Application of the health risk assessment of acetochlor in the development of water quality criteria.

Acetochlor is a widely used herbicide in agricultural production. Studies have shown that acetochlor has obvious environmental hormone effects, and long-term exposure may pose a threat to human health. To quantify the hazards of acetochlor in drinking water, a health risk assessment of acetochlor was conducted in major cities of China based on the data of acetochlor residue concentrations in drinking water. The approach of the Species Sensitivity Distributions (SSD) method is used to extrapolate from animal testing data to reflect worst case human toxicity. Results show that hazard quotients related to acetochlor residues in drinking water for different age groups range from 1.94 × 10-4 to 6.13 × 10-4, so, there are no indication of human risk. Compared to the total estimated hazard quotient from oral intake of acetochlor, the chronic exposure imputed to acetochlor residues in drinking water in China accounts for 0.4%. This paper recommends 0.02 mg/L to be the maximum acetochlor residue concentration level in drinking water and source water criteria.

Sensitive Determination of Acetochlor, Alachlor, Metolachlor and Fenthion Utilizing Mechanical Shaking Assisted Dispersive Liquid-Liquid Microextraction Prior to Gas Chromatography-Mass Spectrometry.

A green, sensitive and accurate dispersive liquid-liquid microextraction (DLLME) method was used to preconcentrate four selected pesticides in dam lake water samples for determination by gas chromatography-mass spectrometry (GC-MS). Conditions of the DLLME method were comprehensively investigated and optimized according to type/volume of extraction solvent, type/volume of dispersive solvent, and type/period of mixing. The developed method was validated according to the limits of detection and quantitation, accuracy, precision and linearity. Under the optimum conditions, limit of detection values calculated for alachlor, acetochlor, metolachlor and fenthion were 1.7, 1.7, 0.2 and 7.8 µg/kg (mass based), respectively. The method recorded 202, 104, 275 and 165 folds improvement in detection power values for acetochlor, alachlor, metolachlor and fenthion, respectively, when compared with direct GC-MS measurements. In order to evaluate the accuracy of the developed method, real sample application with spiking experiments was performed on dam lake water samples, and satisfactory percent recovery results in the range of 81%-120% were obtained.

Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor.

A gas chromatography-single quadrupole mass spectrometry method was developed and validated for compound-specific chlorine isotope analysis (Cl-CSIA) of three chlorinated herbicides, atrazine, acetochlor, and metolachlor, which are widespread contaminants in the environment. For each compound, the two most abundant ions containing chlorine (202/200 for atrazine, 225/223 for acetochlor, and 240/238 for metolachlor) and a dwell time of 30 ms were determined as optimized MS parameters. A limit of precise isotope analysis for ethyl acetate solutions of 10 mg/L atrazine, 10 mg/L acetochlor, and 5 mg/L metolachlor could be reached with an associated uncertainty between 0.5 and 1‰. To this end, samples were measured 10-fold and bracketed with two calibration standards that covered a wide range of δ37Cl values and for which amplitudes matched those of the samples within 20% tolerance. The method was applied to investigate chlorine isotope fractionation during alkaline hydrolysis of metolachlor, which showed a shift in δ37Cl of +46‰ after 98% degradation, demonstrating that chlorine isotope fractionation could be a sensitive indicator of transformation processes even when limited degradation occurs. This method, combined with large-volume solid-phase extraction (SPE), allowed application of Cl-CSIA to environmentally relevant concentrations of widespread herbicides (i.e., 0.5-5 µg/L in water before extraction). Therefore, the combination of large-volume SPE and Cl-CSIA is a promising tool for assessing the transformation processes of these pollutants in the environment.

Determination of pararosaniline hydrochloride in workplace air.

