-
Chemosphere Oct 2023The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land...
The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.
Topics: Pesticides; Ecuador; Insecticides; Water Quality; Ecosystem; Palm Oil; Urbanization; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Fresh Water; Rivers; Chlorpyrifos
PubMed: 37379974
DOI: 10.1016/j.chemosphere.2023.139286 -
Environmental Health Perspectives Mar 2017Recent studies have highlighted the increased potency of oxygen analogs of organophosphorus pesticides. These pesticides and oxygen analogs have previously been...
BACKGROUND
Recent studies have highlighted the increased potency of oxygen analogs of organophosphorus pesticides. These pesticides and oxygen analogs have previously been identified in the atmosphere following spray applications in the states of California and Washington.
OBJECTIVES
We used two passive sampling methods to measure levels of the ollowing organophosphorus pesticides: chlorpyrifos, azinphos-methyl, and their oxygen analogs at 14 farmworker and 9 non-farmworker households in an agricultural region of central Washington State in 2011.
METHODS
The passive methods included polyurethane foam passive air samplers deployed outdoors and indoors and polypropylene deposition plates deployed indoors. We collected cumulative monthly samples during the pesticide application seasons and during the winter season as a control.
RESULTS
Monthly outdoor air concentrations ranged from 9.2 to 199 ng/m for chlorpyrifos, 0.03 to 20 ng/m for chlorpyrifos-oxon, < LOD (limit of detection) to 7.3 ng/m for azinphos-methyl, and < LOD to 0.8 ng/m for azinphos-methyl-oxon. Samples from proximal households (≤ 250 m) had significantly higher outdoor air concentrations of chlorpyrifos, chlorpyrifos-oxon, and azinphos-methyl than did samples from nonproximal households ( ≤ 0.02). Overall, indoor air concentrations were lower than outdoors. For example, all outdoor air samples for chlorpyrifos and 97% of samples for azinphos-methyl were > LOD. Indoors, only 78% of air samples for chlorpyrifos and 35% of samples for azinphos-methyl were > LOD. Samples from farmworker households had higher indoor air concentrations of both pesticides than did samples from non-farmworker households. Mean indoor and outdoor air concentration ratios for chlorpyrifos and azinphos-methyl were 0.17 and 0.44, respectively.
CONCLUSIONS
We identified higher levels in air and on surfaces at both proximal and farmworker households. Our findings further confirm the presence of pesticides and their oxygen analogs in air and highlight their potential for infiltration of indoor living environments. Citation: Gibbs JL, Yost MG, Negrete M, Fenske RA. 2017. Passive sampling for indoor and outdoor exposures to chlorpyrifos, azinphos-methyl, and oxygen analogs in a rural agricultural community. Environ Health Perspect 125:333-341; http://dx.doi.org/10.1289/EHP425.
Topics: Agriculture; Air Pollutants; Air Pollution, Indoor; Atmosphere; Azinphosmethyl; California; Chlorpyrifos; Environmental Exposure; Environmental Monitoring; Humans; Insecticides; Oxygen; Rural Population; Washington
PubMed: 27517732
DOI: 10.1289/EHP425 -
Scientific Reports Oct 2022Transcriptional analysis of the network of transcription regulators and target pathways in exposed organisms may be a hard task when their genome remains unknown. The...
Transcriptional analysis of the network of transcription regulators and target pathways in exposed organisms may be a hard task when their genome remains unknown. The development of hundreds of qPCR assays, including primer design and normalization of the results with the appropriate housekeeping genes, seems an unreachable task. Alternatively, we took advantage of a whole transcriptome study on Rhinella arenarum larvae exposed to the organophosphorus pesticides azinphos-methyl and chlorpyrifos to evaluate the transcriptional effects on a priori selected groups of genes. This approach allowed us to evaluate the effects on hypothesis-selected pathways such as target esterases, detoxifying enzymes, polyamine metabolism and signaling, and regulatory pathways modulating them. We could then compare the responses at the transcriptional level with previously described effects at the enzymatic or metabolic levels to obtain global insight into toxicity-response mechanisms. The effects of both pesticides on the transcript levels of these pathways could be considered moderate, while chlorpyrifos-induced responses were more potent and earlier than those elicited by azinphos-methyl. Finally, we inferred a prevailing downregulation effect of pesticides on signaling pathways and transcription factor transcripts encoding products that modulate/control the polyamine and antioxidant response pathways. We also tested and selected potential housekeeping genes based on those reported for other species. These results allow us to conduct future confirmatory studies on pesticide modulation of gene expression in toad larvae.
