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To analyze the dioxin content of samples, including dibenzo-p-dioxins/dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs), a large volume is usually necessary. This is difficult, however, when analyzing clinical samples, such as serum and tissue. We therefore sought to increase the sensitivity of high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) in analyzing dioxins by injecting most of the extract from a small clinical sample. The concentration of each congener was estimated by injecting extracts of 5-g samples into a gas chromatography capillary pre-column (AT column) and by assaying extracts of 25-g samples by conventional splitless methods. We found that the limit of detection with the AT column was lower than that obtained by the splitless technique. In the AT column technique, 100 [micro]L of the 110-[micro]L final solution, equivalent to 4.5 g of the original sample, was injected into HRGC/ HRMS. In contrast, 2 [micro]L of the 20-[micro]L final solution, equivalent to 2.5 g of original sample, was assayed using the splitless method. Moreover, when 25 fg of ultratrace dioxin was added to 100 [micro]L of HRGC/HRMS sample and injected into the AT column, the peak area was almost the same as that obtained with 2 [micro]L of HRGC/HRMS sample injected using the splitless method. Although assaying 10-20 [micro]L of sample by the splitless method presents difficulties due to sample volatility, this problem can be reduced by using volumes larger than 100 [micro]L. We tested this application by quantifying the parts-per-trillion levels, on a lipid weight basis, of each congener in a serum sample of 5 g using the AT column HRGC/HRMS method. We found this application to be successful and practical for mass screening of dioxin exposure in clinical samples.

In this study, we developed an approach for sequential nontarget and target screening for the rapid and efficient analysis of multiple samples as an environmental monitoring using a comprehensive two-dimensional gas chromatograph coupled to a high resolution time-of-flight mass spectrometer (GC × GC-HRTOFMS). A key feature of the approach was the construction of an accurate mass spectral database learned from the sample via nontarget screening. To enhance the detection power in the nontarget screening, a global spectral deconvolution procedure based on non-negative matrix factorization was applied. The approach was applied to the monitoring of rivers in the Tokyo Bay basin. The majority of the compounds detected by the nontarget screening were alkyl chain-based compounds (55%). In the quantitative target screening based on the output from the nontarget screening, particularly high levels of organophosphorus flame retardants (median concentrations of 31, 116 and 141 ng l −1 for TDCPP, TCIPP and TBEP, respectively) were observed among the target compounds. Flame retardants used for household furniture and building materials were detected in river basins where buildings and arterial traffic were dominated. The developed GC × GC-HRTOFMS approach was efficient and effective for environmental monitoring and provided valuable new information on various aspects of monitoring in the context of environmental management. [ABSTRACT FROM AUTHOR]

To be able to gauge the health risks and biological effects of e-waste fires, it is of key importance to know what types and amounts of chemicals are released when they occur. In this case study, we pumped 6–24 L of air from an accidental fire at a recycling depot through a Tenax-TA tube and conducted comprehensive (non-targeted) analysis by thermal desorption/comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (TD/GC × GC/ToFMS). A special focus was placed on the search for halogenated compounds. More than 5000 components were detected in the atmosphere around the fire; however, component separation was insufficient, even when using GC × GC. The number of organohalogen compounds retrieved was increased about 1.8-fold by the refinement process of the exact mass spectrum using mass defect filtering (MDF) software. After processed by MDF, 386 peaks were concluded to be halogenated compounds. The major retrieved substances included chlorinated (or chlorinated-brominated) dioxins, chlorinated (or brominated) phenols, benzene, and various other halogenated aromatic compounds. Direct comparison of mass spectra was carried out to investigate the potential for qualitative and quantitative comparison of detected peaks without specific identification. The approximate quantitative values are summarized for each compound in the estimated substance group. Their ratios were estimated to be halogenated phenols: 13%, benzenes: 9.6%, dibenzo- p -dioxins: 9.6%, dibenzofurans: 8.4%, biphenyls; 7.4% and toluenes: 6.4%. [Display omitted] • Quick sampling with portable active air sampler for use in any location. • No pre-treatment and direct sample introduction for non-targeted analysis. • in silico cleanup to remove mass spectra of large amounts of hydrocarbons in fire smoke. • Carried out the method in real fire accident. [ABSTRACT FROM AUTHOR]

