Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).     

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.     

Plant uptake and dissipation of PBDEs in the soils of electronic waste recycling sites

Plant uptake and dissipation of weathered PBDEs in the soils of e-waste recycling sites were investigated in a greenhouse study. Eighteen PBDE congeners (tri- through deca-) were detected in the plant tissues. The proportion of lower brominated PBDEs (mono- through hexa-) in plant roots was higher than that in the soils. A concentration gradient was observed of PBDEs in plants with the highest concentrations in the roots followed by the stems and lowest in the leaves. Reduction rates of the total PBDEs in the soils ranged from 13.3 to 21.7% after plant harvest and lower brominated PBDEs were associated with a higher tendency to dissipate than the higher brominated PBDEs. This study provides the first evidence for plant uptake of weathered PBDEs in the soils of e-waste recycling sites and planting contributes to the removal of PBDEs in e-waste contaminated soils.     

Effects of different treatments on soil-borne DDT and HCH dynamics and plant uptake

Pot experiments were conducted to examine the effects of various fertilizers, as well as soil dilution treatments on the dynamics of soil-borne DDTs [sum of dichlorodiphenyltrichloroethane (DDT), chlorodiphenyldichloroethylene (DDE) and di- chlorodiphenyldichloroethane (DDD)] and hexachlorocyclohexanes (HCHs, sum of α-HCH, β-HCH, γ-HCH and δ-HCH) and their subsequent impacts on the uptake of DDTs and HCHs by a test plant. The results show that the soil residual DDTs and HCHs concentrations in the iron-rich fertilizer-treated soil were significantly lower than those in other fertilizer-treated soils. There was a close relationship between the soil residual DDTs and the plant tissue DDTs. This suggests that the uptake rate of DDTs by the plant was dependent on the concentration of soil-borne DDTs. A less close relationship between soil residual HCHs and plant tissue HCHs was also observed. Dilution of pesticide-contaminated soil with the non-contaminated soil not only physically reduced the concentration of pesticides in the soil but also enhanced the loss of soil-borne pesticides, possibly through the improvement of soil conditions for microbial degradation. Soil dilution had a better effect on promoting the loss of soil-borne HCHs, relative to soil-borne-DDTs. The research findings obtained from this study have implications for management of heavily contaminated soils with DDTs and HCHs. Remediation of DDTs and HCHs-contaminated soils in a cost-effective way can be achieved by incorporating treatment techniques into conventional agricultural practices. Applications of iron-rich fertilizer and soil dilution treatments could cost-effectively reduce soil-borne DDTs and HCHs, and subsequently the uptake of these organochlorine pesticides by vegetables.     

芽孢杆菌DQ02吸附摄取、运输和降解正十六烷的机理研究

使用大庆油田石油污染土壤中分离出的优势菌种(芽孢杆菌DQ02),研究其对正十六烷吸附摄取、运输和降解的机理.结果表明,芽孢杆菌DQ02细胞可能与比其小得多的被溶解、似溶解的烷烃颗粒作用,也可能会与比细胞大的烷烃颗粒直接接触这种方式摄取正十六烷,并且DQ02对正十六烷的吸附过程为快速表面吸附过程.芽孢杆菌DQ02运输正十...     

The persistence of insecticidal chemicals in soils treated with granular formulations of disulfoton and their uptake by potato plants

Abstract

Potatoes were grown from cut seed in Plainfield sand treated in‐furrow with disulfoton (Di‐Syston 15G, 3.36 kg Al/ha) in 1983 and from whole seed in similarly treated loam in 1991. Soils were contained in 2 m² field plots. Soil, seed potato and foliage were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 8–12 wk following planting. Disulfoton disappeared at different rates from the two soils (k_sand=0.024 day^‐1, k_loam=0.056 day^‐1) with partial conversion to the sulfoxide and sulfone in both. Larger quantities of the three insecticidal components were absorbed by the seed potato in the cut‐seed/sand combination. The relative amounts of these components in the seed potato also differed between treatments with disulfoton being the largest component of the cut‐seed/sand and smallest in the whole‐seed/loam. Disulfoton sulfoxide and sulfone were the major insecticidal components of the foliage and concentrations in the initial foliage (each ca. 10 ppm) were similar for both treatments. Sulfoxide concentrations in the foliage decreased more rapidly than the sulfone and the decrease in concentration of each of the components was similar for the two treatments.     

