Studies on the dissipation of 14C‐DDT from water and solid surfaces

Abstract

Dissipation of ¹⁴C‐p,p'‐DDT from water was studied for 180 days under outdoor conditions. DDT dissipated rapidly with overall half‐life of 53 days. The main degradation products were p,p'‐DDE and p,p'‐DDD. A portion of ¹⁴C‐residues was found in the sediment plus biomass (pellet) and on the inner surface of the glass container. This amounted to 7.2 and 6.7% of the initially added radioactivity, respectively. After 6 months, bound¹⁴C was more as compared to extractable ¹⁴C and p,p'‐DDD was the major metabolite of p,p'‐DDT in the extractable fraction. DDT dissipated from clay plates under indoor conditions with an overall half‐life of 160 days.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Fate and residues of 14C‐chloramphenicol in laying chickens 1

Abstract

Studies were conducted to determine the metabolic fate of chloramphenicol (CAP) in White Leghorn using the ^l4C‐labelled compound. In one experiment birds were administered orally via intra‐crop, a single dose of 100 mg (equivalent to 66 mg kg^‐1 body weight) of CAP containing 14 μCi ¹⁴C‐CAP, and its absorption, elimination and distribution in plasma were recorded. Orally dosed ¹⁴C‐compound was rapidly absorbed, efficiently distributed in plasma and eliminated in excreta (>70% in 5 hr). After 5 h, CAP equivalent residues in tissues were lower than 15 μg g^‐1 for this treatment. In a second experiment birds were given intra‐crop dose of either 0.5 or 5 mg of CAP (each dose contained 2.5 μCi ¹⁴C‐CAP) daily for five consecutive days followed by a seven day withdrawal period and elimination of ¹⁴C in excreta and eggs was monitored. More than 95% of the administered ¹⁴C was eliminated within the first 24 h after dosing. Radiocarbon (¹⁴C) was deposited preferentially in yolks compared to albumen or other tissues. Residues declined when feeding was stopped. Various metabolites were isolated and identified by a combination of TLC, LC, and LC‐MS. The main metabolic route of CAP in laying hens appears to be the glucuronidation. Cleavage of the dichloroacetate moiety was only a minor route.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Dissipation of chlorpyrifos,oxon, and 3,5,6‐trichloro‐2‐pyridinol in litter and elm forest soil

Abstract

After chlorpyrifos was applied to the basal 1 meter of elm tree trunks for control of elm bark beetles at two different application times and sites, initial chlorpyrifos residues in forest floor litter ranged from 120 to 916 μg/g depending on the application time. Residues dissipated by approximately 99% after 791 d with the DT₅₀ from 3.9 to 59 d and DT₉₀ from 55 to 310 d. The initial residues of chlorpyrifos in elm forest soil varied from 0.8 to 28 μg/g and were 1 to 2 μg/g at 791 d after application. The dissipation half‐lives of chlorpyrifos in fortified soil placed in the field ranged from 116 to 121 d.     

Fate of 14C‐lindane in a rice‐fish model ecosystem*

Abstract

A model ecosystem has been used to evaluate the impact of ¹⁴C‐lindane on rice‐fish agricultural system. The distribution of ¹⁴C‐residues among the constituents of the model ecosystem was studied over a period of 90 days. The insecticide was found to be readily absorbed by the roots and translocated to all parts of the rice plant. The peak level in the shoots (26 ppm) and roots (105 ppm) of plants was reached to within three weeks. Lindane was concentrated in fish and residues as high as 90 ppm could be detected after 30 days.

The major part of the residues present in the different constituents of the ecosystem could be extracted with hexane and proved to contain soley the parent compound. The data obtained show that lindane possesses a relatively low biodegradability in fish and in rice plant. The insecticide accumulates in fish and rice plant to considerable extent.     

The degradation of anilazine and dihydroxy‐anilazine at various soil depths of an orthic luvisol

Abstract

In conformity with Guideline 4.1 of the Federal German Biological Agency, degradation experiments with the fungicide active ingredient [benzene ring‐U‐¹⁴C]anilazine and its major metabolite [triazine ring‐U‐¹⁴C]dihydroxy‐anilazine were carried out in an orthic luvisol. Mineralization of the benzene ring carbon of anilazine amounted to less than 2 % in 110 days and that of the triazine ring carbon of dihydroxy‐anilazine to less than 8 %. Increasing the incubation temperature from 22 °C to 30 °C and adding organic substance influenced the mineralization slightly. In soils which received two or three applications in succeeding years with subsequent ageing in the open‐air lysimeter no stimulation of the mineralization was observed. Extractions after incubation showed that only 10.2 to 18.6 % of the ¹⁴C‐activity applied with anilazine was extractable with acetone/CaCl₂. The major proportion was bound in the fractions of the soil organic matter, namely 45.0 to 59.6 % of the radiocarbon applied was accounted for by the humin fraction, 12.0 to 27.4 % by the fulvic acids, and 9.4 to 15.0 % by the humic acids. In the case of dihydroxy‐anilazine, 28.9 to 89.7 % of the applied ¹⁴C‐activity was extractable with acetone/CaCl₂. Of tJhe radiocarbon bound in the soil, the greatest proportion, i.e. 18.5 to 35.5 % of the radiocarbon applied, was accounted for by the fulvic acids.     