he hydrothermal degradation pathways of decabromodiphenyl ether during hydrothermal treatment were investigated. After an initial “Heating time”, the reaction runs were carried out at constant temperature (heating to 300°C and keeping temperature) and pressure (8MPa) in a SUS316 stainless steel micro autoclave filled with water. Some decomposition of decabromodiphenyl ether was observed over 200°C, and it was decomposed by more than 99% after 10min at 300°C. The reactivities of bromine on para and meta substituents were relatively high, while its reactivity on ortho bromine was extremely low. The formations of polybrominated dibenzo-p-dioxins and furans (PBDD/DFs) were observed in the early stages of the reactions at around 300°C. The TCDD toxicity equivalency (TCDD-EQs) of the by-products was determined based on relative potencies (REPs EC5TCDD) with the Dioxin-Responsive-Chemical Activated Luciferase gene eXpression (DR-CALUX) bioassays technology. These results indicated that the risk of formation of PBDD/DFs in the hydrothermal degradation of deca-BDE was low, and it would be possible to reduce the TCDD-EQs value by adding some catalyst or alkali, or extending processing time. [Copyright &y& Elsevier]

The effectiveness of subcritical water extraction (SCWE) was examined for removing dioxins from contaminated soil. Most dioxins in the soil sample were reduced at 300 °C or more, but decreased dioxin concentrations were also observed at 150 °C. After 4 h of extraction, 99.4%, 94.5% and 60% of PCDDs were removed from samples at 350, 300 and 150 °C, respectively. It was also determined that degradation of dioxins had occurred, since the sum of dioxins in the soil plus water extracts after the experiments had considerably decreased. This study revealed that pressurizing is not essential for the removal of dioxins. Reduction was complete within 30 min at 350 °C; however, it took a much longer time at lower temperatures. The results of addition experiments in which OCDDs were added to different types of soil samples have shown that dechlorination is one of the major reaction pathways. After addition of OCDD to soil samples, experiments were carried out to examine in detail the degradation pathways of PCDDs. The removal rates and congener profiles varied among soil types. Although it was previously assumed that removal rates and congener profiles depended on the chemical components in soil, nonparametric statistical analysis revealed no significant relationship between the rate of reduction and elements present in the soil. It was confirmed from isomer patterns that dechlorination of the 2,3,7,8-positions in PCDDs takes place somewhat faster than for the 1,4,6,9-positions. [Copyright &y& Elsevier]

