Gas Chromatography-high Resolution Mass Spectrometry Research Articles

Polychlorinated biphenyl (PCB) concentrations and congener composition in masu salmon from Japan: A study of all 209 PCB congeners by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS)

We collected two subspecies of masu salmon: Oncorhynchus masou masou from four localities (southern Sea of Japan northward to Hokkaido) and O. masou ishikawae from upstream from Ise Bay close to a heavy industrial area. All 209 PCB congeners were analyzed using HRGC/HRMS. PCA ordination of congener concentrations divided data into three groups: (i) ssp. masou from Hokkaido, (ii) ssp. masou from the other regions and (iii) ssp. ishikawae. The highest ∑ PCB concentration (40.39ng/wet wt) was in ssp. ishikawae followed by ssp. masou from southern waters; however the TEQdioxin-like PCBs was highest in ssp. masou from southern water (1.96pg-TEQdioxin-like PCBs/g wet wt.) due to the high proportion of congener #126 in its complement (#126 has the highest toxic equivalency factor among congeners). There is likely a contamination source offshore in the southern Sea of Japan and/or along the migratory route of ssp. masou.

Dechlorane Plus and decabromodiphenyl ether in atmospheric particles of northeast Asian cities

Atmospheric particles were collected in several cities in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing) using a high-volume air sampler equipped with a quartz fiber filter. The summer and winter samples were analyzed using gas chromatography-high-resolution mass spectrometry for Dechlorane Plus (DP). Decabromodiphenyl ether (BDE-209) was also analyzed for the samples from Kanazawa and Beijing. DP was detected in all samples. The mean total DP (ΣDP) concentration was highest (6.7 pg/m(3)) and lowest (0.87 pg/m(3)) in the winter samples from Sagamihara and Busan, respectively. The seasonal variation of DP concentrations varied by sampling site in this study. BDE-209 was detected in all the analyzed samples except for one of the Kanazawa winter samples. BDE-209 concentration was considerably higher in Beijing than in Kanazawa. Significant correlations were found between the concentrations of ΣDP and BDE-209 in the winter samples from Kanazawa and in both summer and winter samples from Beijing. This similarity in the atmospheric behavior of DP and BDE-209, especially in winter, is assumed to reflect a common end usage and release mechanism.

Determination of PCDD/Fs in breast milk of women living in the vicinities of Da Nang Agent Orange hot spot (Vietnam) and estimation of the infant's daily intake

Seventeen toxic congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in breast milks using the high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) method. Twenty seven breast milk samples were collected from primiparae who have lived over 5years in wards namely Chinh Gian, An Khe, Khue Trung, and Hoa Thuan Tay which are located near the Da Nang Agent Orange hot spot (the AO/Dioxin hot spot). The samples were then analyzed for PCDD/F residues in order to assess the human exposure to dioxins from the AO/Dioxin hot spot, especially health risk to the breast-fed infants. The average TEQ levels in the four studied cohorts ranged from 8.1 to 26pg/g lipid, with the highest level up to 51pgTEQ/g lipid found in the An Khe ward. The TEQ level was correlated with geographical position and ranking in the order of Khue Trung, Hoa Thuan Tay, Chinh Gian and An Khe. The mean estimated PCDD/Fs infant's daily intake in the cohort of Khue Trung, Hoa Thuan Tay, Chinh Gian and An Khe was about 41, 122, 124, and 134pgTEQ/kg bw/day, respectively, which are much higher than the tolerable daily intake proposed by the World Health Organization (4pgTEQ/kgbw/day).

Circulating levels of p,p'-DDE are related to prevalent hypertension in the elderly

BackgroundPolychlorinated biphenyls (PCBs) and dioxin given to experimental animals increase the blood pressure. We therefore investigated if circulating levels of persistent organic pollutants (POPs) were related to hypertension in a population-based sample of men and women. MethodsOne thousand and sixteen subjects aged 70 years were investigated in the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) study. Twenty-three POPs were analyzed using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Hypertension was defined as a systolic blood pressure ≥140mmHg or a diastolic blood pressure ≥90mmHg, and/or use of antihypertensive medication. ResultsSeven hundred and thirty-two subjects (72%) showed hypertension. When the POPs were treated as continuous variables and adjusted for gender only, two PCBs with a low number of chlorine atoms (PCB 105 and 118) were related to prevalent hypertension. Also the OC pesticide p,p'-DDE was related to hypertension. The strongest of these associations was seen for p,p'-DDE (OR 1.35 for a 1 SD change, 95% CI 1.17–1.56, p<0.0001). Following further adjustment also for BMI, smoking status, education level and exercise habits, only p,p'-DDE was still significantly related to hypertension (OR 1.23 for a 1 SD change, 95% CI 1.06–1.43, p=0.006). ConclusionIn this cross-sectional analysis of an elderly population, high levels of circulating levels of p,p'-DDE were associated with prevalent hypertension, further strengthening the experimental findings that POPs might influence blood pressure.

