Pesticides in surface water of the Ondas river watershed, western Bahia, Brazil: Spatial-seasonal distribution and risk assessment.

This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential risks to the aquatic health and human water consumption in the western region of Bahia state, Brazil. Two gas chromatography-mass spectrometry analytical methods were applied to monitor 34 pesticides in water samples collected during both the dry and rainy seasons at 17 sites. Upon individual analysis, only γ-HCH, methoxychlor, demeton-S, methyl parathion, fenitrothion, chlorpyrifos, and azoxystrobin exhibited statistically significant differences between seasons. During rainy season, concentration medians of residues were higher for γ-HCH (74.7 ng L-1), methoxychlor (25.1 ng L-1), and azoxystrobin (47.2 ng L-1), potentially linked to historical contamination or illegal use. Conversely, pesticides like methyl parathion, fenitrothion, and chlorpyrifos, belonging to the organophosphate class, showed higher concentration medians in the dry period, measuring 75.1, 5.50, and 10.8 ng L-1, respectively, probably due to region crop activities. The risk quotient (RQ) assessment for aquatic life indicated that 59.0% of the samples in the dry season and 76.0% in the rainy season had RQ values greater than one, signifying a critical scenario for species conservation. Regarding human consumption, elevated risks were observed for heptachlor in both sampling periods and for azoxystrobin during the rainy season, surpassing RQ levels above 1, indicating danger in untreated water ingestion. Additionally, 24.0% and 53.0% of the samples in the dry and rainy seasons, respectively, contained at least one pesticide exceeding the EU resolution limit (100 ng L-1). Therefore, considering this information, implementing mitigation measures to avoid the river's contamination becomes imperative.

Levels of pesticides and trace metals in water, sediment, and fish of a large, agriculturally-dominated river.

Basin land-use interacts with hydrology to deliver chemical contaminants to riverine environments. These chemicals are eventually taken up by aquatic organisms, where they can cause harmful effects. However, knowledge gaps related to the connections between hydrological, chemical, and biological processes currently limit our ability to forecast potential future changes in contaminant concentrations accurately. In this study, concentrations of three pesticide classes (organochlorines, organophosphates, and herbicides) and a standard suite of trace metals were analyzed in the South Saskatchewan River, Canada in 2020 and 2021 in water, sediments, and fishes. Organochlorine pesticides have been banned in Canada since the 1970s, yet there were some detections for methoxychlor and lindane, predominantly in sediment and fish samples, which could be attributed to legacy contamination. Except for malathion and parathion, organophosphate pesticides were scarcely detected in both sampling years in all matrices, and neonicotinoids were below detection in all samples. Conversely, the herbicides 2,4-D and dicamba were detected consistently throughout all locations in water samples for both sampling years. Overall, concentrations were 3 times higher in 2020 when river discharge was ∼2 times higher, suggesting run-off from the surrounding catchment or disturbance of contaminated sediments. Analysis for trace metals revealed that Cu and Zn exceeded sediment quality guidelines in some locations. Mercury concentrations exceeded the guidelines for about 18% of the samples (water and sediment) analyzed. These findings fill gaps in monitoring datasets and highlight key links between hydrology and chemistry that can be further explored in computational models to predict future contaminant trends in freshwater systems.

Potential occupational exposures in the Reiss-Engelhorn-Museen Mannheim/Germany.

The Reiss-Engelhorn-Museen in Mannheim, Germany requested support from a toxicological laboratory in evaluating occupational exposures before a cleanup and renovation period in 2006. Samples of dust and dirt and scrapings of exhibits were collected from several locations. Following toxicologically relevant compounds could be identified by gas chromatography - mass spectrometry (GC/MS) by comparison with a mass spectra library: dichlorodiphenyl trichloroethane (DDT) and its breakdown product dichlorodiphenyl dichloroethane (DDD) as well as dichlorodiphenyl dichlorethylene (DDE), methoxychlor, nicotine, and camphor. In recent times various insecticides have been used to protect museum artefacts against moths, woodborers and other insect pests. Caution has to be made because the presence of hazardous compounds can result in security problems for museum staff as well as for visitors.

Metabolism of methoxychlor by the P450-monooxygenase CYP6G1 involved in insecticide resistance of Drosophila melanogaster after expression in cell cultures of Nicotiana tabacum.