An enormous number of pollutants must be investigated to be able to understand which types threaten human health and environmental biota. In this study, we propose a workflow for screening polybromochlorodibenzo- p -dioxins and dibenzofurans (PBCDD/Fs), which are compounds that have thousands of isomers and congeners, by combining measurement of a sample without any in-laboratory-cleanup with the results of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and post-data processing. This process can be regarded as "in silico sample cleanup." The post-data processing stage comprises two methods in which the extracted mass spectra are matched to exact mass and isotopic ratios specified as formulae and filtering via mass deficiency. We applied this workflow to wastewater samples from industrial facilities to identify mixtures of halogenated dioxins. As a result, it was estimated that dioxins in an absolute quantity of 10–500 pg could be detected with sufficient accuracy by recovery testing of a standard mixture against sample crude extracts. Tri- to octa-halogenated dioxins were detected in 8 of 13 samples. Leachate from an industrial landfill was found to contain relatively large numbers of PBCDD/Fs, and several congeners were found in wastewater from an industrial fabric facility that handles decabromodiphenyl ether. The workflow, including the post-data processing method developed and applied in this study, has the advantage that additional identifications can be performed at any time from a single set of measurement data. This also enables the screening of substances that have thousands of homologous isomers, such as chlorinated and brominated dioxins, as well as other non-halogenated compounds. [Display omitted] • Comprehensive GC × GC/ToFMS for PXDD/Fs. • PXDD/Fs in wastewater from industrial facilities. • A quick and easy screening method for PXDD/Fs. • Other compounds searchable from the measured data at any time. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel comprehensive assessment system with chemical analysis and bioassay. • Rapid evaluation of environmental pollution and human health risk in emergencies. • AIQS-GC as chemical analysis and Yeast-two-hybrid assay as bioassay. • DDT contamination in sediment due to the typhoon Hagibis. • Risk assessment of human health on the DDT. A novel comprehensive assessment system, consisting of a bioassay and chemical analysis, was developed to quickly evaluate the human health risk posed by toxic chemicals discharged due to natural disasters. To analyze samples quickly, a yeast-two-hybrid assay (Y2H) and GC–MS equipped with an automated identification and quantification system (AIQS-GC) were employed for the bioassay and chemical analysis, respectively. Since the analysis of 1000 substances by AIQS could be finished within two days following the Y2H assay for screening, this method would complete the risk assessment within three days. To confirm the applicability of this method in real environmental samples, we examined it using sediments circulated by Typhoon Hagibis. In one sediment sample, a distinctive response was indicated by the Y2H assay, and relatively high DDT concentration was identified by AIQS-GC in the same sediment. Therefore, using the results obtained from this method, a human health risk assessment of DDT was conducted, which indicated that the risk could be ignored. Additionally, the contamination of PAHs and alkanes was suggested as well. In this study, the pollution risk assessment could be completed within three days. Therefore, to our knowledge, this is the first study to demonstrate an assessment system with a rapid combination method for emergencies. Consequently, it is believed that this type of novel system would be needed in the future due to the increasing number of natural disasters predicted worldwide. [ABSTRACT FROM AUTHOR]

Examines the concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar polychlorinated biphenyls in Japanese human adipose tissue. Temporal trends in the compounds; Mean toxic equivalents level; Background human exposure.

Highlights • PAHs degradation from diesel fuel aromatic fraction was investigated. • Novel method was applied for the visualization degraded compounds in the GC × GC-TOF MS chromatograms. • Oerskovia sp. CHP-ZH25 has successfully degraded different PAHs from diesel fuel aromatic fraction. Abstract Polycyclic aromatic hydrocarbons (PAHs) from petroleum and fossil fuels are one of the most dominant pollutants in the environment. Since aromatic fraction from petroleum diesel fuel is mainly composed of PAHs, it is important to discover new microorganisms that can biodegrade these compounds. This article describes the biodegradation of the aromatic fraction separated from petroleum diesel fuel using the strain Oerskovia sp. CHP-ZH25 isolated from petroleum oil-contaminated soil. The biodegradation was monitored by gravimetry and GC × GC-TOF MS. An innovative method was applied to visualize degraded compounds in the data provided by a GC × GC-TOF MS. It was shown that Oerskovia sp. CHP-ZH25 degraded 77.4% based on gravimetric analysis within 30 days. Average rate of degradation was 14.4 mg/L/day, 10.5 mg/l/day and 4.0 mg/l/day from 0 to 10 day, 10–20 and 20–30 day, respectively. The order of PAH degradation based on decrease in peak volume after 30 days of incubation was as follows: dibenzothiophene derivatives > benzo[ b ]thiophene derivatives > naphthalene derivatives > acenaphthene derivatives > acenaphthylene/biphenyl derivatives > fluorene derivatives > phenanthrene/anthracene derivatives. Here we demonstrated that Oerskovia sp. CHP-ZH25 could potentially be a suitable candidate for use in bioremediation of environments polluted with different PAHs. [ABSTRACT FROM AUTHOR]