The persistence of insecticidal chemicals in soils treated with granular formulations of aldicarb and their uptake by potato plants

Abstract

Potatoes were grown in Plainfield sand and muck treated, in furrow, with aldicarb (Temik 15G, 3.36 kg Al/ha). .Soils were contained in 2 m^z field plots and had not been treated previously with pesticides. Soil, seed pieces, foliage and tubers were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 12 wk following planting. The disappearance of aldicarb from the soil was accompanied by partial conversion to the sulfoxide and sulfone. After increasing rapidly during the first 2 wk, the aldicarb concentration in the seed piece declined and a similar concentration of aldicarb sulfoxide accumulated which subsequently slowly disappeared. Aldicarb sulfoxide was the major insecticidal material in the new foliage. High initial concentrations, observed at 3–4 wk, declined by about 90% after 6 wk. Aldicarb sulfoxide residues of 2–4 ppm in the first new tubers at 6 wk declined by 90% by 12 wk. Potatoes were also grown under greenhouse conditions in Plainfield sand treated with Temik 10G at rates equivalent to 1.68, 3.36 and 6.72 kg Al/ha. Maximum aldicarb sulfoxide concentrations in soil, seed piece and foliage increased with application rate. The sulfoxide was much more persistent in the soil and foliage than in the field experiment indicating the importance of environmental factors to its behaviour in both soil and potato plants.     

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.     

Chemical leasing: cooperative business models for sustainable chemicals management. Summary of research projects commissioned by the Austrian Federal Ministry of Agriculture, Forestry, Environment and Water Management

- Sustainable chemistry - Section editors: Klaus Günter Steinhäuser, Steffi Richter, Petra Greiner, Jutta Penning, Michael AngrickBackground, Aim and Scope Chemicals play a vital role in the day-to-day life of industrialised societies. Their use is not restricted to the chemical enterprises per se, but is a crucial part of production processes in a lot of industrial sectors. Traditional instruments of environmental policy (such as bans, restrictions) can only deal with the most hazardous substances. The Johannesburg Implementation Plan of 2002 calls for more sustainable patterns of production and consumption, and sets the year of 2020 as a goal to use chemicals in a way that human health and the environment are not endangered. Political instruments should not only gather more knowledge about the properties of chemicals, but should also stimulate the environmentally sound use of chemicals. Existing business models should therefore be reviewed in relation to this strategic approach to encourage marketing options with respect to the environmental focus.Main Features Business models were examined for their effects on the consumption of chemicals and amount of waste emissions in relation to their economic potential. Different possibilities for cooperation of supplier, user and disposal companies were elaborated and examined with a view to the specific situation in Austria.Results and Discussion A range of cooperative models – summarised under the term ‘chemical leasing’ - was identified, which can contribute to a more efficient use of resources. 12 main possible application areas (cleaning, lubrication, paint stripping and others) have been identified in Austria. If chemical leasing models were applied in these areas, the amounts of chemicals currently used could be reduced by one third (53,000 tonnes per year). Cost reductions of up to 15 % can be expected.Conclusion The application of chemical leasing models can contribute considerably to achieving more sustainable and resource-efficient patterns of production. The Austrian Ministry for Environment has therefore decided to subsidise the further practical implementation of these new service-oriented business models. Pilot projects in 4 enterprises, which are supervised by consulting companies, are currently being carried out. Recommendation and Outlook The experiences of the pilot projects will serve as valuable building blocks for the wider use of chemical leasing models. Furthermore, the UNIDO Cleaner Production Centres have expressed their clear interest and will examine the possibility to use chemical leasing as a part of their Cleaner Production Programmes.     