Cytochrome P450 monooxygenase CYP6G1 of Drosophila melanogaster was heterologously expressed in a cell suspension culture of Nicotiana tabacum. This in vitro system was used to study the capability of CYP6G1 to metabolize the insecticide methoxychlor (=1,1,1-trichloro-2,2-bis(4-methoxyphenyl)ethane, 1) against the background of endogenous enzymes of the corresponding non-transgenic culture. The Cyp6g1-transgenic cell culture metabolized 96% of applied methoxychlor (45.8 microg per assay) within 24 h by demethylation and hydroxylation mainly to trishydroxy and catechol methoxychlor (16 and 17%, resp.). About 34% of the metabolism and the distinct formation of trishydroxy and catechol methoxychlor were due to foreign enzyme CYP6G1. Furthermore, methoxychlor metabolism was inhibited by 43% after simultaneous addition of piperonyl butoxide (458 microg), whereas inhibition in the non-transgenic culture amounted to 92%. Additionally, the rate of glycosylation was reduced in both cultures. These results were supported by the inhibition of the metabolism of the insecticide imidacloprid (6; 20 microg, 24 h) in the Cyp6g1-transgenic culture by 82% in the presence of piperonyl butoxide (200 microg). Due to CYP6G1 being responsible for imidacloprid resistance of Drosophila or being involved in DDT resistance, it is likely that CYP6G1 conveys resistance to methoxychlor (1). Furthermore, treating Drosophila with piperonyl butoxide could weaken the observed resistance phenomena.

Organochlorine pesticide residues in wheat from Konya region, Turkey.

The present study has been carried out to evaluate the organochlorine pesticide contamination in wheat from Konya region. This region is the largest area of cereal production in Turkey. The contamination level has been determined according to the European Community Directives. Different wheat samples (36) were obtained from local farmers and wheat factories in this region. All the wheat samples examined were found to be contaminated by organochlorine pesticide residues of cis-Chlordane and methoxychlor. Chlordane isomers, methoxychlor, DDT and its metabolites, aldrin, beta HCH, heptachlor and lindane have been found to be the highest organochlorine pesticide residues. In some of these samples, various organochlorine pesticide residues have been determined to be higher than European Community maximum residual limits. The residues of aldrin in one sample, trans-Chlordane in one sample, oxy-chlordane in eight samples and methoxychlor in one sample were found to be in excess of EC MRLs. Since most of the samples have been found to be contaminated with residues and some residues exceed EC MRLs, a control of organochlorine pesticide residues in wheat is necessary.

Anaerobic biodegradation of organochlorine pesticides in contaminated soil - significance of temperature and availability.

Anaerobic biodegradation of the pesticides: gamma-hexachlorocyclohexane, methoxychlor, o,p'- and p,p'-DDT in field polluted soil was tested at 12, 22 and 30 degrees C, using methanogenic granular sludge as inoculum. The contaminants were removed quite effectively at all temperatures and their removal rates increased 1.2-1.7 times with the increase in temperature. In most cases pesticide concentrations after an initial substantial decline remained almost constant until the end of experiment. These residual concentrations were also temperature dependent and they were 1.4-8.2 times higher at 12 degrees C than at 30 degrees C. DDT was degraded via DDD and accumulation of this metabolite was lower (19-64%) than the corresponding amount of removed DDT, especially at higher temperatures. Further transformation of DDD was confirmed by formation of p,p'-dichlorobenzophenone. Additional experiment demonstrated that removal was limited to readily desorbing fractions of pesticides, while their desorption-resistant fractions persisted in the soil. However, DDD metabolite was only partially removed despite its good desorbability.

Removal of endosulfan and methoxychlor from water on carbon slurry.

A carbon slurry, produced in generators of fuel-oil-based industrial generators was converted into an effective and efficient adsorbent for the removal of endosulfan and methoxychlor from aqueous solution. The adsorbent was chemically treated, activated, characterized, and used for the adsorption of endosulfan and methoxychlor pesticides. The maximum adsorption was found at 90 min, 6.5 pH, 0.025 g/L dose, and 25 degrees C temperature. Langmuir and Freundlich adsorption models were applied to analyze adsorption data, and the former was found applicable to this adsorption system in terms of relatively high regression values. The thermodynamic aspect of the process was also investigated by evaluating certain important parameters (enthalpy, free energy, and entropy of system). Kinetics of adsorption was found to follow the pseudo second order rate equation. The diffusion of pesticides into carbon slurry pores was suggested to be the rate controlling step by applying Bangham's equation. Adsorption on a column was also investigated in a continuous flow system. Adsorption efficiencies of endosulfan and methoxychlor were 34.11 and 36.06 mg/g in batch processes and 32.62 and 33.52 mg/g in column operations, respectively.

Organochlorine contaminants in complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs from Belize.

Seven complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs were collected in northern Belize and examined for organochlorine (OC) pesticide residues. The primary OC detected, p,p-DDE, was found in every egg analyzed (n=175). Other OCs detected included p,p-DDT, p,p-DDD, methoxychlor, aldrin, and endosulfan I. Concentrations of individual OCs ranged from 4 ppb (ng chemical/g egg wet weight) to greater than 500 ppb. A statistical evaluation of p,p-DDE levels in three complete clutches was used to derive the minimum number of eggs needed from a clutch to precisely determine the mean p,p-DDE concentration representative of that clutch. Sample sizes of 8 (80% confidence level) and 11 (90% confidence level) were determined to yield an accurate estimate of contaminant levels in a full clutch of eggs. The statistically recommended sample size of 11 eggs (at 90% confidence level) was successfully tested on the four additional clutches.

