Organic Bromine Compounds Research Articles

Study on Corrosion Characteristics of Aluminum Alloy Al3102 in Sulfate-reducing Bacteria Environment and Investigating the Use of Azadirachta indica Leaves Extract in its Control

An effort to understand the corrosion characteristics of aluminium Al3102 alloy in a neutral medium in the presence of Desulfovibrio desulfuricans was made. The corrosion rate increased up to tenfold in the bacterial medium in comparison to the control (abiotic) medium. Scanning electron microscopy (SEM) studies showed substantial sulfate-reducing bacteria (SRB) adhesion on the alloy surface and pit formation. Supplementation of 1000 ppm Azadirachta indica leaves extract decreased corrosion by 82%. Sulfide analysis, SEM, and X-ray photoelectron spectroscopy (XPS) studies showed a significant effect of neem leaf extract (NLE) on bacterial metabolic activity and confirmed the adsorption of the inhibitor molecules on Al3102 surface. Electrochemical impedance spectroscopy studies showed that the NLE formed a highly resistive external layer which protected the alloy surface from the corrosive effects. The gas chromatography-mass spectroscopy studies (GC-MS) showed appreciable amount of esters, terpenoids, heterocyclic nitrogen, sulfur compounds, and organic bromine compounds in NLE.

Organic bromine compounds produced in sea ice in Antarctic winter

During polar springtime, active bromine drives ozone, a greenhouse gas, to near-zero levels. Bromine production and emission in the polar regions have so far been assumed to require sunlight. Here, we report measurements of bromocarbons in sea ice, snow, and air during the Antarctic winter that reveal an unexpected new source of organic bromine to the atmosphere during periods of no sunlight. The results show that Antarctic winter sea ice provides 10 times more bromocarbons to the atmosphere than Southern Ocean waters, and substantially more than summer sea ice. The inclusion of these measurements in a global climate model indicates that the emitted bromocarbons will disperse throughout the troposphere in the southern hemisphere and through photochemical degradation to bromine atoms, contribute ~ 10% to the tropospheric reactive bromine budget. Combined together, our results suggest that winter sea ice could potentially be an important source of atmospheric bromine with implications for atmospheric chemistry and climate at a hemispheric scale.

Stratospheric Injection of Brominated Very Short‐Lived Substances: Aircraft Observations in the Western Pacific and Representation in Global Models

AbstractWe quantify the stratospheric injection of brominated very short‐lived substances (VSLS) based on aircraft observations acquired in winter 2014 above the Tropical Western Pacific during the CONvective TRansport of Active Species in the Tropics (CONTRAST) and the Airborne Tropical TRopopause EXperiment (ATTREX) campaigns. The overall contribution of VSLS to stratospheric bromine was determined to be 5.0 ± 2.1 ppt, in agreement with the 5 ± 3 ppt estimate provided in the 2014 World Meteorological Organization (WMO) Ozone Assessment report (WMO 2014), but with lower uncertainty. Measurements of organic bromine compounds, including VSLS, were analyzed using CFC‐11 as a reference stratospheric tracer. From this analysis, 2.9 ± 0.6 ppt of bromine enters the stratosphere via organic source gas injection of VSLS. This value is two times the mean bromine content of VSLS measured at the tropical tropopause, for regions outside of the Tropical Western Pacific, summarized in WMO 2014. A photochemical box model, constrained to CONTRAST observations, was used to estimate inorganic bromine from measurements of BrO collected by two instruments. The analysis indicates that 2.1 ± 2.1 ppt of bromine enters the stratosphere via inorganic product gas injection. We also examine the representation of brominated VSLS within 14 global models that participated in the Chemistry‐Climate Model Initiative. The representation of stratospheric bromine in these models generally lies within the range of our empirical estimate. Models that include explicit representations of VSLS compare better with bromine observations in the lower stratosphere than models that utilize longer‐lived chemicals as a surrogate for VSLS.

Airborne measurements of organic bromine compounds in the Pacific tropical tropopause layer

Very short-lived brominated substances (VSLBr) are an important source of stratospheric bromine, an effective ozone destruction catalyst. However, the accurate estimation of the organic and inorganic partitioning of bromine and the input to the stratosphere remains uncertain. Here, we report near-tropopause measurements of organic brominated substances found over the tropical Pacific during the NASA Airborne Tropical Tropopause Experiment campaigns. We combine aircraft observations and a chemistry-climate model to quantify the total bromine loading injected to the stratosphere. Surprisingly, despite differences in vertical transport between the Eastern and Western Pacific, VSLBr (organic + inorganic) contribute approximately similar amounts of bromine [∼6 (4-9) parts per trillion] [corrected] to the stratospheric input at the tropical tropopause. These levels of bromine cause substantial ozone depletion in the lower stratosphere, and any increases in future abundances (e.g., as a result of aquaculture) will lead to larger depletions.

