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Journal of Chromatography. A Dec 2021Quantitative determination of targeted and untargeted pesticide residues from food products is very important for the assessment of safety of the food products. In the...
Quantitative determination of targeted and untargeted pesticide residues in coconut milk by liquid chromatography - Atmospheric pressure chemical ionization - high energy collisional dissociation tandem high-resolution mass spectrometry.
Quantitative determination of targeted and untargeted pesticide residues from food products is very important for the assessment of safety of the food products. In the present work, a simple, selective and sensitive method based on liquid chromatography atmospheric pressure chemical ionization high energy collisional dissociation high-resolution tandem mass spectrometry (LC-APCI-HCD-HRMS/MS) for quantification of 19 priority organophosphorus and carbamate pesticides and 10 untargeted pesticides from coconut milk samples was developed and validated. The pesticide residues were extracted by solvent partition followed by dispersive solid-phase extraction clean-up and quantified by LC-APCI-HRMS/MS technique. The method showed the linearity for targeted pesticides in the range of 0.5-1000 ng/g with a limit of detection of ranging 0.5-5 ng/g and limit of quantification of ranging 1-10 ng/g measured at 3:1 and 10:1 signal to noise ratios, respectively. The untargeted pesticide residues were quantified by the response factor method. The method was validated for intraday and interday precision, which was less than 15%. The recovery of the analytes varied between 82 and 117%, and the developed method was applied for the analysis of the coconut milk samples. The analyzed samples showed the presence of quinalphos, malathion, and methiocarb at concentrations of 4.55, 5.54, and 206.99 ng/g.
Topics: Animals; Atmospheric Pressure; Chromatography, High Pressure Liquid; Chromatography, Liquid; Cocos; Pesticide Residues; Tandem Mass Spectrometry
PubMed: 34742133
DOI: 10.1016/j.chroma.2021.462649 -
The Science of the Total Environment Jun 2020Climate change and the increased demand for food amplified the global problem with water supply for irrigation. This work deals with the reclamation of municipal...
Climate change and the increased demand for food amplified the global problem with water supply for irrigation. This work deals with the reclamation of municipal wastewater (MWW) for irrigation by a membrane bioreactor (MBR), nanofiltration (NF), and reverse osmosis (RO). The emphasis was on the comparison of physico-chemical and microbiological parameters with the World Health Organization (WHO) and the European Union (EU) guidelines. In addition, the detection and removal of contaminants of emerging concern (CEC) from the Watch List (EU Decision 2015/495) were examined. Firstly, the MWW was monitored (physico-chemical and microbiological parameters, trace elements, and occurrence of CECs) for six months. Thereafter, the MWW was treated with MBR, NF, and RO. The reclaimed water satisfied the physico-chemical and microbiological quality requirements only after additional NF/RO treatment. Membrane bioreactor efficiently removed methiocarb (>99.9%), tri-allate (>99.9%), clothianidin (88.0%), and clarithromycin (71.9-74.2%), while the removal of azithromycin, acetamiprid, and oxadiazon was around 30%. The low and even negative removal during MBR treatment was observed for diclofenac (15%), clothianidin (-14%), imidacloprid (-18%), and diclofenac (-157%). Additional treatment of MBR effluent with NF90 and XLE membranes resulted in complete rejection of detected CECs, while NF270 membrane achieved results between 75% and 91%.
Topics: Bioreactors; Membranes, Artificial; Osmosis; Waste Disposal, Fluid; Wastewater; Water Purification
PubMed: 32208282
DOI: 10.1016/j.scitotenv.2020.137959 -
International Journal of Environmental... Feb 2022Pesticides are widely applied all over the world, and pesticide exposure can induce different biological effects posing a possible threat to human health. Due to their...
Pesticides are widely applied all over the world, and pesticide exposure can induce different biological effects posing a possible threat to human health. Due to their effects on the endocrine system, some pesticides are classified as endocrine disruptors. The aim of the study is to assess the interference of five pesticides on estrogen biosynthesis and estrogen signaling. Three neonicotinoid insecticides (Acetamiprid, Clothianidin, and Thiamethoxam), a carbamate insecticide (Methiocarb) and a herbicide (Oxadiazon) were tested. The effect of pesticides on estrogen biosynthesis was studied through an ELISA assay using a recombinant form of human aromatase, the enzyme that catalyzes the transformation of androgens to estrogens. Moreover, the effect of pesticides on estrogen signaling was assessed using a gene reporter assay on MELN cells, which measures estrogen receptor-mediated estrogenic activity. The results of the ELISA assay showed that the pesticides did not alter aromatase activity (no interference with estrogen biosynthesis), while the results of the gene reporter assay showed that only Methiocarb was able to alter estrogen signaling at high doses. The estrogenic activity of Methiocarb, expressed as 17β-estradiol equivalency factor (EEF), was equal to 8.0 × 10. In conclusion, this study suggested that Methiocarb should be considered a potential endocrine disruptor.
