Gas Chromatography-high Resolution Mass Spectrometry Research Articles

A method for the analysis of multiple novel halogenated flame retardants in cow’s milk

ABSTRACTA method was developed for the extraction and analysis of cow’s milk to measure 21 halogenated flame retardants (FRs), including individual isomers plus eight methoxy-polybrominated diphenyl ethers (MeO-PBDEs). Extraction was performed using homogenisation with acetone:hexane with size exclusion chromatography followed by adsorption chromatography clean-up. Analysis was undertaken using gas chromatography high-resolution mass spectrometry. The method was validated in fortified cow’s milk with FRs and 2-methoxy-PBDE 68 at three levels (low [12.5–1250 pg g–1], mid [37.5–5000 pg g–1] and high [400–10 000 pg g–1]). Additional methoxy-PBDEs were tested at two fortification levels. Isotope dilution was used to correct for losses during sample preparation and average recoveries ranged from 58% (allyl 2,4,6-tribromophenyl ether [ATE]) to 121% (γ-tetrabromoethylcyclohexane (γ-TBECH)). Limits of detection ranged from 0.055 pg g–1 (6-methoxy-PBDE 47) to 38.9 pg g–1 (decabromodiphenylethane (DBDPE)). Matrix effects were overcome through the use of surrogate and performance standards. A single FR (1-bromomethyl-2,3,4,5,6-pentabromobenzene [PBBB]) and two methoxy-PBDEs were detected in commercially available cow’s milk collected from local supermarkets in Ottawa, ON, Canada. Detection frequency was < 25% for these compounds and, where present, concentrations were low.

ChemInform Abstract: An Overview of Detection Techniques for Monitoring Dioxin‐Like Compounds: Latest Technique Trends and Their Applications

AbstractReview: 117 refs.

Quantitative determination of hydroxy polycylic aromatic hydrocarbons as a biomarker of exposure to carcinogenic polycyclic aromatic hydrocarbons

A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method was developed for quantitative analysis of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs). Four hydroxy metabolites of known and suspected carcinogenic PAHs (benzo[a]pyrene (B[a]P), benz[a]anthracene (B[a]A), and chrysene (CRY)) were selected as suitable biomarkers of PAH exposure and associated risks to human health. The analytical method included enzymatic deconjugation, liquid − liquid extraction, followed by derivatization with methyl-N-(trimethylsilyl) trifluoroacetamide and instrumental analysis. Photo-induced oxidation of target analytes − which has plagued previously published methods − was controlled by a combination of minimizing exposure to light, employing an antioxidant (2-mercaptoethanol) and utilizing a nitrogen atmosphere. Stability investigations also indicated that conjugated forms of the analytes are more stable than the non-conjugated forms. Accuracy and precision of the method were 77.4–101% (<4.9% RSD) in synthetic urine and 92.3–117% (<15% RSD) in human urine, respectively. Method detection limits, determined using eight replicates of low-level spiked human urine, ranged from 13 to 24pg/mL. The method was successfully applied for analysis of a pooled human urine sample and 78 mouse urine samples collected from mice fed with PAH-contaminated diets. In mouse urine, greater than 94% of each analyte was present in its conjugated form.

Polychlorinated dibenzo-p-dioxins/furans and dioxin-like polychlorinated biphenyls in food and feed in the Lithuanian market

ABSTRACTFoods and feeds were analyzed during the period of 2007–2014 employing validated and accredited methods based on gas chromatography–high-resolution mass spectrometry. Sampling has been carried out in-line with national monitoring programs as well as during import controls into Lithuania. Food samples such as eggs, milk, beef, pork, poultry, fats of plant and animal origin, fish, cod liver, and feed samples such as premixes, feeds of plant origin, compound feed, mineral feed, vegetable oil, and fish meals were analyzed. Most of the samples exhibited concentrations below maximum limits, except cod liver. Health impacts were assessed in respect to human daily intakes. Data between groups are compared.

Comprehensive evaluation of dioxins and dioxin-like compounds in surface soils and river sediments from e-waste-processing sites in a village in northern Vietnam: Heading towards the environmentally sound management of e-waste

The management of electronic waste (e-waste), which can be a source of both useful materials and toxic substances, depending on the processing method, is important for promoting material cycling. In this study, we used the dioxin-responsive chemical-activated luciferase gene expression (DR-CALUX) assay combined with gas chromatography–high-resolution mass spectrometry to evaluate the levels of dioxin-like compounds in surface soils and river sediments collected in and around an e-waste-processing village in northern Vietnam. The WHO-TEQs (Toxic equivalents) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (Co-PCBs), and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in soils collected in January 2012 ranged from 0.29 to 310 pg/g (median 2.9 pg/g, n = 32), and the WHO-TEQs in sediments ranged from 0.96 to 58 pg/g (median 4.4 pg/g, n = 8). Dioxin-like activities (CALUX-TEQs [2,3,7,8-TCDD equivalent]) in soils collected in January 2012, 2013, and 2014 ranged from <30 to 4300 pg/g (median <30 pg/g, n = 96), and the activities in sediments ranged from <30 to 4000 pg/g (median 33 pg/g, n = 24). Dioxin-like compounds accumulated in samples collected around e-waste-processing areas such as open-burning sites and e-waste-processing workshops, and the compounds may be transported from their sources to surrounding areas over the course of several years. Some of the CALUX-TEQs, but not WHO-TEQs, values were higher than the maximum acceptable WHO-TEQs promulgated by various authorities, indicating that all dioxin-like compounds should be evaluated in samples collected from e-waste-processing areas. Our findings suggest that open burning and open storage of e-waste should be prohibited and that wastewater treatment should be implemented at each workshop to reduce contamination by dioxin-like compounds from e-waste.

Quantification of Short-Chain Chlorinated Paraffins by Deuterodechlorination Combined with Gas Chromatography-Mass Spectrometry.

Analysis of short-chain chlorinated paraffins (SCCPs) is extremely difficult because of their complex compositions with thousands of isomers and homologues. A novel analytical method, deuterodechlorination combined with high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS), was developed. A protocol is applied in the deuterodechlorination of SCCPs with LiAlD4, and the formed deuterated n-alkanes of different alkane chains can be distinguished readily from each other on the basis of their retention time and fragment mass ([M](+)) by HRGC-HRMS. An internal standard quantification of individual SCCP congeners was achieved, in which branched C10-CPs and branched C12-CPs were used as the extraction and reaction internal standards, respectively. A maximum factor of 1.26 of the target SCCP concentrations were determined by this method, and the relative standard deviations for quantification of total SCCPs were within 10%. This method was applied to determine the congener compositions of SCCPs in commercial chlorinated paraffins and environmental and biota samples after method validation. Low-chlorinated SCCP congeners (Cl1-4) were found to account for 32.4%-62.4% of the total SCCPs. The present method provides an attractive perspective for further studies on the toxicological and environmental characteristics of SCCPs.

Quantification of brown dog tick repellents, 2-hexanone and benzaldehyde, and release from tick-resistant beagles, Canis lupus familiaris.

We have recently shown that repellency of the tick Rhipicephalus sanguineus sensu lato by the tick resistant dog breed, the beagle, is mediated by volatile organic compounds (VOCs) 2-hexanone and benzaldehyde present in beagle odour. Ectoparasite location of animal hosts is affected by variation in these odour components and their ratios. The aim of this study was to quantify the release rate, and the ratio, of 2-hexanone and benzaldehyde from beagles. The odour of three beagles was collected, for four days, over one week (day 0, day 1, day 4 and day 7). The compounds were identified using coupled high-resolution gas chromatography-mass spectrometry (GC-MS), and authentic standards of compounds were used to generate external calibration curves for quantification. Both compounds were found in all dogs on all days. The amount of benzaldehyde was always higher than that of 2-hexanone and so their ratio varied from unity, on average (over time) being 3.128±0.365, 1.902±0.390, 1.670±0.671ngmL(-1) for beagle 1, 2 and 3, respectively. There was no significant (p<0.05, F-test) effect of time. The overall mean was 2.233±0.387ngmL(-1). These results further previous findings by documenting the presence of 2-hexanone and benzaldehyde in beagle odour samples covering a 7-day period. This knowledge enables development of repellents to protect dogs from R. sanguineus s. l. infestation.