Highlights: [•] We obtained the respiratory uptake efficiencies (E W) of 99 compounds by fish. [•] The relationship between the E W values and log K OW was analyzed. [•] The E W of the compounds increased with increasing the log K OW up to a log K OW of 5. [•] We derived an equation for predicting E W based on a two-phase resistance model. [Copyright &y& Elsevier]

A clean-up method for polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples. [Copyright &y& Elsevier]

• Tris(2,6-dimethylphenyl) phosphate (TDMPP) was evaluated through a mouse model. • TDMPP directly entered fetal and neonatal mice brains. • TDMPP induced changes in sex-related brain structures. • The reproductive functions of female mice were impaired by TDMPP. Developmental exposure to environmental chemicals with estrogen-like activity is suspected to permanently impair women's health. In this study, a mouse model was used to evaluate whether tris(2,6-dimethylphenyl) phosphate (TDMPP), a chemical with a putative estrogen-like action, impairs sexual differentiation of the brain. Either TDMPP and 17β-estradiol (E 2) as positive controls or sesame oil as a negative control were administered subcutaneously to dams from gestational day (GD) 14 to parturition, and to pups from postnatal day (PND) 0 to 9. Precocious puberty, irregular estrous cycles, and a lowered lordosis response were found in the TDMPP- and E 2 -treated groups. A certain amount of TDMPP and its metabolites in the perinatal brain and the masculinization of sexual dimorphic nuclei in the hypothalamus of female mice after treatment were also detected. The experimental evidence demonstrates that TDMPP directly enters the fetal and neonatal brain, thereby inducing changes of sex-related brain structures and impairing female reproductive functions. [ABSTRACT FROM AUTHOR]

Complex chemical mixtures need to be evaluated to, for example, aid in medical diagnoses, assess product quality, and assess environmental conditions. Two-dimensional gas chromatography (GC × GC), which is a comprehensive analytical technique, combined with data classification techniques, has attracted great interest for assessing mixtures. In this study, a nontarget cross-sample analysis-based unsupervised direct classification method using non-negative matrix factorization was developed for assessing mixtures analyzed by GC × GC. The method was developed using GC × GC data for more than 30 river water samples as image data. The retention time shift correction data processing step was important to the classification accuracy because the compound signals were found at slightly different times for different samples. The maximum likelihood estimates of the matching ratios for the 30 samples, with retention time shift correction, were 86.8% and 77.0% using two and three ranks, respectively. The method is easy to perform and intuitive, requiring no specific knowledge or labeled data. This direct classification method will therefore be particularly useful for performing initial screens of large numbers of samples and for identifying major differences between samples.

Neonicotinoids, a widely used group of pesticides designed to selectively bind to insect nicotinic acetylcholine receptors, were considered relatively safe for mammalian species. However, they have been found to activate vertebrate nicotinic acetylcholine receptors and could be toxic to the mammalian brain. In the present study, we evaluated the developmental neurotoxicity of acetamiprid (ACE), one of the most widely used neonicotinoids, in C57BL/6J mice whose mothers were administered ACE via gavage at doses of either 0 mg/kg (control group), 1.0 mg/kg (low-dose group), or 10.0 mg/kg (high-dose group) from gestational day 6 to lactation day 21. The results of a battery of behavior tests for socio-sexual and anxiety-related behaviors, the numbers of vasopressin-immunoreactive cells in the paraventricular nucleus of the hypothalamus, and testosterone levels were used as endpoints. In addition, behavioral flexibility in mice was assessed in a group-housed environment using the IntelliCage, a fully automated mouse behavioral analysis system. In adult male mice exposed to ACE at both low and high doses, a significant reduction of anxiety level was found in the light-dark transition test. Males in the low-dose group also showed a significant increase in sexual and aggressive behaviors. In contrast, neither the anxiety levels nor the sexual behaviors of females were altered. No reductions in the testosterone level, the number of vasopressin-immunoreactive cells, or behavioral flexibility were detected in either sex. These results suggest the possibility that in utero and lactational ACE exposure interferes with the development of the neural circuits required for executing socio-sexual and anxiety-related behaviors in male mice specifically.