Topics: Aromatase; Endocrine Disruptors; Estrogens; Humans; Pesticides; Receptors, Estrogen
PubMed: 35206146
DOI: 10.3390/ijerph19041959 -
The Science of the Total Environment Apr 2020This work aims at achieving a better understanding of the mechanisms and the operative conditions regulating the removal of a set of relevant micropollutants in...
This work aims at achieving a better understanding of the mechanisms and the operative conditions regulating the removal of a set of relevant micropollutants in conventional activated sludge (CAS) systems to maximize their removal and, if possible, biodegradation. Eight compounds from the EU Watch list (clothianidin, thiacloprid, methiocarb, E1, E2, EE2, diclofenac and erythromycin) were spiked at 2 μg/L in CAS systems and their behaviour was studied in 6-h batch tests. The role of sorption was also investigated. Information on the removal of the pesticides clothianidin, thiacloprid and methiocarb is here presented for the first time to the best of the authors' knowledge. With the aim of enhancing the removal of the selected compounds in wastewater treatment, four parameters were explored: biomass concentration, temperature, pH and redox conditions. For each parameter, a low and a high value were chosen, based on the ranges usually applied in wastewater treatment plants (WWTPs). Results show that biomass concentration is the most relevant parameter among the ones investigated, followed by the redox conditions. The operational conditions that maximized removal rates were: 5 g/L of biomass, aerobic conditions, 25 °C and pH 7.5. High variability in removal rates was observed for compounds such as E1, erythromycin and methiocarb. The pesticides clothianidin and thiacloprid did not prove to be easily degradable. The highest removal rates were recorded for the hormones, particularly E2, with a transformation rate of at least 96% under all conditions. Sorption proved to be a relevant removal route for EE2, for which the highest sorption rates were recorded, and diclofenac, where the adsorption mechanisms was hypothesised for its prevalence at lower pH values.
Topics: Biodegradation, Environmental; Sewage; Waste Disposal, Fluid; Wastewater; Water Pollutants, Chemical
PubMed: 32018966
DOI: 10.1016/j.scitotenv.2020.136773 -
The Science of the Total Environment Feb 2022The presence of micropollutants (MPs), including pharmaceutical, industrial, and pesticidal compounds, threatens both human health and the aquatic ecosystem. The...
The presence of micropollutants (MPs), including pharmaceutical, industrial, and pesticidal compounds, threatens both human health and the aquatic ecosystem. The development and extensive use of new chemicals have also inevitably led to the accumulation of MPs in aquatic environments. Recreational beaches are especially vulnerable to contamination, affecting humans and aquatic animals via the absorption of MPs in water during marine activities (e.g., swimming, sailing, and windsurfing). Additionally, marine outfalls in an urbanized coastal city can cause serious chemical and microbial pollution on recreational beaches, leading to an increase in adverse effects on public health and the ecological system. Therefore, the aim of this study was to, with the use of network and decision tree analyses, identify the features and factors that influence the change in MP concentrations in a marine outfall. These analyses were conducted to inspect the relationship between each MP and its hierarchical structure as well as hydrometeorological variables. Additionally, a risk analysis was conducted in this study in which the MPs were prioritized based on their optimized risk quotient values. During our monitoring of MP concentrations over time at the marine outfall, high concentrations of pharmaceutical and industrial compounds were detected when the tide level was low after rainfall. Furthermore, results of the risk analysis and the prioritization revealed that a total of 18 substances identified in our study posed a risk to the ecosystem; these include major ecotoxicologically hazardous substances such as telmisartan, mevinphos, and methiocarb. Results of the network analysis demonstrated distinct trends for pharmaceutical and industrial substances, whilst those for pesticide compounds were irregular. Additionally, the hierarchical structures for most MPs consisted of rainfall, tide level, and antecedent dry hours; this implies that these factors influence MP dynamics. These findings will be helpful for establishing chemical contamination management plans for recreational beaches in the future.
