Relationship between herbicide concentration and the rates of enzymatic degradation of14C-diallate and14C-triallate in soil

The influence of concentration on the rates, routes and patterns of loss of [carbonyl-¹⁴C] diallate and [allyl-2-¹⁴C] triallate from an agricultural soil was studied in the laboratory for up to 52 weeks using an incubation system that allowed 95 to 98% recoveries of the added¹⁴C. Based on comparison of the half-lives, diallate was dissipated from soil at three to four times the rate of triallate at all five concentrations (0.25 to 50 g/g) tested. The major routes of loss, in descending order of importance, were degradation, bound residue formation, and volatilization. With both herbicides,¹⁴CO₂ was the only degradation product identified; however, large quantities of bound residue and traces of benzene- and water-soluble radioactivity were also detected. Evidence for the biodegradability of the bound residue of diallate was given. Although dissipation rates could not be described by zero-, half-, first-, or second-order kinetics, a reaction order between first- and second- was indicated. Enzymatic material in the soil had the potential to degrade at least one g/g diallate within 24 hr and 0.5 g/g triallate within 72 hr. However, when these quantities of herbicide were applied as initial dosages to the soil, measurable amounts of the parent molecules could be detected after 30 (diallate) and 52 (triallate) weeks of incubation. It was concluded that a primary factor influencing the rates of enzymatic degradation of herbicides in the soil is a physical separation of the herbicide molecules and the enzymatic systems responsible for degradation.     

Effects of the benzoxazoid DIMBOA, selected degradation products, and structure-related pesticides on soil organisms

Both lethal and sublethal effects of the benzoxazoid 2,4-dihydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA), the degradation products 6-methoxy-benzoxazolin-2(3H)-one (MBOA), 2-amino-7-methoxy-(3H)-phenoxazin-3-one (AMPO), and 2-acetylamino-7-methoxy-3(H)-phenoxazin-3-one (AAMPO) and the structure-related compounds 2-methoxy-N-(2-oxo-1,3-oxazolidin-3yl)acet-2'=6'-xylidide (oxadixyl), and O,O-diethyl S-[6-chloro-2-oxobenzoxazolin-3-yl)methyl]phosphorodithioate (phosalone) on the collembola Folsomia candida and on the carabid beetle Poecilus cupreus (except phosalone) were determined. Validated laboratory standard methods including reference and control treatments were applied in compliance with prescribed validity criteria. A risk assessment according to the EPPO risk assessment scheme for plant protection products (2003) was carried out. DIMBOA, MBOA, AMPO, AAMPO, and oxadixyl were classified as low-risk compounds for both test organisms. The reference compounds methyl-m-hydroxy-carbanilate-methyl-carbanilate (phenmedipham) and O,O-dimethyl S-[2-(methylamino)-2-oxoethyl]phosphoro-dithioate (dimethoate) were of low and medium risk respectively, to F. candida, but final assessment of the risk to P. cupreus requires further testing. Phosalone was of high risk to F. candida. The results obtained suggest that neither DIMBOA nor the tested degradation products pose a risk to either nontarget soil organism in the field.     

Influence of sewage and pharmaceuticals on soil microbial function

Although sewage effluent application to land is a common approach to recycle water and provide nutrients to plants, bioactive pharmaceuticals contained in sewage may change soil quality by affecting soil microbial communities. Establishing causal effects, however, is difficult, because trace levels of pharmaceuticals are confounded with other effluent constituents. Therefore, two originally similar soil microbial communities, one irrigated in situ with sewage effluent for 12 years and another nonirrigated, were exposed to high levels of acetaminophen, aspirin, carbamazepine, chlorpromazine, and tetracycline. The objectives of the current study were to determine the influence of high levels of pharmaceuticals on several soil microbial properties, the effect that prolonged effluent irrigation with ambient levels of pharmaceuticals had on soil microbial function, and how this effect would change in response to pharmaceutical exposure. Several pharmaceuticals, at high exposure levels, imposed stress on the soil microbial community as judged by increased CO(2) respiration, decreased biomass carbon, and altered substrate utilization affinities. Prolonged effluent irrigation, which altered the genetic fingerprint of the microbial community, also mitigated the response that exposure to pharmaceuticals had on the microbial community and enabled degradation of the antimicrobial salicylic acid after aspirin exposure. In conclusion, prolonged irrigation with sewage effluent containing pharmaceuticals at ambient levels influenced the microbial community so that they were able to better cope with sudden exposure to high levels of pharmaceuticals.     

Enhancement of aerobic microbial degradation of polychlorinated biphenyl in soil microcosms

This article reports the results of various biodegradation experiments on polychlorinated biphenyl (PCB)-contaminated sandy soil employing a mixed culture of acclimatized bacteria. Following the optimization of different variables without chemical pretreatment, the elimination rate achieved of Aroclor 1242 in slurry-phase reactors was 61% after four months of treatment, with the presence of biphenyl as cosubstrate being the most important factor affecting PCB biodegradation. The biodegradation occurred as a first-order process, and it proved most effective in respect to dichlorinated biphenyls (100% removal), followed by trichlorinated (92%) and tetrachlorinated biphenyls (24%). The results also showed that the degradability of PCBs in soil may be enhanced by an advanced oxidation pretreatment (Fenton reaction), producing almost 100% elimination of PCBs at the end of the integrated chemical-biological process and 72% mineralization of the intermediates generated during the chemical pretreatment.     

Leaching and degradation of 4-aminopyridine-14C in several soil systems

Leaching and degradation of 4-aminopyridine (a frightening agent for protecting grain crops from blackbirds) was studied in seven soils. Carbon-14-labeled 4-aminopyridine was strongly adsorbed onto soil colloids, with the degree of adsorption related to pH. Application of seven in. of simulated rainfall over 20 days to surface-treated alkaline soils leached 0.02% to 0.18% of the¹⁴C; radioactivity was detected in the runoff from only one of the four acidic soils. Degradation of 4-aminopyridine-¹⁴C to¹⁴CO₂ was negligible in soils incubated up to two months under anaerobic conditions. Under aerobic incubation, there was a one-week lag before extensive breakdown began. Degradation rates increased with increasing temperature and soil moisture during incubation, but soil composition had a greater influence. After three months at 30°C and 50% moisture, evolution of¹⁴CO₂ ranged from 0.4% for a highly acidic loam (pH 4.1) to more than 50% for a lighter-textured, alkaline, loamy sand (pH 7.8); the half-life of 4-aminopyridine in soils under these test conditions ranged from 3 to more than 22 months. A theoretical scheme is presented for the degradation of 4-aminopyridine in soils.     

Agricultural pesticides and selected degradation products in five tidal regions and the main stem of Chesapeake Bay, USA

Nutrients, sediment, and toxics from water sources and the surrounding airshed are major problems contributing to poor water quality in many regions of the Chesapeake Bay, an important estuary located in the mid-Atlantic region of the United States. During the early spring of 2000, surface water samples were collected for pesticide analysis from 18 stations spanning the Chesapeake Bay. In a separate effort from July to September of 2004, 61 stations within several tidal regions were characterized with respect to 21 pesticides and 11 of their degradation products. Three regions were located on the agricultural Delmarva Peninsula: The Chester, Nanticoke, and Pocomoke Rivers. Two regions were located on the more urban western shore: The Rhode and South Rivers and the Lower Mobjack Bay, including the Back and Poquoson Rivers. In both studies, herbicides and their degradation products were the most frequently detected chemicals. In 2000, atrazine and metolachlor were found at all 18 stations. In 2004, the highest parent herbicide concentrations were found in the upstream region of Chester River. The highest concentration for any analyte in these studies was for the ethane sulfonic acid of metolachlor (MESA) at 2,900 ng/L in the Nanticoke River. The degradation product MESA also had the greatest concentration of any analyte in the Pocomoke River (2,100 ng/L) and in the Chester River (1,200 ng/L). In the agricultural tributaries, herbicide degradation product concentrations were more strongly correlated with salinity than the parent herbicides. In the two nonagricultural watersheds on the western shore, no gradient in herbicide concentrations was observed, indicating the pesticide source to these areas was water from the Bay main stem.     

Influence of earthworm activity on microbial communities related with the degradation of persistent pollutants

Earthworms may promote the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in soil, but the mechanism through which they exert such influence is still unknown. To determine if the stimulation of PAH degradation by earthworms is related to changes in microbial communities, a microcosm experiment was conducted consisting of columns with natural uncontaminated soil covered with PAH-contaminated dredge sediment. Columns without and with low and high Eisenia andrei densities were prepared. Organic matter and PAH content, microbial biomass, and dehydrogenase activity (DHA) were measured in soil and sediment over time. Biolog Ecoplate? and polymerase chain reaction using denaturing gradient gel electrophoresis were used to evaluate changes in metabolic and structural diversity of the microbial community, respectively. Earthworm activity promoted PAH degradation in soil, which was significant for biphenyl, benzo[a]pyrene, and benzo[e]pyrene. Microbial biomass and DHA activity generally did not change over the experiment. Earthworm activity did change microbial community structure, but this did not affect its functioning in terms of carbon substrate consumption. Results suggest no relationship between changes in the microbial community by earthworm activity and increased PAH disappearance. The role of shifts in soil microbial community structure induced by earthworms in PAH removal needs further investigation.     

Some considerations on the safety evaluation of nonviral microbial pesticides

The tactics and rationale of maximum challenge safety tests for nonviral microbial pesticides have been reviewed. Maximum challenge tests and a tier approach to data collection for regulatory purposes offer the best opportunities to detect the acute effects of entomopathogenic organisms in mammals. Premature condemnation of promising organisms that are based on incomplete results of maximum challenge tests must be avoided. Further investigations should be conducted on the role of mammalian immune response in resistance to entomopathogenic organisms and on the value of medium- or long-term exposure tests.     

Endocrine-disrupting pesticides and selected hormonally dependent cancers

Pesticides and other endocrine disrupters represent a credible "new" risk factor for hormonally dependent cancers. To date, most work has centered on breast cancer, and most studies have not shown increased risks. Additional epidemiologic investigations are warranted, but they would benefit from a better understanding of the mechanisms, dose, and co-factors involved.     

Fate and stability of 14C-labeled 2,4,6-trinitrotoluene in contaminated soil following microbial bioremediation processes

Biological treatment of 2,4,6-trinitrotoluene (TNT) in soil rarely results in complete mineralization of the parent compound. More often, the largest proportion of the TNT carbon is incorporated into the soil organic matrix. Therefore, we evaluated the stability of nonextractable residues from various bioremediation processes of 14C-TNT in soils. The extractable amounts of the residual radioactivity varied between 7 and 33% and thus the nonextractable amount between 93 and 67% (3-15% in fulvic acids, 26-46% in humic acids, and 27-44% in the humin fraction). The residue-containing soils were analyzed for the release of radioactivity after treatment by physical (freeze and thaw, grinding of soil, and steam extraction), chemical (acid rain and addition of metal complexing agent), and biological methods (addition of compost, white rot fungi, radical-generating enzymes, and germination of plants). Freeze and thaw treatment and grinding of the soil did not alter the partitioning of the label significantly. Steam extraction and acid rain extraction increased the water extractability to 11 to 29% and to 51.6% in the native TNT-contaminated soil. The addition of ethylenediamine-tetraacetate (EDTA) increased the extractability from 7 to 12%. After biological treatment, only slightly increased extractability (<10%) was observed. No increase of extractable TNT or known metabolites was observed with any of the treatments. Thus, under the treatment conditions applied in this study, the residues formed during microbial transformation of TNT may be biogenic residues with low mobilization potential and low hazardous impact.     

Dietary exposures to selected metals and pesticides.

Average daily dietary exposures to 11 contaminants were estimated for approximately 120,000 U.S. adults by combining data on annual diet, as measured by a food frequency questionnaire, with contaminant residue data for table-ready foods that were collected as part of the annual U.S. Food and Drug Administration Total Diet Study. The contaminants included in the analysis were four heavy metals (arsenic, cadmium, lead, mercury), three organophosphate pesticides (chlorpyrifos, diazinon, malathion), and four organochlorine pesticides (dieldrin, p,p'-DDE, lindane, heptachlor epoxide). Dietary exposures to these contaminants were highly variable among individuals, spanning two to three orders of magnitude. Intraindividual exposures to the metals, organophosphates, and organochlorines were estimated to be strongly correlated; Pearson's correlation coefficients ranged from 0.28 for lindane:dieldrin to 0.84 for lead:mercury. For some of the compounds (e.g., arsenic and dieldrin), a substantial fraction of the population was estimated to have dietary intakes in excess of health-based standards established by the EPA. Before use for risk assessment or epidemiologic purposes, however, the validity of the exposure estimates must be evaluated by comparison with biological indicators of chronic exposure. Because of their low detection rate in table-ready foods, the estimated distributions of exposures for dieldrin, p,p'-DDE, heptachlor epoxide, lindane, diazinon, and chlorpyrifos were found to be sensitive to assumed values for nondetect samples. Reliable estimates of the population distribution of dietary exposures to most other contaminants cannot be made currently, due to their low rate of detection in table-ready foods. Monitoring programs that use more sensitive study designs and population-based assessments for other subpopulations should be a priority for future research.