Toxaphene levels in retail food from the Pearl River Delta area of South China and an assessment of dietary intake

Limited literature exists on toxaphene contamination in food worldwide, particularly in mainland China. In this study, three toxaphene congeners, Parlar 26 (B8-1413), Parlar 50 (B9-1679) and Parlar 62 (B9-1025), were analyzed in five different food categories from the Pearl River Delta Area in China using isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS), and toxaphene levels in food were reported and toxaphene dietary intake by local residents estimated. The results showed that fish contained the highest toxaphene level with a median of 12.87 pg/g wet weight (ww), followed by poultry meat, egg products, livestock meat and vegetable, which had median levels of 5.8, 2.2, 1.89 and 0.67 pg/g ww, respectively. Parlar 50 and Parlar 26 were the predominant characteristic congeners in fish, and Parlar 26 was the predominant congener not only in poultry products and eggs, but also in livestock and vegetable. The estimated average daily intake found by local residents was 35.57 pg/kg body weight/day. Overall toxaphene levels and estimated dietary intake in the Pearl River Delta Area of South China are far lower than the European Maximum Residue Limits (EU MRLs), the German MRL for fish, and other international literature data. Therefore, the risk of adverse health effects from dietary intakes of toxaphene for the local residents is not considerable at the current time, but follow-ups are warranted to study dynamic changes of toxaphene in food in this area.

Bioanalytical and instrumental screening of the uptake of sediment-borne, dioxin-like compounds in roach (Rutilus rutilus).

To examine the uptake of dioxin-like compounds (DLCs), common roaches (Rutilus rutilus) were exposed for 28days to differently contaminated sediments from two major European rivers in a purpose-built facility. Dietary transfer of DLCs was investigated by exposing fish to sediments inoculated or non-inoculated with black worms (Lumbriculus variegatus). Dioxin-like polychlorinated biphenyls (DL-PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), measured via high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) in sediments and whole fish, were used to calculate toxicity equivalent quotients (TEQs). TEQs were compared with biological toxicity equivalent quotients (BEQs) determined via the 7-ethoxyresorufin-O-deethylase (EROD) assay, performed with mammalian (H4IIE) and fish (RTL-W1) liver cell lines. TEQs and BEQs indicated an uptake of sediment-borne DLCs by roach, which was independent of sediment contamination levels, but rather reflected sediment-specific characteristics. For most sediment treatments, DLC uptake did not increase with time. Highest congener-specific uptake (DL-PCB 123) was 10-fold compared to control. Exposure to worm-inoculated sediment of highest overall DLC contamination caused a 2-fold (TEQ and H4IIE BEQ) greater uptake of DLCs by fish compared to the respective non-inoculated treatment. H4IIE cells showed the greatest sensitivity (0.37 ± 0.25pM TCDD) and the strongest correlation with TEQs (r (2) = 0.79), hence, they seem to be best suited for DLC screening of sediments and biota, amended by compound-specific instrumental analysis if required.

Estimated dietary intake and risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls from fish consumption in the Korean general population.

We analyzed 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) in samples from various fish species available at food markets in nine Korean cities. The estimated dietary intake of these chemicals was calculated from the raw concentrations of PCDD/Fs and DL-PCBs in each sample and from the food consumption of the Korean general population, and a comparison was made with the provisional tolerable monthly intake (PTMI). The average daily dietary exposure and the 95th percentile of intake of PCDD/Fs and DL-PCBs were 0.21 and 0.49 pg WHO05-toxic equivalents (TEQ) kg(-1) body weight d(-1) representing 5.27% and 12.26%, respectively, of the Korean tolerable daily intake (TDI). We applied the monthly fish consumption limits to the evaluation of improved risk assessment and concluded that unlimited consumption of most fish species does not contribute to the elevated cancer risk. This investigation was the first such large-scale study in Korea, and incorporated 37 species, including a species of whale, and 480 samples. The major aims of this study were to demonstrate the health risks associated with fish intake and to ensure food safety through total analysis of PCDD/Fs and DL-PCBs using gas chromatography/high-resolution mass spectrometry (GC-HRMS).

Effects of dioxin-related compounds on bone mineral density in patients affected by the Yusho incident.