Topics: Animals; Decision Trees; Ecosystem; Environmental Monitoring; Humans; Pesticides; Water Pollutants, Chemical
PubMed: 34655621
DOI: 10.1016/j.scitotenv.2021.150938 -
Journal of Colloid and Interface Science May 2021Present work reports preparation of colloidal single/few layer TiCT MXene flakes using minimally intensive layer delamination (MILD) method for rapid electroanalytical...
Present work reports preparation of colloidal single/few layer TiCT MXene flakes using minimally intensive layer delamination (MILD) method for rapid electroanalytical screening of carbamate pesticides. Lithium fluoride salt and hydrochloric acid (7.5 M LiF/9M HCl) was used to produce in-situ generated HF as etchant to remove Al successfully from TiAlC MAX phase. Unlike the clay method (5 M LiF/6M HCl), this methodology simplified TiCT synthesis protocol resulting in Li ions intercalated TiCT which was delaminated without further sonication. The delaminated TiCT flakes were found to be single/few layered sheets with mostly -OH and -O terminated surface groups. The characteristic 002 peak observed in X-ray diffraction (XRD) at 2θ = 6.4° with interplaner distance of 1.1137 nm suggested broadening of the peak attributed to the presence of Li ions between TiCT flakes. Delaminated TiCT flakes were utilized as working electrode which demonstrated simultaneous and selective detection of carbamate pesticides methiocarb and diethofencarb by voltammetry. The oxidation peaks of the two pesticides were well separated by a potential difference of 0.35 V in 0.5 M HSO and DPV detection limits were calculated as 0.19 μg mL and 0.46 μg mL for methiocarb and diethofencarb respectively. TiCT flakes as electrochemical sensor exhibited long term stability and acceptable recoveries in real sample for environmental applications.
PubMed: 33549895
DOI: 10.1016/j.jcis.2021.01.063 -
The Science of the Total Environment Nov 2023Sublethal effects are becoming more relevant in ecotoxicological test methods due to their higher sensitivity compared to lethal endpoints and their preventive nature....
Sublethal effects are becoming more relevant in ecotoxicological test methods due to their higher sensitivity compared to lethal endpoints and their preventive nature. Such a promising sublethal endpoint is the movement behavior of invertebrates which is associated with the direct maintenance of various ecosystem processes, hence being of special interest for ecotoxicology. Disturbed movement behavior is often related to neurotoxicity and can affect drift, mate-finding, predator avoidance, and therefore population dynamics. We show the practical implementation of the ToxmateLab, a new device that allows monitoring the movement behavior of up to 48 organisms simultaneously, for behavioral ecotoxicology. We quantified behavioral reactions of Gammarus pulex (Amphipoda, Crustacea) after exposure to two pesticides (dichlorvos and methiocarb) and two pharmaceuticals (diazepam and ibuprofen) at sublethal, environmentally relevant concentrations. We simulated a short-term pulse contamination event that lasted 90 min. Within this short test period, we successfully identified behavioral patterns that were most pronounced upon exposure to the two pesticides: Methiocarb initially triggered hyperactivity, after which baseline behavior was restored. On the other hand, dichlorvos induced hypoactivity starting at a moderate concentration of 5 μg/L - a pattern we also found at the highest concentration of ibuprofen (10 μg/L). An additional acetylcholine esterase inhibition assay revealed no significant impact of the enzyme activity that would explain the altered movement behavior. This suggests that in environmentally realistic scenarios chemicals can induce stress - apart from mode-of-action - that affects non-target organisms' behavior. Overall, our study proves the practical applicability of empirical behavioral ecotoxicological approaches and thus represents a next step towards routine practical use.
Topics: Animals; Ecosystem; Ibuprofen; Dichlorvos; Methiocarb; Ecotoxicology; Invertebrates; Pesticides; Water Pollutants, Chemical; Amphipoda
PubMed: 37433332
DOI: 10.1016/j.scitotenv.2023.165418 -
Toxics Oct 2018Structural isomeric pesticides are used in agriculture and may be challenging to differentiate for accurate identification in pesticide monitoring programs. Due to...