A global spectral deconvolution, based on non-negative matrix factorization (NMF) in comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry, was developed. We evaluated the ability of various instrumental parameters and NMF settings to derive high-performance detection in nontarget screening using a sediment sample. To evaluate the performance of the process, a NIST library search was used to identify the deconvoluted spectra. Differences of the instrumental scan rates (25 and 50 Hz) in deconvolution were evaluated and results show that a high scan rate enhanced the number of compounds detected in the sediment sample. A higher mass resolution in the range of 1,000 to 10,000 and a higher m/z precision in the deconvolution were needed to obtain an accurate mass database. After removal of multiple duplicate hits, which occurred in batch processes of NIST library search on the deconvolution result, 62 unique assignable spectra with a match factor ≥900 were obtained in the deconvoluted chromatogram from the sediment sample, including 54 spectra that were refined by the deconvolution. This method will help to detect and build up well-resolved reference spectra from various complex mixtures and will accelerate nontarget screening.

We have previously described the use of a tandem simplified multilayer silica gel-activated carbon dispersed silica gel (TS-ML-AC) column for the cleanup of blood samples for the analysis of 29 hazardous organochlorine compounds (OCs)--the 17 major polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/DFs) and 4 non-ortho- and 8 mono-ortho-polychlorinated biphenyls (PCBs). We noted that the performance of the activated carbon-silica gel (ACS) column (lower column) varied with the lot number of the ACS. In this study, we compared the elution profiles of OCs eluted on 5 ACS columns, each with a different ACS lot number, and found that only mono-ortho-PCBs #114 and #123 were affected by lot number. The problem was that the 50 ml of n-hexane required to elute all the OCs from the simplified multilayer silica gel (MLS) column (upper column) into the AC column (lower column) also eluted varying amounts of PCBs #114 and #123 from the ACS column by ACS lot number. Although we could prevent PCBs #114 and #123 from being eluted from the ACS column by reducing the n-hexane volume to 10 ml, this volume was not sufficient to elute all the OCs from the MLS column. We solved this by separating the two columns; the sample solution was eluted with 50 ml of n-hexane from the MLS column, this eluate was concentrated to about 0.3 ml using a rotary evaporator, and then the concentrated solution was cleaned up on the ACS column. The recovery rates of #114 and #123 from blood samples were above 70% and the relative standard deviations of their concentration were below 10%, irrespective of the lot number, compared with recovery rates of 45-79% for #114 and 59-89% for #123, and relative standard deviations of their concentration above 15% when 50 ml of n-hexane was run through the tandem column. Our modified method affords reliable and reproducible cleanup of blood samples for analysis of 29 OCs, irrespective of the ACS lot number.

Dioxins, including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs) and coplanar polychlorinated biphenyls (Co-PCBs), such as mono-ortho-PCBs and non-ortho-PCBs, are environmental pollutants that have deleterious effects on human health. Although screening of blood samples for dioxins is necessary, the current methods are time-, reagent- and labor-intensive. To optimize the extraction and cleanup of dioxins, we have designed a column chromatography method, coupled with a water washing step. We used a tandem simplified multilayer silica gel-activated carbon dispersed silica gel column (TS-ML-AC) rather than the conventional two columns. We compared three liquid-liquid extraction (LLE) methods and two pressurized liquid extraction (PLE) methods, when used with this column. For each of these extraction methods, we compared the quantity of lipid obtained when the water washing step was omitted and when it was performed by shaking 30 times by hand or 30 min by a machine. We found that TS-ML-AC was superior to the conventional pair of columns in that only about one third of the solvent and only one quarter of the time was necessary. Of the five extraction methods, the acetone/hexane PLE (AcP) method was superior, since it reduced the amount of organic solvent to half or less of the amount required for the LLE methods. The cleanup step using water was best accomplished by the hand-shaking method. Our results indicate that, for the analysis of dioxin in whole blood samples, the use of AcP together with TS-ML-AC and water washing by hand shaking should be used.