Adsorbable organic bromine compounds (AOBr) in aquatic samples: a nematode-based toxicogenomic assessment of the exposure hazard

Elevated levels of adsorbable organic bromine compounds (AOBr) have been detected in German lakes, and cyanobacteria like Microcystis, which are known for the synthesis of microcystins, are one of the main producers of natural organobromines. However, very little is known about how environmental realistic concentrations of organobromines impact invertebrates. Here, the nematode Caenorhabditis elegans was exposed to AOBr-containing surface water samples and to a Microcystis aeruginosa-enriched batch culture (MC-BA) and compared to single organobromines and microcystin-LR exposures. Stimulatory effects were observed in certain life trait variables, which were particularly pronounced in nematodes exposed to MC-BA. A whole genome DNA-microarray revealed that MC-BA led to the differential expression of more than 2000 genes, many of which are known to be involved in metabolic, neurologic, and morphologic processes. Moreover, the upregulation of cyp- and the downregulation of abu-genes suggested the presence of chronic stress. However, the nematodes were not marked by negative phenotypic responses. The observed difference in MC-BA and microcystin-LR (which impacted lifespan, growth, and reproduction) exposed nematodes was hypothesized to be likely due to other compounds within the batch culture. Most likely, the exposure to low concentrations of organobromines appears to buffer the effects of toxic substances, like microcystin-LR.

Gas chromatography plasma-assisted reaction chemical ionization mass spectrometry for quantitative detection of bromine in organic compounds.

We have recently introduced plasma-assisted reaction chemical ionization mass spectrometry (PARCI-MS) for elemental analysis of halogens in organic compounds. Here, we utilize gas chromatography (GC) coupled to PARCI-MS to investigate the mechanism of Br(-) ion generation from organobromines and to evaluate analytical performance of PARCI for organobromine analysis. Bromine atoms in compounds eluting from GC are converted to HBr in a low-pressure microwave induced helium plasma with trace amounts of hydrogen added as a reaction gas. Ionization is achieved by introducing nitrogen into the afterglow region of the plasma, liberating electrons via penning ionization and leading to formation of negative ions. We demonstrate that N2 largely affects the ionization process, whereas H2 affects both the ionization process and in-plasma reactions. Our investigations also suggest that dissociative electron capture is the main ionization route for formation of Br(-) ions. Importantly, GC-PARCI-MS shows a uniform response factor for bromine across brominated compounds of drastically different chemical structures, confirming PARCI's ability to quantify organobromines in the absence of compound-specific standards. Over 3 orders of magnitude linear dynamic range is demonstrated for bromine quantification. We report a detection limit of 29 fg of bromine on-column, ~4-fold better than inductively coupled plasma-MS.

Instrumental neutron activation analysis of extractable organohalogens in marine mammal, harbour porpoise (Phocoena phocoena) and its feed, Atlantic herring (Clupea harengus), from the Baltic Sea

Instrumental neutron activation analysis (INAA) was conducted for the analysis of extractable organohalogens (EOX) in the blubber samples of harbour porpoise (Phocoena phocoena) and whole body samples of Atlantic herring (Clupea harengus) from the Baltic Sea. The concentration order of EOX was: extractable organochlorine (EOCl) > extractable organobromine (EOBr) > extractable organoiodine (EOI). As the results of investigation into the biomagnification properties of EOX, EOBr in low molecular weight fraction was the highest among the organic halogens investigated, suggesting the presence of high persistent organic bromine compounds in the marine environment, and accumulation through food chains.