Pararosaniline hydrochloride (CPR) is a dye used for colouring paper, leather and natural and artificial fibres. It is also used in analytical and microbiological laboratories. It is a carcinogenic substance of category 1B. In analytical chemistry, it is used for detecting the following among others: bromates, formaldehyde, ozone, sulphite and sulfur dioxide. CPR is a dye commonly used in microbiology for staining preparations, for staining bacteria, antibodies or other organisms. In Poland, about 800 employees were exposed to this substance. The lack of methods for the determination of pararosaniline hydrochloride in workplace air makes it impossible to assess the occupational exposure of workers to this substance. For this reason, a determination method has been developed, which allows for the determination of pararosaniline hydrochloride in the air. This method makes it possible to determine the concentration of CPR in the air at the workplace within the range from 0.002 to 0.04 mg/m3 (for an air sample of 120 L). The method is based on the adsorption of pararosaniline hydrochloride present in the workplace air on a polypropylene filter, eluting the substance deposited on the filter with methanol and analysing the solution thus obtained using high-performance liquid chromatography with a diode array detector (wavelength of 544 nm). Using an Ultra C18 (250 mm length) chromatographic column at a temperature of 23 °C and the mobile phase of methanol:0.1% phosphoric acid(V) (95:5, v/v) at flow rate of 0.6 mL/min makes it possible to determine the content of pararosaniline hydrochloride in the presence of aniline, nitrobenzene and 4-tolylamine. Limit of detection and limit of quantification were 0.17 ng/mL and 0.51 ng/mL, respectively.

Development and validation of stability indicating reversed-phase liquid chromatographic method for simultaneous quantification of methotrexate and teriflunomide in nanoparticles and marketed formulation.

Methotrexate (MTX) and teriflunomide (TEF) are the two most effective disease-modifying antirheumatic drugs used as combination therapy for rheumatoid arthritis and no robust high-performance liquid chromatography (HPLC) method is available for their simultaneous estimation to date. Therefore, we have developed and validated an isocratic reversed-phase HPLC method for simultaneous analysis of MTX and TEF spiked in the form of active pharmaceutical ingredients, tablets and nanoformulations. The best separation was achieved on a BDS, C18 , 4.6 × 250 mm, 5 µm analytical column (Thermo Hypersil) with methanol-ethylammonium formate-potassium dihydrogen phosphate buffer (55 mm, pH 3.5; 65:5:30, v/v) as mobile phase at a flow rate of 0.8 mL/min. All the samples were subjected to force degradation studies. Responses of MTX and TEF were found to be a linear function of concentration over the range 1-50 µg/mL (r2 = 0.9976 and 0.9982). The limits of detection and limit of quantification were 7.74 and 25.82 ng/mL and 10.74 and 35.80 ng/mL, respectively. Degradation products produced under the stress studies did not interfere with the detection of MTX and TEF and therefore the developed method can be regarded as stability indicating.

Comparison of Some Soil Fungi in Bioremediation of Herbicide Acetochlor Under Agitated Culture Media.

In this study, we aimed to find out the biodegradation efficiency of some soil fungi types on herbicide acetochlor with acetochlor active material, chemical oxygen demand (COD), biochemical oxygen demand (BOD5) and total organic carbon (TOC) parameters. We also try to determine the population dynamics of these fungi via turbidity. The fungi cultures were isolated from agricultural field in in Thrace region of Turkey. Each fungi enriched in malt extract broth media and 1 mL of these enriched media was inoculated into 100 mL of acetochlor solutions that suggested for using application concantrations in agricultural field for farmers (11000 mg L-1) for sunflower and corn agriculture. Bioremediation results of acetochlor have shown different results according to the types of fungi. Our results indicate that Tolypocladium geodes and Cordyceps cicadae might be used in acetochlor bioremediation with a significant acetochlor, COD, TOC and BOD5 reduction and can be used for rehabilitation of agricultural fields or receiving environments for removal the opposite effects of acetochlor or other herbicides.

Homogeneous liquid-liquid extraction coupled to ion mobility spectrometry for the determination of p-toluidine in water samples.