Exposure to dioxin-related compounds results in many adverse health effects. Several studies have examined the effects of dioxin-related compounds on human bone metabolism with inconsistent results. In Japan in 1968, accidental human exposure to rice oil contaminated with dioxin-related compounds led to the development of Yusho oil disease. The aim of this study was to determine whether exposure to dioxin-related compounds was associated with bone mineral density in Yusho patients. In 2010, 262 women and 227 men underwent dual-energy X-ray absorptiometry bone scans as part of the nationwide Yusho health examination. Serum levels of polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofurans, and non-ortho polychlorinated biphenyls were measured using high-resolution gas chromatography and high-resolution mass spectrometry. When adjusted for prefecture, 1,2,3,4,7,8-HxCDD and 2,3,7,8-TCDF were significantly positively associated with Z-scores in men. No congeners were positively associated with Z-scores in women. After adjustment for prefecture and body mass index, one congener, 1,2,3,4,6,7,8-HpCDD, was negatively associated with Z-scores in women. In contrast, no congeners remained significant in men after adjusting for body mass index. This may suggest that 1,2,3,4,6,7,8-HpCDD has a negative effect on bone mineral density in women; however, the findings should be interpreted carefully, because no increase in the serum level of this congener was observed in patients with Yusho disease.

Markers of mesterolone abuse in sulfate fraction for doping control in human urine.

This manuscript describes the direct detection of mesteroloe sulfo-conjugated metabolites by liquid chromatography/quadrupole/time of flight mass spectrometry (LC/Q/TOFMS) with special focus on evaluation of their retrospective detectability and their structure elucidation. A comparison of their long-term detectability, with the mesterolone main metabolite (1α-methyl-5α-androstan-3α-ol-17-one) excreted in glucuronide fraction and detected by gas chromatography/high resolution mass spectrometry (GC/HRMS), is also presented. Studies on mesterolone were performed with samples obtained from two excretion studies after single oral administration of Proviron© by healthy volunteers. Potential sulfate metabolites were detected in post administration samples after liquid-liquid extraction (LLE) with ethyl acetate and LC/TOFMS analysis, in negative mode. Twelve mesterolone sulfate metabolites from the first excretion study and nine from the second were subsequently confirmed by LC/Q/TOFMS. Finally, six mesterolone sulfate metabolites were considered important taking into account their abundance and long-term detectability, encoded as M1, M2, M4, M5, M6 and M7. The proposed mesterolone sulfate metabolites M1, M2, M4 and M5 (excreted as sulfates) have the same retrospectivity with the main mesterolone metabolite, excreted in glucuronide fraction. For metabolite characterization, LC fractionation was performed. The metabolites were identified and characterized by GC/MS, after solvolysis and derivatization. Combined mass spectra data from trimethyl-silyl (TMS), TMS-enolTMS and methoxime-TMS derivatives were taken into account for the characterization of these metabolites. It was concluded that M1 is 1α-methyl-5α-androstan-3β-ol-17 one, M2 is 1α-methyl-5α-androstan-3α-ol-17 one, M4 is 1α-methyl-5a-androstan-3β, 16z-diol-17-one, M5 is 1α-methyl-5α-androstan-17z,4ξ-diol-3one, M6 is 1α-methyl-5α-androstan-3z,6z-diol-17-one and M7 is 4z-hydroxy-1α-methyl-5α-androstan-3,17-dione.

PCDD/Fs in soil and air and their possible sources in the vicinity of municipal solid waste incinerators in northeastern China

Fly ash, flue gas, ambient air, and soil samples were collected to investigate concentrations, profiles, gas–particle partitioning, and air–soil exchange of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of two municipal solid waste incinerators (MSWIs) in Harbin in northeastern China. The PCDD/F concentrations were 11 600–12 300 pg g−1 (597–615 pg WHO-TEQ g−1) in fly ash and 873–1120 fg m−3 (51.2–61.9 fg WHO-TEQ m−3) in air. The results of gas–particle partitioning possibly indicated the equilibrium state of PCDD/F during sampling period. For soil samples, both Enzyme-linked immuno-sorbent assay (ELISA) and high-resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) were used. Significant correlations between the results from these two methods indicated that both methods are useful for PCDD/Fs analysis in soil. PCDD/Fs concentrations in soil samples ranged from 17.2 to 157 pg g−1 (0.59–8.81 pg WHO-TEQ g−1). Both Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) suggested the sources of the emission from MSWIs and the historical emission from a petroleum refinery to PCDD/Fs in adjacent soils. The air–soil exchange analysis showed a net flux of PCDD/F from air to soil at all soil-sampling sites.

