Cariton Kubwabo

Serum levels of perfluoroalkyl compounds in human maternal and umbilical cord blood samples

Perfluoroalkyl compounds (PFCs) are end-stage metabolic products from industrial flourochemicals used in the manufacture of plastics, textiles, and electronics that are widely distributed in the environment. The objective of the present study was to quantify exposure to perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorodecanoic acid (PFDeA), perfluorohexane sulfonate (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA) in serum samples collected from pregnant women and the umbilical cord at delivery. Pregnant women (n=101) presenting for second trimester ultrasound were recruited and PFC residue levels were quantified in maternal serum at 24-28 weeks of pregnancy, at delivery, and in umbilical cord blood (UCB; n=105) by liquid chromatography-mass spectrometry. Paired t-test and multiple regression analysis were performed to determine the relationship between the concentrations of each analyte at different sample collection time points. PFOA and PFOS were detectable in all serum samples analyzed including the UCB. PFOS serum levels (mean+/-S.D.) were significantly higher (p<0.001) in second trimester maternal serum (18.1+/-10.9 ng/mL) than maternal serum levels at delivery (16.2+/-10.4 ng/mL), which were higher than the levels found in UCB (7.3+/-5.8 ng/mL; p<0.001). PFHxS was quantifiable in 46/101 (45.5%) maternal and 21/105 (20%) UCB samples with a mean concentration of 4.05+/-12.3 and 5.05+/-12.9 ng/mL, respectively. There was no association between serum PFCs at any time point studied and birth weight. Taken together our data demonstrate that although there is widespread exposure to PFCs during development, these exposures do not affect birth weight.

Occurrence of perfluorosulfonates and other perfluorochemicals in dust from selected homes in the city of Ottawa, Canada

A series of perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been recently measured in a variety of environmental samples and biological matrices. In order to better understand the human exposure routes of these chemicals, levels of PFOS, PFOA, perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonamide (PFOSA) in house dust samples were investigated. The data revealed a correlation between the concentrations of PFCs and the percentage of carpeting in the house; older houses tended to have less carpeting, hence lower levels of these perfluorinated compounds in their dust.

Migration of bisphenol A from plastic baby bottles, baby bottle liners and reusable polycarbonate drinking bottles

Human exposure to bisphenol A (BPA) has recently received special attention. It has been shown that exposure to BPA may occur through the consumption of beverages or foods that have been in contact with polycarbonate (PC) plastic containers or epoxy resins in food packaging. A BPA migration study was conducted using a variety of plastic containers, including polycarbonate baby bottles, non-PC baby bottles, baby bottle liners, and reusable PC drinking bottles. Water was used to simulate migration into aqueous and acidic foods; 10% ethanol solution to simulate migration to low- and high-alcoholic foods; and 50% ethanol solution to simulate migration to fatty foods. By combining solid-phase extraction, BPA derivatization and analysis by GC-EI/MS/MS, a very low detection limit at the ng l−1 level was obtained. Migration of BPA at 40°C ranged from 0.11 µg l−1 in water incubated for 8 h to 2.39 µg l−1 in 50% ethanol incubated for 240 h. Residual BPA leaching from PC bottles increased with temperature and incubation time. In comparison with the migration observed from PC bottles, non-PC baby bottles and baby bottle liners showed only trace levels of BPA. Tests for leachable lead and cadmium were also conducted on glass baby bottles since these represent a potential alternative to plastic bottles. No detectable lead or cadmium was found to leach from the glass. This study indicated that non-PC plastic baby bottles, baby bottle liners and glass baby bottles might be good alternatives for polycarbonate bottles.

A pilot study on the determination of perfluorooctanesulfonate and other perfluorinated compounds in blood of Canadians

A pilot study was conducted to provide preliminary data on the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonamide (PFOSA) in the blood of Canadians. A set of 56 human serum samples was collected from non-occupationally exposed Canadians and analyzed by microbore HPLC-negative ion electrospray tandem mass spectrometry. PFOS was the main component of perfluorinated organic compounds (PFCs) and was detected in all 56 blood specimens at an average concentration of 28.8 ng mL(-1) and a range from 3.7 to 65.1 ng mL(-1). The concentration of PFOA was an order of magnitude lower than that of PFOS and was found only in 16 samples (29%) at concentrations above the limit of quantification (LOQ). PFOSA was not detected at levels above the method detection limit (MDL) in any of the samples. The levels of PFCs observed in the sample group of non-occupationally exposed humans in Canada were similar to the levels reported in a previous US study with a similar sample pool size. Two distinct PFOS isomers in human serum were identified by accurate mass determination.

