The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries

Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.     

Volatile organic compounds in some urban locations in United States

Volatile organic compounds (VOCs) have been determined to be human risk factors in urban environments, as well as primary contributors to the formation of photochemical oxidants. Ambient air quality measurements of 54 VOCs including hydrocarbons, halogenated hydrocarbons and carbonyls were conducted in or near 13 urban locations in the United States during September 1996 to August 1997. Air samples were collected and analyzed in accordance with US Environmental Protection Agency-approved methods. The target compounds most commonly found were benzene, toluene, xylene and ethylbenzene. These aromatic compounds were highly correlated and proportionally related in a manner suggesting that the primary contributors were mobile sources in all the urban locations studied. Concentrations of total hydrocarbons ranged between 1.39 and 11.93 parts per billion, by volume (ppbv). Ambient air levels of halogenated hydrocarbons appeared to exhibit unique spatial variations, and no single factor seemed to explain trends for this group of compounds. The highest halogenated hydrocarbon concentrations ranged from 0.24 ppbv for methylene chloride to 1.22 ppbv for chloromethane. At participating urban locations for the year of data considered, levels of carbonyls were higher than the level of the other organic compound groups, suggesting that emissions from motor vehicles and photochemical reactions strongly influence ambient air concentrations of carbonyls. Of the most prevalent carbonyls, formaldehyde and acetaldehyde were the dominant compounds, ranging from 1.5-7.4 ppbv for formaldehyde, to 0.8-2.7 ppbv for acetaldehyde.     

Organic compounds in the flue gas from a power station with circulating fluid bed combustion of coal

Numerous organic compounds have been analyzed by coupled gas chromatography-mass spectroscopy (GC-MS) in flue gas after fluid bed combustion of four coal species from South Africa, Poland, Spitsbergen and Ruhr area (Germany). Polynuclear aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated, heterocyclic and nitro compounds as well as phthalate esters are detected.     

Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster

Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.     

Determination of some aliphatic and polycyclic aromatic hydrocarbons in marine sediments of the Baltic Sea

Two representative samples of surficial marine sediments have been studied, one from the northern Baltic Proper and the other from the Gulf of Finland. Aliphatic hydrocarbons were determined by gas chromatography on a fused silica capillary column, and six polyaromatic hydrocarbons were determined by gas chromatography-mass fragmentography. Hydrocarbons were extracted with a benzene-methanol mixture and ultrasonic agitation. The aliphatic hydrocarbons were tentatively identified by their retention times. The polyaromatic hydrocarbons (PAHs) were identified on the basis of their retention times and mass fragmentograms by direct comparison with those of standard compounds. The aliphatic hydrocarbon contents ranged from 0,1 to 2,6 μg/g dry matter. In both samples there was a clear maximum at n-C₁₇ and also a clear odd-carbon predominance. The PAH contents ranged from 4 to 120 ng/g dry matter. The PAH concentration was about 58 per cent higher in the sample from the Gulf of Finland than in the sample from the Baltic Proper.     

Destruction of halogenated hydrocarbons with solvated electrons in the presence of water

Model halogenated aromatic and aliphatic hydrocarbons and halogenated phenols were dehalogenated in seconds by solvated electrons generated from sodium in both anhydrous liquid ammonia and ammonia/water solutions. The minimum sodium required to completely dehalogenate these model compounds was determined by increasing the Na/substrate ratio until halogen loss was complete. Minimum sodium consumptions were determined in both anhydrous liquid ammonia and with a (5, 20, 50-fold molar excess of water per mole of halide). While more Na was consumed in the presence of water, these dehalogenations were still efficient when a 50-fold water excess was present. Dehalogenation is faster than competiting reactions with water. CCl4 and CH3CCl3 in the presence of a stoichiometric deficiency of sodium produced only CH4 and CH3CH3 and recovered CCl4 or CH3CCl3, respectively. No partially dechlorinated products were detected, indicating dechlorination was diffusion controlled. Na consumption per chlorine removed (as NaCl) was lower than that of Li, K or Ca and this advantage increased in the presence of water. Na consumption was lower using Na chunks instead of a thin Na mirror. Chloroaromatic compounds gave the parent aromatic hydrocarbon and aminated products in anhydrous ammonia but aminated products did not form when water was present.     

Ambient concentrations and correlations of hydrocarbons and halocarbons in the vicinity of an airport

Concentrations of sixteen volatile hydrocarbons present in internal combustion engine exhaust gases and two halogenated hydrocarbons have been measured in ambient air samples at six sites around Gatwick Airport. Correlations between their concentrations have been drawn in an attempt to establish the exact nature of the sources of these emissions, together with consideration of the overall hydrocarbon profiles.     

Oil residues in Baltic sediment,mussel and fish. I. Development of the analysis methods

Sediment, sediment trap, Mytilus, Macoma and flounder samples from Northern Baltic (Finnish archipelago) have been analyzed for their contents of aliphatic and aromatic hydrocarbons. Androstane and hexaethylbenzene were used as internal standards. The analysis procedure consisted of alkaline degradation of fat, column fractionation of the two residue groups and final determination by glass capillary gas chromatography with FID for aliphatic hydrocarbon group and with mass spectrometry for non-polar aromatic residue group. The latter group was also determined by high pressure liquid chromatography. The residues due to oil pollution were distinguished from compounds of pure natural origin on the basis of statistical treatment of the determination results.     

