Hydroxyquinol pathway for microbial degradation of halogenated aromatic compounds

Several peripheral metabolic pathways can be used by microorganisms to degrade toxic aromatic compounds that are known to pollute the environment. Hydroxyquinol (1,2,4-trihydroxybenzene) is one of the central intermediates in the degradative pathway of a large variety of aromatic compounds. The present review describes the microorganisms involved in the degradative pathway, the key enzymes involved in the formation and splitting of the aromatic ring of (chloro)hydroxyquinol as well as the central intermediates formed. An attempt was also made to provide some estimation for genetic basis of the hydroxyquinol pathway.     

Sorption and Biodegradation of Vapor-Phase Organic Compounds with Wastewater Sludge and Food Waste Compost

ABSTRACT

To test the possible use of composted food waste and wastewater sludge as biofilters to treat gas-phase volatile organic compounds (VOCs), batch experiments were conducted with an isolated strain that could degrade aromatic compounds under aerobic conditions. A benzene and trichloroethylene (TCE) mixture was used as the gas-phase pollutant in experiments with composted food waste, sludge, and soil. Under aerobic conditions, benzene was degraded as a primary substrate and TCE was degraded cometabolically, with water contents varying from 6 to 60% (volume of water added/volume of solid). Optimal water content for VOC removal was 12% for the soil, 36% for the composted food waste, and 48% for the sludge.

The extent of VOC sorption and biodegradation at the optimal water content was different for each material. With the same initial VOC concentration, more VOCs were removed by sorption onto the composted food waste and the sludge, while less VOCs were biodegraded in comparison with the results using soil. The reason the biodegradation in the soil was greater may be partly attributed to the fact that, due to less sorption, the aqueous-phase concentration of VOCs, which microorganisms could utilize as a carbon source or cometabolize, was higher. We also speculate that the distribution of microorganisms in each medium affects the rate of biodegradation. A large number of microorganisms were attached to the composted food waste and sludge. Mass transfer of VOCs and oxygen to these microorganisms, which appear to have been heterogeneously distributed in clusters, may have been limited, resulting in hindered biodegradation.     

Atmospheric Polycyclic Aromatic Hydrocarbons at a Point Source of Emissions. Part A: Identification and Determination of Polycyclic Aromatic Compounds in Airborne Particulate Matter Near a Horizontal Stud Soderberg Plant

Abstract

This paper summarizes the sampling and analytical methods developed to identify and measure polycyclic aromatic hydrocarbons (PAH) and related aromatic compounds near a Horizontal Stud Soderberg plant at Jonquiere, Quebec, Canada. The primary source of PAH is the coal tar pitch used as a binder in Soderberg anodes. Twice a week at a number of sampling sites, airborne particulate matter was collected on glass-fiber filters using a Hi-Vol sampler for a twenty-four hour period. Organics on the filter were Soxhlet extracted with benzene.

Identification was done by gas chromatography-mass spectrometry (GC-MS). The vast majority of compounds present were PAH, but small amounts of alkyl PAH and polycyclic aromatic compounds with heteroatoms such as nitrogen, oxygen and sulfur were also identified. Based on the GC-MS identification, a group of 14 PAH was selected for monitoring. Frequent PAH determinations revealed that the ratio of Benzo(a- )Pyrene to total PAH on the Hi-Vol filters is relatively constant in ambient air from one sampling station to another.     

Assessment of Arthrobacter viscosus as reactive medium for forming permeable reactive biobarrier applied to PAHs remediation

Polycyclic aromatic hydrocarbons (PAHs) are significant environmental contaminants as they are present naturally as well as anthropogenically in soil, air and water. In spite of their low solubility, PAHs are spread to the environment, and they are present in surface water, industrial effluent or groundwater. Amongst all remediation technologies for treating groundwater contaminated with PAHs, the use of a permeable reactive biobarrier (PRBB) appears to be the most cost-effective, energy efficient, and environmentally sound approach. In this technology, the microorganisms are used as reactive medium to degrade or stabilize the contaminants. The main limits of this approach are that the microorganisms or consortium used for forming the PRBB should show adequate characteristics. They must be retained in the barrier-forming biofilm, and they should also have degradative ability for the target pollutants. The aim of the present work is to evaluate the viability of Arthrobacter viscosus as bioreactive medium for forming PRBB. Initially, the ability of A. viscosus to remove PAHs, benzo[a]anthracene 100 μM and phenanthrene 100 μM was evaluated operating in a batch bench-scale bioreactor. In both cases, total benzo[a]anthracene and phenanthrene removals were obtained after 7 and 3 days, respectively. Furthermore, the viability of the microorganisms was evaluated in the presence of chromium in a continuous mode. As a final point, the adhesion of A. viscosus to sepiolite forming a bioreactive material to build PRBB was demonstrated. In view of the attained results, it can be concluded that A. viscosus could be a suitable microorganism to form a bioreactive medium for PAHs remediation.     

