2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.     

Uncertainty associated with the gravimetric measurement of particulate matter concentration in ambient air

This work applied a propagation of uncertainty method to typical total suspended particulate (TSP) sampling apparatus in order to estimate the overall measurement uncertainty. The objectives of this study were to estimate the uncertainty for three TSP samplers, develop an uncertainty budget, and determine the sensitivity of the total uncertainty to environmental parameters. The samplers evaluated were the TAMU High Volume TSP Sampler at a nominal volumetric flow rate of 1.42 m³ min^–1 (50 CFM), the TAMU Low Volume TSP Sampler at a nominal volumetric flow rate of 17 L min^–1 (0.6 CFM) and the EPA TSP Sampler at the nominal volumetric flow rates of 1.1 and 1.7 m³ min^–1 (39 and 60 CFM). Under nominal operating conditions the overall measurement uncertainty was found to vary from 6.1 x 10^–6 g m^–3 to 18.0 x 10^–6 g m^–3, which represented an uncertainty of 1.7% to 5.2% of the measurement. Analysis of the uncertainty budget determined that three of the instrument parameters contributed significantly to the overall uncertainty: the uncertainty in the pressure drop measurement across the orifice meter during both calibration and testing and the uncertainty of the airflow standard used during calibration of the orifice meter. Five environmental parameters occurring during field measurements were considered for their effect on overall uncertainty: ambient TSP concentration, volumetric airflow rate, ambient temperature, ambient pressure, and ambient relative humidity. Of these, only ambient TSP concentration and volumetric airflow rate were found to have a strong effect on the overall uncertainty. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.

Implications:?This work addresses measurement uncertainty of TSP samplers used in ambient conditions. Estimation of uncertainty in gravimetric measurements is of particular interest, since as ambient particulate matter (PM) concentrations approach regulatory limits, the uncertainty of the measurement is essential in determining the sample size and the probability of type II errors in hypothesis testing. This is an important factor in determining if ambient PM concentrations exceed regulatory limits. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.     

Global population collapse in a superabundant migratory bird and illegal trapping in China

Persecution and overexploitation by humans are major causes of species extinctions. Rare species, often confined to small geographic ranges, are usually at highest risk, whereas extinctions of superabundant species with very large ranges are rare. The Yellow‐breasted Bunting (Emberiza aureola) used to be one of the most abundant songbirds of the Palearctic, with a very large breeding range stretching from Scandinavia to the Russian Far East. Anecdotal information about rapid population declines across the range caused concern about unsustainable trapping along the species’ migration routes. We conducted a literature review and used long‐term monitoring data from across the species’ range to model population trend and geographical patterns of extinction. The population declined by 84.3–94.7% between 1980 and 2013, and the species’ range contracted by 5000 km. Quantitative evidence from police raids suggested rampant illegal trapping of the species along its East Asian flyway in China. A population model simulating an initial harvest level of 2% of the population, and an annual increase of 0.2% during the monitoring period produced a population trajectory that matched the observed decline. We suggest that trapping strongly contributed to the decline because the consumption of Yellow‐breasted Bunting and other songbirds has increased as a result of economic growth and prosperity in East Asia. The magnitude and speed of the decline is unprecedented among birds with a comparable range size, with the exception of the Passenger Pigeon (Ectopistes migratorius), which went extinct in 1914 due to industrial‐scale hunting. Our results demonstrate the urgent need for an improved monitoring of common and widespread species’ populations, and consumption levels throughout East Asia.     

Atmospheric Volatile Organic Compound Monitoring. Ozone Induced Artefact Formation

Assessment of population exposure to VOC in ambient atmospheres is receiving heightened interest as the adverse health effects of chronic exposure to certain of these compounds are identified. Active (pumped) and passive samplers are the most commonly used devices for this type of monitoring. It has been shown, however, that these devices, along with all other preconcentration techniques, are susceptible to ozone interference. It is demonstrated that this interference occurs even at low ozone concentrations and that it may result in the under-estimation of population exposure. A convenient and effective ozone scrubbing method is identified and successfully applied and validated for both active and passive samplers for a range of VOC.     

Thio arsenosugars in freshwater mussels from the Danube in Hungary

In contrast to the large body of data on naturally-occurring arsenic compounds in marine organisms, relatively little is known about arsenic speciation in freshwater biota. We report an investigation using HPLC-ICPMS into the arsenic compounds in five species of freshwater mussels collected from five sites from the Danube in Hungary. Total arsenic concentrations in the mussels ranged from 3.8-12.8 mg As kg(-1). The arsenic speciation patterns were broadly similar for mussels representing each of the five species and five sites, but quite different from those reported for marine mussels. The major extractable arsenicals were two oxo arsenosugars (glycerol sugar and phosphate sugar), and their thio analogues (thio glycerol sugar and thio phosphate sugar). Arsenobetaine, usually the major arsenical in marine organisms, was not a significant compound in the freshwater mussels and was detected in only three of the 11 samples. This is the first report of thio arsenosugars in freshwater biota and suggests that these compounds may be common and widespread naturally-occurring arsenicals.     

Prenatal diagnosis of cystic fibrosis by methylumbelliferylguanidinobenzoate protease titration in amniotic fluid

Amniotic fluids were obtained from 19 mothers who had previously given birth to a child with cystic fibrosis. Measurement of methylumbelliferyl guanidinobenzoate (MUGB) reactive proteases suggested that all 19 would have unaffected babies. Amongst the first 10 cases to come to term there were 5 infants with cystic fibrosis. It is concluded that MUGB protease titration is not suitable for the early prenatal diagnosis of cystic fibrosis.