Nanoscale zerovalent iron, n-ZVI, was found to be highly effective in reductively debrominating decabromodiphenyl ether (BDE209) at ambient conditions and without the catalysis of noble metals. A method was developed to immobilize n-ZVI particles on a cation-exchange resin. The n-ZVI coated resin was then mixed with BDE209 in a water/ acetone (1:1) solution, and the reaction was allowed to proceed for up to 10 days. The first-order rate constant of BDE209 disappearance was estimated to be 0.28 - 0.04 h(-1). The debromination was found to be stepwise, and less-brominated congeners were produced with increasing reaction time. Dechlorination of decachlorobiphenyl (PCB209) was also investigated, but the reaction rate was much slower than the debromination of BDE209. Identification of the reaction products was highly challenging and was assisted by regression equations between experimental and reference gas chromatographic relative retention times, with confirmation by high-resolution mass spectrometry and reference to quantitative structure retention relationships. For randomly selected PBDE and PCB congeners, the net charges of individual atoms were calculated using the quantum chemical computation to explore the difference in relative vulnerability of halogens at different substitution positions between PBDEs and PCBs.

The concentrations of 13 currently used brominated flame retardants (BFRs) were analyzed in 16 sediment cores collected from the North American Great Lakes. Among them, 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), and hexachlorocyclopentadienyl dibromocyclooctane (HCDBCO) were more frequently detected than others. In general, these emerging BFRs have much lower concentrations than polybromodiphenyl ethers (PBDEs) and dechloranes. Inventories of the five BFRs named above, given on a logarithm basis, were found to decrease linearly with the increasing latitude of the sampling locations, but with weaker statistics than those previously reported for the dechloranes. Logarithm of surface fluxes, on the other hand, was found to be a better parameter in correlating with the longitude. With regard to time trends, the exponential increases in concentrations of these BFRs, particularly DBDPE and BTBPE, in recent years are particularly disturbing. The sediment concentration of DBDPE doubles every 3−5 years in Lake Michigan, and approximately every 7 years in Lake Ontario. The corresponding doubling times for BTBPE are about 5 and 7 years in Lakes Ontario and Michigan, respectively, although declines or leveling off were observed in the top sediment layers in Lake Ontario. In contrast to PCBs, PBDEs, and most dechloranes, the correlations between the surface concentration of emerging BFRs and the latitude or longitude of the sampling sites were not strengthened by normalization of the concentration based on the organic matter content of the sediment.

Polybrominated diphenyl ethers (PBDEs) have been extensively used as flame retardants in consumer goods. Sufficient evidence shows that PBDEs have been rapidly accumulating in the environment worldwide. In Asia, deca-bromodiphenyl ether has been produced and used in large quantities, while penta-BDE has largely ceased in the mid-1990s. This paper summarizes and critically reviews the status of PBDE pollution in East Asia, with emphases on the comparisons with Europe and North America and the interpretation of the differences. In general, the concentrations of PBDEs in atmosphere, sludge, human and biological samples of East Asia are comparable to or lower than those in Europe and North America. However, in the sediments of waters near densely populated and heavily industrialized areas, PBDE levels are among the highest ever reported in the literature. In Japan and China, concentrations of PBDEs in sediment cores showed an increasing trend for the past 20-30 years. Also, PBDEs levels in human breast milk in Japan increased about 10-fold in the past 20 years. The presence of PBDEs in fur seal has increased about 150-fold in 1994 than that in 1972. Regional and inter-continental transport cannot be confirmed due to insufficient information. However, the detection of a number of PBDE congeners in a pristine lake on the Qinghai-Tibet Plateau may be an evidence of their long-range transport.

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Abstract. Multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations of trace gases can be strongly influenced by clouds and aerosols. Thus it is important to identify clouds and characterize their properties. In a recent study Wagner et al. (2014) developed a cloud classification scheme based on the MAX-DOAS measurements themselves with which different "sky conditions" (e.g., clear sky, continuous clouds, broken clouds) can be distinguished. Here we apply this scheme to long-term MAX-DOAS measurements from 2011 to 2013 in Wuxi, China (31.57° N, 120.31° E). The original algorithm has been adapted to the characteristics of the Wuxi instrument, and extended towards smaller solar zenith angles (SZA). Moreover, a method for the determination and correction of instrumental degradation is developed to avoid artificial trends of the cloud classification results. We compared the results of the MAX-DOAS cloud classification scheme to several independent measurements: aerosol optical depth from a nearby Aerosol Robotic Network (AERONET) station and from two Moderate Resolution Imaging Spectroradiometer (MODIS) instruments, visibility derived from a visibility meter and various cloud parameters from different satellite instruments (MODIS, the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment (GOME-2)). Here it should be noted that no quantitative comparison between the MAX-DOAS results and the independent data sets is possible, because (a) not exactly the same quantities are measured, and (b) the spatial and temporal sampling is quite different. Thus our comparison is performed in a semi-quantitative way: the MAX-DOAS cloud classification results are studied as a function of the external quantities. The most important findings from these comparisons are as follows: (1) most cases characterized as clear sky with low or high aerosol load were associated with the respective aerosol optical depth (AOD) ranges obtained by AERONET and MODIS; (2) the observed dependences of MAX-DOAS results on cloud optical thickness and effective cloud fraction from satellite confirm that the MAX-DOAS cloud classification scheme is sensitive to cloud (optical) properties; (3) the separation of cloudy scenes by cloud pressure shows that the MAX-DOAS cloud classification scheme is also capable of detecting high clouds; (4) for some cloud-free conditions, especially with high aerosol load, the coincident satellite observations indicated optically thin and low clouds. This finding indicates that the satellite cloud products contain valuable information on aerosols.

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Previously unknown halogenated compounds were detected during the analysis of halogenated flame retardants in two sediment cores collected from Lake Michigan. Gas chromatography coupled with high- or low-resolution mass spectrometry (MS) was used to determine the chemical structures for a total of 15 novel polyhalogenated carbazoles (PHCs) with the general molecular formula C12H9-x-y-zNClxBryIz. On the basis of the mass spectra generated by electron impact (EI) and electron capture negative ionization (ECNI) MS, eight PHCs were tentatively identified as polybrominated carbazoles, while the others were mixed halogenated carbazoles containing, in addition to bromine, either chlorine or iodine or both. Patterns of halogen substitution of PHCs included Br2 to Br5, ClBr2, ClBr3, ClBr4, ClBr3I, Br4I, and Br3I2. 3,6-Dibromocarbazole and 1,3,6,8-tetrabromocarbazole were also found among the PHCs. Profiles of the concentration versus depth of sediment at the two sites showed various patterns among polybrominated carbazoles. The abundance of mixed halogenated carbazoles peaked at depths of 12-16 cm, remained at relatively constant levels in deeper sediment, but declined markedly in more recently deposited sediments. This is the first study discovering the seven mixed halogenated carbazoles in the environment. Detailed methods for their detection and identification are provided.

Abstract. A first direct intercomparison of aerosol vertical profiles from Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations, performed during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI) in summer 2009, is presented. Five out of 14 participants of the CINDI campaign reported aerosol extinction profiles and aerosol optical thickness (AOT) as deduced from observations of differential slant column densities of the oxygen collision complex (O 4 ) at different elevation angles. Aerosol extinction vertical profiles and AOT are compared to backscatter profiles from a ceilometer instrument and to sun photometer measurements, respectively. Furthermore, the near-surface aerosol extinction coefficient is compared to in situ measurements of a humidity-controlled nephelometer and dry aerosol absorption measurements. The participants of this intercomparison exercise use different approaches for the retrieval of aerosol information, including the retrieval of the full vertical profile using optimal estimation and a parametrised approach with a prescribed profile shape. Despite these large conceptual differences, and also differences in the wavelength of the observed O 4 absorption band, good agreement in terms of the vertical structure of aerosols within the boundary layer is achieved between the aerosol extinction profiles retrieved by the different groups and the backscatter profiles observed by the ceilometer instrument. AOTs from MAX-DOAS and sun photometer show a good correlation (R>0.8), but all participants systematically underestimate the AOT. Substantial differences between the near-surface aerosol extinction from MAX-DOAS and from the humidified nephelometer remain largely unresolved.