Topics: Animals; Azinphosmethyl; Chlorpyrifos; Pesticides; Larva; Transcriptome; Organophosphorus Compounds; Antioxidants; Bufo arenarum; Esterases; Polyamines; Transcription Factors
PubMed: 36271284
DOI: 10.1038/s41598-022-21748-6 -
Dalton Transactions (Cambridge, England... Dec 2023The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b)...
The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b) were prepared by employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,5-BPTA) as the primary ligand and 2,2'-bipyridine (1a-5a) and 1,10-phenanthroline (1b-5b) as the secondary ligands. Single-crystal structural studies on [Gd(BPTA)(Bpy)]·0.5DMF (3a) and [Dy(BPTA)(Phen)]·0.5DMF (5b) indicated that the compounds have a two-dimensional structure. The Y compound exhibits blue emission, and the other compounds exhibit emission in the expected regions ( = 350 nm). White light emission was achieved by careful mixing of the red (Eu) and green (Tb) components in the blue emitting Y compound. Thus, YTbEu (bpy) and YTbEu (phen) were found to show white emission when excited using a wavelength of 350 nm. The introduction of N-N-containing ancillary ligands (, bpy and phen) increased the overall quantum yield (QY) of white light emission to 31% and 43%, respectively. The high QY observed for the Tb and Eu compounds was found to be sensitive and selective for the fluorometric detection of azinphos-methyl pesticide and trinitrophenol (TNP) in an aqueous medium at the ppb level. The same behaviour was observed when utilising the compounds as onsite paper strip sensors. Their magnetic properties were also studied, revealing for the Tb and Dy derivatives slow relaxation of the magnetisation at low temperature. The present study highlights the usefulness of rigid π-conjugated molecules such as 2,2'-bipyridine and 1,10-phenanthroline in enhancing the many utilities of rare-earth-containing MOFs towards white light emission, the sensing of harmful and dangerous substances and magnetic properties.
PubMed: 38013491
DOI: 10.1039/d3dt01882b -
Pesticide Biochemistry and Physiology Feb 2020The organophosphorus pesticides azinphos-methyl (AZM) and chlorpyrifos (CPF) exert their toxic action by inhibition of acetylcholinesterase, but non-target processes...
Differential effects of azinphos-methyl and chlorpyrifos on polyamine oxidative metabolism during the embryonic development of Rhinella arenarum and its relation to oxidative stress.
The organophosphorus pesticides azinphos-methyl (AZM) and chlorpyrifos (CPF) exert their toxic action by inhibition of acetylcholinesterase, but non-target processes such as polyamine metabolism can also be affected. Our objective was to evaluate the effects of different concentrations of AZM (0.5-, 2- and 9 mg L) and CPF (0.5- and 1 mg L) on polyamine oxidative metabolism along Rhinella arenarum embryonic development and to explore its relationship to oxidative stress. Free and conjugated polyamines were measured by HPLC. The activity of spermine oxidase (SMOX), N-acetylpolyamine oxidase (PAOX) and diamine oxidase (DAO) were measured through kinetic spectrofluorometry. Free putrescine and spermine were significantly increased in open mouth embryos exposed to AZM. Free polyamine levels were not affected by CPF exposure. In embryos exposed to AZM, DAO was increased in tail bud stage and SMOX was increased in open mouth stage, while embryos exposed to CPF showed an increase of PAOX activity in tail bud stage and a decrease of DAO and SMOX activity in open mouth stage. Polyamine levels and oxidative degradation enzymes respond differently if R. arenarum embryos are exposed to AZM or CPF, despite that both insecticides belong to the same chemical family. The early increase of DAO and PAOX would play a protective role to guarantee the normal progression of embryonic development. The increased production of reactive species might contribute to an oxidative stress situation generated by exposure to the insecticides and to the alteration of the antioxidant defense system. In tail bud stage embryos, PAOX and SMOX were positively correlated to acetylcholinesterase activity and reduced glutathione levels (GSH), and negatively correlated to the antioxidant enzymes catalase (CAT) and glutathione S-transferase (GST). In complete operculum embryos, a negative correlation between antioxidant parameters and polyamine levels and polyamine oxidative metabolism was observed, except for SMOX, which showed a low positive correlation with CAT and GSH and a negative correlation to PAOX and DAO. We suggest the use of DAO and PAOX as biomarkers of exposure to AZM and CPF, respectively, as they respond earlier than the classical biomarker acetylcholinesterase.