Human maternal and umbilical cord blood concentrations of polybrominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs), widely used as flame retardants in commercial products, have become ubiquitous environmental contaminants. Although adult human exposure to PBDEs is well documented, developmental exposure is less well characterized. The objectives of this study were to measure maternal and fetal exposure to nine PBDE congeners and to investigate potential associations with birth weight. PBDE congeners were quantified in maternal serum at 24-28 weeks of pregnancy, delivery, and umbilical cord serum (UCS) by gas chromatography-mass spectrometry (GC/MS/MS). Complete blood sample sets were obtained from 97 pregnant women (mean age 33.1±0.5 years). PBDE-28, -47 and -99 were quantified in all samples tested and PBDE-47 was the most abundant congener measured in both maternal (mid-pregnancy and delivery samples geometric mean=26.9 and 26.9, respectively) and UCS (GM=56.0 ng g(-1) lipid). The UCS concentration for all congeners with the exception of PBDE-153 was higher vs. maternal delivery samples (p<0.001). Only the UCS concentration of PBDE-17 and -99 were significantly associated (β=-49.860, p=0.032, and β=-3.645, p=0.05) with birth weight. However, after adjustment for potential confounders only the association between PBDE-99 and birth weight remained significant (β=-3.951 and p=0.016). We conclude that: the fetus is exposed to PBDEs from at least the second trimester of pregnancy onward; PBDE congeners are higher in UCS compared to maternal serum samples collected at delivery; and that developmental PBDE exposure is potentially associated with lower birth weight.

A novel method for the quantitative determination of free and conjugated bisphenol A in human maternal and umbilical cord blood serum using a two-step solid phase extraction and gas chromatography/tandem mass spectrometry

Bisphenol A is widely used as a monomer in the manufacture of polycarbonates and epoxy resins, as an antioxidant in polyvinyl chloride (PVC) plastics and as an inhibitor of end polymerisation in PVC. Several different methods have been used to quantify total BPA in biological specimens. However, quantification of both free and conjugated BPA continues to present challenges. Moreover, there is limited data concerning fetal exposure. Therefore, the objective of this study was to develop a new method for the analysis of both free and conjugated BPA in human maternal and umbilical cord blood serum. For the analysis of free BPA, the method consisted of a liquid-liquid extraction followed by a two-step solid-phase extraction sample cleanup on Florisil and Oasis HLB sorbents, derivatization of the extract using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and analysis by gas chromatography/tandem mass spectrometry (GC/EI-MS/MS). To determine the amount of conjugated BPA in serum samples, bisphenol A-d6 β-glucuronide (4-[1-(4-hydroxyphenyl)-1-methylethyl-d6]phenyl β-D-glucopyranosiduronic acid) was added to each sample prior to enzymatic deconjugation. The MDL and LOQ for BPA were 0.026 ng/mL and 0.087 ng/mL, respectively. The observed recoveries ranged between 65% and 88%. The new method was applied to the determination of paired human maternal and umbilical cord blood serum samples. The results demonstrated that total BPA concentrations in human maternal serum at mid-pregnancy and at delivery ranged from <0.026 ng/mL to 10.425 ng/mL (median 0.548 ng/mL, n=12) and <0.026 ng/mL to 3.048 ng/mL (median 1.461 ng/mL), respectively. Results for matching umbilical cord blood serum BPA concentrations were in the range of <0.026-2.569 ng/mL (median 1.823 ng/mL). The concentrations measured in this study agreed well with BPA levels in human serum reported internationally. Only 2 mid-pregnancy serum samples out of 12 contained quantifiable amounts of conjugated BPA, indicating that BPA-glucuronide is not abundant in either human maternal or umbilical cord blood serum.

