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1.
Huan Jing Ke Xue ; 45(5): 2678-2685, 2024 May 08.
Artigo em Chinês | MEDLINE | ID: mdl-38629531

RESUMO

Xingkai Lake, located in Heilongjiang Province, is an important fishery and agricultural base and is seriously polluted by agricultural non-point sources. To clarify the residual status of many pesticides in the surface water of Xingkai Lake, 27 types of pesticides, herbicides, and their degradation products were analyzed in rice paddy, drainage, and surface water around Xingkai Lake (China) during the rice heading and maturity periods. The results showed that all 27 types of pesticides, herbicides, and their degradation products were detected during the rice heading period, and the total concentration ranged from 247.97 to 6 094.49 ng·L-1. Additionally, 25 species were detected during the rice maturity period, and the total concentration ranged from 485.36 to 796.23 ng·L-1. In comparison, more pesticides, herbicides, and derived degradation products were detected during the heading period, and their total concentration was higher as well. During the rice heading period, atrazine, simetryn, and paclobutrazol were the main detected pesticides, atrazine and isoprothiolane were the main pesticides detected during the maturity period. The distribution characteristics of pesticides and herbicides in the surface water around Xingkai Lake (China) was similar to that in drainage, so they were probably imported from the drainage and rice paddy. The average risk quotient (RQ) values of atrazine, simetryn, prometryn, butachlor, isoprothiolane, and oxadiazon were higher than 0.1 in drainage and Xingkai Lake (China), which showed a potential risk to aquatic organisms.


Assuntos
Atrazina , Herbicidas , Resíduos de Praguicidas , Praguicidas , Tiofenos , Poluentes Químicos da Água , Praguicidas/análise , Resíduos de Praguicidas/análise , Lagos , Monitoramento Ambiental , Água/química , China , Medição de Risco , Poluentes Químicos da Água/análise
2.
Anal Chem ; 96(15): 6072-6078, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38577757

RESUMO

The urgent need for sensitive and accurate assays to monitor acetylcholinesterase (AChE) activity and organophosphorus pesticides (OPs) arises from the imperative to safeguard human health and protect the ecosystem. Due to its cost-effectiveness, ease of operation, and rapid response, nanozyme-based colorimetry has been widely utilized in the determination of AChE activity and OPs. However, the rational design of nanozymes with high activity and specificity remains a great challenge. Herein, trace amount of Bi-doped core-shell Pd@Pt mesoporous nanospheres (Pd@PtBi2) have been successfully synthesized, exhibiting good peroxidase-like activity and specificity. With the incorporation of trace bismuth, there is a more than 4-fold enhancement in the peroxidase-like performance of Pd@PtBi2 compared to that of Pd@Pt. Besides, no significant improvement of oxidase-like and catalase-like activities of Pd@PtBi2 was found, which prevents interference from O2 and undesirable consumption of substrate H2O2. Based on the blocking impact of thiocholine, a colorimetric detection platform utilizing Pd@PtBi2 was constructed to monitor AChE activity with sensitivity and selectivity. Given the inhibition of OPs on AChE activity, a biosensor was further developed by integrating Pd@PtBi2 with AChE to detect OPs, capitalizing on the cascade amplification strategy. The OP biosensor achieved a detection limit as low as 0.06 ng mL-1, exhibiting high sensitivity and anti-interference ability. This work is promising for the construction of nanozymes with high activity and specificity, as well as the development of nanozyme-based colorimetric biosensors.


Assuntos
Técnicas Biossensoriais , Nanosferas , Agentes Neurotóxicos , Praguicidas , Humanos , Acetilcolinesterase/metabolismo , Compostos Organofosforados , Praguicidas/análise , Peróxido de Hidrogênio , Ecossistema , Oxirredutases , Peroxidase , Colorimetria
3.
Environ Monit Assess ; 196(5): 421, 2024 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-38570395

RESUMO

This study aimed to estimate the carcinogenic and non-carcinogenic risk as well as the attributable cases due to exposure to organochlorine pesticides (OCPs): hexachlorobenzene (HCB), dichlorophenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), heptachlor, and chlordane. From serum concentrations of pesticides of interest in a sample of 908 women from Northern Mexico, the risk for both cancer and non-cancer health effects was evaluated. The population attributable fraction (PAF) was also calculated based on summary association estimates between exposure to OCPs and different health events. Findings revealed that due to their OCP exposure slightly less than half of the women in the sample were at increased risk of developing non-cancerous diseases. Moreover, approximately 25% and 75% of participants were at risk of develop some type of cancer associated with their HCB and DDE concentrations, respectively. In addition, it was estimated that 40.5% of type 2 diabetes, 18.7% of endometriosis, and 23.1% of non-Hodgkin's lymphoma cases could have been prevented if women had not been exposed to these OCPs. Results suggest that the use of OCPs may have contributed to the disease burden in the study area and, based on the time required for these substances to be eliminated from the body, there are probably some women who are still at elevated risk of developing diseases associated to OCPs.