Topics: Azinphosmethyl; Chlorpyrifos; Embryonic Development; Oxidative Stress; Polyamines
PubMed: 31973851
DOI: 10.1016/j.pestbp.2019.10.007 -
Journal of Exposure Science &... Jul 2017Since 1998, the University of Washington's Center for Child Environmental Health Risks Research has followed a community-based participatory research strategy in the... (Comparative Study)
Comparative Study
Since 1998, the University of Washington's Center for Child Environmental Health Risks Research has followed a community-based participatory research strategy in the Lower Yakima Valley of Washington State to assess pesticide exposure among families of Hispanic farmworkers. As a part of this longitudinal study, house dust samples were collected from both farmworker and non-farmworker households, across three agricultural seasons (thinning, harvest and non-spray). The household dust samples were analyzed for five organophosphate pesticides: azinphos-methyl, phosmet, malathion, diazinon, and chlorpyrifos. Organophosphate pesticide levels in house dust were generally reflective of annual use rates and varied by occupational status and agricultural season. Overall, organophosphate pesticide concentrations were higher in the thinning and harvest seasons than in the non-spray season. Azinphos-methyl was found in the highest concentrations across all seasons and occupations. Farmworker house dust had between 5- and 9-fold higher concentrations of azinphos-methyl than non-farmworker house dust. Phosmet was found in 5-7-fold higher concentrations in farmworker house dust relative to non-farmworker house dust. Malathion and chlorpyriphos concentrations in farmworker house dust ranged between 1.8- and 9.8-fold higher than non-farmworker house dust. Diazinon showed a defined seasonal pattern that peaked in the harvest season and did not significantly differ between farmworker and non-farmworker house dust. The observed occupational differences in four out of five of the pesticide residues measured provides evidence supporting an occupational take home pathway, in which workers may bring pesticides home on their skin or clothing. Further, these results demonstrate the ability of dust samples to inform the episodic nature of organophosphate pesticide exposures and the need to collect multiple samples for complete characterization of exposure potential.
Topics: Agriculture; Agrochemicals; Air Pollutants; Air Pollution, Indoor; Community-Based Participatory Research; Dust; Environmental Monitoring; Farmers; Hispanic or Latino; Housing; Humans; Longitudinal Studies; Markov Chains; Occupational Exposure; Organothiophosphates; Pesticides; Seasons; Washington
PubMed: 27553992
DOI: 10.1038/jes.2016.45 -
Environmental Science and Pollution... Aug 2022In this study, we examined the dose-dependent effects of an environmentally relevant pesticide cocktail (metalachlor, linuron, isoproturon, tebucanazole, aclonifen,...
Potential mechanisms of Na/K-ATPase attenuation by heat and pesticides co-exposure in goldfish: role of cellular apoptosis, oxidative/nitrative stress, and antioxidants in gills.
In this study, we examined the dose-dependent effects of an environmentally relevant pesticide cocktail (metalachlor, linuron, isoproturon, tebucanazole, aclonifen, atrazine, pendimethalin, and azinphos-methyl) and temperature change (22 vs. 32 °C for 4-week exposure) on Na/K-ATPase, 3-nitrotyrosine protein (NTP), dinitrophenyl protein (DNP), catalase (CAT), and superoxide dismutase (SOD) expressions in gills of goldfish (Carassius auratus). Histopathological analysis showed widespread damage to gill in elevated temperature (32 °C) and pesticide co-exposure groups, including fusion of secondary lamellae, club-shaped primary lamellae, rupture of epithelial layer, loss of normal architecture, and hemorrhaging. Immunohistochemical and qRT-PCR analyses showed significant decreases in Na/K-ATPase protein and mRNA expressions in gills exposed to higher temperature and pesticides; however, combined exposure to heat and pesticides significantly increases NTP, DNP, CAT, and SOD expressions. In situ TUNEL assay revealed elevated levels of apoptotic cells in response to combined exposure. Collectively, our results suggest the combined effects of heat and pesticide stress cause cellular damage, upregulate oxidative/nitrative stress biomarkers, and increase apoptotic cells, downregulate Na/K-ATPase expression in gills. This provides new evidence for oxidant/antioxidant-dependent mechanisms for downregulation of Na/K-ATPase expression in gills during combined exposure.
Topics: Adenosine Triphosphatases; Animals; Antioxidants; Apoptosis; Gills; Goldfish; Hot Temperature; Oxidative Stress; Pesticides; Sodium-Potassium-Exchanging ATPase; Superoxide Dismutase; Water Pollutants, Chemical
PubMed: 35352221
DOI: 10.1007/s11356-022-19779-7 -
Insect Science Jun 2017The control program of codling moth (Cydia pomonella L.) in the Río Negro and Neuquén Valley is intended to neonate larvae. However, adults may be subjected to...