Umbilical cord blood levels of perfluoroalkyl acids and polybrominated flame retardants

Perfluoroalkyl acids (PFAAs) and polybrominated diphenyl ethers (PBDEs) are persistent organic pollutants representing two classes of environmental contaminants of toxicological concern, especially for infants. Canadian biomonitoring data on these chemicals are limited. The objectives of this study were to measure PFAAs and PBDEs in umbilical cord blood from approximately 100 hospital deliveries in Ottawa (Ontario, Canada) and examine associations with characteristics of the mother and infant. Geometric means were 1.469 ng/mL for perfluorooctanoate (PFOA) (95% confidence interval of 1.292-1.671 ng/mL), 4.443 ng/mL for perfluorooctane sulfonate (PFOS) (95% CI of 3.735-5.285 ng/mL), 0.359 ng/mL for perfluorononanoic acid (PFNA) (95% CI of 0.318-0.404 ng/mL), and 0.579 ng/mL for perfluorohexanesulfonate (PFHxS) (95% CI of 0.473-0.709 ng/mL). The final multiple regression models indicated that lower gravida, term gestational age, smoking during pregnancy and vaginal delivery were significantly associated with higher levels of PFOS. Similarly, a vaginal delivery was significantly associated with higher PFOA, while weak associations were found with lower gravida and birth weight less than 2500 g. Furthermore, higher PFNA concentrations were significantly associated with older mothers, and vaginal delivery, while weakly associated with term gestational age. Elevated PFHxS concentrations were significantly associated with smoking during pregnancy and lower gravida. Similar to reports from other countries, the preponderant PBDE congener measured in the cord blood was PBDE-47. Questions remain on why various studies have reported conflicting results on the association between PFAAs and birth weight.

Purification and identification of several sulphonated azo dyes using reversed-phase preparative high-performance liquid chromatography

Abstract Reversed-phase preparative HPLC has been successfully used to isolate several sulphonated azo dyes (Acid Red 1, Acid Red 8, Acid Red 106, Acid Violet 5, Chromotrope 2R, Reactive Orange 16 and Cibacron Brilliant Red 3B-A) from their impurities. The separations were achieved using mobile phases of methanol and ammonium acetate. The major components of these azo dyes were collected and then identified by electrospray mass spectrometry using the characteristic ions [M−2Na]2−, [M−2Na+H]− and [M−Na]−. The degree of purification, as measured by electrospray mass spectroscopy, was variable.

Quantitative determination of nine urinary metabolites of organophosphate flame retardants using solid phase extraction and ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS).

Over the last few years, the use of organophosphate flame retardants (OPFRs) has been on the rise; however, there are knowledge gaps in both the human health effects of OPFRs and levels of human exposure. Currently, human biomonitoring data on the levels of OPFR metabolites in the Canadian population are still non-existent. Herein we describe a novel method to measure nine urinary OPFR metabolites using solid phase extraction and ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). The method detection limits were between 0.08 and 0.25ng/mL for target metabolites. The newly developed and validated method was applied to the analysis of 24 urine samples collected in 2010-12 from pregnant Canadian women. The most frequently detected OPFR metabolite in urine of study participants (detection frequency: 97%) was diphenyl phosphate (DPHP), with concentrations ranging between <0.13-25.2ng/mL, followed (75%) by the sum of two metabolites (DoCP: Di-o-cresyl phosphate and DpCP: Di-p- cresyl phosphate) of tricresyl phosphate, with concentrations between <0.13-4.38ng/mL. With the exception of desbutyl-tris-(2-butoxy-ethyl) phosphate which was not detected in any of the samples, all other OPFR metabolites measured were found among study participants with variable detection frequency, suggesting pregnant Canadian women may be exposed to OPFRs.

Improved derivatization technique for gas chromatography-mass spectrometry determination of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone in drinking water.

The quantification of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (Mutagen X or MX) in drinking water is difficult due to the low concentration of MX in drinking water, its high sensitivity to pH change, and matrix effects that interfere with the derivatization and analysis. Typically, the quantification of MX involves derivatization by methylation. We present a one-step derivatization procedure for MX using N-methyl-bis-trifluoroacetamide (MBTFA) and analysis by ion trap GC/MS/MS. The new method resulted in a significant reduction in analysis time, and improved detection limits. The abundant and selective ions in the mass spectrum of the trifluoroacylated MX (trifluoroacetic acid-4-chloro-3-dichloromethyl-5-oxo-2-hydro-furan-2-yl ester) allowed for a clear identification and quantification of the compound, with a method detection limit of 7.7 ng L(-1), and a limit of quantitation of 24.4 ng L(-1). The trifluoroacylated MX was shown to be stable for 30 days in an excess of the derivatization reagent. The new method was applied for the determination of MX in several drinking water samples, with a concentration range from not-detected to 517 ng L(-1); these values are comparable to those obtained in previous studies. The development of this new simplified analytical method for MX is an important step forward in the field of disinfection by-product (DBP) research, particularly in light of the recent scientific recognition of halogenated furanones as emerging drinking water contaminants. Increased analytical ability may well be a decisive factor in the monitoring of these disinfection by-products.