Assuntos
Diabetes Mellitus Tipo 2 , Hidrocarbonetos Clorados , Neoplasias , Praguicidas , Humanos , Feminino , Hexaclorobenzeno/análise , Carcinógenos , México/epidemiologia , Monitoramento Ambiental , Praguicidas/análise , Hidrocarbonetos Clorados/análise , Neoplasias/induzido quimicamente , Neoplasias/epidemiologia
4.
J Environ Manage ; 357: 120700, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38565029

RESUMO

To protect human health, wildlife and the aquatic environment, "safe uses" of pesticides are determined at the EU level while product authorization and terms of use are established at the national level. In Sweden, extra precaution is taken to protect drinking water, and permits are therefore required for pesticide use within abstraction zones. This paper presents MACRO-DB, a tool for assessing pesticide contamination risks of groundwater and surface water, used by authorities to support their decision-making for issuing such permits. MACRO-DB is a meta-model based on 583,200 simulations of the physically-based MACRO model used for assessing pesticide leaching risks at EU and national level. MACRO-DB is simple to use and runs on widely available input data. In a qualitative comparative assessment for two counties in Sweden, MACRO-DB outputs were in general agreement with groundwater monitoring data and matched or were more protective than the national risk assessment procedure for groundwater.


Assuntos
Água Potável , Água Subterrânea , Praguicidas , Poluentes Químicos da Água , Humanos , Praguicidas/análise , Suécia , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Medição de Risco/métodos , Internet
5.
J Chromatogr A ; 1721: 464854, 2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38579528

RESUMO

Developing adsorbents with high performance and long service life for effective extracting the trace organochlorine pesticides (OCPs) from real water is attracting numerous attentions. Herein, a self-standing covalent organic framework (COF-TpPa) membrane with fiber morphology was successfully synthesized by using electrospun nanofiber membranes as template and employed as solid-phase microextraction (SPME) coating for ultra-high sensitivity extraction and analysis of trace OCPs in water. The as-synthesized COF-TpPa membrane exhibited a high specific surface area (800.83 m2 g-1), stable nanofibrous structure, and excellent chemical and thermal stability. Based on the COF-TpPa membrane, a new SPME analytical method in conjunction with gas chromatography-mass spectrometry (GC-MS) was established. This proposed method possessed favorable linearity in concentration of 0.05-2000 ng L-1, high sensitivity with enrichment factors ranging from 2175 to 5846, low limits of detection (0.001-0.150 ng L-1), satisfactory precision (RSD < 10 %), and excellent repeatability (>150 cycles), which was better than most of the reported works. Additionally, the density functional theory (DFT) calculations and XPS results demonstrated that the outstanding enrichment performance of the COF-TpPa membrane was owing to synergistic effect of π-π stacking effects, high specific surface area and hydrogen bonding. This work will expect to extend the applications of COF membrane to captures trace organic pollutants in complex environmental water, as well as offer a multiscale interpretation for the design of effective adsorbents.


Assuntos
Hidrocarbonetos Clorados , Estruturas Metalorgânicas , Nanofibras , Praguicidas , Poluentes Químicos da Água , Água , Porosidade , Poluentes Químicos da Água/análise , Microextração em Fase Sólida/métodos , Praguicidas/análise , Hidrocarbonetos Clorados/análise
6.
Environ Sci Technol ; 58(15): 6744-6752, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38568876

RESUMO

During the growing season of 2021, 201 soil samples from conventionally and organically managed fields from 10 European countries and 8 cropping systems were taken, and 192 residues of synthetic pesticides were analyzed. Pesticide residues were found in 97% of the samples, and 88% of the samples contained mixtures of at least 2 substances. A maximum of 21 substances were found in conventionally managed fields, and a maximum of 12 were found in organically managed fields. The number and concentration of pesticide residues varied significantly between conventional and organic fields in 70 and 50% of the case study sites, respectively. Application records were available for a selected number of fields (n = 82), and these records were compared to the detected substances. Residues from 52% of the applied pesticides were detected in the soils. Only 21% of the pesticide residues detected in the soil samples were applied during the 2021 growing season. From the application data, predicted environmental concentrations of residues in soil were calculated and compared to the measured concentrations. These estimates turned out not to be accurate. The results of this study show that most European agricultural soils contain mixtures of pesticide residues and that current calculation methods may not reliably estimate their presence.