On the aliphatic,and polycyclic aromatic hydrocarbon levels in the southern baltic sea atmosphere

Samples of marine aerosols from the S Baltic Sea have been analysed for aliphatic hydrocarbons from pentadecane to dotriacontane, and for polycyclic aromatic hydrocarbons (PAHs) from anthracene and phenantrene to benzo(ghi)perylene. Some of the sampling stations were situated near industrialized areas (Gdańsk Bay, Pommeranian Bay) and some others in the open Baltic Sea. The aliphatic hydrocarbons were analysed by gas chromatography, polycyclic aromatic hydrocarbons by HPLC. Quantitative composition of the hydrocarbons in the Baltic aerosols is presented and discussed.     

Vertical distribution of aliphatic and aromatic hydrocarbons in mussels from the Amposta offshore oil production platform (Western Mediterranean)

The qualitative distributions of aliphatic hydrocarbons in mussels adhered to the legs of an oil production platform (Amposta, Western Mediterranean) have evidenced local (diesel oil) and chronic inputs (middle East crude oils) as the main pollutant sources in the area. Quantitative data have shown that aromatic hydrocarbons are selectively accumulated with the age of mussels and are more evenly distributed through the water column. Background concentrations of petrogenic aliphatic hydrocarbons in mussels living in the vicinity of oil platforms have been established in the range of 25–40 ug/g dry weight.     

Emission of organic compounds by combustion of waste plastics involving vinyl chloride polymer

Organic compounds emitted from combustion of waste plastics involving vinyl chloride polymer were investigated in an actual waste incinerator. The amounts of volatile aliphatic hydrocarbons and volatile chlorinated organic compounds decreased when the secondary combustion temperature was controlled over 900°C. On the other hand, the amounts of some aromatic hydrocarbons increased with a rise of the secondary combustion temperature.     

The occurrence of chlorinated and other organic trace compounds in urban air

The concentrations of 42 chlorinated hydrocarbons (boiling point range from 61 °C to 400 °C) and those of 16 selected volatile hydrocarbons were simultaneously measured in ambient air during the period of one year. The measurements were carried out at 12 sites with different air qualities in the city of Hamburg (FRG). Annual means, medians and peak concentrations are presented. Analyses of the concentration distributions and a comparison with emission data show that traffic is the dominant source of hydrocarbons, whereas chlorinated hydrocarbons are predominantly emitted by industrial sources. This results in a fairly uniform urban pattern of hydrocarbons, but highly variable concentrations of low boiling halogenated compounds.     

Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation

Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min^?1 under water-saturated conditions. Organic analyses were performed by GC–mass spectrometry, GC–flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60–70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions.     

Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

A diesel fuel spill at a concentration of 1 L m(-2) soil was simulated on a 12 m(2) plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill.     

Biological dehalogenation and halogenation reactions

A large number of halogenated compounds is produced by chemical synthesis. Some of these compounds are very toxic and cause enormous problems to human health and to the environment. Investigations on the degradation of halocompounds by microorganisms have led to the detection of various dehalogenating enzymes catalyzing the removal of halogen atoms under aerobic and anaerobic conditions involving different mechanisms. On the other hand, more than 3500 halocompounds are known to be produced biologically, some of them in great amounts. Until 1997, only haloperoxidases were thought to be responsible for incorporation of halogen atoms into organic compounds. However, recent investigations into the biosynthesis of halogenated metabolites by bacteria have shown that a novel type of halogenating enzymes, FADH(2)-dependent halogenases, are involved in biosyntheses of halogenated metabolites. In every gene cluster coding for the biosynthesis of a halogenated metabolite, isolated so far, one or several genes for FADH(2)-dependent halogenases have been identified.     

Marine macroalgae in polar regions as natural sources for volatile organohalogens

Marine macroalgae species from the polar regions were investigated for their importance as natural sources of volatile halogenated compounds released into the biosphere. Several different halogenated C1 to C4 hydrocarbons were identified and their release rates determined. The compounds contained mainly bromine and iodine, and form was the dominant compound released. Although an annual atmospheric input of approximately 10(8)-10(10) g bromine and 10(7)-10(8) g iodine was calculated from the release rates, marine macroalgae are apparently not the major source on a global scale, as the release is up to four orders of magnitude lower than a presumed annual flow from the oceans. Despite this, macroalgae may be more important on a local scale due to their occurrence at a high biomass in the coastal regions. The present paper gives an overview about studies done on the release of volatile halocarbons by macroalgae from polar regions. Furthermore, the function of these compounds in the macroalgal metabolism is discussed.     

QSAR generated octanol-water partition coefficients of selected mixed halogenated dibenzodioxins and dibenzofurans

We have calculated the values of pk_ow, water solubility, and K_oc for chlorinated, brominated and mixed halogenated dibenzodioxins and dibenzofurans that have been identified in environmental samples. From the results it can be concluded that brominated and mixed halogenated dioxins and furans will show an ecological behaviour similar to that of the pure chlorinated compounds.     

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems.