Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings.

Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56), golden eagle (n=12) and white-tailed eagle (n=36) nestlings during three consecutive breeding seasons. We found that blood plasma concentrations of calcium, sodium, creatinine, cholesterol, albumin, total protein, urea, inorganic phosphate, protein:creatinine, urea:creatinine and uric acid:creatinine ratios and liver enzymes ALKP and ALAT were positively correlated to PCBs, chlordanes, p,p'-DDE, HCB, PFCs and/or PBDEs. Total bilirubin and glucose were negatively correlated to PCBs while magnesium and potassium were negatively correlated to HCB and p,p'-DDE. In addition, protein:creatinine and ALAT were also negatively correlated to PCBs and PFCs, respectively. The most significant relationships were found for the highly contaminated northern goshawks and white-tailed eagles. The statistical relationships between OHCs and BCCPs indicate that biochemical pathways could be influenced while it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles.

Toward a consistent evaluative framework for POP risk characterization.

The purpose of Annex E in the Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) is to assess whether a chemical is likely, as a result of its long-range environmental transport, to lead to significant adverse human health or environmental effects, such that global action is warranted. To date, risk profiles for nominated POPs have not consistently selected assessment endpoints or completed mandated risk characterizations. An assessment endpoint hierarchy is proposed to facilitate risk characterization for the implementation of the SC. The framework is illustrated for a nominated POP, hexabromocyclododecane (HBCD), using three risk estimation methods. Based on current monitoring and toxicity data, the screening-level results indicate that humans and ecological receptors in remote regions such as the Arctic are unlikely to experience significant adverse effects (i.e., low risk) due to long-range environmental transport of HBCD. The results for birds are more uncertain than the results for fish and mammals due to the paucity of avian toxicity data. Risk characterization results for HBCD and for some listed POPs are compared to illustrate how the proposed methods can further assist decision-making and chemical management.

FR garment program development: easier said than done.

Budget pressures are relatively common these days, and this may entice purchasing departments to look only at the initial cost of an FR garment. But there is more to it than that, especially for protective clothing. To make the best choice for safety and economy, check the details for yourself and make sure you get the best protection, comfort, and value for your money.

Facile synthesis of a high efficiency and durability L-citrulline flame retardant for cotton.

A novel flame retardant (FR), the ammonium salt of citrulline-penta (methylphosphonic acid) (ACPMPA) based on L-citrulline was synthesized, and its structure was characterized by 13C, 1H, and 31P nuclear magnetic resonance (NMR) spectroscopy. The ACPMPA flame retardant molecule contains five ammonium salts of phosphorus acid and one ammonium salt of carboxylic acid, which allowed the covalent attachment of ACPMPA onto cellulose via -P=O(-O-C) and -COOC bonds. The results showed that the treated cotton fabrics had very high flame retardance and excellent durability. The limiting oxygen index (LOI) of cotton fabric treated with 35%-ACPMPA reached 49.2% and only decreased to 34.2% after 50 laundry cycles. Vertical flame tests also demonstrated that the treated cotton fabric acquired good flame retardance. The thermogravimetry (TG) and TG-IR results showed that the treated cotton left more residues and released almost no flammable volatiles at high temperatures. The cone calorimetry results showed that the treated cotton released less heat than pure cotton. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results demonstrated that the structure of the treated cotton fabric was almost unchanged, and no free formaldehyde was detected, indicating that the treated cotton was safe. The treated cotton fabric also retained good tensile strength and whiteness.

Toxicology and human health assessment of decabromodiphenyl ether.

We evaluated the available pharmacokinetic data and human and animal toxicity data for 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) (CASRN 1163-19-5) with the objective of deriving a reference dose (RfD) based on the best available science. The available studies for deriving an RfD were first screened using the Klimisch criteria and further evaluated using the United States Environmental Protection Agency's general assessment factors for data quality and relevance (i.e., soundness, applicability and utility, clarity and completeness, uncertainty and variability, and evaluation and review). The chronic 2-year dietary feeding study conducted by the United States National Toxicology Program ( NTP, 1986 , Technical Report Series No. 309) was selected for RfD derivation. Hepatocellular degeneration in male rats was chosen as the critical endpoint in the development of an RfD. For dose-response characterization, we applied benchmark-dose modeling to animal data and determined a point of departure (the 95% lower confidence limit for a 10% increase in hepatocellular degeneration) of 419 mg/kg-day for oral exposures. Based on the similar pharmacokinetic characteristics of BDE-209 across species, this value was converted to a human equivalence dose of 113 mg/kg-day by applying a dosimetric adjustment factor based on body weight scaling to the (3/4) power. An oral RfD of 4 mg/kg-day was calculated by using a composite uncertainty factor of 30, which consisted of 10 for intraspecies uncertainty, 3 for interspecies uncertainty (i.e., 3 for toxicodynamics x 1 for toxicokinetics), and 1 for deficiencies with the database. We consider the RfD to be adequately protective of sensitive subpopulations, including women, their fetuses, children, and people with hepatocellular diseases.

Dispersive liquid-liquid microextraction followed by reversed phase HPLC for the determination of decabrominated diphenyl ether in natural water.

A simple, rapid, and efficient method, dispersive liquid-liquid microextraction (DLLME), has been developed for the extraction and preconcentration of decabrominated diphenyl ether (BDE-209) in environmental water samples. The factors relevant to the microextraction efficiency, such as the kind and volume of extraction and dispersive solvent, the extraction time, and the salt effect, were optimized. Under the optimum conditions (extraction solvent: tetrachloroethane, volume, 22.0 microL; dispersive solvent: THF, volume, 1.00 mL; extraction time: below 5 s and without salt addition), the most time-consuming step is the centrifugation of the sample solution in the extraction procedure, which is about 2 min. In this method, the enrichment factor could be as high as 153 in 5.00 mL water sample, and the linear range, correlation coefficient (r(2)), detection limit (S/N = 3), and precision (RSD, n = 6) were 0.001-0.5 microg/mL, 0.9999, 0.2 ng/mL, and 2.1%, respectively. This method was successfully applied to the extraction of BDE-209 from tap, East Lake, and Yangtse River water samples; the relative recoveries were 95.8, 92.9, and 89.9% and the RSD% (n = 3) were 1.9, 2.7, and 3.5%, respectively. Comparison of this method with other methods, such as solid-phase microextraction (SPME), and single-drop microextraction (SDME), indicates that DLLME is a simple, fast, and low-cost method for the determination of BDE-209, and thus has tremendous potential in polybrominated diphenyl ethers (PBDEs) residual analysis in environmental water samples.

Assessing regulatory effectiveness with exogenously declining risk: a case study of the CPSC's 1973 mattress standard.

INTRODUCTION: This paper examines the contribution of the U.S. Consumer Product Safety Commission's (CPSC) 1973 cigarette ignition mattress flammability standard to reduce mattress fires since 1980, when the U.S. Fire Administration's National Fire Incident Reporting System became fully operational. METHOD: The paper attempts to separate the effect of the cigarette ignition standard from the declining trend in mattress fires that would have resulted without the standard. We analyze the impact of the 1973 cigarette standard on smoking material ignition fires, deaths, and injuries as well as its effect on fires, deaths, and injuries from all ignition sources (smoking material ignitions, open-flame ignitions, and other ignition sources). Impacts on Industry: The results suggest that the 1973 mattress standard has effectively reduced the mattress fire risk and that further reductions in risk via actions tied specifically to cigarette ignition are likely to be difficult to achieve.

Hybrid films of chitosan, cellulose nanofibrils and boric acid: Flame retardancy, optical and thermo-mechanical properties.

Chitosan (CS), cellulose nanofibrils (CNF) and boric acid, the latter of which was used as flame retardant, were combined in transparent, hybrid films that were produced by solvent casting. The flammability and the thermal stability of the films were studied with respect to the loading of the inorganic component. Chitosan films displayed fire retardancy properties, which were enhanced in the presence of boric acid. CNF films, in contrast to those from chitosan, were readily flammable; however, when combined with boric acid (30w%), they became self-extinguishing. Most remarkably, bicomponent films comprising CNF and chitosan, displayed better fire retardancy than that of neat CS films. Moreover, boric acid improved the thermal stability of the bicomponent films. The tensile strength and Young's modulus of CS, CNF and CS-CNF films improved at intermediate boric acid addition, although a negative effect on elongation was observed.

An intercalibration study on organobromine compounds: Results on polybrominated diphenylethers and related dioxin-like compounds.

An intercalibration study on organobromine compounds has been conducted to evaluate the accuracy and reliability in the analysis of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and their related compounds like polybrominated and monobromo-polychlorinated dibenzodioxins and -furans (PBDDs/DFs, MoBPCDDs/DFs). This paper reports the results for these compounds in 'Mixed Standard Solutions' and 'Air-Dried Sediment'. The relative standard deviations (RSDs) for PBDEs, PBDDs/DFs and MoBPCDDs/DFs in mixed standard solutions ranged from 9% to 24%, 4% to 20% and 8% to 27%, respectively. The results of this study are better than those reported in earlier international interlaboratory studies due to general improvement in analytical methods and an increasing number of available authentic standards, particularly for PBDEs. In the analysis for higher brominated compounds such as octabromodibenzodioxin, the participants were advised to optimize the calibration curves befitting the range of concentrations found in samples because variation of relative response factors was noted. The results for 'Air-Dried Sediment' were also reasonable with RSDs from 10% to 38% for PBDEs, 8% to 38% for PBDDs/DFs and 17% to 36% for MoBPCDDs/DFs. In the sediment sample, possible errors in the sample pretreatment and/or interference by other compounds/impurities were indicated. The concentrations of pentabromodiphenylether, BDE100, varied more than the other PBDE isomers due to its poor separation in some chromatographic conditions. In addition, interference by PBDEs was observed in the analysis for PBDFs. Potential degradation/secondary formulation of PBDEs and PBDFs during the Soxhlet extraction were suggested when copper powder was added into the sediment samples. Inspite of these observations, the results in this study are better than those reported in other interlaboratory studies due to the advice given to participants for improving the results. Compared with the results for PCDDs/DFs (5-23% RSDs) and Co-PCBs (6-24% RSDs), the RSDs for most of the organobromine compounds were high, indicating an immature QA/QC approach for the analysis of PBDEs and related compounds in comparison to common chlorinated dioxins.

Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1µmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time.

Polybrominated diphenyl ethers (PBDEs) in U.S. computers and domestic carpet vacuuming: possible sources of human exposure.

Polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant chemically and toxicologically similar to polychlorinated biphenyls (PCBs), are a class of emerging environmental and human contaminants. They have recently been detected in U.S. milk, blood, and food at the highest levels in the world. This pilot study was undertaken with the aim of determining levels of PBDE in the U.S. indoor environment, to assess the potential exposure to PBDEs from computer surfaces and carpets. Food of animal origin is the usual source of polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofurans (PCDF), and PCBs in humans, but there may also be environmental sources for intake of PBDEs. It was also our aim to characterize the PBDE congener profile in these indoor environmental samples. Four computer wipe samples and 9 domestic vacuum-sweeping samples were analyzed for 13 PBDE congeners, PBDEs 17 (2,2',4), 28 (2,4,4'?), 47 (2,2',4,4'?), 66 (2,3',4,4'?), 77 (3,3',4,4'?), 85 (2,2',3,4,4'?), 99 (2,2'4,4',5), 100 (2,2',4,4',6), 138 (2,2',3,4,4',5'?), 153 (2,2',4,4',5,5'?), 154 (2,2',4,4',5,6'?), 183 (2,2',3,4,4',5',6), and 209 (2,2',3,3',4,4',5,5',6,6'?). All samples tested positive for PBDEs. PBDE 209 was the dominant congener in all 4 computer wipe samples and in 7 out of the 9 vacuum dust samples. The congener profiles observed in this study varied considerably, a finding that has been observed previously. However these congener profiles differ from the pattern seen in U.S. human milk, human blood and in food, where PBDEs 47 and 99 predominate.

Air Force approach to risk assessment for halon replacements.

Finding safe, environmentally acceptable, and effective replacements for Halon fire-extinguishing agents and other chemicals banned by the Montreal Protocol is a formidable task for Air Force research and development organizations. One factor that makes this task a challenge is the uncertainty in relating toxicology studies in laboratory animals to the human situation. This uncertainty from toxicology studies affects the risk assessment process by calling for very conservative decisions. Because of this uncertainty, public pressure and politics also impact the regulatory process. The Air Force approach to assessing health hazards for Halon replacements is to provide scientific information that directly applies to the parts of the extrapolation process that are responsible for the most uncertainty. Most regulatory agencies readily incorporate scientific information, when it is available, which can reduce uncertainty. These Air Force studies will be used to provide realistic exposure levels for replacement chemicals which will allow mission accomplishment and provide safety for the worker and the populace.