A binary screening assay for pro-oestrogens in food: metabolic activation using hepatic microsomes and detection with oestrogen sensitive recombinant yeast cells.

An assay, employing microsomes prepared from rat liver and a recombinant cell bioassay (RCBA) expressing the human oestrogen receptor (alpha) linked to a reporter gene, was evaluated for the detection of pro-oestrogens in food using methoxychlor and mestranol as model compounds. Bio-activation of the hop phytoestrogen isoxanthohumol to the potent oestrogen 8-prenylnaringenin was also investigated. The oestrogenic potency values for reference standards determined with the RCBA (17beta-oestradiol = 100%) were: methoxychlor 0.0025%, mestranol 1.3%, isoxanthohumol 0.001%, and for their potential respective metabolites were: bishydroxymethoxychlor 0.015%, 17alpha-ethynyl oestradiol 69% and 8-prenylnaringenin 0.4%. Incubation of methoxychlor and mestranol (10 microM) with microsomes prepared from the liver of rats treated with Aroclor 1254 significantly increased (p < 0.001) their oestrogenic potency from 0.0021 and 2.4% to 0.015 and 8.3%, respectively. In contrast, the potency of the hop phytoestrogen isoxanthohumol was unchanged. Metabolites were identified by UV-HPLC-MS/MS as monohydroxy methoxychlor and HPTE from methoxychlor, and the major metabolite of mestranol was 17alpha-ethynyl oestradiol. There was no evidence for the metabolism of isoxanthohumol. Mestranol was also activated by microsomes induced with saline (control), beta-napthoflavone, 3-methylcholantherene, isoniazid or pregnenolone-16alpha-carbonitrile, but not phenobarbitone. These studies demonstrate the principle for use of a binary assay system for the detection of pro-oestrogens and indicate the potential value for risk assessment of endocrine disrupting chemicals.

Diet and organochlorine contaminants in women of reproductive age under 40 years old.

The diet of the breast-feeding mother impacts on the quality and quantity of the milk that she feeds her child. Milk can be a vehicle for toxins, such as drugs and their metabolites, viruses, nicotine, caffeine, alcohol, and organochlorine molecules such as PCBs, DDT, HCB, HCH and dioxins, which can harm the health of the breast-feeding child. The 24-h recall diet was considered appropriate to adequately study the diet of breast-feeding mothers and was used in the present preliminary study to establish the possible relationship between the food items consumed and the presence of pesticides in her milk. Two groups of randomly selected healthy breast-feeding volunteers aged between 17 and 35 years from two different areas were recruited: 34 from intensive agriculture zone, El Ejido (Almeria), from the "Hospital de Poniente" and 21 urban zone, the city of Granada, from the "Clinico" University Hospital. Application of the Spearman Correlation Test to the results from Almeria showed a certain positive correlation between the total intake of fats and both the p,p'DDD (rho=0.53, p< or =0.05) and methoxychlor (rho=0.48, p< or =0.05) in mature milk, and between the energy supplied by vegetables and the endosulfan-lactone in mature milk (rho=0.50, p< or =0.05). Among the group of breast-feeding women from Granada, there was a strong correlation between the intake of fats and both the p,p'DDT in transition milk (rho=0.90, p< or =0.05) and the p,p'DDD in mature milk (rho=0.90, p< or =0.05). In conclusion, there is a statistically significant relationship between the consumption of fatty foods and some organochlorine molecules and between the consumption of vegetables and pesticides, and the latter relationship occurs in Almeria but not in Granada.

Organochlorine contaminants in Morelet's crocodile (Crocodylus moreletii) eggs from Belize.

Non-viable eggs of Morelet's crocodile (Crocodylus moreletii) were collected from Gold Button (GBL) and New River lagoons (NRL) in northern Belize and screened for organochlorine (OC) compounds using gas chromatography (GC) with electron capture detection (ECD). All egg samples from both lagoons (n = 24) tested positive for one or more OCs. Primary contaminants were p,p-DDE and methoxychlor, detected in 100% and 29% of the eggs examined, respectively. Concentrations of individual OC contaminants ranged from 1 ppb (ng chemical/g egg) to > 0.5 ppm (microgram chemical/g egg). Total concentrations of OCs (sum of all OCs) for one egg collected from a nest at GBL reached as high as 0.7 ppm. Sediment samples from both lagoons also tested positive for OCs (lindane, aldrin, methoxychlor, heptachlor epoxide, p,p-DDT, among others). Nest media (soil and plant material) collected from crocodile nests at GBL were positive for p,p-DDT, methoxychlor, aldrin, endosulfan II, and endrin aldehyde. Based on the 24 egg samples analyzed to date, crocodiles from both lagoons are being exposed to OCs. Such exposure may present a health threat to populations of crocodiles in Central America.