The critical levels and the maximum metal uptake for wheat and rice plants when applying metal oxides to soil

Abstract

Wheat is more sensitivity to CdO and ZnO compared with rice plant. The yield of wheat decreased by 30% in the presence of 30 ppm Cd, but that of rice plants by only 8%. The critical levels of meal uptake by wheat and rice plants for applying metal oxides to soil (CdO, ZnO, PbO) were determined. The highest concentration obtained for wheat grain was 141 μg/g Cd at the Cd 10,000 ppm in soil. This value is higher the value of 4.97 μg/g for unpolished rice and higher than any other we have seen in the reports for treatment with CdO. Also, as concentration of more than 1.0 μg/g Cd in wheat was obsertced at 5 ppm Cd, while similar concentrations for rice plants were observed at 30 ppm Cd in soil.     

15N Metabolic test for the determination of phytotoxic effects of chemicals and contaminated environmental samples

A stable isotope¹⁵N-nitrogen test (ESIMA = Ecotoxicological Stable Isotope Metabolic Assay) was developed to assess biological effects and the potential toxicological hazard of chemicals and contaminated environmental samples on plant metabolism. The assay measures the effect of toxicants on the incorporation of a¹⁵N labelled tracer into the total nitrogen fraction (both the nonprotein and protein fraction) of plants. Segments ofPisum arvense epicotyls are used as test substrates because of their high metabolic activity. The plant material is incubated under standardised conditions for two hours; subsequently¹⁵N incorporation is analysed by determining the¹⁵N abundance (¹⁵N atom-%) in the epicotyl segments. The effects of toxicants are evaluated by comparing the¹⁵N incorporation rates of control tissue and epicotyl segments exposed to individual chemicals or complex environmental samples. The specificity and sensitivity of effects as indicated by ESIMA were compared with effects as measured by two established ecotoxicological bioassays, the pollen tube growth test using pollen ofNicotiana sylvestris and the bacterial luminescence inhibition test using pollen ofPhotobacterium phosphoreum. The results of the study clearly indicate the suitability of ESIMA for assessing toxic impacts on plant nitrogen metabolism. Prof. Dr. habil. Hans Faust dedicated to his 70^th birthday.     

Development of models for predicting toxicity from sediment chemistry by partial least squares-discriminant analysis and counter-propagation artificial neural networks

There is strong interest in developing tools to link chemical concentrations of contaminants to the potential for observing sediment toxicity that can be used in initial screening-level sediment quality assessments. This paper presents new approaches for predicting toxicity in sediments, based on 10-day survival tests with marine amphipods, from sediment chemistry, by means of the application of Partial Least Squares-Discriminant Analysis (PLS-DA) and Counter-propagation Artificial Neural Networks (CP-ANNs) to large historical databases of chemical and toxicity data. The exploration of the internal structure of the developed models revealed inherent limitations of predicting toxicity from common chemical analyses of bulk contaminant concentrations. However, the results obtained in the validation of these models combined relevant values of non-error classification rate, sensitivity and specificity of, respectively, 76, 87 and 73% with PLS-DA and 92, 75 and 97% with CP-ANNs, outperforming the results reported for previous approaches.     

Prospects and limitations of phytoremediation for the removal of persistent pesticides in the environment

The environmental problems that have arisen from the use of persistent pesticides in the past, and potential sources of further contamination have been discussed. The potential and limitations of phytoremediation for removal of pesticides in the environment have been reviewed. The enzymatic processes in plants that are known to be involved in phytodegradation of pesticides, and possibilities for enhancing them have also been discussed.     

Response surface models for the formation of PCDD and PCDF in a pilot plant combustion of MSW

Experimental data on PCDD and PCDF emissions in raw gases from municipal solid waste combustion in a pilot plant were processed by Response Surface models to gain information on process parameter values which minimize both the total PCDD/PCDF concentrations and those of a selected congener group.     

First report on development of quantitative interspecies structure-carcinogenicity relationship models and exploring discriminatory features for rodent carcinogenicity of diverse organic chemicals using OECD guidelines

Different regulatory agencies in food and drug administration and environmental protection worldwide are employing quantitative structure-activity relationship (QSAR) models to fill the data gaps related with properties of chemicals affecting the environment and human health. Carcinogenicity is a toxicity endpoint of major concern in recent times. Interspecies toxicity correlations may provide a tool for estimating sensitivity towards toxic chemical exposure with known levels of uncertainty for a diversity of wildlife species. In this background, we have developed quantitative interspecies structure-carcinogenicity correlation models for rat and mouse [rodent species according to the Organization for Economic Cooperation and Development (OECD) guidelines] based on the carcinogenic potential of 166 organic chemicals with wide diversity of molecular structures, spanning a large number of chemical classes and biological mechanisms. All the developed models have been assessed according to the OECD principles for the validation of QSAR models. Consensus predictions for carcinogenicity of the individual compounds are presented here for any one species when the data for the other species are available. Informative illustrations of the contributing structural fragments of chemicals which are responsible for specific carcinogenicity endpoints are identified by the developed models. The models have also been used to predict mouse carcinogenicities of 247 organic chemicals (for which rat carcinogenicities are present) and rat carcinogenicities of 150 chemicals (for which mouse carcinogenicities are present). Discriminatory features for rat and mouse carcinogenicity values have also been explored.     

Development of a nonlocal convective mixing scheme with varying upward mixing rates for use in air quality and chemical transport models

BACKGROUND, AIM, AND SCOPE: Asymmetrical convective non-local scheme (CON) with varying upward mixing rates is developed for simulation of vertical turbulent mixing in the convective boundary layer in air quality and chemical transport models. MATERIALS AND METHODS: The upward mixing rate form the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. RESULTS: This scheme provides a less rapid mass transport out of surface layer into other layers than other asymmetrical convective mixing schemes. DISCUSSION: In this paper, we studied the performance of a nonlocal convective mixing scheme with varying upward mixing in the atmospheric boundary layer and its impact on the concentration of pollutants calculated with chemical and air-quality models. This scheme was additionally compared versus a local eddy-diffusivity scheme (KSC). Simulated concentrations of NO(2) and the nitrate wet deposition by the CON scheme are closer to the observations when compared to those obtained from using the KSC scheme. CONCLUSIONS: Concentrations calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme (of the order of 15-20%). Nitrate wet deposition calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme. RECOMMENDATIONS AND PERSPECTIVES: To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO(2)) and nitrate wet deposition was compared for the year 2002. The comparison was made for the whole domain used in simulations performed by the chemical European Monitoring and Evaluation Programme Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

Development and testing of radionuclide transport models for fractured rock: examples from the Nagra/JNC Radionuclide Migration Programme in the Grimsel Test Site, Switzerland

The joint Swiss National Co-operative for the Disposal of Radioactive Waste (Nagra)/Japan Nuclear Cycle Development Institute (JNC) Radionuclide Migration Programme has now been on-going for over a decade in Nagra's Grimsel Test Site (GTS). The main aim of the programme has been the direct testing of radionuclide transport models in as realistic manner as possible. Although it will never be possible to fully test these models due to the large time and distance scales involved, tests of the model assumptions in scaled down but otherwise realistic conditions will contribute to developing confidence in the predictive power of the models. In this paper, the Nagra/JNC approach is highlighted with examples from a large programme of field, laboratory and natural analogue studies based around the GTS. The successes and failures are discussed as in the general approach to the thorough testing of predictive transport codes which will be used in repository performance assessment (PA). Some of the work is still on-going and this represents the first presentation of a unique set of results and conclusions.