP isoforms in shelducks but no additional form in gulls. Total polychlorinated Biphenyl (PCB) concentrations (ranges: shelducks, 0.073-6.2; gulls, 8.2-330 ng/g wet weight) were high in landfill samples suggesting a link to EROD induction and, in landfill shelducks, EROD was independently associated with Hg and Pb concentration. PCB congener-specific assessments indicated the metabolism of at least two congeners (#28 and #74) is induced in shelducks. DDE concentrations (ranges: shelducks, 0.85-320; gulls, 44-4800 ng/g) were high in birds at the landfill and agricultural sites. Body weight tended to be lower in landfill birds, but whether this reflects the greater energetic demands of pollutant detoxification remains to be investigated.