Assuntos
Resíduos de Praguicidas , Praguicidas , Poluentes do Solo , Resíduos de Praguicidas/análise , Resíduos de Praguicidas/química , Solo/química , Agricultura , Praguicidas/análise , Europa (Continente)
7.
Bull Environ Contam Toxicol ; 112(4): 53, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38565770

RESUMO

The objectives of this study were to: (1) characterize the exposure of aquatic ecosystems in Southern Ontario, Canada to pesticides between 2002 and 2016 by constructing environmental exposure distributions (EEDs), including censored data; and (2) predict the probability of exceeding acute regulatory guidelines. Surface water samples were collected over a 15-year period by Environment and Climate Change Canada. The dataset contained 167 compounds, sampled across 114 sites, with a total of 2,213 samples. There were 67,920 total observations of which 55,058 were non-detects (81%), and 12,862 detects (19%). The most commonly detected compound was atrazine, with a maximum concentration of 18,600 ngL- 1 and ~ 4% chance of exceeding an acute guideline (1,000 ngL- 1) in rivers and streams. Using Southern Ontario as a case study, this study provides insight into the risk that pesticides pose to aquatic ecosystems and the utility of EEDs that include censored data for the purpose of risk assessment.


Assuntos
Praguicidas , Poluentes Químicos da Água , Praguicidas/análise , Ontário , Ecossistema , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Rios , Probabilidade , Medição de Risco
8.
Se Pu ; 42(4): 368-379, 2024 Apr.
Artigo em Chinês | MEDLINE | ID: mdl-38566426

RESUMO

Pesticide residues may be present in olive oil because pesticides are applied to olive trees during their cultivation and growth for pest prevention and some of these pesticides are not easily degraded. Studies on pesticide residues in olive oil have mainly focused on the detection of single types of pesticide residues, and reports on the simultaneous detection of multiple pesticide residues are limited. At present, hundreds of pesticides with different polarities and chemical properties are used in practice. In this study, an analytical method based on fully automatic QuEChERS pretreatment instrument coupled with gas chromatography-quadrupole time-of-flight mass spectrometry (GC-QTOF-MS) was established for the rapid determination of 222 pesticide residues in olive oil. The effects of acetonitrile acidification concentration, n-hexane volume, oscillation time, centrifugation temperature, and purification agent on the determination of the 222 pesticide residues were investigated. First, ions with good responses and no obvious interference were selected for quantification and characterization. The purification process was then developed by setting the parameters of the fully automatic QuEChERS pretreatment instrument to optimal values. The sample was extracted with acetonitrile containing 2% formic acid, and the supernatant was purified by centrifugation in a centrifuge tube containing 400 mg N-propylethylenediamine (PSA), 400 mg octadecylsilane-bonded silica gel (C18), and 1200 mg anhydrous magnesium sulfate. The purified solution was blown dry with nitrogen and then fixed with ethyl acetate for instrumental analysis. Finally, a matrix standard solution was used for quantification. The method was validated in terms of matrix effects, linear ranges, limits of detection (LODs) and quantification (LOQs), accuracies, and precisions. The results showed that 86.04% of the 222 pesticides had linear ranges of 0.02-2.00 µg/mL, 10.81% had linear ranges of 0.10-2.00 µg/mL, and 3.15% had linear ranges of 0.20-2.00 µg/mL. The pesticide residues showed good relationships within their respective linear ranges, and the correlation coefficients (R2) were greater than 0.99. The LODs of all tested pesticides ranged from 0.002 to 0.050 mg/kg, and their LOQs ranged from 0.007 to 0.167 mg/kg. Among the 222 pesticides determined, 170 pesticides had LOQs of 0.007 mg/kg while 21 pesticides had LOQs of 0.017 mg/kg. At the three spiked levels of 0.2, 0.5, and 0.8 mg/kg, 79.58% of all tested pesticides had average recoveries of 70%-120% while 65.92% had average recoveries of 80%-110%. In addition, 93.54% of all tested pesticides had relative standard deviations (RSDs, n=6)<10% while 98.35% had RSDs (n=6)<20%. The method was applied to 14 commercially available olive oil samples, and seven pesticides were detected in the range of 0.0044-0.0490 mg/kg. The residues of fenbuconazole, chlorpyrifos, and methoprene did not exceed the maximum limits stated in GB 2763-2021. The maximum residual limits of molinate, monolinuron, benalaxyl, and thiobencarb have not been established. The method utilizes the high mass resolution capability of TOF-MS, which can improve the detection throughput while ensuring good sensitivity. In addition, high-resolution and accurate mass measurements render the screening results more reliable, which is necessary for the high-throughput detection of pesticide residues. The use of a fully automatic QuEChERS instrument in the pretreatment step reduces personnel errors and labor costs, especially when a large number of samples must be processed, thereby offering significant advantages over other approaches. Moreover, the method is simple, rapid, sensitive, highly automatable, accurate, and precise. Thus, it meets requirements for the high-throughput detection of pesticide residues in olive oil and provides a reference for the development of detection methods for pesticide residues in other types of oils as well as the automatic pretreatment of complex matrices.