Polychlorinated biphenyls (PCBs) in industrial and municipal effluents: Concentrations, congener profiles, and partitioning onto particulates and organic carbon

Wastewater effluent samples were collected in the summer of 2009 from 16 different locations which included municipal and industrial wastewater treatment plants and petrochemical industrial outfalls in the Houston area. The effluent samples were analyzed for all 209 polychlorinated biphenyls (PCBs) congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) using the USEPA method 1668A. The total PCBs (∑209) concentration in the dissolved medium ranged from 1.01 to 8.12ng/L and ranged from 2.03 to 31.2ng/L in the suspended medium. Lighter PCB congeners exhibited highest concentrations in the dissolved phase whereas, in the suspended phase, heavier PCBs exhibited the highest concentrations. The PCB homolog concentrations were dominated by monochlorobiphenyls through hexachlorobiphenyls, with dichlorobiphenyls exhibiting the highest concentration amongst them at most of the effluent outfalls, in the suspended phase. Both total suspended solids (TSS) and various organic carbon fractions played an important role in the distribution of the suspended fractions of PCBs in the effluents. The log Koc values determined in the effluents suggest that effluent PCB loads might have more risk and impact than what standard partitioning models predict.

Polychlorinated Dibenzo-p-dioxin and Dibenzofuran (PCDD/F) Emission Behavior during Incineration of Laboratory Waste. Part 1: Emission Profiles Obtained Using Chemical Assay and Bioassay

This study describes polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) behavior during the incineration of laboratory waste, including combustible laboratory solid waste (LSW), laboratory plastic waste (LPW), and organic laboratory liquid waste (LLW). Stack flue gas (SFG), input materials, bottom ash (BTA), first quenching tower ash (FQA), secondary quenching tower ash (SQA), and baghouse ash (BHA) were sampled and analyzed using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) assay and bioassay. The PCDD/F concentration of SFG met the standard in Taiwan. The Cl levels of LPW and LLW were roughly equivalent to that of municipal solid waste (MSW). Therefore, the SFG concentration, content of fly ash, and distribution behavior of PCDD/Fs are reasonably similar to those of MSW incinerators. The LSW had an extremely high Cl level (11.4%). The emission factor of the whole incineration system was 888 µg I-TEQ/ton-waste, which is 10-fold higher than that of MSW. The PCDD/F was mainly in BTA (31.6 wt.%) and fly ash (63.1 wt.%), resulting in higher PCDD/F level of ashes compared with that of MSW ashes. Both HRGC/HRMS analysis and bioassay results show similar PCDD/F emission characteristics during the incineration of LW. In addition, the linear regression between the values acquired using these two methods show a good relation (R 2 > 0.84), indicating that Ad-DR bioassay is a promising fast-screen method for determining PCDD/F levels.

Identification of two interference peaks during dioxin analysis for biological samples

Two interference peaks which generally appeared in company with 13C labeled 2,3,7,8-tetrachlorodibenzofuran (13C12-2,3,7,8-TCDF) in the same ion channel during dioxin analysis for biological samples were identified using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS). It was firstly inferred that the interference peaks should be the two isomers of dichlorodiphenyldichloroethylene (DDE), which was a breakdown product of dichlorodiphenyltrichloroethane (DDT), one of the typical organic chlorine pesticides (OCPs). Thereafter, the standard solution of DDE including o,p'-DDE and p,p'-DDE was analyzed for confirmation. By evaluation of the peak separation in HRGC/HRMS, comparison of the GC retention times and ion abundance ratios of the two interference peaks in real samples with the two DDE isomers in standard solution, the interference peaks were finally confirmed as o,p'-DDE and p,p'-DDE in sequence on a DB-5MS column. This study provided valuable information for accurate identification of dioxin compounds during the biological sample analysis.

Determination of mono- to tri-chlorinated dibenzo-p-dioxins and dibenzofurans in stack gas using isotope dilution high resolution gas chromatography-high resolution mass spectrometry

A method for the determination of mono- to tri-chlorinated dibenzo-p-dioxins and dibenzofurans (mono- to tri-CDD/Fs) in stack gas using isotope dilution high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS) was developed. The sam- ples were extracted by Soxhlet extraction, and then the extracts were concentrated and purified using a multilayer silica gel column and a basic alumina column. The analytes were separated by HRGC on a DB-5MS column (30 m x 0.25 mm x 0.25 μm) and determined by HRMS. The identi- fication of mono- to tri-CDD/Fs was based on the retention times of 13C-labelled standard and the abundance ratios of the two exacted mass-to-charge ratios. The quantitative analysis was performed using the ratios of the integrated areas of the 13C-labelled standards. This method had the recoveries ranging from 66.6% to 112.5% and the relative standard deviations (RSD) ranging from 19.9% to 40.5% (n = 5). The limits of detection (LODs) of this method for the mono- to tri-CDD/Fs were ranging from 0.027 to 0.485 μg/L. Three stack gas samples from waste incinerators were measured using this method, with the recoveries ranging from 85.7% to 137.0% and the concentrations ranging from 11.4 to 9,183 pg/Nm3. The results indicated that the method can be applied to the precise determination of mono- to tri-CDD/Fs at trace level in stack gas.

Biodegradation of Polychlorinated Dibenzo--Dioxins by Strain NSYSU.

The dioxin-degrading bacterium strain NSYSU (NSYSU strain) has been isolated from dioxin-contaminated soil by selective enrichment techniques. In the present study, the NSYSU strain was investigated for its capability to biodegrade polychlorinated dibenzo--dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) under aerobic and anaerobic conditions. High-resolution gas chromatography-mass spectrometry and a chemically activated luciferase gene expression bioassay were performed to determine the presence of dioxin compounds. The results indicate that the NSYSU strain could degrade PCDDs and PCDFs under anaerobic conditions in liquid cultures. The main intermediates of the dechlorination process were identified. The results of the bioreactor test indicate that the NSYSU strain could also degrade PCDDs and PCDFs effectively in soil slurries under aerobic conditions. Results from the bioreactor experiment show that approximately 98 and 97% of octachlorodibenzofuran and OCDD were degraded, respectively. The dioxin concentrations in soil slurry decreased from 5823 to 1198 pg toxic equivalency g, resulting in total dioxin removal of 79%. These first findings suggest that the NSYSU strain has the potential to be an effective tool for the bioremediation of soils contaminated with highly recalcitrant organic compounds.

Pollution characteristics of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in PM2.5 of Hangzhou City during winter

In order to evaluate the distributions and concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in aerosol, PM2.5 samples were collected concurrently at five sites in January 2014 in Hangzhou. The analytes were analyzed with isotope dilution and high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) based on US EPA 1613B method and US EPA 1668B method. The results showed that the mass concentrations of PM2.5 were in the range of 85-168 μg/m3, which were much higher than the national quality standard. The values suggested that the PM2.5 pollution was relatively serious in Hangzhou City, yet it has been improved when compared with the results of 2004. The toxic equivalent quantities (TEQs) of PCDD/Fs in PM2.5 were in the range of 0.277-0.488 pg I-TEQ/m3, which were much higher than the results in 2004. Octachlorodibenzo-p-dioxin (OCDD) accounted for a large proportion to the total concentrations in PCDD/Fs, while 2,3,4,7,8-pentachlorodibenzofurans (2,3,4,7,8-PeC- DF) contributed the highest to the TEQ. The values of PCBs and dioxin-like PCBs (DL-PCBs) varied from 2.9-8.1 pg/m3 and 2.6-6.1 fg WHO-TEQ/m3, respectively. PCB-28 was the most abundant contributor to the concentrations of PCBs, while PCB-126 contributed the highest to the TEQ of DL-PCBs. Gas-particle distributions of PCDD/Fs and PCBs shows that PCDD/Fs were mainly distributed in the particle phase, but PCBs were preferably adsorbed in the gas phase.

Simple and rapid determination of PCDD/Fs in flue gases from various waste incinerators in China using DR-EcoScreen cells

In developing countries such as China, there is a strong need for simple and rapid bioassays for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in environmental samples; i.e., flue gas and fly ash from waste incinerators. In this study, we applied the DR-EcoScreen cell (DR-cell) assay to determination of PCDD/Fs in 78 flue gas samples obtained from various waste incinerators in China between 2009 and 2011. The flue gas samples were obtained from four kinds of incinerators, classified into hazardous, medical and municipal-solid waste, and iron ore sintering, and the flue gas extracts were cleaned up using an SPD-600 automated-sample preparation device for DR-cell assay. The PCDD/Fs values obtained from the DR-cell assay were compared with those obtained from conventional high resolution gas chromatography–high resolution mass spectrometry (HRGC–HRMS) analysis. The bioanalytical equivalent (BEQ) values obtained from the DR-cell assay were very closely correlated with the international toxicity equivalent (I-TEQ) values from HRGC–HRMS analysis (r2=0.98, n=78), while the BEQ values were 5.52-fold higher than the I-TEQ values, as the PCDFs, which account for 80% of the total I-TEQ value, were overestimated by DR cell-assay. Therefore, we multiplied the BEQ values from the DR-cell assay by a conversion coefficient (0.181, the reciprocal of 5.52), and could approximate the TEQ values from the HRGC–HRMS analysis. These results suggest that the DR-cell assay combined with SPD-600 cleanup provides a promising method for the simple and rapid screening of PCDD/Fs levels in flue gas samples, such as those from various waste incinerators in China.

Screening for PCDD/Fs and dl-PCBs in local and imported food and feed products available across the State of Kuwait and assessment of dietary intake

A total of 318 local and imported meat, milk, eggs, fish, and animal feed samples collected in Kuwait were analyzed by cell-based reporter gene assay (Dioxin-Responsive Chemical Activated LUciferase gene eXpression DR-CALUX) for PCDD/Fs and dl-PCBs. The bioanalytical equivalents (BEQs) obtained by DR-CALUX bioassay were compared with the official maximum limits according to the European Commission (EC) regulations. Suspected and randomly chosen negative samples were analyzed by gas chromatography–high resolution mass spectrometry (GC–HRMS). The results showed that among suspected samples, one sample was confirmed to be non-compliant. The positive sample was of imported origin. The correlation coefficient of 0.98 between DR-CALUX and GC–HRMS was found. Moreover, the average daily intakes of PCDD/Fs and dl-PCBs for the Kuwaiti population were estimated. Results obtained in this study were discussed and compared with other published data.

Atmospheric deposition of persistent organic pollutants and chemicals of emerging concern at two sites in northern Sweden

Bimonthly bulk atmospheric deposition samples (precipitation + dry particle) were taken for one year at an arctic (Abisko, 68°20' N, 19°03' E) and a sub-arctic (Krycklan 64°14' N, 19°46' E) location in northern Sweden using Amberlite IRA-743 as an absorbent for hydrophobic pollutants. The samples were analyzed by gas chromatography-high resolution mass spectrometry (GC-HRMS) for polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCPs = hexachlorocyclohexanes and chlordane-related compounds), polybrominated diphenyl ethers (PBDEs) and emerging chemicals. Higher deposition rates of most compounds were observed at the more northern site despite its receiving less precipitation and being more remote. HCHs and PCBs made up the bulk of the total deposition at both sites. Five emerging chemicals were detected: the current-use pesticides trifluralin and chlorothalonil; and non-BDE flame retardants 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and Dechlorane Plus (DP). A decrease in the fraction of the anti isomer of DP was observed at the arctic site, indicating isomer-selective degradation or isomerization during long range transport. Air parcel back trajectories revealed a greater influence from air originating over the ocean at the more northern site. The differences in these air sources were reflected in higher ∑HCH to ∑PCB ratios compared to the more southern site, as HCHs are related to volatilization from the ocean and Abisko is located <100 km from the Norwegian coast, while PCBs are emitted from continental sources.