Determination of Dechlorane Plus and related compounds (dechlorane 602, 603 and 604) in fish and vegetable oils.

Dechlorane Plus (DP) is a flame retardant used as a substitute of Mirex since 1970s, but it was not detected in the environment until 2006. Since then, this compound and its main relatives, Dechlorane 602, 603 and 604, have been mainly studied in environmental matrices for monitoring purposes, but the dietary exposure to them has been hardly investigated so far. In the present study, we determined this family of compounds in fish and vegetable oil samples from Catalonia (Spain), most of them used as health supplements. Determination was carried out by gas chromatography-high resolution mass spectrometry (GC-HRMS), after a clean up in a multilayer silica column and preparative high performance liquid chromatography (HPLC) equipped with a pyrenyl(ethyl) column. Concentrations of Dechlorane compounds were between below the limit of detection and 384.2 pg g(-1). Although there are only few studies about the presence of these pollutants in food or feed, concentrations obtained indicated that these compounds are in the same order in fish and vegetable oil health supplements as the few other food and feed studies.

Analytical capabilities of high performance liquid chromatography – Atmospheric pressure photoionization – Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish

A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called “emerging” and “novel” BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and where possible, trueness was verified by analysis of certified reference materials (CRMs). Recoveries of analytes were between 80 and 119%, while the repeatability in terms of relative standard deviations (RSDs) was in the range from 1.2 to 15.5%. The measured values for both analyzed CRMs agreed with the provided consensus values, revealing the recovery of reference concentrations in 72–119% range. The elaborated method met the sensitivity criterion according to Commission Recommendation 2014/118/EU on monitoring of BFRs in food products for majority of the compounds. The concentrations of polybrominated diphenyl ethers (PBDEs) in real samples determined by HPLC-APPI-Orbitrap-MS method and validated gas chromatography–high-resolution mass spectrometry (GC–HRMS) method were found to be in a good agreement.

Occurrence of Theaspirane and its Odorant Degradation Products in Hop and Beer.

In model oxidized media, six theaspirane-derived compounds were identified by gas chromatography-high resolution mass spectrometry: 4-hydroxy-7,8-dihydro-β-ionone, 6-hydroxy-7,8-dihydro-α-ionone, dihydrodehydro-β-ionone, two monoepoxides, and a derived alcohol. Only 4-hydroxy-7,8-dihydro-β-ionone and dihydrodehydro-β-ionone have been described previously in the literature. Investigation of hop revealed five of these compounds in free form together with theaspirane (especially in the Mosaic variety), while the Citra and Amarillo hop varieties emerged as very interesting for the release of theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, and dihydrodehydro-β-ionone from glucoside precursors. For the first time, theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, 6-hydroxy-7,8-dihydro-α-ionone, and both monoepoxides were found in a fresh commercial top fermentation beer (only theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, and dihydrodehydro-β-ionone have recently been mentioned as Gueuze constituents).

PCDD/Fs accumulation in pine needles: variation with species and pine needle age.

Pine needles have been used for many decades as a cheap and convenient biosampler to monitor atmospheric levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), collectively known as PCDD/Fs. However, it is unknown whether accumulation of PCDD/Fs varies according to pine tree species or pine needle age, which hampers the precise application of this biosampler. We collected 0.3-2.3-year-old pine needles from four different species of pine at three sites in Hangzhou City, Zhejiang Province, China. The PCDD/Fs were quantitatively analyzed by gas chromatography high-resolution mass spectrometry. The results show that Pinus massoniana and Cedrus deodara absorbed more PCDD/Fs than Pinus thunbergii and Pinus parviflora at the same site. More cuticular wax and cuticular cell secretions in the pine needles from P. massoniana and C. deodara, as observed by scanning electron microscopy (SEM), might explain this discrepancy. The PCDD/Fs concentrations in 0.3-, 1.3-, and 2.3-year-old pine needles, indicated that concentrations increase with ascending age. This may be ascribed to the enhancement of lipids and cuticular waxes with age in pine needles as indicated by the lipid contents and morphologies observed by SEM. Our results may be useful for selecting the species and age of pine needles used for biosampling, especially for monitoring PCDD/Fs in large areas where the pine species growing in one place may differ from those in another place.