Selective detection of unknown organic bromine compounds and quantification potentiality by negative-ion electrospray ionization mass spectrometry with induced in-source fragmentation

For the detection of unknown organic bromine compounds, a liquid chromatography–mass spectrometry (LC-MS) method with negative-ion electrospray ionization (NI-ESI) and induced in-source fragmentation (IISF) was established. After LC separation, the molecules are fragmentized in the source, and bromide is detected via m/z 79 and m/z 81 based on the isotopic occurrence of bromine. In this way, the retention times of the unknown organobromine compounds are determined, and this can be used to extract additional structural information (number of bound bromine atoms, molecular mass and fragmentation scheme) from measurements in the commonly used but less sensitive scan mode. The analysis of known organobromine compounds shows that LC/NI-ESI-IISF mass spectrometry with detection of m/z 79 and 81 is more sensitive than the detection of daughter ions (LC/ESI/MS-MS). Therefore, we present a method not only for the detection of unknown organic bromine compounds, but also for the selective and sensitive detection and quantification of known organobromine compounds.

Natural Production of Organic Bromine Compounds in Berlin Lakes

Berlin surface waters are characterized by elevated concentrations of organic bound bromine (up to 35 microg/L) in late summer. Organic bromine compounds in lakes are of significant importance because human life is closely connected to fresh water. Apart from recreational use, fresh water is frequently used for the production of drinking water, e.g., after bank filtration. Therefore the source, particularly the mechanism responsible for the formation is studied. Field studies indicate that the organic bromine compounds, measured as adsorbable organic bromine (AOBr), are autochthonous. Staggered maxima concentrations of chlorophyll-a, DOC and AOBr indicate that phototrophic organisms might contribute to the AOBr after death. The involvement of phototrophic organisms was established in the laboratory using surface water and/or cultures of organisms. Light and the presence of phototrophic organisms are essential for an AOBr production. Phototrophic organisms incorporate bromide, which is released randomly and after cell death. A part of the incorporated bromide is used for the formation of organic bromine compounds in the cell. After death of the organisms the brominated compounds and the incorporated bromide are released into the water phase, and an extracellular AOBr production can lead to a further formation of AOBr, most probably due to the parallel release of haloperoxidases.

POPs and organic polysufides in sediments of Lake Ladoga

The study included one station close to a pollution source (depth 59 m) and another far from polluted areas (depth 40 m). Samples were analysed for organic chlorine, bromine and sulfur compounds. Samples taken with a corer were sliced to the layers of 0-1, 1-4, 4-7 cm etc. down to the depth of 34 cm. The dating was made with two independent methods, the 210Po method and with the soot particle counting method. The analyses were made with a multiresidue method. Gas chromatography was connected to low resolution mass spectrometry (LRMS) or to high resolution mass spectrometry (HRMS). A different extraction was applied to screen the possible occurrence of polysulfides. Typical chlorophenol and chlorohydrocarbon traces from chlorobleaching of pulp were non-detectable. Also PCDDs, PCDFs, PCBs and various organochloride pesticides, fire retardant residues PBDEs, PBDDs and PBDFs and polychlorinated phenyl salicylates were not detected. Instead, methylated dibenzothiophenes Me-DBTs and Di-Me-DBTs, typical traces of oil based defoamers used in e.g. paper mills were found in the surface layers of the polluted site. Polysulfides were analyzed from layers representing years 1955-1970 from the polluted site. The structures of five congeners were according to GC/MS dimethyl trisulfide, 1,2,3,4-tetrathiepane, pentathiane, 1,2,3,4-tetrathiane and 1,2,4,5-tetrathiepane. Many of the analyzed pollutants have not been reported earlier from Lake Ladoga. The only positive observations were from oil-based defoamers used in paper mills, and from polysulfides, which are either of natural origin or indicate a discharge in the 1950s and 1960s. Owing to the large spreadout and dilution, the concentrations are low even at moderate distances from the pollution centers.

Occurrence and source of brominated organic compounds in surface waters

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.

Distributions of brominated organic compounds in the troposphere and lower stratosphere

A comprehensive suite of brominated organic compounds was measured from whole air samples collected during the 1996 NASA Stratospheric Tracers of Atmospheric Transport aircraft campaign and the 1996 NASA Global Tropospheric Experiment Pacific Exploratory Mission‐Tropics aircraft campaign. Measurements of individual species and total organic bromine were utilized to describe latitudinal and vertical distributions in the troposphere and lower stratosphere, fractional contributions to total organic bromine by individual species, fractional dissociation of the long‐lived species relative to CFC‐11, and the Ozone Depletion Potential of the halons and CH3Br. Spatial differences in the various organic brominated compounds were related to their respective sources and chemical lifetimes. The difference between tropospheric mixing ratios in the Northern and Southern Hemispheres for halons was approximately equivalent to their annual tropospheric growth rates, while the interhemispheric ratio of CH3Br was 1.18. The shorter‐lived brominated organic species showed larger tropospheric mixing ratios in the tropics relative to midlatitudes, which may reflect marine biogenic sources. Significant vertical gradients in the troposphere were observed for the short‐lived species with upper troposphere values 40–70% of the lower troposphere values. Much smaller vertical gradients (3–14%) were observed for CH3Br, and no significant vertical gradients were observed for the halons. Above the tropopause, the decrease in organic bromine compounds was found to have some seasonal and latitudinal differences. The combined losses of the individual compounds resulted in a loss of total organic bromine between the tropopause and 20 km of 38–40% in the tropics and 75–85% in midlatitudes. The fractional dissociation of the halons and CH3Br relative to CFC‐11 showed latitudinal differences, with larger values in the tropics.