Chloroform – concentration gradients in soil air and atmospheric air,and emission fluxes from soil

Since we demonstrated the natural formation of chloroform in soil, the question arose to which extent this contributes to the chloroform present in the atmosphere. Concentration gradients in soil air and atmospheric air of different forests were measured. Chloroform concentration gradients indicating emission occur in forest soils and the atmosphere under the canopy, whereas this was not observed for other chlorinated solvents. Above the canopy all concentration gradients observed for chloroform and 1,1,1-trichloroethane indicate deposition. The emission flux was measured using enclosures and calculated from the observed concentration gradients in soil air and atmospheric air. Wood-degrading areas and soils with a humic layer were found to emit up to 1000 ng chloroform m⁻² h⁻¹ and seem to be larger chloroform sources than the other areas of study. Rather unexpectedly, some points of one sampling site appeared to emit 1,1,1-trichloroethane, tetrachloromethane and tetrachloroethene. A reasonable agreement was found between the fluxes using enclosures and those derived from the concentration gradients in soil air and atmospheric air.     

Effects of alternative electron donors,acceptors, and inhibitors on 2,4‐dichlorophenoxyacetic acid and 2,4,5‐trichlorophenoxyacetic acid dechlorination in soil

Abstract

The potential for dechlorinating 2,4‐dichlorophenoxyacetic acid (2,4‐D) and 2,4,5‐trichlorophenoxyacetic acid (2,4,5‐T) in soil with a consortium showing stable dechlorinating activity was investigated. The effects of adding electron donors and/or acceptors under three anaerobic reducing conditions was compared. Results show that both 2,4‐D and 2,4,5‐T dechlorination rates were enhanced in methanogenic conditions, delayed in sulfate‐reducing conditions, and inhibited in denitrifying conditions. Also under the same three conditions dechlorination was be enhanced by the addition of lactate, pyruvate, and acetate, delayed by the addition of manganese oxide and vitamin B₁₂, and inhibited by the addition of ferric chloride. Response to treatment with such microbial inhibitors as bromoethane sulfonic acid (BESA), vancomycin, and molybdate suggests that the major bacteria involved in 2,4‐D and 2,4,5‐T dechlonnation is methanogen followed joined by sulfate‐reducing bacteria and eubacteria.     

The rate of soil reduction as affected by levels of methyl parathion and 2, 4‐D

Abstract

A simple technique was demonstrated for determining the potential for synthetic organics to stress microbial populations. Oxidized Crowley and Cecil soil materials were amended with varying concentrations of 2,4‐D and methyl parathion, flooded, and then analyzed for changes in pH, redox potential, and levels of soluble plus exchangeable Fe, Mn, and Zn, all of which may be directly or indirectly influenced by the activity of soil microorganisms. At the concentrations tested (up to 75 ppm), there was little effect of 2,4‐D, but methyl parathion apparently did affect microbial activity contributing to changes in the measured soil properties upon flooding. This approach may be a useful technique for screening various compounds for their potential to stress microbial activity that, for many researchers, would be easier than direct observations of microbial parameters such as population numbers and classifications, and enzyme levels.     

Effects of conditioning,cross‐conditioning,and microbial growth on development of enhanced biodegradation of insecticides in soil

Abstract

Pretreatment of a Drummer‐Catlin soil mixture with granular formulations of carbofuran or trimethacarb enhanced biodegradation of subsequent treatments with the technical formulations. Degradation of carbofuran was enhanced by pretreatments with trimethacarb, and degradation of trimethacarb was enhanced by pretreatments with carbofuran. Bendiocarb degradation was enhanced by pretreatments of soil with carbofuran or trimethacarb. In bioassays with southern corn rootworm larvae, biological activity of carbofuran, trimethacarb, and bendiocarb was rapidly lost in soils pretreated with granular formulations. Pretreatment of soil with granular terbufos did not enhance the biodegradation of subsequent applications of technical terbufos. Several microbial biomass assays showed an increase in specific carbofuran‐degrading bacteria in soils that were pretreated with carbofuran. Bacteria were isolated that could grow on carbofuran and apparently degrade it when present with another carbon source.     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

Degradation of atrazine,metolachlor, and pendimethalin in pesticide‐contaminated soils: Effects of aged residues on soil respiration and plant survival

Abstract

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide‐contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160‐day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Applications of isotope differentiation for metabolic studies with di‐(2‐ethylhexyl) phthalate

Abstract

The pervasiveness of the plasticizer di‐(2‐ethylhexyl) phthalate (DEHP) in the environment and especially in the laboratory results in a background that may cause severe interference with analytical studies. Animal‐to‐animal variability in the distribution of DEHP metabolites in excreta normally makes it necessary to use large groups of animals when different treatments are compared. Finally, radioactive tracers are usually considered undesirable for metabolic studies involving human subjects. All of these problems can be overcome through the use of muliple isotopic labels, especially ¹²C/¹³C/¹⁴C. Examples are given involving rats and monkeys, and applicability to humans is discussed. The principles involved are not limited to any particular class of test compounds. In rats, the competing pathways for metabolism of phthalate esters produce a different distribution of metabolites from a small intravenous dose of DEHP than from a large oral dose.     

Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil

Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.     

Contributions to ecological chemistry CXII balance of conversion of buturon‐14C in wheat under outdoor conditions 1

Abstract

The urea herbicide buturon (N‐[p‐chlorophenyl] ‐N’ ‐methyl‐N’ ‐isobutinyl‐urea), ¹⁴C‐labeled, was sprayed on winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Upon harvest (three months after application), a total of 49. 2% of the applied radiocarbon was recovered: 2.0% in the plants, 46.9% in the soil, and 0.3% in the leaching water (depth > 50 cm); less than 0.1% was in the grains (0.464 ppm). Only about half of the radioactivity present in plants could be recovered under mild extraction conditions; about half of this was unchanged buturon. In straw and husk extracts, the following metabolites were identified by gaschromatography/mass spectrometry: N‐(p‐chlorophenyl)‐N‐methyl‐O‐methyl‐carbamate (metabolite I), N‐phenyl‐N’ ‐formyl‐urea (metabolite II), two unstable metabolites giving (p‐chlorophenyl)‐isocyanate upon purification (metabolites III and IV), N‐(p‐chlorophenyl)‐N’ ‐methyl‐N’ ‐isobutenylol‐urea (metabolite V), p‐chloroformanilide (metabolite VI) and biologically bound p‐chloroaniline (metabolite VII). In the root and basal stem extract, the following metabolites were identified by gas chromatography/mass spectrometry: N‐(p‐chlorophenyl)‐O‐methyl‐carbamate (metabolite VIII) and N‐(p‐chlorophenyl)‐N’ ‐methyl‐urea (metabolite IX).     

The variability of processes involved in transgene dispersal—case studies from Brassica and related genera

Background, aim, and scope

We strive to predict consequences of genetically modified plants (GMPs) being cultivated openly in the environment, as human and animal health, biodiversity, agricultural practise and farmers’ economy could be affected. Therefore, it is unfortunate that the risk assessment of GMPs is burdened by uncertainty. One of the reasons for the uncertainty is that the GMPs are interacting with the ecosystems at the release site thereby creating variability. This variability, e.g. in gene flow, makes consequence analysis difficult. The review illustrates the great uncertainty of results from gene-flow analysis.

Main features

Many independent experiments were performed on the individual processes in gene flow. The results comprise information both from laboratory, growth chambers and field trials, and they were generated using molecular or phenotypic markers and analysis of fitness parameters. Monitoring of the extent of spontaneous introgression in natural populations was also performed. Modelling was used as an additional tool to identify key parameters in gene flow.

Results

The GM plant may affect the environment directly or indirectly by dispersal of the transgene. Magnitude of the transgene dispersal will depend on the GM crop, the agricultural practise and the environment of the release site. From case-to-case these three factors provide a variability that is reflected in widely different likelihoods of transgene dispersal and fitness of introgressed plants. In the present review, this is illustrated through a bunch of examples mostly from our own research on oilseed rape, Brassica napus. In the Brassica cases, the variability affected all five main steps in the process of gene dispersal. The modelling performed suggests that in Brassica, differences in fitness among plant genome classes could be a dominant factor in the establishment and survival of introgressed populations.

Discussion

Up to now, experimental analyses have mainly focused on studying the many individual processes of gene flow. This can be criticised, as these experiments are normally carried out in widely different environments and with different genotypes, and thus providing bits and pieces difficult to assemble. Only few gene-flow studies have been performed in natural populations and over several plant generations, though this could give a more coherent and holistic view.

Conclusion

The variability inherent in the processes of gene flow in Brassica is apparent and remedies are wished for. One possibility is to expose the study species to additional experiments and monitoring, but this is costly and will likely not cover all possible scenarios. Another remedy is modelling gene flow. Modelling is a valuable tool in identifying key factors in the gene-flow process for which more knowledge is needed, and identifying parameters and processes which are relatively insensitive to change and therefore require less attention in future collections of data. But the interdependence between models and experimental data is extensive, as models depend on experimental data for their development or testing.

Recommendations

More and more transgenic varieties are being grown worldwide harbouring genes that might potentially affect the environment (e.g. drought tolerance, salt tolerance, disease tolerance, pharmaceutical genes). This calls for a thorough risk assessment. However, in Brassica, the limited and uncertain knowledge on gene flow is an obstacle to this. Modelling of gene flow should be optimised, and modelling outputs verified in targeted field studies and at the landscape level. Last but not least, it is important to remember that transgene flow in itself is not necessarily a thread, but it is the consequences of gene flow that may jeopardise the ecosystems and the agricultural production. This emphasises the importance of consequence analysis of genetically modified plants.