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Screening of selected pesticides for oestrogen receptor activation in vitro.

Twenty pesticides were tested for their ability to activate the oestrogen receptor in vitro using an MCF7 cell proliferation assay and a Yeast Oestrogen Screen. The fungicides fenarimol, triadimefon, and triadimenol were identified as weak oestrogen receptor agonists, which at 10 microM induces a 2.0, 2.4, and 1.9-fold increase in proliferation of human MCF7 breast cancer cells (E3 clone). The relative proliferation efficiency (RPE) was 43-69%, indicating partial agonism at the oestrogen receptor. Several pesticides did not have any effect on the proliferation response after 6 days of exposure, including: chlorpyrifos, diuron, iprodion, linuron, pentachlorphenol, prochloraz, propioconazol, propyzamine, quintozen, tetrachorvinphos and tetradifon. Some pesticides resulted in a negligible proliferation response, which was not statistically significant under the present experimental conditions. These were: bromopropylate, chlorfenvinphos, chlorobenzilate, dicofol, heptachlor, and imazalil. Fenarimol and dicofol also gave rise to a positive oestrogenic response in yeast cells transfected with the oestrogen receptor alpha, whereas the remaining compounds resulted in a negative response due either to biological inactivity or cytotoxocity to the yeast cells. The EC50 for fenarimol was estimated to be 13 microM in the yeast cells, compared with an EC50 of 3 microM in the MCF7 cells, indicating higher sensitivity of the latter assay. No in vivo data for fenarimol, triadimefon or triadimenol have previously been published that support oestrogenic activity in the intact animal. Thus, from the present results we suggest that oestrogen receptor activation may not be an important mode of action for these compounds. The need to include at least two bioassays in a screening procedure and for combining in vitro and in vivo data is emphasized.

Cell Line↗

Determination of commonly used herbicides in surface water using solid-phase extraction and dual-column HPLC-DAD.

The present study describes the application of different solid-phase extraction techniques for the extraction, separation, and quantitative determination of 10 commonly used herbicides with different chemical structures (chlorsulfuron, diuron, bentazone, linuron, chlorpropham, fenoxoprop-ethyl, MCPA, diclofop-methyl, fluazifop-butyl, trifluraline) in water. Octadecyl (C(18)) Empore extraction disks, octadecyl (C(18)), and stryene divinylbenzene (SDB) Bond Elut Env cartridges were compared for solid-phase extraction efficiency. Herbicides were separated and quantified by reversed-phase high performance liquid chromatography with diode-array detection (HPLC-DAD) with simultaneous separation on two columns of differing polarity (C(18) and CN) to confirm identification. Analytical separation was performed simultaneously on C(18) and CN columns. Reanalysis of the sample extracts on a (cyano) CN column were used to confirm the identity of these compounds. Method optimization and validation parameters were presented in this work. Recoveries varied from 76.0% to 99.0% for C(18) disks, from 75.1% to 100.0% for C(18) cartridges, and from 54.0% to 98.0% for SDB cartridges over concentrations at 0.025--0.4 microg L(-1). The limits of detection were 0.012--0.035 microg L(-1).

Chromatography, High Pressure Liquid↗

Organic pollutants in surface waters from Portugal using chemometric interpretation.

Surface water samples from 45 sampling points across Portugal have been analyzed monthly by automated Solid Phase Extraction (SPE) and Gas Chromatography-Mass Spectrometry (GC/MS) in SIM and SCAN modes. Sampling was carried out during a period of six months (April-September, 1999), in order to determine the levels of contamination of 72 organic compounds mainly selected from the EC Council Directive list (CEC 76/464/EEC). Atrazine, simazine, deethylatrazine, alachlor, metolachlor, Irgarol, terbuthylazine, tributhylphosphate, 2,4,6-trichlorophenol, 2-chlorophenol, 3-chlorophenol, pentachlorophenol, dimethoate, lindane, linuron, propanil, o,p'-DDD, o,p'-DDT, o,p'-DDE and malathion were the main detected compounds. Although Irgarol, terbuthylazine, deethylatrazine and deisopropylatrazine are not listed in the EC Directive, these herbicides and transformation products are currently in use and they were also included in the monitoring program and detected at some sites. Fifty-nine percent of the samples were below 0.1 microg l(-1), the detection limit required the EEC Drinking Water Directive (DWD). Some compounds were detected at values higher than the DWD, e.g. atrazine (2.7 microg l(-1)) and alachlor (5.43 microg l(-1)) in April. Simazine was also present with a high value (2.3 microg l(-1)) in September. Tributhylphosphate (5.40 microg l(-1)) and 2,4,6-trichlorophenol (2.31 microg l(-1)) were also found at high concentrations near industrial sites. Chemometric interpretation of the more representative contaminants was performed by means of Principal Component Analysis, allowing the resolution of the more relevant contamination sources and the description of their temporal and spatial (geographical) distributions.

Environmental Monitoring↗

An in vivo bioassay for detecting antiandrogens using humanized transgenic mice coexpressing the tetracycline-controlled transactivator and human CYP1B1 gene.

The typical strategy used in analysis of antiandrogens involves the morphological changes of a marker in castrated rats Hershberger assay for the prostate, seminal vesicle, levator ani plus bulbocavernosus muscles (LABC), Cowper's gland, and glans penis. However, there are disadvantages to this approach, such as the time required, and the results may not correspond to those in actual human exposure. To evaluate its ability for detecting antiandrogens, in vivo the dose effect of di-(2-ethylhexyl) phthalate (DEHP) and time effect of five antiandrogens, DEHP, di-n-butyl phthalate (DBP), diethyl phthalate (DEP), linuron (3-(4-dichlorophenyl)-methoxy-1-methylurea), and 2,4'-DDE (1,1-dichloro-2-(p-chlorophenyl)-2-(o-chlorophenyl)ethylene), were investigated using humanized transgenic mice coexpressing tetracycline-controlled transactivator (tTA) and the human cytochrome P450 (CYP) enzyme CYP1B1 (hCYP1B1). Adult transgenic males were treated with each of the five antiandrogens, and their tTA-driven hCYP1B1 expressions analyzed by real-time polymerase chain reaction (PCR) and/or Western blot and for O-debenzylation activity. Herein, the treatments of adult males with the five antiandrogens were shown to affect the increased levels of tTA-driven hCYP1B1 expression in both dose-dependent and repeated experiments. Thus, this novel in vivo bioassay, using humanized transgenic mice, is useful for measuring antiandrogens, and is a means to a more relevant bioassay relating to actual human exposure.

Androgen Antagonists↗

Biomonitoring of arylamines: hemoglobin adducts of urea and carbamate pesticides.

Hemoglobin adducts of aromatic amines released from pesticides were investigated. Female Wistar rats were dosed orally with pesticides up to 1 mmol/kg body weight. Blood was obtained after 24 h, hemoglobin isolated and hydrolyzed in 1 NaOH. The amines were extracted and quantified by gas chromatography with nitrogen-specific or mass-selective detection. The following binding indices [HBI, hemoglobin binding index = binding (mmol/mol Hb) per dose (mmol/kg)] were obtained: pesticide (arylamine): linuron, diuron (3,4-dichloroaniline) 0.8 and 4.5 respectively; monuron, monolinuron (4-chloroaniline) 39 and 55 respectively; chlorpropham (3-chloroaniline) 2.9; chlordimeform (4-chloro-o-toluidine) 2.4; propham (aniline) 2.4. With vinclozoline and iprodione (3,5-dichloroaniline) and quintozene (pentachloroaniline) no adducts could be found. The results demonstrate the possible use of arylamine-hemoglobin adducts for measuring the bioavailability of potentially hazardous components of pesticides and the extent to which they are formed and metabolically activated.

Animals↗

High-performance liquid chromatography column switching applied to the trace determination of herbicides in environmental and drinking water samples.

A selective and sensitive coupled-column high-performance liquid chromatographic method is developed for the simultaneous determination of 5 phenylurea herbicides (monuron, linuron, isoproturon, monolinuron, and diuron) in environmental and drinking water samples. Sample clean-up is performed automatically by means of a column switching technique. Using 2 octadecyl silica columns connected via two programmable 6-port valves and ultraviolet detection at 244 nm, the aforementioned compounds can be determined at the low concentration levels required for pesticide residue analysis in water samples. A mobile phase consisting of a mixture of methanol-water (55:45, v/v) is pumped at 1 mL/min. For the 5 phenylureas, high recoveries ranging from 94.9 to 101.6%, good reproducibility with relative standard deviations lower than 5%, and wide linear ranges up to 20 micrograms/L are observed with determination limits of 0.05 microgram/L. The method is successfully applied to the screening of different environmental water samples such as surface, ground, rain, and drinking water.

Chromatography, High Pressure Liquid↗

Effects of environmental antiandrogens on reproductive development in experimental animals.

Chemicals that act as androgen receptor (AR) agonists and antagonists or inhibit fetal steroidogenesis can induce reproductive malformations in humans and laboratory animals. Several environmental chemicals disrupt development in rats and/or rabbits at fetal concentrations at, or near, exposure levels seen in some segments of the human population. In rats, fetal tissues concentrations of 10-20 p.p.m. of the DDT metabolite, p,p'-DDE, are correlated with reproductive abnormalities in male offspring. These concentrations are similar to those measured in first-trimester human fetal tissues in the late 1960s. The pesticides vinclozolin, procymidone, linuron and DDT are AR antagonists. They reduce male rat anogenital distance, and induce areolas at relatively low dosages. Hypospadias, agenesis of the sex accessory tissues and retained nipples are seen in the middle dosages, while undescended testes and epididymal agenesis are seen in the highest doses. Phthalate esters (PE) inhibit testosterone synthesis during fetal life, but do not appear to be AR antagonists. Prenatal administration of a single low dose of dioxin (50-1,000 ng TCDD/kg) alters the differentiation of androgen-dependent tissues at p.p.t. concentrations, but the mechanism of action likely involves interaction with a hormone-like nuclear transcription factor, the hormone-like receptor AhR, rather than AR. p,p'-DDT and p,p'-DDE, vinclozolin and di-n-butyl phthalate affect reproductive function in rabbits when administered during prenatal and/or neonatal life. Cryptorchidism and carcinoma in situ-like (CIS) testicular lesions were seen in male rabbits treated during development with p,p'-DDT or p,p'-DDE. Extrapolation of effects from rodents to humans would be enhanced if future studies incorporate determination of tissue concentrations of the active metabolites. Knowledge of the tissue concentrations of the active toxicants also would provide an important link to in-vitro studies, which provide more useful mechanistic information when they are executed at relevant concentrations.

Androgen Antagonists↗

Androgen receptor antagonism by the organophosphate insecticide fenitrothion.

Organophosphate insecticides represent one of the most widely used classes of pesticides with high potential for human exposure in both rural and residential environments. We investigated the interaction of the organophosphothioate pesticide fenitrothion (O,O-dimethyl O-(4-nitro-m-tolyl) phosphorothioate) with the human androgen receptor (AR). Fenitrothion blocked dihydrotestosterone-dependent AR activity in a concentration-dependent and competitive manner in HepG2 human hepatoma liver cells transiently transfected with human AR and an AR-dependent luciferase reporter gene. Schild regression analysis yielded an equilibrium dissociation constant value of 2.18 x 10(-8) M. To determine the antiandrogenic potential of fenitrothion in vivo, 7-week-old castrated Sprague-Dawley rats were dosed once a day for 7 days with testosterone propionate (50 microg/day, sc) plus gavage doses of either corn oil vehicle or fenitrothion (15 or 30 mg/kg/day). An additional group of rats was given testosterone propionate and flutamide (50 mg/kg/day). Motor activity and acetylcholinesterase activity in whole blood and brain were also assessed. Both fenitrothion and the reference antiandrogen flutamide caused significant decreases in the ventral prostate, seminal vesicle, and levator ani plus bulbocavernosus muscles tissue weights. In contrast, blood acetylcholinesterase activity, a standard biomarker of organophosphate poisoning, was only inhibited at the higher dose of fenitrothion (30 mg/kg). Our results demonstrate that fenitrothion is a competitive AR antagonist, comparable in potency to the pharmaceutical antiandrogen flutamide and more potent, based on in vitro assays, than the known environmental antiandrogens linuron and p,p'-, 2,2-bis(p-hydroxyphenyl)-1,1-dichloroethylene ( p,p'-DDE).

Acetylcholinesterase↗

A novel cell line, MDA-kb2, that stably expresses an androgen- and glucocorticoid-responsive reporter for the detection of hormone receptor agonists and antagonists.

The U.S. Environmental Protection Agency has proposed that in vitro assays for estrogen receptor (ER)- and androgen receptor (AR)-mediated actions be included in a Tier-I screening battery to detect hormonally active chemicals. Herein we describe the development of a novel stable cell line, MDA-kb2, for screening of androgen agonist and antagonists and to characterize its specificity and sensitivity to endocrine-disrupting chemicals. The breast cancer cell line, MDA-MB-453, was stably transformed with the MMTV.luciferase.neo reporter gene construct. Since both GR and AR are present in the MDA-MB-453 cells, and both receptors can act through the MMTV promoter, compounds that act through either AR or GR activate the MMTV luciferase reporter. As expected, AR agonists such as dihydrotestosterone (DHT), and GR agonists such as dexamethasone (DEX), corticosterone, and aldosterone induce luciferase expression at appropriate concentrations. DHT consistently produced 3-9-fold induction at concentrations from 0.1 to 10 nM. At 1 to 1000 nM, DEX induced luciferase activity 1.3-19.5-fold. To distinguish AR- from GR-mediated ligands, chemicals were assayed concurrently with the antiandrogen, hydroxyflutamide (OHF), which blocks AR- but not GR-mediated responses. In addition, known AR antagonists, including hydroxyflutamide, vinclozolin, vinclozolin metabolites M1 and M2, p,p'-DDE, and linuron inhibited DHT-induced luciferase gene expression at appropriate concentrations in this system. We have found that these cells are relatively easy to culture and maintain. Responsiveness was monitored over time and was stable for more than 80 passages. Some advantages of this assay are that it is relatively rapid (2 days), eliminates the need for transfection, can be conducted in a 96-well plate format, and produces consistent reproducible results. In summary, we have developed a cell line that can be used to screen chemicals, not just for AR- but for GR-mediated activities as well.

Androgen Antagonists↗

Effects of in utero exposure to the organophosphate insecticide fenitrothion on androgen-dependent reproductive development in the Crl:CD(SD)BR rat.

Fenitrothion [0,0-dimethyl-O-(4-nitro-m-tolyl) phosphorothioate] is an organophosphate insecticide that has been shown to have antiandrogenic activity using in vitro and in vivo screening assays. Studies were performed to evaluate the ability of fenitrothion to disrupt androgen-dependent sexual differentiation in the male rat. Pregnant Crl:CD(SD)BR rats were administered fenitrothion by gavage at 0, 5, 10, 15, 20, or 25 mg/kg/day ( n = 6-11/group) from gestation day (GD) 12 to 21. Maternal toxicity was observed in the dams treated with 20 and 25 mg fenitrothion/kg/day based on muscle tremors and decreases in body weight gain from GD 12 to 21. Fetal death was increased in the 20 and 25 mg/kg/day exposure groups, as evidenced by a decrease in the proportion of pups born alive. Androgen-mediated development of the reproductive tract was altered in male offspring exposed in utero to maternally toxic levels of fenitrothion (25 mg/kg/day), as evidenced by reduction in anogenital distance on postnatal day (PND) 1 and retention of areolae on PND 13. However, these effects were only transient, and there were no indications of abnormal phenotypes or development of androgen-dependent tissues on PND 100. At the dose levels evaluated in this study, fenitrothion was only weakly antiandrogenic in vivo compared with other androgen receptor antagonists such as flutamide, linuron, and vinclozolin. Based on observed fetotoxicity at 20 mg/kg/day, the lowest observed adverse effect level (LOAEL) for developmental effects can be lowered from 25 to 20 mg/kg/day.

Abnormalities, Drug-Induced↗

Engineering herbicide metabolism in tobacco and Arabidopsis with CYP76B1, a cytochrome P450 enzyme from Jerusalem artichoke.

The Jerusalem artichoke (Helianthus tuberosus) xenobiotic inducible cytochrome P450, CYP76B1, catalyzes rapid oxidative dealkylation of various phenylurea herbicides to yield nonphytotoxic metabolites. We have found that increased herbicide metabolism and tolerance can be achieved by ectopic constitutive expression of CYP76B1 in tobacco (Nicotiana tabacum) and Arabidopsis. Transformation with CYP76B1 conferred on tobacco and Arabidopsis a 20-fold increase in tolerance to linuron, a compound detoxified by a single dealkylation, and a 10-fold increase in tolerance to isoproturon or chlortoluron, which need successive catalytic steps for detoxification. Two constructs for expression of translational fusions of CYP76B1 with P450 reductase were prepared to test if they would yield even greater herbicide tolerance. Plants expressing these constructs had lower herbicide tolerance than CYP76B1 alone, which is apparently a consequence of reduced stability of the fusion proteins. In all cases, increased herbicide tolerance results from more extensive metabolism, as demonstrated with exogenously fed phenylurea. Beside increased herbicide tolerance, expression of CYP76B1 has no other visible phenotype in the transgenic plants. Our data indicate that CYP76B1 can function as a selectable marker for plant transformation, allowing efficient selection in vitro and in soil-grown plants. Plants expressing CYP76B1 may also be a potential tool for phytoremediation of contaminated sites.

7-Alkoxycoumarin O-Dealkylase↗

Isolation from agricultural soil and characterization of a Sphingomonas sp. able to mineralize the phenylurea herbicide isoproturon.

A soil bacterium (designated strain SRS2) able to metabolize the phenylurea herbicide isoproturon, 3-(4-isopropylphenyl)-1,1-dimethylurea (IPU), was isolated from a previously IPU-treated agricultural soil. Based on a partial analysis of the 16S rRNA gene and the cellular fatty acids, the strain was identified as a Sphingomonas sp. within the alpha-subdivision of the proteobacteria. Strain SRS2 was able to mineralize IPU when provided as a source of carbon, nitrogen, and energy. Supplementing the medium with a mixture of amino acids considerably enhanced IPU mineralization. Mineralization of IPU was accompanied by transient accumulation of the metabolites 3-(4-isopropylphenyl)-1-methylurea, 3-(4-isopropylphenyl)-urea, and 4-isopropyl-aniline identified by high-performance liquid chromatography analysis, thus indicating a metabolic pathway initiated by two successive N-demethylations, followed by cleavage of the urea side chain and finally by mineralization of the phenyl structure. Strain SRS2 also transformed the dimethylurea-substituted herbicides diuron and chlorotoluron, giving rise to as-yet-unidentified products. In addition, no degradation of the methoxy-methylurea-substituted herbicide linuron was observed. This report is the first characterization of a pure bacterial culture able to mineralize IPU.

Agriculture↗

Genetic diversity among 3-chloroaniline- and aniline-degrading strains of the Comamonadaceae.

We examined the diversity of the plasmids and of the gene tdnQ, involved in the oxidative deamination of aniline, in five bacterial strains that are able to metabolize both aniline and 3-chloroaniline (3-CA). Three strains have been described and identified previously, i.e., Comamonas testosteroni I2 and Delftia acidovorans CA28 and BN3.1. Strains LME1 and B8c were isolated in this study from linuron-treated soil and from a wastewater treatment plant, respectively, and were both identified as D. acidovorans. Both Delftia and Comamonas belong to the family Comamonadaceae. All five strains possess a large plasmid of ca. 100 kb, but the plasmids from only four strains could be transferred to a recipient strain by selection on aniline or 3-CA as a sole source of carbon and/or nitrogen. Plasmid transfer experiments and Southern hybridization revealed that the plasmid of strain I2 was responsible for total aniline but not 3-CA degradation, while the plasmids of strains LME1 and B8c were responsible only for the oxidative deamination of aniline. Several transconjugant clones that had received the plasmid from strain CA28 showed different degradative capacities: all transconjugants could use aniline as a nitrogen source, while only some of the transconjugants could deaminate 3-CA. For all four plasmids, the IS1071 insertion sequence of Tn5271 was found to be located on a 1.4-kb restriction fragment, which also hybridized with the tdnQ probe. This result suggests the involvement of this insertion sequence element in the dissemination of aniline degradation genes in the environment. By use of specific primers for the tdnQ gene from Pseudomonas putida UCC22, the diversity of the PCR-amplified fragments in the five strains was examined by denaturing gradient gel electrophoresis (DGGE). With DGGE, three different clusters of the tdnQ fragment could be distinguished. Sequencing data showed that the tdnQ sequences of I2, LME1, B8c, and CA28 were very closely related, while the tdnQ sequences of BN3.1 and P. putida UCC22 were only about 83% identical to the other sequences. Northern hybridization revealed that the tdnQ gene is transcribed only in the presence of aniline and not when only 3-CA is present.

Aniline Compounds↗

Degradation of chlorbromuron and related compounds by the fungus Rhizoctonia solani.

The ability of the soil fungus Rhizoctonia solani to degrade phenyl-substituted urea herbicides was investigated. The fungus was able to transform chlorbromuron [3-(3-chloro-4-bromophenyl)-1-methyl-1-methoxyurea] to the demethylated product [3-(3-chloro-4-bromophenyl)-1-methoxyurea], which was isolated and identified. Evidence was obtained that further degradation of chlorbromuron occurred. Several other phenylurea compounds (chloroxuron, diuron, fenuron, fluometuron, linuron, metobromuron, neburon, and siduron) were also metabolized by the fungus, indicating that R. solani may possess a generalized ability to attack this group of herbicides.

Aniline Compounds↗

Effects of common-use pesticides on developmental and reproductive processes in Daphnia.

Daphnia magna were evaluated for use as a screen for pesticides that have been demonstrated to have estrogenic (o'p'-DDT, di-n-butyl phthalate, toxaphene), anti-androgenic (p'p-DDE, linuron), thyroid (acetochlor, alachlor, metribuzin), insulin (amitraz) or lutenizing hormone (2,4-D) activity in vertebrates, and to establish daphnid sensitivity to these compounds. Pesticides with unknown effects on vertebrate endocrine systems (chlorosulfuran, cyanazine, diflubenzuron, metolachlor, and diquat) were also evaluated. Compounds were assayed for six days at environmentally relevant concentrations ranging from 0.001 to 100 mirog/L, using female Daphnia and their offspring. Sublethal endpoints included offspring sex (sex determination), clutch size (fecundity), and adult size (growth rate). Toxaphene was the only compound that affected sexual differentiation, increasing male production. Daphnia fecundity declined with exposure to toxaphene, and daphnid growth rates were reduced by acetochlor exposure. Diflubenzuron, o'p'-DDT, and p'p-DDE significantly reduced Daphnia survival. No correlation existed between affected reproductive or developmental processes and specific endocrine systems or subsystems. Results from this study indicate that Daphnia make a good screen for assessing potential environmental impacts but are not a useful indicator of pesticide hormonal activity in vertebrates. This assay consistently detected sublethal but ecologically relevant effects of these pesticides on Daphnia at environmentally relevant concentrations typically below their listed EC50 value.

Animals↗

NTP Technical Report on the Toxicity Studies of 3,3',4,4'-Tetrachloroazobenzene (CAS No. 14047-09-7) Administered by Gavage to F344/N Rats and B6C3F1 Mice.

3,3',4,4'-Tetrachloroazobenzene is not commercially manufactured but is formed as an unwanted byproduct in the manufacture of 3,4-dichloroaniline and its herbicidal derivatives Propanil(R), Linuron(R), and Diuron(R). In addition, environmental contamination by 3,3',4,4'-tetrachloroazobenzene occurs from the degradation of chloranilide herbicides and the photolysis and biolysis of 3,4-dichloroaniline. 3,3',4,4'-Tetrachloroazobenzene was nominated by the United States Environmental Protection Agency for toxicity testing based on concerns over the potential for human exposure, the structural resemblance to 2,3,7,8-tetrachlorodibenzo-p-dioxin, and the reported dioxin-like effects of 3,3',4,4'-tetrachloroazobenzene. The toxicity of 3,3',4,4'- tetrachloroazobenzene was evaluated in 16-day and 13-week gavage studies in male and female F344/N rats and B6C3F1 mice. In addition to histopathology, evaluations included hematology (rats only), clinical chemistry, thyroid hormone analyses (rats only), cytochrome P(450)1A immunohistochemical staining in the liver (rats only), and assessments of male reproductive endpoints and estrous cycle length. Genetic toxicology studies included mutagenicity tests in Salmonella typhimurium and the determination of micronuclei in mouse bone marrow and peripheral blood erythrocytes. In the 16-day studies, groups of five male and five female rats received 3,3',4,4'-Tetrachloroazobenzene in corn oil by gavage 5 days a week at doses of 0, 12.5, 32, 80, 200, or 500 mg per kg body weight. Groups of five male and five female mice received 3,3',4,4'-Tetrachloroazobenzene in corn oil by gavage 5 days a week at doses of 0, 1, 3.2, 10, 32, or 100 mg/kg. Major effects included increases in liver, lung, and spleen weights of rats and liver and heart weights of mice and decreases in thymus weights of rats and mice. No effects were found on survival or mean body weight gains of rats or mice. Incidences of hematopoietic cell proliferation in the spleen were increased in all groups of dosed male rats, in female rats that received 32 mg/kg or greater, and in 100 mg/kg male and female mice. Renal tubule hyaline droplet accumulation in the cytoplasm of renal cortical epithelial cells and chronic nephropathy were observed microscopically in male rats in the 80, 200, and 500 mg/kg groups. Female mice in the 100 mg/kg group had atrophy of the thymus. In the 13-week studies, groups of 10 male and 10 female rats and mice received 3,3',4,4'-Tetrachloroazobenzene in corn oil by gavage 5 days a week at doses of 0, 0.1, 1, 3, 10, or 30 mg/kg. In the 13-week rat study, the major effects included a decrease in the mean body weight gain of 30 mg/kg females and final mean body weights of 30 mg/kg males and females, decreased thymus weights of males and females in the 10 and 30 mg/kg groups accompanied by thymic atrophy observed microscopically, increased incidences of hematopoietic cell proliferation in the spleen in 10 and 30 mg/kg males and females, a responsive anemia in 10 and 30 mg/kg males and females at week 13, and decreased platelet counts in 10 and 30 mg/kg males and females on day 21 and at week 13. Spleen weights were increased in 10 and 30 mg/kg males and females. Liver weights were increased in males that received 1 mg/kg or greater and in 10 and 30 mg/kg females. Furthermore, hepatic cytochrome P(450)1A staining presence and intensity were increased in 30 mg/kg males and females. Sharp decreases in circulating thyroxine concentrations were observed in males and females at all doses. In spite of this sharp decrease, thyroid-stimulating hormone concentrations were marginally increased. Incidences of hyperplasia of the forestomach were increased in males administered 3 mg/kg or greater and females administered 30 mg/kg. In the 13-week mouse study, the major effects included increases in liver and spleen weights of 10 and 30 mg/kg males and females and increased incidences of hyperplasia of the forestomach in males and females that received 1 mg/kg or greater. Furthermore, a decrease in thymus weight of 30 mg/kg males, an increase in centrilobular hypertrophy of hepatocytes in males that received 3 mg/kg or greater, and an increase in the incidences of hematopoietic cell proliferation in the spleen in males that received 3 mg/kg or greater were observed. A significant decrease in epididymal spermatozoal concentration was observed in 3 and 30 mg/kg males. 3,3',4,4'-Tetrachloroazobenzene was mutagenic in S. typhimurium strain TA97 in the presence of rat liver S9 activation enzymes; no mutagenic activity was detected in strain TA98, TA100, TA1535, or TA1537 with or without S9. In vivo, the frequency of micronucleated erythrocytes was significantly increased in peripheral blood samples from male and female mice given 3,3',4,4'-Tetrachloroazobenzene by gavage for 13 weeks. However, results of a 3-day exposure of up to 200 mg/kg by intraperitoneal injection did not demonstrate induction of micronuclei in bone marrow erythrocytes of male mice. In summary, 3,3',4,4'-Tetrachloroazobenzene caused typical dioxin-like effects, such as thymic atrophy, an increase in liver weights, induction of hepatic cytochrome P(450)1A, and decreased mean body weight gains. Furthermore, in the 13-week studies, a sharp decrease in circulating thyroxine concentrations was observed even at the lowest dose (0.1 mg/kg) tested in rats. Other effects included a decrease in epididymal spermatozoal concentration in mice, major effects on the hematopoietic system, and increased incidences of hyperplasia of the forestomach in 3 and 30 mg/kg males and 30 mg/kg females. A no-observable-adverse-effect-level (NOAEL) was not reached in rats. The NOAEL in mice was 0.1 mg/kg. Comparison of various dioxin-like effects in these studies with those reported in the literature indicate that 3,3',4,4'-Tetrachloroazobenzene is six to two orders of magnitude less potent than 2,3,7,8-tetrachlorodibenzo-p-dioxin.

Journal Article↗

Multiresidue determination of pesticides in drinking and related waters by solid-phase extraction and liquid chromatography with ultraviolet detection: interlaboratory study.

As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 17 European laboratories evaluated a method using styrene-divinylbenzene copolymer solid-phase extraction followed by liquid chromatography with diode array detection. The main aim of the study was to evaluate whether the method meets the requirements of EC Drinking Water Directive 98/83 in terms of accuracy, precision, and detection limit for 21 pesticides according to the following requirements: limit of detection, < or =0.025 microg/L; accuracy expressed as recovery, between 75 and 125%; and precision expressed as repeatability relative standard deviation of the method, <12.5%, and as reproducibility relative standard deviation of the method, <25%. Analyses for unknown concentrations were performed with commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except pirimicarb (0.02 microg/L). The criteria for repeatability were met for all compounds. Terbutryn in bottled water and carbendazim in tap water did not meet the criteria for reproducibility. In terms of accuracy, the method met the requirements for all pesticides in both matrixes, except for metamitron. However, several compounds (linuron, terbutryn, propazine, metobromuron, and isoproturon) showed recoveries slightly below 75%.

Chromatography, Liquid↗

Determination of seventeen polar/thermolabile pesticides in apples and apricots by liquid chromatography/mass spectrometry.

A simple liquid chromatography/mass spectrometry (LC/MS) approach for the determination of widely used representatives of polar/thermolabile pesticides in fruits was developed and validated. The group of pesticides comprised benzimidazoles and azoles (carbendazim, thiabendazole, imazalil, propiconazole, prochloraz, epoxiconazole, flusilazole, tebuconazole, bitertanol); N-methylcarbamates (carbaryl, carbofuran, methiocarb); and phenylureas and benzoylphenylureas (linuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron). Matrixes (apple, apricot) were extracted with acetonitrile and crude extracts were cleaned up by solid-phase extraction (SPE) using either mixed cation exchange or hydrophilic lipophilic balance cartridges. LC separation of pesticides was performed on a reversed-phase column, Discovery C18. Electrospray ionization and ion trap MS/MS detection were applied. For most pesticides, overall recoveries ranged from 75 to 122%, and repeatability (as relative standard deviation) from 5 repetitive determinations of recovery ranged from 3 to 21%. Carbofuran was the only compound for which recovery was not satisfactory due to its loss in the SPE cleanup step. Limits of detection were 0.1-3 microg/kg for benzimidazole and azole fungicides and carbamate insecticides. For urea insecticides, detection limits were slightly higher (3-10 microg/kg).

Calibration↗