Assuntos
Resíduos de Praguicidas , Praguicidas , Resíduos de Praguicidas/análise , Azeite de Oliva , Espectrometria de Massas em Tandem/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Praguicidas/análise , Acetonitrilas/análise
9.
Molecules ; 29(5)2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38474618

RESUMO

The analysis of enantiomers in food has significant implications for food safety and human health. Conventional analytical methods employed for enantiomer analysis, such as gas chromatography and high-performance liquid chromatography, are characterized by their labor-intensive nature and lengthy analysis times. This review focuses on the development of rapid and reliable biosensors for the analysis of enantiomers in food. Electrochemical and optical biosensors are highlighted, along with their fabrication methods and materials. The determination of enantiomers in food can authenticate products and ensure their safety. Amino acids and chiral pesticides are specifically discussed as important chiral substances found in food. The use of sensors replaces expensive reagents, offers real-time analysis capabilities, and provides a low-cost screening method for enantiomers. This review contributes to the advancement of sensor-based methods in the field of food analysis and promotes food authenticity and safety.


Assuntos
Técnicas Biossensoriais , Praguicidas , Humanos , Cromatografia Líquida de Alta Pressão/métodos , Alimentos , Praguicidas/análise , Cromatografia Gasosa , Estereoisomerismo
10.
Sci Total Environ ; 926: 171912, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38522545

RESUMO

The assessment of chemical pollution in free-ranging living mammals is viable using remote biopsies and portrays a comprehensive scenario of environmental health. The Southwestern Atlantic Ocean holds incredible biodiversity, but it is under the constant and invisible threat of persistent organic pollutants (POPs) of anthropogenic origin, such as pesticides, brominated flame retardants, and industrial-use compounds (e.g., PCBs). Thus, this study aimed to assess the bioaccumulation of POPs (PCBs, DDTs, HCB, mirex and PBDEs) and natural organobromine compounds (MeO-BDEs) using gas-chromatography coupled to mass spectrometry in biopsy samples of Atlantic spotted dolphins (Stenella frontalis, n = 20) that inhabit and forage both inside and in adjacent areas to degraded (Guanabara Bay) and conserved (Ilha Grande Bay) coastal bays in the Southeastern Brazil. Among the studied compounds, PCBs were predominant in the contamination profile with median concentration of 97.0 µg.g-1 lipid weight (lw), followed by the sum of the p,p' isomers of DDT, DDD, and DDE of 11.0 µg.g-1 lw, the brominated flame retardants PBDEs of 1.6 µg.g-1 lw, and the other organochlorine pesticides mirex of 0.78 µg.g-1 lw, and HCB of 0.049 µg.g-1 lw. The MeO-BDEs were detected with a median concentration of 22.8 µg.g-1 lw. 85 % of the Atlantic spotted dolphins analyzed in this study presented PCB concentration that exceeded even the less conservative threshold limits for adverse health effects (41 µg.g-1 lw). This study shows that despite the conservation status of preserved bays, cetacean species foraging in these locations are still under increased threat. Hence chemical pollution demands local and global efforts to be mitigated.