The control program of codling moth (Cydia pomonella L.) in the Río Negro and Neuquén Valley is intended to neonate larvae. However, adults may be subjected to sublethal pesticide concentrations generating stress which might enhance both mutation rates and activity of the detoxification system. This study assessed the exposure effects of chlorpyrifos on target enzyme and, both detoxifying and antioxidant systems of surviving adults from both a laboratory susceptible strain (LSS) and a field population (FP). The results showed that the FP was as susceptible to chlorpyrifos as the LSS and, both exhibited a similar chlorpyrifos-inhibitory concentration 50 (IC ) of acetylcholinesterase (AChE). The FP displayed higher carboxylesterase (CarE) and 7-ethoxycoumarine O-deethylase (ECOD) activities than LSS. Both LSS and FP showed an increase on CarE activity after the exposure to low-chlorpyrifos concentrations, followed by enzyme inhibition at higher concentrations. There were no significant differences neither in the activities of glutathione S-transferases (GST), catalase (CAT) and superoxide dismutase (SOD) nor in the reduced glutathione (GSH) content between LSS and FP. Moreover, these enzymes were unaffected by chlorpyrifos. In conclusion, control adults from the FP exhibited higher CarE and ECOD activities than control adults from the LSS. AChE and CarE activities were the most affected by chlorpyrifos. Control strategies used for C. pomonella, such as rotations of insecticides with different modes of action, will probably delay the evolution of insecticide resistance in FPs from the study area.
Topics: 7-Alkoxycoumarin O-Dealkylase; Acetylcholinesterase; Animals; Antioxidants; Azinphosmethyl; Carboxylesterase; Chlorpyrifos; Insecticides; Moths
PubMed: 26703366
DOI: 10.1111/1744-7917.12307 -
Risk Analysis : An Official Publication... Jun 2018Implementation of probabilistic analyses in exposure assessment can provide valuable insight into the risks of those at the extremes of population distributions,... (Comparative Study)
Comparative Study
Implementation of probabilistic analyses in exposure assessment can provide valuable insight into the risks of those at the extremes of population distributions, including more vulnerable or sensitive subgroups. Incorporation of these analyses into current regulatory methods for occupational pesticide exposure is enabled by the exposure data sets and associated data currently used in the risk assessment approach of the Environmental Protection Agency (EPA). Monte Carlo simulations were performed on exposure measurements from the Agricultural Handler Exposure Database and the Pesticide Handler Exposure Database along with data from the Exposure Factors Handbook and other sources to calculate exposure rates for three different neurotoxic compounds (azinphos methyl, acetamiprid, emamectin benzoate) across four pesticide-handling scenarios. Probabilistic estimates of doses were compared with the no observable effect levels used in the EPA occupational risk assessments. Some percentage of workers were predicted to exceed the level of concern for all three compounds: 54% for azinphos methyl, 5% for acetamiprid, and 20% for emamectin benzoate. This finding has implications for pesticide risk assessment and offers an alternative procedure that may be more protective of those at the extremes of exposure than the current approach.
Topics: Agriculture; Air Pollutants; Algorithms; Azinphosmethyl; Databases, Factual; Humans; Inhalation Exposure; Ivermectin; Neonicotinoids; Occupational Exposure; Pesticides; Probability; Protective Clothing; Risk Assessment; Skin; United States; United States Environmental Protection Agency
PubMed: 29105804
DOI: 10.1111/risa.12936 -
Journal of Water and Health Jun 2024Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the...
Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the world's agricultural production depends on them. The purpose of this study was to determine selected residual concentrations of pesticides (diazinon, ethion, malathion, alachlor, methyl-parathion, trifluralin, atrazine, chlorpyrifos, and azinphos-methyl) in samples from Shiraz potable water sources. For this purpose, water treatment plant, groundwater wells, treated surface water, and a mixture of groundwater and treated surface water were taken. In addition, statistical and risk analyses (carcinogenic and non-carcinogenic) were used. According to the results, chlorpyrifos with 84.4% had the highest removal efficiency and methyl-parathion with 10% had the lowest removal rate in the Shiraz water treatment plant process. The highest mean concentration was related to azinphos-methyl (1.5 μg/L) and chlorpyrifos (0.59 μg/L) in the groundwater samples. All measured compounds in water source samples were below standard levels, except for chlorpyrifos and azinphos-methyl, which were reported in groundwater above the limit recommended by the Environmental Protection Agency (EPA). The results showed that while the selected pesticides measured had a low non-carcinogenic risk for both adults and children, malathion and trifluralin posed a high carcinogenic risk for adults.
Topics: Water Pollutants, Chemical; Herbicides; Risk Assessment; Insecticides; Groundwater; Water Wells; Environmental Monitoring; Water Purification; Drinking Water; Humans; Iran
PubMed: 38935459
DOI: 10.2166/wh.2024.076