電子部品用エポキシ樹脂組成物からの熱分解による有価物の回収技術

A pyrolysis-based technology was applied to recover high purity silica filler from epoxy resin compounds (molding resins) for electronic components, and to reuse it as a filler in the present paper. Molding resins mainly contain epoxy resin, harder, silica filler (70-85 wt %) and flame retardant consisting of brominated epoxy resin and antimony trioxide. Most effective conditions to reduce impurities in the recovered silica were found as heat around 1,000-1,100 °C and to keep oxygen concentration 5-10 vol. %. On the basis of these results, we have developed a practical process for recovering silica filler from molding resins using a roller kiln-type furnace. The recovered silica achieved a purity of C < 0.01 wt %, Sb < 0.4 wt %, and PO43- < 0.002 wt %. A jet-mil treatment was effective to grind the aggregates of recovered silica powder and to increase the reactivity of its surfaces. The recovered silica treated with the jet-mill showed good properties as a filler for a cast insulating epoxy resin compound. A secondary combustion method was successfully applied to the decomposition of the combustion gas. The treatment of the gas by heating at 1,100 °C decreased the toxic organic bromine compounds to a safe level and converted the antimony tribromide to diantimony trioxide, which could be collected by a dry recovery process at high recovery rate.

Pyrolysis-Based Material Recovery from Molding Resin for Electronic Parts

Pyrolysis-based technology for the epoxy resin compounds (molding resin) used for molding electronic components has been studied for the purpose of recovering useful materials and reusing them. The molding resin contains silica filler (70–85% by weight) and flame retardant consisting of bromine compounds and antimony oxides. This study has clarified those pyrolysis conditions best suited to reduction of the impurities (carbon, antimony, and ionic substances) in the recovered silica filler. This has contributed to the development of a practical pyrolysis technology in which a roller kiln-type furnace is used to recover high-purity silica filler. The recovered silica was sufficiently pure to be employed as an inorganic filler in epoxy resin compounds to be used as cast-insulating materials and original molding resins. The combustion exhaust gas generated in the pyrolysis of the molding resin has been successfully treated by a secondary combustion method that decomposed organic bromine compounds in the gas to a safe level, and it converted antimony bromides to antimony oxides, which could then be collected by a dry recovery process at a useful purity.

Skin injuries afflicting three oil workers following contact with calcium bromide and/or calcium chloride

Calcium bromide brine is a highly concentrated aqueous solution of calcium bromide and calcium chloride. It is used extensively in the oil industry. This solution and its components are recognized as causes of skin injury and information is available from the manufacturers on their safe use and handling. Two patients who were injured following unprotected skin exposure to this solution and one patient who was injured following exposure to calcium chloride powder are reported. All sustained skin injuries characterised by an absence of pain and a delayed clinical appearance of the full extent of the injury. Furthermore healing was complicated by graft loss or was slow. Although organic bromine compounds are recognized as a cause of skin injuries1,2, no previous reports of such injuries to humans secondary to calcium chloride or bromide exposure were found in the medical literature. Our experience with these patients is described.

Bromoform emission from Arctic ice algae

DESTRUCTION of surface ozone in the Arctic environment during the spring is thought to be caused by photochemical reactions involving bromine compounds1. Berg et al.2 reported a pulse of bromine particles and gases in the Arctic lower atmosphere in spring, which may be responsible for this surface ozone destruction and for which biogenic sources have been hypothesized1–3. Here we report laboratory and in situ measurements which indicate that Arctic ice microalgae emit significant quantities of bromoform (CHBr3), which may be converted photochemically into active forms of bromine. Our estimates of total annual bromoform release indicate that polar ice algae might contribute globally significant amounts of organic bromine compounds, comparable with anthropogenic and macrophyte sources.