Assuntos
Retardadores de Chama , Hidrocarbonetos Clorados , Praguicidas , Bifenilos Policlorados , Stenella , Poluentes Químicos da Água , Animais , Stenella/metabolismo , Bifenilos Policlorados/análise , Mirex , Éteres Difenil Halogenados/análise , Retardadores de Chama/análise , Cromatografia Gasosa-Espectrometria de Massas , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Cetáceos/metabolismo , Monitoramento Ambiental , Poluentes Químicos da Água/análise
11.
Sci Total Environ ; 926: 171948, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38527545

RESUMO

The exponential growth of the global population has resulted in a significant surge in the demand for food worldwide. Additionally, the impact of climate change has exacerbated crop losses caused by pests and pathogens. The transportation and utilization of traditional agrochemicals in the soil are highly inefficient, resulting in significant environmental losses and causing severe pollution of both the soil and aquatic ecosystems. Nanotechnology is an emerging field with significant potential for market applications. Among metal-based nanomaterials, copper-based nanomaterials have demonstrated remarkable potential in agriculture, which are anticipated to offer a promising alternative approach for enhancing crop yields and managing diseases, among other benefits. This review firstly performed co-occurrence and clustering analyses of previous studies on copper-based nanomaterials used in agriculture. Then a comprehensive review of the applications of copper-based nanomaterials in agricultural production was summarized. These applications primarily involved in nano-fertilizers, nano-regulators, nano-stimulants, and nano-pesticides for enhancing crop yields, improving crop resistance, promoting crop seed germination, and controlling crop diseases. Besides, the paper concluded the potential impact of copper-based nanomaterials on the soil micro-environment, including soil physicochemical properties, enzyme activities, and microbial communities. Additionally, the potential mechanisms were proposed underlying the interactions between copper-based nanomaterials, pathogenic microorganisms, and crops. Furthermore, the review summarized the factors affecting the application of copper-based nanomaterials, and highlighted the advantages and limitations of employing copper-based nanomaterials in agriculture. Finally, insights into the future research directions of nano-agriculture were put forward. The purpose of this review is to encourage more researches and applications of copper-based nanomaterials in agriculture, offering a novel and sustainable strategy for agricultural development.


Assuntos
Cobre , Praguicidas , Cobre/análise , Ecossistema , Agricultura/métodos , Praguicidas/análise , Nanotecnologia/métodos , Fertilizantes/análise , Solo
12.
Ecotoxicol Environ Saf ; 274: 116199, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38492485

RESUMO

This study established a residue detection method based on the QuEChERS pre-treatment method and combined it with high-performance liquid chromatography-tandem mass spectrometry to test six herbicides (metamitron, clopyralid, desmedipham, phenmedipham, ethofumesate, and haloxyfop-p-methyl) in sugar beet plants, soil, and roots. The degradation dynamics and terminal residues of each herbicide in sugar beets were analysed. Finally, the dietary risks of various herbicides in sugar beets were evaluated based on the dietary structure of Chinese people, and the risk quotient values were below 100%. Using this detection method, all reagents exhibited good linearity (0.9724 ≤ R2 ≤ 0.9998), The limit of quantification (LOQ) ranged from 0.01 to 0.05 mg/L, the matrix effect ranged from -1.2% to -50%, the addition recovery rate ranged from 77.00% to 103.48%, and the relative standard deviation ranged from 1.61% to 16.17%; therefore, all indicators of this method met the residue detection standards. Under field conditions, the half-lives (t1/2) ranged about 0.65 ∼ 2.96 d and 0.38 ∼ 27.59 d in sugar beet plants and soil, respectively. All herbicides were easily degraded in sugar beet plants and soil (t1/2 < 30 d). The terminal residue amounts in the beet plants, soil, and roots ranged from < LOQ to 0.243 mg/kg. The dietary risk assessment of each pesticide was conducted based on the residual median of the terminal residues and the highest residual values on the edible part of the beetroot. The chronic exposure risk quotient (RQc) and acute exposure risk quotient (RQa) values were < 100%, indicating that the residue of each pesticide in beetroot posed low risks to consumers in China at the recommended dosage.