In this research, homogeneous liquid-liquid extraction followed by ion mobility spectrometry (HLLE-IMS) with corona discharge ionization source has been developed for the determination of p-toluidine. The analyte was extracted by single-phase extraction in a ternary solvent system and then the extracted p-toluidine was injected into IMS for analysis. Optimization of different parameters which could influence HLLE-IMS was performed. Under optimum conditions, the dynamic linear range was obtained over 2.0-40.0 ng/mL with R (2) = 0.9966 while relative standard deviation was below 10 %. The limits of detection and quantification were 0.6 and 2.0 ng/mL of p-toluidine, respectively. The proposed method was applied to determine p-toluidine in environmental water samples which resulted in acceptable recoveries of the analyte, ranging from 85.3 %-90 %.

Sensitive ionization of non-volatile analytes using protein solutions as spray liquid in desorption electrospray ionization mass spectrometry.

RATIONALE: Desorption electrospray ionization (DESI) is the most popular ambient ionization technique for direct analysis of complex samples without sample pretreatment. However, for many applications, especially for trace analysis, it is of interest to improve the sensitivity of DESI-mass spectrometry (MS). METHODS: In traditional DESI-MS, a mixture of methanol/water/acetic acid is usually used to generate the primary ions. In this article, dilute protein solutions were electrosprayed in the DESI method to create multiply charged primary ions for the desorption ionization of trace analytes on various surfaces (e.g., filter paper, glass, Al-foil) without any sample pretreatment. The analyte ions were then detected and structurally characterized using a LTQ XL mass spectrometer. RESULTS: Compared with the methanol/water/acetic acid (49:49:2, v/v/v) solution, protein solutions significantly increased the signal levels of non-volatile compounds such as benzoic acid, TNT, o-toluidine, peptide and insulin in either positive or negative ion detection mode. For all the analytes tested, the limits of detection (LODs) were reduced to about half of the original values which were obtained using traditional DESI. The results showed that the signal enhancement is highly correlated with the molecular weight of the proteins and the selected solid surfaces. CONCLUSIONS: The proposed DESI method is a universal strategy for rapid and sensitive detection of trace amounts of strongly bound and/or non-volatile analytes, including explosives, peptides, and proteins. The results indicate that the sensitivity of DESI can be further improved by selecting larger proteins and appropriate solid surfaces.

Assessment of groundwater pollution in Tokyo using PPCPs as sewage markers.

While the occurrence of pharmaceuticals and personal care products (PPCPs) in groundwater has typically been reported in bank filtration sites, irrigated fields, septic tanks, and sewage disposal practices, fewer studies have been conducted in highly urbanized areas, where infiltration of treated or untreated sewage is not supposed to be a source of groundwater recharge. Furthermore, little is known about the occurrence of various kinds of PPCPs in relation to microbial indicators in groundwater from different types of aquifers. Thus, we examined the city-wide occurrence of selected PPCPs (diethyltoluamide, crotamiton, ethenzamide, propyphenazone, carbamazepine, and caffeine) and E. coli in 50 groundwaters from unconfined aquifers (<30 m in depth) and confined aquifers (up to 500 m in depth) in Tokyo, where unintended groundwater contamination could take place due to decrepit sewer networks. PPCPs were detected in unconfined aquifers and springs (23/34 samples, 68%), and in confined aquifers (7/16 samples, 44%). Compared with published results for sewage influents, concentrations of PPCPs, excluding caffeine, were generally 1-2 orders of magnitude lower, while in some samples concentrations were quite comparable. The high occurrence rate of PPCPs, even in confined aquifers, indicated that such aquifers are not always protected from pollution by sewage near the land surface. Among the PPCPs analyzed, carbamazepine and crotamiton were most frequently detected, which would appear to be owing to their high persistence, combined with the high concentration of crotamiton in sewage. Crotamiton was detected in all four E. coli-positive groundwaters, and thus may potentially serve as a precautionary indicator of E. coli contamination. Using carbamazepine as a sewage marker, we estimated that 0.8%-1.7% of the dry-weather flow of sewage was leaking out into the unconfined aquifers.

Assessing the impact of chloroacetanilide herbicides and their metabolites on periphyton in the Leyre River (SW France) via short term growth inhibition tests on autochthonous diatoms.

