Measurements of atmospheric halogenated organic compounds during polar night

<p>A number of volatile halogenated organic compounds (halocarbons) have been shown to be emitted from the oceans and more lately from sea ice. Several of these contribut to halogens to the troposphere which are involved in a number of atmospheric processes amongst these the destruction of ozone and the speciation of mercury. Historically, most measurements in the Arctic has been performed during summer conditions, but no campaign to the high Arctic has been performed during winter time.</p><p>Here we present the first suite of measurements of halocarbons in air and surface water during polar night during the MOSAiC (Multi-disciplinary Drifting Observatory for the Study of the Arctic Climate) expedition from October 2019 to May 2020. Comparisons will be made with measurements during summer in August 2018.</p>

Effect on water quality and control of chemically enhanced backwash by-products (CEBBPs) in the adsorption-ultrafiltration process

The overall purpose of this research was to investigate the typical types of chemically enhanced backwash by-products (CEBBPs) produced in the chemically enhanced backwash (CEB) process and the influence of variability of CEB factors on typical CEBBPs in the adsorption-ultrafiltration process. Moreover, health risk assessment was utilized to assess the potential adverse health effects from exposure to effluent after the optimal online CEB. The results of the study found the NaClO backwash reagent could react with organic matter to produce CEBBPs, including 9 kinds of volatile halogenated organic compounds (VHOCs) and 9 kinds of haloacetic acids (HAAs) during the CEB process. After a comprehensive consideration of the influence of a single factor on the CEBBPs formation and membrane cleaning effect, the optimal CEB parameters were 6 min of BD, 120 min of BI, 30 L/(m2·h) of BF and 50 mg/L of RC. Under the optimum CEB cleaning parameters, the effluent does not pose a non-carcinogenic risk and posed potential carcinogenic risk to local residents. The lifetime carcinogenic risk (LCR) value for HAAs (6.68E-06) is very close to the LCR value of CEBBPs (6.78E-06), indicating that the HAAs are the main substances in the effluent after CEB.

The Spatial Distribution of the Microbial Community in a Contaminated Aquitard below an Industrial Zone

The industrial complex Neot Hovav, in Israel, is situated above an anaerobic fractured chalk aquitard, which is polluted by a wide variety of hazardous organic compounds. These include volatile and non-volatile, halogenated, organic compounds. In this study, we characterized the indigenous bacterial population in 17 boreholes of the groundwater environment, while observing the spatial variations in the population and structure as a function of distance from the polluting source. In addition, the de-halogenating potential of the microbial groundwater population was tested through a series of lab microcosm experiments, thus exemplifying the potential and limitations for bioremediation of the site. In all samples, the dominant phylum was Proteobacteria. In the production plant area, the non-obligatory organo-halide respiring bacteria (OHRB) Firmicutes Phylum was also detected in the polluted water, in abundancies of up to 16 %. Non-metric multidimensional scaling (NMDS) analysis of the microbial community structure in the groundwater exhibited clusters of distinct populations following the location in the industrial complex and distance from the polluting source. Dehalogenation of halogenated ethylene was demonstrated in contrast to the persistence of brominated alcohols. Persistence is likely due to the chemical characteristics of brominated alcohols, and not because of the absence of active de-halogenating bacteria.

Emission of volatile halogenated organic compounds over various Dead Sea landscapes

Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X is Br, Cl and I) and very short-lived halogenated substances (VSLSs; bromoform – CHBr3, dibromomethane – CH2Br2, bromodichloromethane – CHBrCl2, trichloroethylene – C2HCl3, chloroform – CHCl3 – and dibromochloromethane – CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere and for their key role in aerosol formation. Insufficient characterization of the sources and the emission rate of VHOCs limits our ability to understand and assess their impact in both the troposphere and stratosphere. Over the last two decades, several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge of emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and fluxes of several chlorinated and brominated VHOCs from different landscapes and natural and agricultural vegetated sites at the Dead Sea during different seasons. Fluxes were generally positive (emission into the atmosphere), corresponding to elevated mixing ratios, but were highly variable. Fluxes (and mixing ratios) for the investigated VHOCs ranged as follows: CHBr3 from −79 to 187 nmol m−2 d−1 (1.9 to 22.6 pptv), CH2Br2 from −55 to 71 nmol m−2 d−1 (0.7 to 19 pptv), CHBr2Cl from −408 to 768 nmol m−2 d−1 (0.4 to 11 pptv), CHBrCl2 from −29 to 45 nmol m−2 d−1 (0.5 to 9.6 pptv), CHCl3 from −577 to 883 nmol m−2 d−1 (15 to 57 pptv), C2HCl3 from −74 to 884 nmol m−2 d−1 (0.4 to 11 pptv), methyl chloride (CH3Cl) from -5300 to 10,800 nmol m−2 d−1 (530 to 730 pptv), methyl bromide (CH3Br) from −111 to 118 nmol m−2 d−1 (7.5 to 14 pptv) and methyl iodide (CH3I) from −25 to 17 nmol m−2 d−1 (0.4 to 2.8 pptv). Taking into account statistical uncertainties, the coastal sites (particularly those where soil is mixed with salt deposits) were identified as sources of all VHOCs, but this was not statistically significant for CHCl3. Further away from the coastal area, the bare soil sites were sources for CHBrCl2, CHBr2Cl, CHCl3, and probably also for CH2Br2 and CH3I, and the agricultural sites were sources for CHBr3, CHBr2Cl and CHBrCl2. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHCl3 > CHBr3 > CHBrCl2 and lowest positive flux incidence for CHCl3 among all trihalomethanes; this finding can be explained by the soil's enrichment with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the emission of CHBr2Cl and CHBrCl2 and likely also for CHBr3. There were no indications for correlation of the brominated trihalomethanes with CHCl3. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the flux correlations between these compounds and methyl halides (particularly CH3I) suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevated emission of VHOCs from bare soil under semiarid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes.

Emission of volatile halogenated organic compounds over various landforms at the Dead Sea

Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr3, CH2Br2, CHBrCl2, C2HCl3, CHCl3 and CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH3I and C2HCl3 over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHBr3 > CHBrCl2 > CHCl3. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH2Br2. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH3I, suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes.

Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere is based on observations and modeling studies using low resolution oceanic emission scenarios derived from top down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1° × 1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol I yr−1 for CH3I (Robust Fit/Ordinary Least Square regression technique). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic region. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An underrepresentation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom up emission estimate and top down approaches.