Organochlorine contaminants in Morelet's crocodile (Crocodylus moreletii) eggs from Belize

Non-viable eggs of Morelet's crocodile (Crocodylus moreletti) were collected from Gold Botton (GBL) and New River lagoons (NRL) in northern Belize and screened for organochlorine (OC) compounds using gas chromatography (GC) with electron capture detection (ECD). All egg samples from both lagoons (n=24) tested positive for one or more OCs. Primary contaminants were p,p-DDE and methoxychlor, detected in 100 percent and 29 percent of the eggs examined, respectively. Concentrations of individual OC contaminants ranged from 1 ppb (ng chemical/g egg). Total concentrations of OCs (sum of all OCs) for one egg collected from a nest at GBL reached as high as 0.7 ppm. Sediment samples from both lagoons also tested positive for OCs (lindane, aldrin, methoxychlor, heptachlor epoxide, p, p-DDT, among others). Nest media (soil and plant material) collected from crocodile nests at GBL were positive for p, p-DDT, methoxychlor, aldrin, endosulfan II, and endrin aldehyde. Based on the 24 egg samples analyzed to date, crocodiles from both lagoons are being exposed to OCs. Such exposure may present a health threat to populations of crocodiles in Central America. (AU)

Homogeneity of fruits and vegetables comminuted in a vertical cutter mixer.

The homogeneity of comminuted composites of 20 lb samples of apples, cabbage, and green beans containing field-incurred residues of p, p'-methoxychlor was studied to determine whether a 5 min comminution in a 40 qt vertical cutter mixer produces a homogeneous composite and whether the size of test portions used accurately represents the composite. Duplicate test portions of 100, 50, 25, 10, 5, and 2 g taken from each of 6 separate sections of the mixer were analyzed by standard pesticide residue methodology for p, p'-methoxychlor. Results of this study confirmed that comminution of fresh produce in a 40 qt vertical cutter mixer, according to instructions described in the U.S. Food and Drug Administration's Pesticide Analytical Manual, Volume I, Section 203B, produces a homogeneous composite. No significant differences were found in the data for the 3 crops taken from the 6 sections of the mixer. Test portion weights of 100, 50, and 25 g produced equivalent results for all 3 crops. Statistically significant differences were observed for cabbage at 2, 5, and 10 g and for green beans at 2 g.

[Determining the levels of selected pesticides, nitrates, nitrites, ammonium ions, sulfates, chlorides and urea in surface and underground waters. VII]. / Oznaczanie wybranych pestycydów, azotanów, azotynów, jonów amonowych, siarczanów, chlorków i mocznika w wodach powierzchniowych i podziemnych. Cz. VII.

The subjects of the study was determination of the residues of pesticides: lindane, metoxychlor and chlorphenvinphos, nitrates, nitrites, ammonium ions, sulphates, chlorides and urea in surface waters and underground waters in the southeastern part of the Province of Szczecin in 1983-1988. The certain pesticides and urea in none of determined samples of waters were present. The concentrations of nitrates, ammonium and chlorides below the permitted value have been. Nitrites in surface waters and in underground waters in 48 per cent and 82 percent of the samples have been respectively.

Evidence for surface effects in an electron-capture detector.

We have found surface effects in a conventional electron-capture detector that are significantly reduced in an experimental, more inert version of this detector, both by Varian. These surface effects generate unique patterns of solute response for both pesticides-herbicides, and derivatized cytosine strong electrophores. They also cause a minimum followed by a more pronounced maximum in the response factor with increasing solute concentration, demonstrated with lindane. Certain speculations are presented to account for these observations.

Methoxychlor residues in milk of cattle treated with Marlate 50 insecticide as a dermal spray.

Lactating Holstein cattle were treated twice at an interval of 14 days with methoxychlor (Marlate 50 insecticide) as a 0, .25, or .50% dermal spray, with 2 quarts of spray mix applied to each animal. Residues of methoxychlor in whole milk were highest on the 1st or 2nd day after treatment and, when expressed as part per million equivalent in milk fat, were as high as 2.0 and 3.0 ppm in samples from the low and high dosage sprays. Residues in milk dropped rapidly after residues were at most only slightly above the sensitivity limit (.005 ppm in whole milk) of the analytical method. Applicative specifications for Marlate 50 insecticide use on lactating dairy cattle might result in violative methoxychlor residues in milk during the first 1 to 3 days after treatment.