Trends in flame retardant levels in upholstered furniture and children's consumer products after regulatory action in California.

In 2013, California revised its upholstered furniture flammability standard TB 117-2013 to improve fire safety without the need for flame retardant (FR) chemicals. Subsequent legislation (SB 1019) required disclosure of FR content. In 2020 California expanded restriction on FR chemicals to include juvenile products and upholstered furniture (AB 2998). To monitor trends in FR use, and assess the effectiveness of the new regulations, we analyzed 346 samples from upholstered furniture (n = 270) and children's consumer products (n = 76), collected pre- and post-regulatory intervention for added FR chemicals (i.e., ∑FR > 1000 mg/kg). Upholstered furniture samples, collected from products before enactment of the new regulations, had a median FR concentration of 41,600 mg/kg (range: 1360-92,900 mg/kg), with 100% of the foam samples and 13.7% of the textile samples containing ∑FR > 1000 mg/kg. Firemaster formulations (FM 550 and FM 600), a mixture of triphenyl phosphate (TPHP), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEH-TEBP) and a mixture of isopropyl- or tert-butyl-triphenyl phosphates (ITPs or TBPPs), were the most frequently detected FR (34%), followed by tris(1,3-dichloroisopropyl) phosphate (TDCIPP; 25%), TPHP with a mixture of polybrominated diphenyl ethers (BDE-47, 99, 100, 153 and 154; 20%) and tris(2-chloroethyl) phosphate (TCEP; 11%). Upholstered furniture components collected after enactment of the new legislation had a median FR concentration of 2600 mg/kg (range: 1160-49,800 mg/kg, outlier sample 282,200 mg/kg), with 11.9% of the foam samples and no textile samples containing ∑FR > 1000 mg/kg. Of these samples, tris(1-chloro-2-propyl) phosphate (TCIPP) was the most frequently detected FR (55%), followed by TDCIPP (30%) and Firemaster (FM 550, 15%). No PBDEs were detected in the post-regulatory intervention products. Our initial work on children's products showed 15% of the samples contained ∑FR > 1000 mg/kg. In our post- AB 2998 work, no regulated children's product components failed compliance (i.e., ∑FR > 1000 mg/kg). The data confirm successful adoption of the new regulations with most samples in compliance, demonstrating the efficacy of regulatory intervention. Given these results, environmental FR exposure is expected to decrease as older FR treated consumer products are replaced with FR free products.

Risk assessment of PFASs in drinking water using a probabilistic risk quotient methodology.

We evaluated health risks associated with perfluorinated and polyfluorinated alkyl substances (PFASs) found in drinking water applying human risk assessment (HRA) methodology. Using data on worldwide occurrence of PFASs in drinking water and recent guidelines for PFASs in drinking water, we applied four scenarios based on different toxicological threshold values to calculate age-dependent risk quotients (RQ) for different PFASs. The mean concentrations of the most frequently detected compounds (PFOS and PFOA) were highest in North America (99.2 and 30.7 ng L-1, respectively), and lowest in Asia (PFOS: 3.0 ng L-1) and Europe (PFOA: 4.87 ng L-1). Using HRA methodology and maximum reported concentrations, only PFOS and PFOA, examined individually, showed any threat to human health. Specifically, calculations with the average and maximum concentrations of PFOS showed RQ values higher than 0.2 or 1, respectively, for some age groups under specific scenarios. Similarly, using maximum PFOA concentrations, a RQ equal to 0.2 for infants up to 3 months was calculated under scenario 4. Regional differences on RQ values were observed when PFOS concentrations from Europe, North America and Asia were used. Estimation of the human health risk due to mixtures of PFASs using average concentrations showed that the RQmix was higher than 0.2 for infants up to 3 months (scenario 3) and infants and children up to 6 years old (scenario 4). More importantly, evaluation of the guideline values set by the EU and the Health Advisory Levels issued by the USEPA resulted (under some scenarios) in RQ values higher than 0.2 for PFOS and PFOA for specific age groups, indicating that further discussion is needed for the monitoring and prioritization of these compounds.

Pilot study to assess effects of collection tube types and processing delay on measurements of persistent organic pollutants and lipids in human serum.