Polychlorinated Biphenyls in Residential Dust: Sources of Variability

We characterized the variability in concentrations of polychlorinated biphenyls (PCBs) measured in residential dust. Vacuum cleaner samples were collected from 289 homes in the California Childhood Leukemia Study during two sampling rounds from 2001 to 2010 and 15 PCBs were measured by high resolution gas chromatography-mass spectrometry. Median concentrations of the most abundant PCBs (i.e., PCBs 28, 52, 101, 105, 118, 138, 153, and 180) ranged from 1.0-5.8 ng per g of dust in the first sampling round and from 0.8-3.4 ng/g in the second sampling round. For each of these eight PCBs, we used a random-effects model to apportion total variation into regional variability (6-11%), intraregional between-home variability (27-56%), within-home variability over time (18-52%), and within-sample variability (9-16%). In mixed-effects models, differences in PCB concentrations between homes were explained by home age, with older homes having higher PCB levels. Differences in PCB concentrations within homes were explained by decreasing time trends. Estimated half-lives ranged from 5-18 years, indicating that PCBs are removed very slowly from the indoor environment. Our findings suggest that it may be feasible to use residential dust for retrospective assessment of PCB exposures in studies of children's health.

Metabolomics of the tumor microenvironment in pediatric acute lymphoblastic leukemia.

The tumor microenvironment is emerging as an important therapeutic target. Most studies, however, are focused on the protein components, and relatively little is known of how the microenvironmental metabolome might influence tumor survival. In this study, we examined the metabolic profiles of paired bone marrow (BM) and peripheral blood (PB) samples from 10 children with acute lymphoblastic leukemia (ALL). BM and PB samples from the same patient were collected at the time of diagnosis and after 29 days of induction therapy, at which point all patients were in remission. We employed two analytical platforms, high-resolution magnetic resonance spectroscopy and gas chromatography-mass spectrometry, to identify and quantify 102 metabolites in the BM and PB. Standard ALL therapy, which includes l-asparaginase, completely removed circulating asparagine, but not glutamine. Statistical analyses of metabolite correlations and network reconstructions showed that the untreated BM microenvironment was characterized by a significant network-level signature: a cluster of highly correlated lipids and metabolites involved in lipid metabolism (p<0.006). In contrast, the strongest correlations in the BM upon remission were observed among amino acid metabolites and derivatives (p<9.2×10-10). This study provides evidence that metabolic characterization of the cancer niche could generate new hypotheses for the development of cancer therapies.

Identification of Designer Drugs using Gas Chromatography High-Resolution Mass Spectrometry and A Soft-Ionization Source

A small set of amphetamines has been analyzed by gas chromatography (GC) high-resolution time-of-flight mass spectrometry (TOFMS) using a microplasma photoionization (MPPI) soft-ionization source. This plasma-based, wavelength selectable ionization source enables ionization of the test compounds and their corresponding derivatives at ~8-12 eV that is a softer alternative to electron ionization at 70 eV. Three plasma gases were used in this study: Xe plasma that emits photons at resonance lines of 9.57 eV and 8.44 eV; Kr plasma at 10.63 eV and 10.02 eV, and Ar plasma at 11.82 eV and 11.61 eV. Derivatization of the test compounds with trifluoroacetic anhydride and α-methoxy-α-(trifluoromethyl)-phenylacetyl pyrazole was evaluated because the MPPI mass spectra of the underivatized amphetamines yield primarily iminium ions, which make the identification of the test compounds by GC-TOFMS inconclusive. The MPPI mass spectra of the TFA-derivatized amphetamines yield abundant molecular ions, when using Xe as plasma gas, and enough fragment ions with the Ar plasma that can help in formula generation. The structure elucidation of two “known unknowns” designer drugs using this “tunable” soft-ionization source and a high-resolution TOF mass spectrometer is presented in this study.

Serum concentrations of polybrominated diphenyl ethers (PBDEs) and a polybrominated biphenyl (PBB) in men from Greenland, Poland and Ukraine

Many brominated flame retardants (BFRs)—including polybrominated diphenyl ethers (PBDEs)—have been shown to persist in the environment, and some have been associated with adverse health effects. The aim of the present study was to quantify serum concentrations of common brominated flame retardants in Inuit men from across Greenland, and in men from Warsaw, Poland and Kharkiv, Ukraine. Serum was sampled between 2002 and 2004 from men 19 to 50years of age. 299 samples were analyzed for BDE-28, 47, 99, 100, 153, 154 and 183 and the brominated biphenyl BB-153 using gas chromatography–high resolution mass spectrometry. BDE-47 and BDE-153 were detected in more than 95% of samples from all three populations. All other congeners, except BDE-154, were detected in more than 70% of samples from Greenland; lower detection frequencies were observed in Polish and Ukrainian samples. Concentrations of individual congeners were 2.7 to 15 fold higher in Greenlandic relative to Polish and Ukrainian men. Geometric mean concentrations of the sum of the most abundant PBDEs of the Penta-BDE commercial mixture (BDE-47, 99, 100, 153 and 154) were 6.1, 1.7 and 0.87ng/g lipids in the Greenlandic, Polish and Ukrainian men, respectively. Furthermore, significant geographical differences in BFR concentrations were observed within Greenland. Principal component analysis revealed distinct clustering of samples by country of origin. The associations between ΣPBDEs and age were inconsistent, varying from no association in Greenlandic and Polish study populations to a U-shaped relationship in Ukrainians. We report BFR levels for three populations for which sparse biomonitoring data exists.

EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents

In the year 2010, effluents from 90 European wastewater treatment plants (WWTPs) were analyzed for 156 polar organic chemical contaminants. The analyses were complemented by effect-based monitoring approaches aiming at estrogenicity and dioxin-like toxicity analyzed by in vitro reporter gene bioassays, and yeast and diatom culture acute toxicity optical bioassays. Analyses of organic substances were performed by solid-phase extraction (SPE) or liquid–liquid extraction (LLE) followed by liquid chromatography tandem mass spectrometry (LC-MS-MS) or gas chromatography high-resolution mass spectrometry (GC-HRMS). Target microcontaminants were pharmaceuticals and personal care products (PPCPs), veterinary (antibiotic) drugs, perfluoroalkyl substances (PFASs), organophosphate ester flame retardants, pesticides (and some metabolites), industrial chemicals such as benzotriazoles (corrosion inhibitors), iodinated x-ray contrast agents, and gadolinium magnetic resonance imaging agents; in addition biological endpoints were measured. The obtained results show the presence of 125 substances (80% of the target compounds) in European wastewater effluents, in concentrations ranging from low nanograms to milligrams per liter. These results allow for an estimation to be made of a European median level for the chemicals investigated in WWTP effluents. The most relevant compounds in the effluent waters with the highest median concentration levels were the artificial sweeteners acesulfame and sucralose, benzotriazoles (corrosion inhibitors), several organophosphate ester flame retardants and plasticizers (e.g. tris(2-chloroisopropyl)phosphate; TCPP), pharmaceutical compounds such as carbamazepine, tramadol, telmisartan, venlafaxine, irbesartan, fluconazole, oxazepam, fexofenadine, diclofenac, citalopram, codeine, bisoprolol, eprosartan, the antibiotics trimethoprim, ciprofloxacine, sulfamethoxazole, and clindamycine, the insect repellent N,N′-diethyltoluamide (DEET), the pesticides MCPA and mecoprop, perfluoroalkyl substances (such as PFOS and PFOA), caffeine, and gadolinium.

Quantitative determination of common urinary odorants and their glucuronide conjugates in human urine.

Our previous study on the identification of common odorants and their conjugates in human urine demonstrated that this substance fraction is a little-understood but nonetheless a promising medium for analysis and diagnostics in this easily accessible physiological medium. Smell as an indicator for diseases, or volatile excretion in the course of dietary processes bares high potential for a series of physiological insights. Still, little is known today about the quantitative composition of odorous or volatile targets, as well as their non-volatile conjugates, both with regard to their common occurrence in urine of healthy subjects, as well as in that of individuals suffering from diseases or other physiological misbalancing. Accordingly, the aim of our study was to develop a highly sensitive and selective approach to determine the common quantitative composition of selected odorant markers in healthy human subjects, as well as their corresponding glucuronide conjugates. We used one- and two-dimensional high resolution gas chromatography-mass spectrometry in combination with stable isotope dilution assays to quantify commonly occurring and potent odorants in human urine. The studies were carried out on both native urine and on urine that had been treated by glucuronidase assays, with analysis of the liberated odor-active compounds using the same techniques. Analytical data are discussed with regard to their potential translation as future diagnostic tool.

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample (ASKAREL Nr 1740) from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls (PCBs), polychlorinated dibenzo-p- dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil (ASKAREL Nr 1740) in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS). The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260 was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners (i.e., #153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181) account for more than 50% of the total PCB concentrations. Total concentration of PCDDs, PCDFs and dioxin-like PCBs (DL-PCBs) was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF>HxCDFs>HpCDFs>PeCDFs>TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners (i.e., #118, #156, #157) accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.