Biofiltration of a Mixture of Volatile Organic Emissions

ABSTRACT

Air biofiltration is now under active consideration for the removal of the volatile organic compounds (VOCs) from polluted airstreams. To optimize this emerging environmental technology and to understand compound removal mechanisms, a biofilter packed with peat was developed to treat a complex mixture of VOCs: oxygenated, aromatic, and chlorinated compounds. The removal efficiency of this process was high. The maximum elimination capacity (ECmax) obtained was ~120 g VOCs/m³ peat/hr. Referring to each of the mixture's components, the ECmax showed the limits in terms of biodegradability of VOCs, especially for the halogenated compounds and xylene.

A stratification of biodegradation was observed in the reactor. The oxygenated compounds were metabolized before the aromatic and halogenated ones. Two assumptions are suggested. There was a competition between bacterial communities. Different communities colonized the peat-based biofilter, one specialized for the elimination of oxygenated compounds, the others more specialized for elimination of aromatic and halogenated compounds. There was also substrate competition. Bacterial communities were the same over the height of the column, but the more easily biodegradable compounds were used first for the microorganism metabolism when they were present in the gaseous effluent.     

Organic contaminates in water

Abstract

The carbon adsorption method was used for separating organic matter from large samples of drainage, river and tap water. The carbon chloroform extract (CCE) was separated into different solubility fractions and the neutral fraction was separated into aliphatic, aromatic and oxy‐compounds using column chromatography. The aromatic fraction was subjected to TLC, IR and UV analysis. The pesticide endrin was present in both river and tap water at concentrations of 0.7 and 1.5 ppb, respectively.     

Recalcitrance of polycyclic aromatic hydrocarbons in soil contributes to background pollution

The microbial accessibility of native phenanthrene and pyrene was determined in soils representing background scenarios for pollution by polycyclic aromatic hydrocarbons (PAHs). The soils were selected to cover a wide range of concentrations of organic matter (1.7-10.0%) and total PAHs (85-952 μg/kg). The experiments included radiorespirometry determinations of biodegradation with ¹⁴C-labeled phenanthrene and pyrene and chemical analyses to determine the residual concentrations of the native compounds. Part of the tests relied on the spontaneous biodegradation of the chemicals by native microorganisms; another part also involved inoculation with PAH-degrading bacteria. The results showed the recalcitrance of PAHs already present in the soils. Even after extensive mineralization of the added ¹⁴C-PAHs, the concentrations of native phenanthrene and pyrene did not significantly decrease. We suggest that aging processes operating at background concentrations may contribute to recalcitrance and, therefore, to ubiquitous pollution by PAHs in soils.     

Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

The Distribution of Particle-Phase Organic Compounds in the Atmosphere and Their Use for Source Apportionment during the Southern California Children’s Health Study

Abstract

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children’s Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), ho-panes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM₁₀ organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Deltamethrin degradation and effects on soil microbial activity

Deltamethrin [(S)-cyano-3-phenoxybenzyl-cis-(1R,3R)-2,2-dimethyl) cyclo–propane carboxylate),1] labelled at gem-dimethyl groups of the cyclopropane ring was applied on two Egyptian soils at a level of 10 mg/kg soil for a laboratory incubation experiment under aerobic and anaerobic conditions. A steady decrease of soil extractable¹⁴C-residues, accompanied by a corresponding increase of non- extractable bound ¹⁴C-residues was observed over a 90-day incubation period. The percentage of evolved ¹⁴CO₂ increased with time under aerobic and anaerobic conditions in both soils. The effect of deltamethrin on soil microorganisms as well as the counter effect of microorganisms on the insecticide was also investigated. As the incubation period increased, the inhibitory effect of the insecticide on the microorganisms decreased and the evolution of carbon dioxide depended on the applied dose. The nature of soil methanol soluble residues was determined by chromatographic analysis which revealed the presence of the parent insecticide as the main product in addition to four metabolites: 3-(2′,2′-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (II); 3-phenoxybenzaldehyde (III); 3-phenoxybenzoic acid (IV); 3-phenoxybenzyl alcohol (V).     

Biodegradation of organic pollutants in saline wastewater by halophilic microorganisms: a review

Agro-food, petroleum, textile, and leather industries generate saline wastewater with a high content of organic pollutants such as aromatic hydrocarbons, phenols, nitroaromatics, and azo dyes. Halophilic microorganisms are of increasing interest in industrial waste treatment, due to their ability to degrade hazardous substances efficiently under high salt conditions. However, their full potential remains unexplored. The isolation and identification of halophilic and halotolerant microorganisms from geographically unrelated and geologically diverse hypersaline sites supports their application in bioremediation processes. Past investigations in this field have mainly focused on the elimination of polycyclic aromatic hydrocarbons and phenols, whereas few studies have investigated N-aromatic compounds, such as nitro-substituted compounds, amines, and azo dyes, in saline wastewater. Information regarding the growth conditions and degradation mechanisms of halophilic microorganisms is also limited. In this review, we discuss recent research on the removal of organic pollutants such as organic matter, in terms of chemical oxygen demand (COD), dyes, hydrocarbons, N-aliphatic and N-aromatic compounds, and phenols, in conditions of high salinity. In addition, some proposal pathways for the degradation of aromatic compounds are presented.     

Effects of Metsulfuron-Methyl on the Microbial Population and Enzyme Activities in Wheat Rhizosphere Soil

The effects of metsulfuron-methyl, a sulfonylurea herbicide, on the wheat soil microorganisms were evaluated by the methods of microbial inoculation culture, and the activities of three enzymes were measured using the colorimetric method. The tolerant microorganisms that can resist 500 μ g·g^?1 metsulfuron-methyl in the counting culture medium were studied specially. Metsulfuron-methyl distinctly inhibited the common aerobic heterotriphic bacteria, but the effects on common fungi and common actinomycete were not evident. In the meantime, the number of tolerant fungi increased greatly in the rhizosphere after the application of metsulfuron-methyl in contrast to the significant decrease of the amount of tolerant actinomycete. It indicates that fungi might turn into the dominant microbial type and actinomycete is the sensitive factor in the soil polluted by sulfonylurea residues. The population of aromatic compounds–decomposing bacteria, aerobic azotobacter, and nitrite bacteria all increased in the earlier period, but the aerobic azotobacter decreased rapidly in number 30 days later, and the amount of nitrite bacteria also showed a temporary decrease with time 15 days later. However, the denitrifying bacteria just began to increase significantly after the crops had grown for 50 days. The amount of sulfur-oxidizing bacteria gradually decreased with the growth of crops, and so were the sulfate-reducing bacteria after metsulfuron-methyl application. To all types of microorganisms, there were more microbes in rhizosphere samples than those in nonrhizosphere except aerobic azotobacter. It means the growth of wheat root system can stimulate the growth of most microorganisms. The activities of hydrogen peroxidase and polyphenol oxidase in soil samples after metsulfuron-methyl application were notably lower than those in the control, and the difference of the activities between the samples of rhizosphere and nonrhizosphere was evident. On the contrary, the activity of dehydrogenase was not inhibited by the application of metsulfuron-methyl, and the rhizosphere effect was not obvious either.     

Preliminary evaluation of bitumen contamination in environmental samples using comprehensive gas chromatography GcxGc – Time of flight mass spectrometry (GCxGC-TOFMS)

Abstract

Bitumen and bitumen impacted soil and water samples were investigated for their relative chemical composition using comprehensive gas chromatography GcxGc – time of flight mass spectrometry (GCxGC-TOFMS). The results reveal the presence of key compounds which could serve as environmental biomarkers for bitumen impacted soils and aquifers. Prominent alkanes such as 3-methylpentane; 2,2,4-trimethylpentane; 1,3,5-trimethyladamantane; 2,6,10-trimethyldodecane; 3-ethyl-2,2-dimethyl pentane were tentatively identified and are likely potent biomarkers in environmental forensic assessment of bitumen contamination while the presence of some aromatic compounds: 1,2-benzenedicarboxylic acid, 1,2-dimethyl-3-propylbenzene; 3,4-bis(methoxycarbonyl)benzoic acid; 1,3-bezenedicarboxylic acid, 1,2-benzenediol; 1,3-dimethylbenzene; 1,2-2-(2-ethylhexoxycarbonyl)benzoic acid; (4-methylpentan-2-yl)benzene; 2,4-dimethyl benzo(H)quinolone will further confirm the bitumen contamination in an area under investigation. A host of additional compounds were tentatively identified, mainly in the bitumen samples. The results obtained in this study provides baseline data for effective monitoring, and source apportionment of oil/oil products spills.     