Glass red top tubes (RTs), traditionally used to draw blood for biomonitoring studies, have some limitations during field sampling (e.g., tube breakage, timely processing may be difficult). This pilot study examined whether serum separation tubes (SSTs) with delayed processing time (48 h) can be used instead of red top tubes (RTs) to accommodate field conditions. Using state-of-the-art methodologies, PBDEs, PCBs, OCPs, PFCs, cholesterol and triglycerides were measured to evaluate any differences among 2 test conditions (RTs with 2h processing time; SSTs with 48 h processing time). Between the 2 test conditions, we observed high rank correlations among the measured compounds and no statistically significant differences in the levels of measured compounds. We conclude that SSTs with delayed processing time (48 h) produce similar results as RTs with short processing time (2h), suggesting that SSTs could be good substitutes for RTs for new epidemiological and biomonitoring field studies. The use of SSTs offers a tremendous opportunity for the use of samples archived in various SSTs.

Hydroxylated PCB metabolites (OH-PCBs) in archived serum from 1950-60s California mothers: a pilot study.

We are studying participants selected from the Child Health and Development Studies (CHDS), a longitudinal birth cohort of over 20,000 California pregnancies between 1959 and 1967, for associations between maternal body burden of organochlorine contaminants and thyroid function. We designed a pilot study using 30 samples selected among samples with high and low PCB concentrations to evaluate the feasibility of measuring OH-PCBs in the larger study population. GC-ECD and GC-NCI/MS were used to determine PCBs and OH-PCBs as methyl derivatives, respectively. Maternal serum levels of Sigma11PCBs and Sigma8OH-PCB metabolites varied from 0.74 to 7.99 ng/mL wet wt. with a median of 3.05 ng/mL, and from 0.12 to 0.98 ng/mL wet wt. with a median of 0.39 ng/mL, respectively. Average concentrations of Sigma8OH-PCB metabolites in the high PCB group were significantly higher than those in the low PCB group (p < 0.05). The levels of OH-PCB metabolites were dependent on PCB levels (r = 0.58, p < 0.05) but approximately an order of magnitude lower (p < 0.05). The average ratio of Sigma8OH-PCBs to Sigma11PCBs was 0.14 +/- 0.08. The primary metabolite was 4-OH-CB187 followed by 4-OH-CB107. Both of these metabolites interfere with the thyroid system in in vitro, animal, and human studies. OH-PCBs were detectable in all archived sera analyzed, supporting the feasibility to measure OH-PCB metabolites in the entire cohort.

Polybrominated diphenyl ethers and polychlorinated biphenyls in human breast adipose samples from Brazil.

Twenty five human breast adipose tissue samples were collected in Porto Alegre, Brazil during 2004-2005 and analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). SigmaPBDE concentrations (sum of tri- to hepta-BDEs) ranged from 0.19 to 132 ng/g lipid with a median of 1.51 ng/g lipid. These concentrations are 3- to 100-times lower than those reported from other countries, with the exception of Japan, probably reflecting lower usage of PBDE-containing products or lower exposures to these chemicals. The predominant congener was BDE-47, followed by BDEs 99, 183, 153 and 100. One individual in the dataset had about 70-times higher PBDE concentrations than the rest of the participants. SigmaPCB (sum of PCBs 118, 138, 153, 180) ranged from 30 to 339 ng/g lipid, with a median of 51 ng/g lipid. No age dependency was found for PBDEs (r=-0.800-0.374, p>0.05) or PCB 180 (r=0.278, p>0.05). On the other hand, PCBs 118, 138 and 153 did show age dependency (r=0.410-0.458, p<0.05). This is the first study to report levels of PBDEs in human breast adipose from Brazil.

Analysis of breast milk to assess exposure to chlorinated contaminants in Kazakhstan: sources of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) exposures in an agricultural region of southern Kazakhstan.

High levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD; up to 208 pg/g fat) were measured in samples of breast milk collected in 1997 from 64 donors [41 first-time mothers (primiparae)] living on state farms in southern Kazakhstan. TCDD was the major contributor (70%) to the toxic equivalents, matching the congener patterns found in breast milk and serum samples collected in 1994 and 1996 from donors in nearby villages. The highest TCDD levels were found in state farms adjacent to a reservoir (zone A), which receives agricultural runoff from cotton fields. TCDD levels in zone A were significantly higher than levels in a region more distant (zone B; > 10 miles) from the reservoir (zone A: mean 53 pg/g, n = 17; zone B: mean 21 pg/g, n = 24; p = 0.0017). Levels of TCDD in breast milk and animal-derived foodstuffs were 10 times U.S. levels. Body burden and dietary data suggest that exposures to TCDD are chronic, environmental, and long term and may be related to the use of chemicals in cotton agriculture. The data suggest that the most likely source is the use of cotton defoliants contaminated with TCDD, and the most likely pathway for human exposure is via the consumption of contaminated foodstuffs.

Analysis of breast milk to assess exposure to chlorinated contaminants in Kazakstan: high levels of 2,3,7, 8-tetrachlorodibenzo-p-dioxin (TCDD) in agricultural villages of southern Kazakstan.

To assess levels of chlorinated contaminants in breast milk, we measured organochlorine pesticides, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) in breast milk samples collected in 1994 according to the World Health Organization protocol from 92 donors that were representative of regional populations in southern Kazakstan. High levels (10-120 pg/g fat) of 2,3,7, 8-tetrachlorodibenzo-p-dioxin (TCDD), the most toxic of the PCDD/PCDF congeners, were found in breast milk samples from an agricultural region. TCDD was the major contributor (75%) to the international toxicity equivalents of these samples. The same distinctive PCDD/PCDF congener pattern was found in 15 breast milk samples and 4 serum samples collected in 1996 in a follow-up study, and has now been confirmed by three analytical laboratories.

Congener-specific analysis of PCBs in human milk from Kazakhstan.

We have characterized the spectrum of PCB contaminants in human milk samples from 95 women in Kazakhstan using GC/MS congener specific analysis. In these samples, 12 PCBs comprised 83% of total PCB concentration, and were similar to the major PCBs reported in other published human milk studies. By summing concentration levels of 80 PCB congeners in the Kazakhstan samples, a mean total PCB concentration of 368 ng/g fat was obtained. This is lower than levels reported in human milk samples from Western Europe. Six indicator PCBs were summed in Kazakh milk samples; their aggregate value was similar to literature values published for human milk from the former Soviet Union. Using WHO's recent TEF scheme, the mean sum of PCDD/F, coplanar PCB, mono-ortho PCB, and di-ortho PCB TEQ is 42 pg TEQ/g fat.

Analysis of breast milk to assess exposure to chlorinated contaminants in Kazakstan: PCBs and organochlorine pesticides in southern Kazakstan.

Organochlorine pesticides (OC) and polychlorinated biphenyls (PCBs) were measured in samples of breast milk taken from 92 donors representative of regional populations in southern Kazakstan. The World Health Organization protocol for assessing levels of chlorinated contaminants in breast milk was followed. The most prevalent OC residues were beta-hexachlorocyclohexane (beta-HCH), p,p'-DDE, p,p'-DDT, hexachlorobenzene, and alpha-HCH. The measured levels of beta-HCH were among the highest reported in the published literature. Data from Aralsk, near the Aral Sea, indicated continuing DDT exposure. Overall PCB-toxic equivalent levels (22 pg/g fat) were similar to those reported in industrialized European countries. PCBs were highest in Atyrau in the Caspian oilfields.

Biotransfer and bioaccumulation of dioxins and furans from soil: chickens as a model for foraging animals.

Chickens were used as a model for foraging animals to examine the bioavailability of all 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDFs) from soil. Three groups of chickens were exposed through their diet to soil contaminated with PCDD/PCDFs at less than 0.5 pg/g I-TEQ (control group), 42 pg/g I-TEQ (low exposure group), and 460 pg/g I-TEQs (high exposure group). Eggs, tissues, feces and feed were analysed throughout the exposure and depuration period. Daily intake was estimated at 2.5 ng/kg-day for the high and 0.3 ng/kg-day for the low exposure groups. Bioavailability was chlorination-dependent ranging from 80% for tetrachlorinated to less than 10% for octachlorinated congeners. During exposure, tissue distribution was congener-dependent with 5-30% of the intake excreted in the eggs, 7-54% deposited in the adipose and less than 1% present in the liver. On a fat weight basis, the highest concentrations were observed in the liver, implying that mechanisms other than lipid solubility operate in that tissue. Bioconcentration factors and elimination half-lives were also congener- and tissue-dependent. Results from this study indicate that animals foraging on soil contaminated at low ppt PCDD/PCDF levels may bioaccumulate these compounds to unacceptable levels.