Determination of bromide and nitrite by indirect redox titration using phenyl iodosoacetate

Bromide has been determined by its oxidation with an excess of phenyl iodosoacetate in the presence of acetanilide to give bromine which subsequently reacts with acetanilide to form 4-bromoacetanilide. The residual amount of phenyl iodosoacetate was evaluated iodometrically. Thus, for every mol of bromide one mol of phenyl iodosoacetate was consumed. For the determination of bromine in organic compounds, the test substance was decomposed by fusion with alkali peroxide to liberate bromide which was then evaluated by the phenyl iodosoacetate method. For its determination, nitrite has been reacted with an excess of isoniazid in acid medium to form isonicotinyl azide (which does not react with phenyl iodosoacetate) and the residual amount of isoniazid was titrated with phenyl iodosoacetate in the presence of acidified bromide and methyl red indicator (when isoniazid and phenyl iodosoacetate react in a 1∶2 molar ratio). Each mol of nitrite is equivalent to 2 mol of phenyl iodosoacetate.

Determination of bromine in organic compounds by high-performance liquid chromatography

A method is proposed for the determination of bromine in organic compounds (which may also contain chlorine and iodine) by oxygen-flask combustion of the compound followed by pre-column reaction of bromide with acetanilide and 2-iodosobenzoic acid to form 4-bromoacetanilide which is then chromatographed on an ODS column with a mobile phase of methanol: water, 65:35 v/v, detection at 240 nm, and 4- N-acetylaminotoluene as internal standard. The method is rapid and precise (RSD ≤ 1%), and applicable to a variety of bromine-containing organic compounds; the limit of detection is 0.2 ng of bromine.

Some observations on the indirect spectrophotometric microdetermination of iodine or bromine in organic compounds using chloranil

An indirect spectrophotometric method for the microdetermination of iodine or bromine in organic compounds is described. The method is based on an oxygen flask combustion yielding iodide or bromide, which is then reacted with an excess of potassium iodate or potassium bromate in acidic medium. The iodine or bromine is then reacted with an excess of chloranil and the absorbance of the unconsumed chloranil is measured in a solution of pH 9 at 292 nm. The method is applied satisfactorily to a wide range of iodine- or bromine-containing organic compounds with an average absolute error of ±0.36% and a coefficient of variation (six determinations) of better than 1.1%.

Oxidation of Halogenated Compounds by Cytochrome P-450, Peroxidases, and Model Metalloporphyrins

Incubation of iodosylbenzene and [125I]iodobenzene with cytochrome P-450 (P-450) leads to the formation of [125I]iodosylbenzene (Burka, L.T., Thorsen, A., and Guengerich, F.P. (1980) J. Am. Chem. Soc. 102, 7615-7616), but to date it has not been possible to observe directly the oxidation of organic halides in NADPH-supported P-450 reactions because of the intrinsic instability of haloso compounds. 4-tert-Butyl-2,5-bis[1-hydroxy-1-(trifluoromethyl)- 2,2,2-trifluoroethyl]iodobenzene (RI) and the corresponding bromine analog (RBr) were utilized as model compounds because their oxidized derivatives (iodinane and brominane) are relatively stable. Several model metalloporphyrins efficiently oxidized RI to the iodinane in the presence of iodosylbenzene. Rates of reduction of Mn(V) = O tetraphenylporphin chloride by RI were considerably faster than for several other organic halides. NADPH-fortified rat liver microsomes oxidized RI to the iodinane, identified by its chromatographic retention time and characteristic UV spectrum. Purified P-450 enzymes also catalyzed the oxidation of RI to the iodinane; more selectivity among individual proteins was seen when the reaction was supported by NADPH and NADPH-P-450 reductase than by iodosylbenzene. Free thiol groups in P-450 and NADPH-P-450 reductase could be oxidized by iodosylbenzene, the iodinane or brominane, or by incubation with NADPH and RI or other organic halides. These results provide evidence that P-450 can oxidize organic halogen atoms. Iodo compounds are definitely oxidized, even though the apparent oxidation-reduction potential differences seem unfavorable. The halogen order seen for the reaction is a function of the oxidation potential. Organic bromine compounds are probably also oxidized by P-450, although the rates are much slower. Chloroperoxidase did not oxidize RI to the iodinane but horseradish peroxidase did so at a lower rate; in this case the iodinane is postulated to form via electron abstraction without oxygen transfer.