For the analysis of dioxins, polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs) and coplanar polychlorinated biphenyls (Co-PCBs), devising simple and economical methods is important, especially for mass screening of human exposure. Pretreatment of samples, namely the extraction and cleanup methods that are widely used at present, needs to be improved for savings in time, manpower, and solvent consumption. In the present study, we applied solid phase extraction (SPE) using octadecyl (C18) and a blue-chitin column in place of liquid-liquid extraction (LE) and an active-carbon column with serum samples, frequently used for assessment of human exposure. Efficacy of the new pretreatment methods was demonstrated by successful high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS) of the major 17 PCDDs/Fs and 12 Co-PCBs that are on the list of WHO/IPCS (1997) hazardous dioxins with toxic equivalent factor (TEF) values. SPE is timesaving and requires less manpower and organic solvent as compared with the LE that is presently widely used. Concerning cleanup with blue-chitin, the amount of toluene applied as eluent could be reduced to 1/3, as compared with the active-carbon case. The combination of SPE and blue-chitin for pretreatment of serum saves time and manpower, is accurate and uses less organic solvent than LE with active carbon cleanup.

Human adipose samples collected in Tokyo, Japan in 1970 and 2000 were analyzed for the presence of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and diphenyl ethers (PBDEs), and the concentrations in the two groups were compared. As far as we know, the concentrations of the PBDD/Fs in adipose tissue from the general Japanese population are reported for the first time. Three PBDD/F congeners were found in the following adipose tissues: 2,3,7,8-TeBDD, 2,3,7,8-TeBDF, and 2,3,4,7,8-PeBDF. The median concentrations (ranges) of three PBDD/Fs in 1970 and 2000 were 5.1 (3.4-8.3) and 3.4 (1.9-5.3) pg/g lipid wt (l.w.), respectively. For PBDEs, seven PBDE congeners were determined in the following samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5',6-hexabromodiphenyl ether (BDE-154), and 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183). Median concentrations (ranges) of PBDEs showed a significant increase from 29.2 (6.8-78.4) pg/g l.w. in 1970 to 1288 (466-2,753) pg/g l.w. in 2000. BDE-47, the major congener of PBDEs, was 56.2% and 35.6% of the total in 1970 and 2000, respectively, whereas the BDE-153 was < 1% and 29.7% of the total in 1970 and 2000, respectively. This may indicate that the source of PBDEs had changed during this period. Further analysis of archived human samples from 1970 to 2000 is needed to describe the details of the contamination trends of PBDD/Fs and PBDEs in the Japanese population. Furthermore, PBDD/F monitoring, particularly 2,3,7,8-TeBDD and 2,3,7,8-TeBDF, may give more toxicological information based on TeCDD toxic equivalents (TEQs).

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar biphenyls (Co-PCBs) were determined in Japanese human adipose tissues. Temporal trends were assessed by comparing data collected during 1970-1971, 1994-1996 and 2000. Mean TEQ levels of PCDD/Fs in human adipose tissue showed a significant decrease from 31.6 +/- 9.2 pg-TEQ/g fat wt in 1970-1971 to 11.9 +/- 7.4 pg-TEQ/g fat wt in 2000, and coplanar PCBs decreased from 35.4 +/- 21.9 pg-TEQ/g fat wt in 1970-1971 to 15.3 +/- 8.2 pg-TEQ/g fat wt in 2000. However, some PCB congener concentrations did not change during this time. A comparison of data using the latest PCB-TEQ showed no significant changes. Therefore, research on source characterization and monitoring of short-term temporal trends on these compounds should be carried out continuously.