Workshop on perinatal exposure to dioxin-like compounds. I. Summary.

An international workshop reviewed 20 ongoing or recently completed studies of the effects of perinatal exposures to dioxins, dibenzofurans, and PCBs on the reproductive, endocrine, neurodevelopmental, and immune systems. Many of the observed effects are consistent with these compounds acting as "environmental hormones" or endocrine disrupters. This report summarizes the conclusions and future directions described at the workshop.

Retention of styrene following controlled exposure to constant and fluctuating air concentrations.

An experiment was designed to determine whether the respiratory retention of styrene vapor, as estimated from measurements of end-exhaled air, was the same during periods of both constant and fluctuating exposure. Six human subjects were exposed to styrene inside a experimental chamber. A computer-controlled system was used to generate time-varying air concentrations of styrene over 4-5h in both multistep sequences of constant exposure (four subjects exposed to 15-99 ppm of styrene in 100-min steps) and fluctuating patterns representative of occupational exposures (two subjects exposed to mean concentrations of styrene of 50 ppm). In the latter case, lognormally distributed exposures, which fit one of two first-order autoregressive models, were generated at intervals of 2.5 min. It was found that the concentration of styrene in end-exhaled air was reduced by about half if the subject inhaled one to three breaths of clean air prior to sampling. This suggests that significant amounts of styrene were desorbed from the lining of the lungs during the initial exhalation. The retention of styrene vapor during constant exposures was 0.935 and was independent of the level. During each of the two sets of fluctuating exposure the retention of styrene was also constant and was independent of both the variance and autocorrelation coefficient. However, the retention of styrene during the fluctuating exposure (estimates ranged from 0.957 to 0.973) was significantly higher than that observed during the constant exposures.(ABSTRACT TRUNCATED AT 250 WORDS)

A field method for measuring solvent vapors in exhaled air--application to styrene exposure.

A method is described for measuring solvent vapors in mixed-exhaled air. The subject exhales through a carbon-containing tube connected to a Wright respirometer. Adsorbed vapors are subsequently eluted by carbon disulfide and analyzed by gas chromatography. Twenty-minute exposures to styrene and the corresponding concentrations of styrene in the breath and venous blood were repeatedly measured for two subjects. Regression analyses indicated that the breath measurements were highly correlated with both the exposures and the blood concentrations of styrene. In another study, styrene was measured simultaneously in the mixed-exhaled air by this technique and in the end-exhaled air by a portable gas chromatograph. The mixed-exhaled air obtained with this method contained about half alveolar air. Analysis of the components of the variance obtained from all the data indicated that the error in measurement by this method was about one-fourth of the total variance.

A laboratory evaluation of two methods for measuring low levels of formaldehyde in indoor air.

Two methods for measuring formaldehyde at ppb levels--the modified pararosaniline (PRA) and the modified chromotropic acid (CTA)--were evaluated in a laboratory study. A dynamic double dilution system was used to generate controlled test atmospheres of formaldehyde by the catalytic depolymerization of trioxane. Impinger samples were collected from the sampling manifold and analyzed accordingly. Both methods demonstrated good precision (3.5% for the PRA and 3.4% for the CTA) but differed in accuracy and collection efficiency. Accuracy was 87.7 +/- 7.5% for the PRA and 92.5 +/- 4.2% for the CTA, while collection efficiency was 91.9 +/- 6.9% and 98.7 +/- 4.7% respectively. These differences were mainly due to the use of 1% NaHSO3 as the absorbing solution in the CTA method. Additionally, the NaHSO3 solution has the advantage of long sample preservation, making the modified CTA the method of choice in most non-industrial indoor air sampling situations.