Identification of Selected Hormonally Active Agents and Animal Mammary Carcinogens in Commercial and Residential Air and Dust Samples

ABSTRACT

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m³). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

Effect of Gas and Kerosene Space Heaters on Indoor Air Quality: A Study in Homes of Santiago,Chile

Abstract

The impact of outdoor and indoor pollution sources on indoor air quality in Santiago, Chile was investigated. Toward this end, 16 homes were sampled in four sessions. Each session included an outdoor site and four homes using different unvented space heaters (electric or central heating, compressed natural gas, liquefied petroleum gas, and kerosene). Average outdoor fine particulate matter (PM_2.5) concentrations were very high (55.9 μg·m^-3), and a large fraction of these particles penetrated indoors. PM_2.5 and several PM_2.5 components (including sulfate, elemental carbon, organic carbon, metals, and polycyclic aromatic hydrocarbons) were elevated in homes using kerosene heaters. Nitrogen dioxide (NO₂) and ultrafine particles (UFPs) were higher in homes with combustion heaters as compared with those with electric heaters or central heating. A regression model was used to assess the effect of heater use on continuous indoor PM_2.5 concentrations when windows were closed. The model found an impact only for kerosene heaters (45.8 μg m^-3).     

Exceedances of the National Ambient Air Quality Standard for Ozone Occurring at a “Pristine” Area Site

Abstract

This paper presents a comparative study of the biodegradation of three aromatic volatile compounds in a compost-based biofilter: toluene, xylene, and 1,2,4-trimethyl-benzene, used in the course of this work for the first time in the field of biofiltration. Hence, three identical biofiltration units have been operated at the laboratory scale. During the experiments, nitrogen (as urea) was supplied at various concentrations to each reactor, via irrigated nutrient solutions. A comparative analysis of the results showed that the biodegradability scale followed the degree of substitution around the aromatic ring: toluene > xylene > trimethylbenzene, with 95, 80, and 70% maximum conversions, respectively. In addition, and despite the different removal levels achieved in the three biore-actors, it was established that from a reaction viewpoint, the degradation of the three compounds seemed to follow similar metabolic pathways involving methylcatechol isomers. Finally, by varying the nitrogen input concentrations in the three reactors, three degradation regimes have been highlighted: an N-limitation regime and an N-optimum regime, common to the three solvents, and an N-excess regime, favorable to the colonization of the filter beds by nitrifying species, which particularly affected the xylene and trimethylbenzene biodegradation.     

Aircraft Release of Sulfur Hexafluoride as an Atmospheric Tracer

Abstract

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600°C, with low emissions recorded at 300 and 900°C. There was a close correlation (R² = 0.97) among polychlorinated bi-phenyls (PCBs), hexachlorobenzene, pentachloroben-zene, and polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600°C and as a gas phase at 900°C. For some PAHs, chloroben-zenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = ?A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

Alkylcyclohexanes in Environmental Geochemistry

The n -alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n -alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953–1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels. Published by Elsevier Science Ltd on behalf of AEHS.     

The effect of multiple soil applications of disulfoton on enhanced microbial degradation in soil and subsequent uptake of insecticidal chemicals by potato plants

Abstract

Potatoes were grown during 1992 in 2 m² plots of loam which had received 1, 2 or 3 annual treatments of Di‐Syston 15G, equivalent to 3.36 kg AI/ha, in furrow at planting. The presence of enhanced degradative activity to the sulfoxide and sulfone metabolites of disulfoton in the soil treated in the previous two years was confirmed by laboratory tests prior to the 1992 treatments. Soil, seed potato and foliage from the three treatments were analyzed for disulfoton and its sulfoxide and sulfone metabolites for 12 wk following planting/treatment. Disulfoton was the major insecticidal component of the soil, a minor component of the seed piece and was not detected (<0.02 ppm) in potato foliage. Disulfoton concentrations in each of the three substrates sampled were similar for the three treatments. Disulfoton sulfoxide and sulfone were the major insecticidal components of the seed piece and foliage. Their maximum concentrations in 1st year soil, seed pieces and foliage were ca. 2x, 2x and 6x, respectively, those measured in the 2nd and 3rd year treatments. The results demonstrate that enhanced microbial degradation of relatively minor insecticidal compounds in the soil can profoundly affect insecticide levels in the plant when these compounds are the major insecticidal components accumulated. The broader implications for crop protection using soil‐applied systemic insecticides are discussed.