Structural isomeric pesticides are used in agriculture and may be challenging to differentiate for accurate identification in pesticide monitoring programs. Due to structural similarity, isomeric pesticides are difficult to separate chromatographically, and thus, their accurate identification may rely solely on mass spectrometric analysis (MS). In this study, we challenged the ability of high-resolution quadrupole-orbitrap (Q-Orbitrap) mass spectrometry to produce and evaluate the tandem mass spectrometry (MS/MS) product ions for the selected five pairs of isomeric pesticides from different classes: Pebulate and vernolate, methiocarb and ethiofencarb, uniconazole and cyproconazole, sebuthylazine and terbuthylazine, and orbencarb and thiobencarb. The use of Q-Orbitrap instrument with a mass error <3 ppm allowed proposed elucidation of the product ion structures with consideration of the ion formulae, data interpretation, and literature searches. Product ions unique to pebulate, vernolate, methiocarb, ethiofencarb, and uniconazole were observed. Elucidation of the observed MS/MS product ion structures was conducted, and the fragmentation pathways were proposed. This information is valuable to increase selectivity in MS/MS analysis and differentiate isomeric pesticides, and thereby reduce the rates of false positives in pesticide monitoring programs.
PubMed: 30279398
DOI: 10.3390/toxics6040059 -
Ecotoxicology and Environmental Safety Jan 2017The use of fungal bioaugmentation represents a promising way to improve the performance of biomixtures for the elimination of pesticides. The ligninolyitc fungus...
The use of fungal bioaugmentation represents a promising way to improve the performance of biomixtures for the elimination of pesticides. The ligninolyitc fungus Trametes versicolor was employed for the removal of three carbamates (aldicarb, ALD; methomyl, MTM; and methiocarb, MTC) in defined liquid medium; in this matrix ALD and MTM showed similar half-lives (14d), nonetheless MTC exhibited a faster removal, with a half-life of 6.5d. Then the fungus was employed in the bioaugmentation of an optimized biomixture to remove the aforementioned carbamates plus carbofuran (CFN). Bioaugmented and non-bioaugmented systems removed over 99% ALD and MTM after 8d of treatment, nonetheless a slight initial delay in the removal was observed in the bioaugmented biomixtures (removal after 3d: ALD 87%/97%; MTM 86%/99%, in bioaugmented/non-bioaugmented systems). The elimination of the other carbamates was slower, but independent of the presence of the fungus: >98% for MTM after 35d and >99.5% for CFN after 22d. Though the bioaugmentation did not improve the removal capacity of the biomixture, it favored a lower production of transformation products at the first stages of the treatment, and in both cases, a marked decrease in the toxicity of the matrix was swiftly achieved along the process (from 435 to 448 TU to values <1TU in 16d).
Topics: Aldicarb; Biodegradation, Environmental; Carbamates; Carbofuran; Half-Life; Inactivation, Metabolic; Insecticides; Laccase; Methiocarb; Methomyl; Soil; Time Factors; Trametes
PubMed: 27750092
DOI: 10.1016/j.ecoenv.2016.10.011 -
Environmental Research May 2024This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three...
This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three hormones, six pharmaceutical compounds (diclofenac and five antibiotics, three of which are macrolides), nine pesticides (methiocarb, oxadiazon, metaflumizone, triallate, and five neonicotinoids), one antioxidant (BHT), and one UV filter (EHMC). Water and sediment samples were collected in seven sites in four seasons, with the aim of investigating the occurrence, distribution, and possible emission sources of the selected CECs in the studied transitional environment. The most frequently detected contaminants in water were neonicotinoid insecticides (with a frequency of quantification of single contaminants ranging from 73% to 92%), and EHMC (detected in the 77% of samples), followed by BHT (42%), diclofenac (39%), and clarithromycin (35%). In sediment the highest quantification frequencies were those of BHT (54%), estrogens (ranging from 35% to 65%), and azithromycin (46%). Although this baseline study does not highlight seasonal or spatial trends, results suggested that two of the major emission sources of CECs in the Venice Lagoon could be tributary rivers from its drainage basin and treated wastewater, due to the limited removal rates of some CECs in WWTPs. These preliminary results call for further investigations to better map priority emission sources and improve the understanding of CECs environmental behavior, with the final aim of drawing up a site-specific Watch List of CECs for the Venice Lagoon and support the design of more comprehensive monitoring plans in the future.
Topics: Geologic Sediments; Water Pollutants, Chemical; Italy; Environmental Monitoring; Pesticides; Pharmaceutical Preparations
PubMed: 38331156
DOI: 10.1016/j.envres.2024.118401