The Leyre River is the main tributary to the Bassin d'Arcachon lagoon. Herbicides belonging to the chloroacetanilide class have been found in the river (S-metolachlor and acetochlor) as well as some of their metabolites at higher concentrations. As the environmental toxicity of these molecules is not well known, ecotoxicological tests have been carried out on river periphyton at different levels of biological diversity: from the clone of one diatom species (Nitzschia nana) to the population of the same species (several clones) up to the multi-specific species community dominated by diatoms. Moreover, tests were performed on diatoms coming from an unpolluted upstream site and from a contaminated downstream site, in order to investigate possible tolerance acquisition to pollutants. The method consisted in measuring diatom growth inhibition at different doses of each substance from the increase of chlorophyll-a concentration after 4 days. It resulted that acetochlor was clearly more toxic than S-metolachlor at all levels of biological diversity. EC(50) values estimated from the tests suggest no effect of contaminants on diatom growth or biomass in the river. The toxicity of the metabolites appeared very low compared to that of their parent compounds. No difference in tolerance to the herbicides was demonstrated between summer diatom communities from the two sites in spite of different specific compositions. However, concerning the populations of N. nana isolated in winter following the highest herbicide concentrations in the river (about 0.5 µg L(-1)), the downstream population showed a higher tolerance to acetochlor but there was no co-tolerance to S-metolachlor. Thus, it appeared that acetochlor represents the highest toxic pressure on periphyton among the other contaminants in the Leyre River.

Exposure to o-toluidine, aniline, and nitrobenzene in a rubber chemical manufacturing plant: a retrospective exposure assessment update.

The National Institute for Occupational Safety and Health previously conducted a retrospective cancer incidence and mortality study of workers employed at a rubber chemical manufacturing plant. Compared with New York State incidence, the bladder cancer risk was 6.5 times higher for workers considered to have definite exposure to ortho-toluidine and aniline, and 4 times higher for workers with possible exposure. Exposure characterization in the original study utilized a surrogate measure based only on departments in which each worker was ever employed. As part of an update of that study, some departments in the three original exposure groups were reclassified based on a follow-up site visit; interviews with employees, management, and union representatives; and review of records including exposure data. An additional evaluation of department-job combinations, rather than only departments, was used to stratify exposure into four categories. An approximate rank of "relative" exposure level for each department-job-year combination was also assigned using a ranking scale of 0 to 10. The ranks were supported by quantitative exposure levels and by professional judgment. The numerical ranking scale was applied to each worker by multiplying the exposure rank by duration for each job held based on comprehensive individual work histories. The cumulative rank scores for this cohort ranged from 0 to 300 unit-years. The medians of the cumulative rank scores for the exposure categories showed very good agreement with increasing exposure classifications (e.g., 0.72, 4.6, 11, 14 unit-years for the four exposure categories). Workers' breathing zone air sampling data collected at this plant from 1976-2004 were well below published occupational exposure limits for these chemicals, but additional cases of bladder cancer have been reported. The exposure assessment revisions and rank estimates will be used to analyze the updated bladder cancer incidence data.

Superabsorbent hydrogel as a formulation to promote mineralization and accelerate degradation of acetochlor in soils.

The excessive use of herbicides had caused serious environmental pollution and ecological problems. Therefore, it is imperative to explore an effective method to reduce herbicide residues and pollution. In the present study, we used superabsorbent hydrogels coated 14C-acetochlor (SH-ACE) to investigate its behavior in different soils under oxic conditions. After 100 days, the mineralization by SH-ACE was increased by 2.3%, 2.5% and 3.3% in the red clay soils, fluvio-marine yellow loamy soils and coastal saline soils, respectively, compared to the control group. This result indicated that the SH-ACE treatment resulted in more complete degradation and detoxification of acetochlor. In addition, the dissipation rates of acetochlor were significantly faster in the SH-ACE treatment, which reduced the persistence of acetochlor. The probable degradation pathways of acetochlor involved dechlorination, hydroxylation, deethoxymethylation, and the formation of thioacetic acid derivatives in the two treatments, but the contents of transformation products were completely different. These findings suggest that the SH-ACE treatment has a significant effect to accelerate the degradation of acetochlor. When developing green pesticides, we emphasize that superabsorbent hydrogel coating treatment should be considered as a promising method for ecological safety in the environment.

DNA adducts of ortho-toluidine in human bladder.

BACKGROUND: 4-Aminobiphenyl (4-ABP) and o-toluidine are known human bladder carcinogens, but only 4-ABP-releasing DNA adducts are known. METHODS: Determination of 4-ABP and o-toluidine-releasing DNA adducts in epithelial and submucosal bladder tissues of sudden death victims (SDV: n=46), and bladder tumours (n=12) by gas chromatography/mass spectrometry. RESULTS: Above background, 4 and 11 of 12 tumour samples contained adducts of 4-ABP (0.057 ± 0.125 fmol/µg DNA) and o-toluidine (8.72 ± 4.49 fmol/µg DNA), respectively. Lower adduct levels were present in both epithelial and submucosal bladder tissues of SDV (4-ABP: 0.011 ± 0.022 and 0.019 ± 0.047 fmol/µg DNA; o-toluidine: 0.24 ± 0.63 and 0.27 ± 0.70 fmol/µg DNA). CONCLUSION: Detection of o-toluidine-releasing DNA adducts support the carcinogenicity of o-toluidine in the human bladder.

New sensitive and quantitative analysis method for organic nitrogen compounds in urban aerosol samples.

Atmospheric aerosols contain a highly complex mixture of organic and inorganic compounds; however, as a chemical class relatively little is known about organic nitrogen (ON) content, with few satisfactory methods for speciated analysis. In this paper we report a sensitive and quantitative method for the speciation of ON within ambient atmospheric aerosol. Aerosol samples, collected on quartz microfiber filters, were extracted in water followed by solid phase extraction, elution, and concentration before analysis by comprehensive gas chromatography with a nitrogen chemiluminescence detection system (GCxGC-NCD). The NCD detection method was optimized using liquid standards. The GCxGC-NCD method showed high selectivity, sensitivity, and equimolarity in its response to individual organic compounds. Limits of detection (LOD) and limits of quantitation (LOQ) for four ON standards (1-nitropentane, o-toluidine, nonanenitrile, and quinoline) were determined to be in the range 0.16-0.27 pgN and 0.71-1.19 pgN, respectively. Between 21 and 57 different ON compounds were found in urban aerosol, (including 10 nitriles, 9 alkyl nitro compounds, 4 nitro-phenols, 4 amides, 3 nitrosamines, and 2 nitro-PAHs) on different dates from a city center location. Pyrrole (8.26-39.21 ngN m(-3) air) and N-butyl-benzenesulfonamide (6.23-20.87 ngN m(-3) air) were the most abundant ON compounds observed in all samples analyzed. The average mass loading of the total identified ON was 532.51 ngON m(-3) air. The sensitivity, selectivity, and relative ease of quantitation of unknown ON components makes the technique a significant improvement over previous laboratory methods.

Assessment of dermal exposure to pesticide residues during re-entry.

Currently, the determination of health risks to pesticide applicators from dermal exposure to these chemicals is assessed using either a concentrate of the compound or a relevant aqueous dilution. Neither of these conditions reflects a normal exposure of an individual when re-entering an area after pesticide application, that is, contact with dried residue of the diluted product on foliage. Methodology has therefore been developed to determine a relevant estimate of this potential dermal re-entry exposure from pesticide residues. Potential delivery platforms have been characterized for the transfer of pesticide residue to skin. Spin coating has been used to deposit uniform pesticide layers on to each platform. Five pesticides have been chosen to encompass a wide range of physicochemical properties: atrazine, 2,4-dichlorophenoxyacetic acid (2,4-D), chlorpyrifos, monocrotophos, and acetochlor. In vitro (Franz diffusion cell) experiments have been performed to monitor the transfer of these pesticides from the delivery platforms onto and through excised porcine skin. Parallel experiments were also conducted with aqueous pesticide dilutions for comparison, and a final in vivo measurement using ibuprofen (as a model compound) complemented the in vitro data. The results demonstrate that transfer of chemical residue onto and subsequently through the skin is dependent on the physical attributes of the residue formed. Thus, assessing dermal exposure to pesticides based on skin contact with either the chemical concentrate or a relevant aqueous dilution may incorrectly estimate the risk for re-entry scenarios.

Simultaneous determination of acetochlor and propisochlor residues in corn and soil by solid phase extraction and gas chromatography with electron capture detection.

A sensitive and simple method for simultaneous analysis of acetochlor and propisochlor in corn and soil has been developed. Two herbicides were extracted from soil and corn matrices with methanol/water and acetone, respectively, followed by solid phase extraction (SPE) to remove co extractives, prior to analysis by gas chromatography with electron capture detection (GC-ECD). Primary secondary amine (PSA) SPE cartridges (500 mg, 3 mL) were used for sample preparation. The analytes from corn and soil matrices were eluted with 5 mL petroleum ether-acetic ether (95/5, v/v) and 3 mL petroleum ether-acetic ether (95/5, v/v), respectively. The recoveries of two pesticides ranged from 73.8% to 115.5% with relative standard deviations (RSD) less than 11.1% and sensitivity of 0.01 mg/kg, in agreement with directives for method validation in residue analysis. The method was successfully applied to determine the fate of acetochlor and propisochlor in real corn and soil samples. For acetochlor and propisochlor, the half-life times (t1/2) in soil was 5.541 and 6.074 days, respectively. No acetochlor and propisochlor residues (<0.01 mg/kg) were detected in corn at harvest time withholding period of 2.5 months after treatments of the pesticides. Direct confirmation of the analytes in samples was achieved by gas chromatography-mass spectrometry (GC-MS).

Spatial and temporal distribution of acetochlor in sediments and riparian soils of the Songhua River Basin in northeastern China.

The Songhua River Basin is a burgeoning agricultural area in the modern times in China. Particularly in recent years, increasing chemical fertilizers and pesticides have been applied with the development of agricultural production. However, the situation of non-point source pollution (NSP) from agricultural production in this basin is still obscure. In order to solve the problem, the occurrence and distribution of acetochlor in sediments and riparian soils of the Songhua River Basin before rain season and after rain season were investigated. In addition, total organic carbon was analyzed. The result showed that the concentration of acetochlor ranged from 0.47 to 11.76 microg/kg in sediments and 0.03 to 709.37 microg/kg in riparian soils. During the high flow period in 2009, the mean concentration was 4.79 microg/kg in sediments and 0.75 microg/kg in riparian soils, respectively. Similarly, the mean concentration was 2.53 microg/kg in sediments and 61.36 microg/kg in riparian soils, during the average flow period in 2010. There was a significant correlation between the concentration of acetochlor and total organic carbon in surface sediments. Moreover, the distribution of acetochlor in sediments of the Songhua River was significantly correlated to land use and topography of the watershed. The investigated data suggested that the concentration of acetochlor in the Songnen Plain and the Sanjiang Plain was higher than that in the other areas of the basin, and riparian buffering zones in these areas had been destroyed by human activities. The optimal agricultural measures to alleviate the contamination of pesticides should be adopted, including controlling agricultural application of acetochlor and ecological restoration of riparian buffering strips.

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In this study, we examined the toxic effect of sublethal doses of acetochlor (1, 2, 4, 8 mg·kg-1) on earthworms by exogenous addition. The growth inhibition rate, cytochrome P450 isozymes (CYP1A2, 2C9 and 3A4) activities and the metabolomics were analyzed after seven days of exposure, to infer the toxicity threshold of acetochlor, screen the sensitive biomarkers from the levels of the individual, detoxified enzymes and small molecular metabolites, and elucidate the underlying toxicity mechanism. The results showed that CYP1A2, 2C9 and 3A4 activities were all significantly inhibited, and that the levels of ten metabolites (fructose-6-diphosphate, cytosine monophosphate, uridine monophosphate, adenosine monophosphate, adenosine, xanthine, fumaric acid, dihydroxyglutaric acid, ornithine and 16-hydroxyeicosatetraenoic acid) were significantly decreased by acetochlor exposure. The levels of six metabolites (adenosine succinic acid, succinic acid, arginine, tryptophan, asparagine and phenylalanine) were significantly increased when earthworms being exposed to 2-8 mg·kg-1 acetochlor. Acetochlor exposure caused oxidative damage to earthworms, weakened the glycolysis, disturbed the tricarboxylic acid cycle, disordered the purine and pyrimidine metabolism, and impaired the amino acids metabolism. Compared with the end point at individual level, the above 16 small molecule metabolites and CYP isozymes activities were more sensitive to acetochlor exposure. It was thus recommended that CYP isozymes (1A2, 2C9, and 3A4) activities and small molecular metabolites could be used as a set of biomarkers to diagnose the acetochlor pollution, given their high sensitivity and accuracy.

Environmental disappearance of acetochlor and its bioavailability to weed: A general prototype for reduced herbicide application instruction.

The consecutive application of herbicide acetochlor has resulted in the widespread drug resistance of weeds and the high risks to environment and human health. To assess environmental behaviors and minimal dosage of acetochlor application in the realistic soil, we systematically investigated the acetochlor adsorption/desorption, mobility, leaching, degradation, weed bioavailability and lethal dosage of acetochlor in three soil types including Nanjing (NJ), Yancheng (YC) and Yingtan (YT). Under the same conditions (60% moisture and darkness), acetochlor had a half-life of disappearance 3 days in NJ, 4.9 days in YC and 25.7 days in YT soils. The HRLC-Q-TOF-MS/MS analyses identified ten metabolites and eight conjugates generated through dealkylation, hydroxylation, thiol conjugation and glycosylation pathways. The acetochlor adsorption to soils ranked in the order of YT > YC > NJ and was committed to the Freundlich model. By examining the effects of soil moisture, microbial activity, illumination/darkness, etc. on acetochlor degradation in soils, we showed that the chemical metabolisms could undergo multiple processes through soil microbial degradation, hydrolysis or photolysis-mediated mechanisms. The longitudinal migration assay revealed that acetochlor leaching ability in the three soils was YT > YC > NJ, which was negatively associated with the order of adsorption behavior. Four kinds of weed were grown in the acetochlor-contaminated NJ soil. The lethal concentrations for the weed plantlets were 0.16-0.3 mg/kg, much lower than the dosage of realistic field application. Overall, our work provided novel insights into the mechanism for acetochlor behaviors in soils, the natural degradation process in the environment, and the lethal concentration to the tested weed plants.

Derived Reference Doses (RfDs) for the environmental degradates of the herbicides alachlor and acetochlor: results of an independent expert panel deliberation.

An independent peer expert panel was convened under the auspices of the Alliance for Risk Assessment (ARA) to review toxicology data and derive oral Reference Doses (RfDs) for four environmental degradates of the acetanilide herbicides, alachlor and acetochlor. The degradates included in this evaluation were (1) alachlor tertiary-ethanesulfonic acid (ESA), (2) alachlor tertiary-oxanilic acid (OXA), (3) acetochlor ESA, and (4) acetochlor OXA. Each degradate was judged to have sufficient data for developing low to medium confidence RfD, with use of an additional uncertainty factor (UF) to cover data gaps. Body weight decreases were identified as the most sensitive treatment-related adverse effect for RfD development. A composite UF of 1000 (10 for human variability in sensitivity, 10 for interspecies differences in sensitivity, and 10 for subchronic to chronic and database deficiency combined; i.e., 10(A)x10(H)x10(S&D)) for each degradate was considered reasonable, while noting that an argument could be made for an UF of 3000 (10(A)x10(H)x30(S&D)). Based on the available data, an oral RfD of 0.2 mg/kg-day is recommended for both acetochlor ESA and acetochlor OXA and an oral RfD of 0.8 mg/kg-day is recommended for both alachlor ESA and alachlor OXA.