Blood concentrations and risk assessment of persistent organochlorine compounds in newborn boys in Turkey. A pilot study.

Even early life in utero cannot provide a safe place for newborns. The first acquaintance with chemicals takes place in utero and/or with mother's milk after delivery. Besides legislations and bans to persistent organic pollutants (POPs), these chemicals are still affecting the general population especially the children as they are one of the populations most susceptible to chemicals, and also the health problems may arise in the future. Our objective is to collect the first data in newborns in Turkey to determine baseline levels of POPs in the general population and estimate the potential cancer risk related to exposure. Twenty-nine organochlorine pesticides (OCPs) and 18 polychlorinated biphenyl (PCB) congeners in blood samples of newborn boys (0-1 month old) who were born in İstanbul, Turkey, in 2010-2012 were evaluated with high-resolution gas chromatography-high-resolution mass spectrometry (HRGC/HRMS). Results for analyzed chlorinated compounds are as follows: hexachlorocyclohexane (ΣHCH) 1828 ± 3650 pg/g lipid, dichlorodiphenyltrichloroethane (ΣDDT) 10,000 ± 15,398 pg/g lipid, and ΣPCB 1068 ± 1823 pg/g lipid. 4,4'-DDT, 4,4'-dichlorodiphenyldichloroethylene (4,4'-DDE), hexachlorobenzene, and PCB 138 and 153 are the major contaminants. New POPs as lindane 61 ± 268 pg/g lipid, pentachlorobenzene 13 ± 74 pg/g lipid, and endosulfan 29 ± 106 pg/g lipid are also detected in blood. Estimated total risk for lifetime PCB exposure is less than 1 × 10(-5), an acceptable risk. Blood concentration levels will be important base data in the assessment of health concerns of newborns as well as for studies about how endocrine disruptors affect humans.

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in sediments from the Yellow and Yangtze Rivers, China.

Polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) are toxic environmental pollutants that are often found in sediments. The Yangtze and Yellow rivers in China are two of the largest rivers in Asia and are therefore important aquatic ecosystems; however, few studies have investigated the PCDD/F and PCB content in the sediments of these rivers. Accordingly, this study was conducted to generate baseline data for future environmental risk assessments. In the present study, 26 surface sediments from the middle reaches of the Yellow and Yangtze rivers were analyzed for PCDD/Fs and dioxin-like (dl) PCBs by high-resolution gas chromatography and high-resolution mass spectrometry. The ranges of PCDD/F, dl-PCB, and WHO-TEQ content in sediments from the Yellow River were 2.1-19.8, 1.11-9.9, and 0.08-0.57 pg/g (dry weight), respectively. The ranges of PCDD/F, dl-PCB, and WHO-TEQ content in sediments from the Yangtze River were 6.1-84.9, 1.8-24.1, and 0.13-0.29 pg/g (dry weight), respectively. Total organic carbon and dl-PCB contents in the Yellow River were significantly correlated (Spearman's correlation coefficient, r = 0.64, P < 0.05). It is well known that total organic carbon plays a role in the transport and redistribution of dl-PCB. Principal component analysis indicated that PCDD/Fs may arise from pentachlorophenol, sodium pentachlorophenate, and atmospheric deposition, while dl-PCBs likely originate from burning of coal and wood for domestic heating. The dioxin levels in the river sediments examined in this study were relatively low. These findings advance our knowledge regarding eco-toxicity and provide useful information regarding contamination sources.

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1–10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3–10%, for PCDD/Fs, and 0.2–15%, for DL-PCBs) and low instrumental limits of detection, 0.07–0.75 pg μL−1 (for dioxins) and 0.05–0.63 pg μL−1 (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g−1. The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g−1, in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments.