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Assessment of risk reduction strategies for the management of agricultural nonpoint source pesticide runoff in estuarine ecosystems.

Agricultural nonpoint source (NPS) runoff may result in significant discharges of pesticides, suspended sediments, and fertilizers into estuarine habitats adjacent to agricultural areas or downstream from agricultural watersheds. Exposure of estuarine fin fish and shellfish to toxic levels of pesticides may occur, resulting in significant declines in field populations. Integrated pest management (IPM), best management practices (BMP), and retention ponds (RP) are risk management tools that have been proposed to reduce the contaminant risk from agricultural NPS runoff into estuarine ecosystems. Field studies were conducted at three sites within coastal estuarine ecosystems of South Carolina (SC) from 1985 to 1990 that varied in terms of the amount and degree of risk reduction strategies employed. An intensively managed (IPM, BMP, and RP) agricultural treatment site (TRT) was studied for pesticide runoff impacts. From 1985 to 1987, there were minimal (some IPM and BMP) management activities at TRT, but from 1988 to 1990, TRT was managed using an intensive risk reduction strategy. A second unmanaged agricultural growing area, Kiawah (KWA), was also studied and compared with TRT in terms of pesticide runoff and the resulting impacts on grass shrimp (Palaemonetes pugio) and mummichogs (Fundulus heteroclitus). A third, non-agricultural, reference site (CTL) was used for comparing results from the managed and unmanaged agricultural sites. In situ toxicity tests and field samples of the grass shrimp populations were conducted at each site and compared in terms of survival and the effectiveness of current risk reduction strategies. Significant runoff of insecticides (azinphosmethyl, endosulfan, and fenvalerate) along with several fish kills were observed at TRT prior to the implementation of rigorous risk reduction methods. A significant reduction of in stream pesticide concentrations (up to 90%) was observed at TRT following the implementation of strict NPS runoff controls, which greatly reduced impacts on estuarine fish and shellfish. At the unmanaged KWA, continued impacts due to the runoff of these insecticides were observed, along with several fish kills. Additional monitoring indicated that gravid female grass shrimp populations from KWA had elevated levels of P-glycoprotein (P-gp), a multidrug resistance protein, which may transport various pesticides across cellular membranes. Comparison of field results with laboratory toxicity tests established that pesticide exposure was the primary cause of observed field impacts at each site. These findings clearly indicate the value of an integrated risk reduction strategy (BMP, IPM, and RP) for minimizing impacts from NPS agricultural pesticide runoff.

ATP Binding Cassette Transporter, Subfamily B, Mem↗

Pesticides in household dust and soil: exposure pathways for children of agricultural families.

Child of agriculture families are likely to be exposed to agricultural chemicals, even if they are not involved in farm activities. This study was designed to determine whether such children are exposed to higher levels of pesticides than children whose parents are not involved in agriculture and whose homes are not close to farms. Household dust and soil samples were collected in children's play areas from 59 residences in eastern Washington State (26 farming, 22 farmworker, and 11 nonfarming families). The majority of the farm families lived within 200 feet of an operating apple or pear orchard, whereas all reference homes were located at least a quarter of a mile from an orchard. Four organophosphorous (OP) insecticides commonly used on tree fruit were targeted for analysis: azinphosmethyl, chlorpyrifos, parathion, and phosmet. Samples were extracted and analyzed by gas chromatography/mass selective detection. Pesticide concentrations in household dust were significantly higher than in soil for all groups. OP levels for farmer/farm-worker families ranged from nondetectable to 930 ng/g in soil (0.93 ppm) and from nondetectable to 17,000 ng/g in dust (17 ppm); all four OP compounds were found in 62% of household dust samples, and two-thirds of the farm homes contained at least one OP above 1000 ng/g. Residues were found less frequently in reference homes and all levels were below 1000 ng/g. Household dust concentrations for all four target compounds were significantly lower in reference homes when compared to farmer/farmworker homes (Mann Whitney, U test; p < 0.05). These results demonstrate that children of agricultural families have a higher potential for exposure to OP pesticides than children of nonfarm families in this region. Measurable residues of a toxicity, I compound registered exclusively for agricultural use, azcnphosmettyl were found in household dust samples from all study homes, suggesting that low level exposure to such chemicals occurs throughout the region. Children's total and cumulative exposure to this pesticide class from household dust, soil, and other sources warrants further investigation.

Adult↗

Evaluation of various deployment strategies of imidacloprid-treated spheres in highbush blueberries for control of Rhagoletis mendax (Diptera: Tephritidae).

Biodegradable, ammonium-baited spheres treated with the neonicotinoid insecticide Provado (imidacloprid) at 2% (AI) were evaluated for controlling blueberry maggot flies, Rhagoletis mendax Curran. Three strategies for sphere deployment in highbush blueberries, Vaccinium corymbosum L., were compared with untreated control plots in 1999 and once again compared against control plots and organophosphate insecticide sprays in 2000. The patterns of sphere deployment were as follows: (1) perimeter deployment in which spheres were hung individually and spaced equally around the perimeter of experimental plots; (2) cluster deployment in which four groups of three spheres were hung in equally spaced perimeter locations of experimental plots; and (3) uniform deployment in which spheres were placed 10 m apart (in a grid-like pattern) within experimental plots. In 1999, there were no significant differences in fruit injury levels based on observed R. mendax oviposition scars and reared larvae among plots containing imidacloprid-treated spheres in perimeter, cluster, and internal-grid patterns. However, all plots containing spheres had significantly lower fruit infestation levels (<2%), compared with unsprayed control plots with no spheres deployed, which had infestation levels (>20%). In 2000, there were no significant differences in fruit injury based on observed R. mendax oviposition scars between plots containing imidacloprid-treated spheres in the three deployment strategies tested and plots that received Guthion (Azinphosmethyl) spray applications. However, significantly fewer R. mendax larvae were reared from berries collected from plots that received two applications of Guthion compared with plots in which imidacloprid-treated spheres were deployed. Irrespective of sphere deployment strategies, all sphere-treated and sprayed plots had significantly lower injury levels (<1.5%), based on numbers of reared larvae compared with berries collected from the control plots (>4.0%). Based on captures of flies on unbaited Pherocon AM boards placed in the center of treatment plots, we observed a suppression of R. mendax in plots containing imidacloprid-treated spheres compared with control plots. The potential of using imidacloprid-treated spheres as a behavioral control integrated pest management tactic for blueberry maggot flies is discussed.

Animals↗

Effects of kaolin-based particle film application on boll weevil (Coleoptera: Curculionidae) injury to cotton.

This study examined a non-insecticidal tactic for suppressing boll weevil, Anthonomus grandis grandis Boheman, damage to cotton, Gossypium hirsutum L. In cage assays, kaolin, a reflective white mineral, applied to excised cotton squares or to the cotton foliage, initially resulted in lower levels of boll weevil injury to squares than nontreated squares. Boll weevil oviposition and feeding on kaolin-treated squares and squares on kaolin-treated cotton plants increased when nontreated squares and cotton plants were in short supply. A laboratory assay and field trials suggested that boll weevils distinguished between cotton plots based on color differences caused by kaolin and this appeared to influence levels of damage to squares. Random sampling in small plots indicated that oviposition damage to squares in plots treated with kaolin was reduced (P < 0.05) compared with nontreated controls, except when rain washed the kaolin off the foliage. Lint yield differences were not detected between the small plots, but the kaolin-treated small plots yielded as much as 2.36 times more cotton lint than a large but unreplicated adjacent nontreated control plot, and up to 1.39 times more than another large but unreplicated adjacent plot sprayed twice with preemptive applications of azinphosmethyl when cotton squares were first developing (pinhead stage). Potentially important avenues for future research on boll weevil injury suppression using kaolin are discussed.

Animals↗

Determination of insecticides in honey by matrix solid-phase dispersion and gas chromatography with nitrogen-phosphorus detection and mass spectrometric confirmation.

A multiresidue method was developed for the determination of 12 organophosphorus insecticides (diazinon, parathion methyl, fenitrothion, pirimiphosmethyl, malathion, fenthion, chlorpyrifos, quinalphos, methidathion, ethion, azinphosmethyl, coumaphos), one carbamate (pirimicarb), and one amidine (amitraz) in unifloral and multifloral honeys. The analytical procedure was based on the matrix solid-phase dispersion of honey on a mixture of Florisil and anhydrous sodium sulfate in small glass columns and subsequent extraction with a low volume of hexane-ethyl acetate (90 + 10, v/v), assisted by sonication. The insecticide residues were determined by capillary chromatography with nitrogen-phosphorus detection and confirmed by mass spectrometry. Average recoveries at the 0.05-0.5 microg/g levels were >80% for organophosphorus insecticides and about 60% for the other insecticides, pirimicarb and amitraz, with relative standard deviations <10%. The detection limit for the different insecticides ranged between 6 and 15 microg/kg. The main advantages of the proposed method are that extraction and cleanup are performed in a single step with a low volume of organic solvent. The method is simple, rapid, and less laborious than conventional methods. Several Spanish honeys were analyzed with the proposed method and no residues of the studied insecticides were found.

Gas Chromatography-Mass Spectrometry↗

Size exclusion chromatographic cleanup for GC/MS determination of organophosphorus pesticide residues in household and vehicle dust.

Size exclusion chromatography (SEC) was used as a cleanup method for the analysis of organophosphorus pesticides in household and vehicle dusts. The pesticides investigated were diazinon, methyl parathion, chlorpyrifos, malathion, phosmet, and azinphosmethyl. These compounds are of interest due to their use in agricultural tree fruit production and/or urban pest control. Pesticides were determined via gas chromatography/mass spectrometry with selected-ion monitoring and cool on-column injection. The lower limit of method validation was 0.20 microg/g. Method limits of detection in dust ranged from 0.012-0.055 microg/g. Dust samples were collected with vacuums from the homes and vehicles of people living and working in a rural agricultural region in the central part of Washington State. The analytes were extracted from the dust by sonication in acetone. The extracts were solvent-exchanged to cyclohexane, frozen, thawed, and centrifuged prior to SEC injection. Following SEC, the eluent was split into 2 fractions, concentrated, and injected on-column into the gas chromatograph. This method represents the first complete publication describing the SEC cleanup of organophosphorus pesticides in dusts. Recoveries of pesticides in dusts ranged from 63.5-110.8 +/- 4.9-19.6% over a fortification range of 0.20-10.00 microg/g. This optimized, automated, and reproducible SEC method does not require further treatment or cleanup for trace determination of these organophosphorus pesticides.

Air Pollution, Indoor↗

[Evaluation of micronuclei in primary hepatocyte culture in rats treated with organophosphoric compounds].

We have evaluated the genotoxic effect of the three organophosphorous (OPs) insecticides dimethoate (DIM), azinphosmethyl (AZN) and diazinon (DIA) or in combination, at a ratio frequently found in foodstuffs by residual analysis. We have carried out the micronucleus (MN) test on cultured rat hepatocytes which were induced to proliferate by epidermal growth factor (EGF), and treated with the insecticides for 48 hours. The doses tested were chosen on the basis of cytotoxicity tests such as Trypan Blue exclusion and mitotic index inhibition. The results showed that AZN was the most toxic and DIM the least toxic compound. None of the compounds tested showed a genotoxic effect when examined separately. Conversely, a significant increase in MN frequency was observed when the three OPs were used in combination at the lowest concentration used when each compound was tested alone.

Animals↗

Effect of laundering on ability of glove fabrics to decrease the penetration of organophosphate insecticides through in vitro epidermal systems.

Two knit glove fabrics, one of 100% cotton and one of 100% polypropylene, were examined for their capability to decrease the penetration of the organophosphate insecticides (OPs), azinphos-methyl and paraoxon after 4 h at field concentrations (3000 and 15 ppm, respectively) through an in vitro epidermal system (Skin2, Advanced Tissue Systems, LaJolla, CA). The glove fabrics were examined under three different conditions of use: new, after they had been abraded and after they had been abraded and then laundered. New and laundered cotton fabric was also examined for its capability to decrease the penetration of azinphos-methyl through another in vitro epidermal system (Epiderm, MatTek Corp., Ashland, MA), after 4 and 24 h of exposure. Capability of the media under the in vitro epidermal systems to inhibit brain acetylcholinesterase (AChE) was used as the indicator of penetration. Results were compared to OP-caused inhibitions seen in media under the fabric alone and in media under the in vitro epidermal systems alone. Incubations of azinphos-methyl suspensions and the in vitro epidermal systems covered with fabric indicated that both the epidermal cells and fabric provided protection against AChE inhibition caused by this OP and that the protective effects were additive, whether measured after 4 or 24 h of exposure. Therefore, neither laundering nor abrasion followed by laundering altered the capability of the in vitro epidermal systems to absorb azinphos-methyl suspension. For paraoxon solution, however, new cotton glove fabric prevented absorption, and this protective effect, noted after 4 h of exposure, was lost when the fabric was laundered. Abrading the fabric did not cause a greater effect than laundering alone. These results suggest that the pesticide as well as its formulation may be factors of consideration when protective fabrics are chosen, and that, for cotton glove fabric, the protection against some OPs may best be provided before the fabric is laundered.

Absorption↗

Evaluation of mechanisms of azinphos-methyl resistance in the codling moth Cydia pomonella (L.).

Resistance of the codling moth Cydia pomonella (L.) to azinphos-methyl is not based on enhanced detoxifying enzymes like oxidation mediated by mixed function oxidases or by glutathione S-transferases. Synergism by S,S,S-tributylphosphoro-trithioate was evident, but the overall activity of general esterases using p-nitrophenyl acetate as the substrate was similar in resistant and susceptible insects. In comparison to acetylcholinesterase (AChE) from susceptible adult codling moth, the enzyme of insects resistant to azinphos-methyl has low affinities (higher K(m) values) to the substrates acetylthiocholine (ATCh) and propionylthiocholine. This difference indicates a possible amino acid alteration at the catalytic or anionic binding sites of the resistant enzyme. Inhibition studies revealed no apparent differences in sensitivity of AChE enzymes from resistant and susceptible moths to organophosphorus compounds (OPs), carbamate insecticides and quaternary ammonium ligands. MEPQ (7-Methylethoxyphosphinyloxy)-1-methylquinolinium) is the most powerful OP inhibitor acting at a nM range, while chlopyrifos oxon, azinphos-methyl oxon and paraoxon are less inhibitory by 22.9, 82.3 and 475 fold, respectively. The codling moth AChE is a typical enzyme that displays substrate inhibition by ATCh, negligible hydrolysis of butyrylthiocholine, very high sensitivity to the bisquaternary ammonium compound BW284c51 and it is not inhibited by the powerful butyrylcholinesterase inhibitor iso-OMPA. Of the three carbamates examined, only carbaryl was inhibitory at the mM range while pirimicarb and aldicarb were inactive. Of the quaternary ammonium ligands (except for the powerful BW284c51), edrophonium and decamethonium displayed appreciable inhibition rates, while d-tubocuraine was practically inactive.

Acetylcholinesterase↗

Toxicity of azinphos-methyl to various development stages of the codling moth Cydia pomonella (Lepidoptera: Tortricidae).

The response to azinphos-methyl of different life-stages of the codling moth Cydia pomonella (L.) was studied. A similarity in response to azinphos-methyl (LC(50), LC(90)) was observed in neonate larvae obtained from the first and second generations of field populations. Mortality rates for neonate larvae of a field population cross-bred with a laboratory colony were lower (by a factor of 1.2-2.2) in comparison with field neonate larvae. The mortality rate of larvae from a laboratory colony exposed to artificial diet containing azinphos-methyl gradually decreased at older instars. The mortality rates of fifth-instar larvae were remarkably low when exposed to artificial diet mixed with azinphos-methyl or when topically treated with the insecticide. One- to three-day-old females were more sensitive than males of the same age, whereas the opposite was observed in 14-to 17-day-old adults. Mortality rates of 14- to 17-day-old adults were higher than those under 10 days old. No significant difference in sensitivity to the organophosphorus compound was noticed between the sexes of 7- to 10-day-old adults. Neonate larvae of the codling moth can serve as a target life-stage for various groups of pesticides, and the importance of using such a stage as a standardized methodology for monitoring resistance in the codling moth is discussed.

Age Factors↗

Efficacy of the organic-certified insecticide Diatect II against the boll weevil (Anthonomus grandis) in cotton.

The efficacy of the organic insecticide Diatect II against boll weevil (Anthonomus grandis Boheman) in cotton (Gossypium hirsutum L) in the Lower Rio Grande Valley of Texas were assessed in small-plot field trials and greenhouse cage tests using azinphos-methyl treatments as a standard for comparison. Plastic sheets were placed in the furrows of the treated plots to retrieve boll weevils which dropped from the plants after being killed by the insecticides. Samples of live weevils taken by a tractor-mounted vacuum sampler revealed a modest, but significant, reduction in boll weevil populations in Diatect II plots. However, samples of dead weevils indicated that this reduction was due to movement of weevils out of the plots rather than to mortality. This interpretation is supported by greenhouse cage studies, where mortality in Diatect II treated cages was no greater than that in untreated control cages. The effects of insecticide treatments in small plots can be confounded easily and quickly by interplot movement of target insects. Although the relative effects of various compounds can usually be assessed by sampling the populations in plots soon after treatment, the best measure of efficacy is obtained by directly sampling insects that have died in the plot. This parameter is insulated from the effects of interplot movement, unless the toxicant is slow to immobilize the target insect. Taken together, our results indicate little efficacy by Diatect II against boll weevil under our test conditions.

Agriculture↗

Impact of sub-lethal residues of azinphos-methyl on the pheromone-communication systems of insecticide-susceptible and insecticide-resistant obliquebanded leafrollers Choristoneura rosaceana (Lepidoptera: Tortricidae).

The effects of sub-lethal residues of azinphos-methyl on pheromone production, calling, female attractiveness and the ability of males to locate sources of natural and synthetic pheromone were compared in azinphos-methyl-susceptible (susceptible) and azinphos-methyl-resistant (resistant) obliquebanded leafrollers, Choristoneura rosaceana (Harris). The amount of pheromone in susceptible females was reduced by 29-33% after exposure to azinphos-methyl; this treatment did not affect the pheromone content of resistant females. Azinphos-methyl-treated resistant females contained 39-43% less pheromone than azinphos-methyl-treated susceptible females. Resistant females that were not treated with azinphos-methyl contained 35-56% less pheromone than susceptible females that were not treated with insecticide. The incidence of calling was reduced by 67-100% in azinphos-methyl-treated susceptible females; the incidence of calling by resistant females was not affected by exposure to azinphos-methyl. The incidence of calling by azinphos-methyl-treated susceptible females was 58-100% lower than that of azinphos-methyl-treated resistant females. There was no difference in the incidence of calling between susceptible and resistant females that had not been treated with insecticide. In a flight tunnel, treatment with insecticide reduced the attractiveness of susceptible females by 38%; treatment with insecticide did not affect the attractiveness of resistant females. There was no difference in the proportion of males attracted to susceptible and resistant females that had, or had not been treated with insecticide. In an apple orchard, the attractiveness of susceptible and resistant females treated with azinphos-methyl was reduced by 84 and 12%, respectively. The proportion of males attracted to azinphos-methyl-treated susceptible females was 58% lower than the proportion attracted to azinphos-methyl-treated resistant females, whereas, if females were not treated with insecticide, the proportion attracted to resistant females was 57% lower than the proportion attracted to susceptible females. In a flight tunnel, azinphos-methyl did not affect the ability of susceptible or resistant males to locate a source of pheromone gland extract. Likewise, in an apple orchard, the insecticide treatment had no effect on the ability of susceptible or resistant males to locate a source of synthetic pheromone. In a flight tunnel, there was no difference in the proportion of azinphos-methyl-treated susceptible and resistant males locating a source of pheromone gland extract; however, in the orchard, 39% fewer azinphos-methyl-treated resistant males located a source of synthetic pheromone than azinphos-methyl-treated susceptible males. A similar proportion of susceptible and resistant males that had not been treated with insecticide located a source of pheromone gland extract in the flight tunnel, but in the orchard, the proportion of resistant males not treated with azinphos-methyl that located the source of synthetic pheromone was 32% lower than the proportion of susceptible males not treated with this insecticide. The implications of the differences in the effect of sub-lethal residues of azinphos-methyl on the pheromone communication system of susceptible and resistant moths are discussed in relation to the theory of the development of insecticide resistance, the detection of resistance in feral populations of moths using sex pheromone-baited traps, and the control of moths using sex pheromone-mediated mating disruption.

Animals↗

Effects of insecticides and defoliants applied alone and in combination for control of overwintering boll weevil (Anthonomus grandis; Coleoptera: Curculionidae)--laboratory and field studies.

In laboratory, greenhouse and field tests, we determined the effects of combining full rates of the defoliants tribufos and thidiazuron and the herbicide thifensulfuron-methyl with half rates of the insecticides lambda-cyhalothrin or azinphos-methyl, and the combination of tribufos and thidiazuron, both in half rates, on mortality of the boll weevil, Anthonomus grandis grandis Boheman and on the quality of defoliation. Tribufos, 0.47 kg ha(-1) and tribufos, 0.235 kg ha(-1) + thidiazuron, 0.125 kg ha(-1) exhibited a slightly toxic effect to boll weevil, while tribufos, 0.47 kg ha(-1) + lambda-cyhalothrin, 0.019 kg ha(-1), tribufos, 0.47 kg ha(-1) + azinphos-methyl, 0.14 kg ha(-1), and tribufos, 0.235 kg ha(-1) + thidiazuron, 0.125 kg ha(-1) + azinphos-methyl, 0.14 kg ha(-l), provided control of boll weevil as good as or better than full-rate azinphos-methyl or lambda-cyhalothrin alone owing to synergistic effects. Thidiazuron or thifensulfuron-methyl alone or in combination with insecticides did not affect boll weevil mortality. Treatment with tribufos + thidiazuron, both at half rate, significantly increased defoliation compared to full rates of tribufos or thidiazuron alone, and provided adequate defoliation for approximately the same cost per hectare.

Age Factors↗

Behavioral and sex ratio modification of Japanese medaka (Oryzias latipes) in response to environmentally relevant mixtures of three pesticides.

We exposed Japanese medaka (Oryzias latipes) to environmentally relevant concentrations of azinphos-methyl, chlorothalonil, endosulfan, and mixtures of all three to determine if combinations of these pesticides result in additive, less-than-additive, or more-than-additive effects. Medaka were exposed from fertilization until 7 days posthatching, and end points included survival, time to hatch, size at 7 days posthatching, activity level (as measured by distance swam) and foraging ability at 3 weeks posthatching, and adult size, liver size, and sex ratio at 5 months posthatching. Although exposure to individual pesticides or pesticide mixtures did not affect survival, hatching time, or foraging ability, fry exposed to azinphos-methyl were significantly smaller at 1 week of age, and those exposed to chlorothalonil and a combination of the chemicals showed reduced activity. Adult sex ratios were biased toward females in all groups exposed to pesticides, with those exposed to azinphos-methyl, chlorothalonil, and the pesticide mixture departing significantly from an even sex ratio. There was no evidence of additive or synergistic effects of pesticide mixtures.

Animals↗

Characterization of P-S bond hydrolysis in organophosphorothioate pesticides by organophosphorus hydrolase.

The extensive use of organophosphorothioate insecticides in agriculture has resulted in the risk of environmental contamination with a variety of broadly based neurotoxins that inhibit the acetylcholinesterases of many different animal species. Organophosphorus hydrolase (OPH, EC 3.1.8.1) is a broad-spectrum phosphotriesterase that is capable of detoxifying a variety of organophosphorus neurotoxins by hydrolyzing various phosphorus-ester bonds (P-O, P-F, P-CN, and P-S) between the phosphorus center and an electrophilic leaving group. OPH is capable of hydrolyzing the P-X bond of various organophosphorus compounds at quite different catalytic rates: P-O bonds (kcat = 67-5000 s-1), P-F bonds (kcat = 0.01-500 s-1), and P-S bonds (kcat = 0.0067 to 167 s-1). P-S bond cleavage was readily demonstrated and characterized in these studies by quantifying the released free thiol groups using 5,5'-dithio-bis-2-nitrobenzoic acid or by monitoring an upfield shift of approximately 31 ppm by 31P NMR. A decrease in the toxicity of hydrolyzed products was demonstrated by directly quantifying the loss of inhibition of acetylcholinesterase activity. Phosphorothiolate esters, such as demeton-S, provided noncompetitive inhibition for paraoxon (a P-O triester) hydrolysis, suggesting that the binding of these two different classes of substrates was not identical.

Aryldialkylphosphatase↗

Relationship of aquatic natural organic material characteristics to the toxicity of selected insecticides.

Toxicities of the commercial insecticide formulations of azinphos methyl, chlorpyrifos, fenvalerate, and methyl parathion were evaluated in streamwater samples containing natural organic material (NOM) using a modification of a bacterial bioluminescence assay. Toxicity reduction of azinphos methyl was significantly (P < 0.05) correlated with water sample nonvolatile total solids (NVTS) concentration. Toxicity reductions of fenvalerate and of methyl parathion were significantly correlated to E4/E6 absorbance ratio of NOM, and to the proportion of NOM having molecular weight greater than 3700 Da. Toxicity reductions of fenvalerate and methyl parathion had significant correlations to the concentration of NVTS in water samples. Linear regressions of insecticide EC50 values to these NOM characteristics were used to mathematically model the effect of NOM on insecticide toxicity. Insecticide logKOW values were significantly correlated to the slopes of the EC50-total organic carbon (TOC) concentration regression lines. This confirms that the level of association of some nonionic organic contaminants with NOM is a function of the contaminant's water solubility. No single NOM characteristic was the best predictor of toxicity for all insecticides examined. However, these findings suggest that the influence of NOM on toxicity results primarily from differences in TOC content and abundance of larger molecular size NOM.

Animals↗

Persistence and distribution of azinphos-methyl following application to littoral enclosure mesocosms.

The organophosphorus insecticide azinphos-methyl was applied once to the surface of 12 of 18 littoral enclosure mesocosms (5x10 m) constructed in a 2-ha pond near Duluth, Minnesota. Water, sediment, macrophytes, and adult fathead minnows were analyzed for residue to determine the persistence, distribution, and mass balance of azinphos-methyl. Nominal treatment concentrations were 0, 0.2, 1, 4, and 20 microg/liter active ingredient. The maximum residue concentration in the water was measured 1h after treatment. The half-life in the water column ranged from 1.2 to 2 days and 95% of the residue dissipated in 5.4 to 10.2 days. Measurable residues were found in the sediment, macrophytes, and fish. Maximum residues in these media were measured at 4, 1, and 0.12 days. respectively. The water and sediment were the most important sorptive compartments for azinphos-methyl residue. The macrophytes and fish were of minor importance, containing only trace amounts of the mass applied.

Animals↗

Analysis of the additivity of in vitro inhibition of cholinesterase by mixtures of chlorpyrifos-oxon and azinphos-methyl-oxon.

Organophosphorus (OP) insecticides or their active metabolites act through a common mechanism of toxicity, the inhibition of cholinesterase (ChE). The effects of in vitro exposure of brain (target) and serum (biomarker) ChE to chlorpyrifos-oxon (C horizontal lineO) and azinphos-methyl-oxon (AZM horizontal lineO), the active metabolites of the insecticides chlorpyrifos and azinphos-methyl, respectively, were investigated to determine if simultaneous or sequential exposure to these two OP compounds results in purely additive effects. Additive was defined by the theoretical calculated percent inhibition (dose additivity), which takes into account the fraction of ChE molecules assumed to be available for inhibition by the second compound following inhibition by the first compound, not simple mathematical summation of percent inhibition (response additivity). Brain ChE simultaneously exposed to the two compounds resulted in additive effects, which were less than the simple mathematical summation of percent inhibition. However, serum ChE simultaneously exposed to the two compounds resulted in a nonlinear response, presumably due in part to the presence of detoxifying enzymes in the serum. Sequential exposure of both brain and serum ChE to the two compounds resulted in greater than additive effects at the higher concentrations of each compound. There was no departure from additivity at the lower concentrations of the two compounds. These data suggest that simple mathematical summation of percent inhibitions, i.e., response additivity, is not the appropriate method for describing the combined effects of C horizontal lineO and AZM horizontal lineO on ChE in vitro. In addition, there are other mechanisms involved, such as the presence of detoxication enzymes, that must be taken into account when analyzing the effects of combined exposure of ChE to these two compounds.

Animals↗