Assuntos
Beta vulgaris , Compostos de Flúor , Herbicidas , Resíduos de Praguicidas , Praguicidas , Piridinas , China , Herbicidas/análise , Resíduos de Praguicidas/análise , Praguicidas/análise , Solo/química , Açúcares , Verduras
13.
Anal Chim Acta ; 1301: 342464, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38553122

RESUMO

BACKGROUND: Organophosphorus pesticides (OPs) play important roles in the natural environment, agricultural fields, and biological prevention. The development of OPs detection has gradually become an effective strategy to avoid the dangers of pesticides abuse and solve the severe environmental and health problems in humans. Although conventional assays for OPs analysis such as the bulky instrument required analytical methods have been well-developed, it still remains the limitation of inconvenient, inefficient and lab-dependence analysis in real samples. Hence, there is an urgent demand to develop efficient detection methods for OPs analysis in real scenarios. RESULTS: Here, by virtue of the highly efficient catalytic performance in Fe7S8 nanoflakes (Fe7S8 NFs), we propose an OPs detection method that rationally integrated Fe7S8 NFs into the acetylcholine (ACh) triggered enzymatic cascade reaction (ATECR) for proceeding better detection performances. In this method, OPs serve as the enzyme inhibitors for inhibiting ATECR among ACh, acetylcholinesterase (AChE), and choline oxidase (CHO), then reduce the generation of H2O2 to suppress the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) that catalyzed by Fe7S8 NFs. Benefiting from the integration of Fe7S8 NFs and ATECR, it enables a sensitive detection for OPs (e.g. dimethoate). The proposed method has presented good linear ranges of OPs detection ranging from 0.1 to 10 µg mL-1. Compared to the other methods, the comparable limits of detection (LOD) of OPs are as low as 0.05 µg mL-1. SIGNIFICANCE: Furthermore, the proposed method has also achieved a favorable visual detection performance of revealing OPs analysis in real samples. The visual signals of OPs can be transformed into RGB values and gathered by using smartphones, indicating the great potential in simple, sensitive, instrument-free and on-site analysis of pesticide residues in environmental monitoring and biosecurity research.


Assuntos
Técnicas Biossensoriais , Praguicidas , Piperidinas , Humanos , Praguicidas/análise , Acetilcolina/química , Acetilcolinesterase/química , Compostos Organofosforados/análise , Peróxido de Hidrogênio/química , Catálise , Técnicas Biossensoriais/métodos
14.
Bull Environ Contam Toxicol ; 112(3): 48, 2024 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-38459992

RESUMO

This study aimed on the development of a SPE-UHPLC-MS/MS method for the simultaneous determination of pesticide residues in drinking water samples. A chemometric approach was applied to optimize the efficiency of the SPE pretreatment procedure. This study involved (i) the application of a Full Factorial Design for the screening of the significant factors, (ii) the application of a Central Composite Design for the determination of the optimal conditions and (iii) the evaluation and validation of the significance of the statistically proposed models. Oasis HLB cartridges were used for the extraction. The optimum sample volume was 300 mL and the elution solvent 3 mL of the mixture of methanol:ethylacetate 70:30 v/v. The method was validated according to the international guidelines. Recoveries were ranged from 63 to 116% and the detection limits were between 0.1 and 1.5 pg mL- 1. The validated method could be used in routine analysis for pesticides screening.


Assuntos
Praguicidas , Praguicidas/análise , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Quimiometria , Extração em Fase Sólida/métodos , Água
15.
J Chromatogr A ; 1720: 464807, 2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38461769

RESUMO

A method based on novel restricted access materials (RAMs) for the determination of neonicotinoid pesticides in Goji samples using offline and online solid phase extraction (SPE) coupled with high-performance liquid chromatography (LC). RAMs were synthesized using poly(chloromethylstyrene-co-divinylbenzene) (PVBC/DVB) microspheres as substrate, styrene (St) and n-vinylpyrrolidone (NVP) were first copolymerized on the interior to construct adsorption sites, and sulfobetaine methacrylate (SBMA) was then polymerized on the exterior to form exclusion sites via two-step surface initiated-atom transfer polymerization. The prepared PVBC/DVB@poly(St-co-NVP)@poly(SBMA) RAMs could efficiently extract neonicotinoid pesticides and automatically exclude proteins. Under the optimized conditions, the developed methods of offline (magnetic SPE and SPE column) and online extraction coupled with LC both using PVBC/DVB@poly(St-co-NVP)@poly(SBMA) RAMs as the extractant, exhibit a wide linearity, low limits of detection and limit of quantification and good inter-day and intra-day precision with satisfactory recoveries. Among these methods, online extraction coupled with LC based on novel RAMs exhibits clear advantages for the determination of neonicotinoid pesticides in Goji samples has clear advantages, such as simple operation by direct injection, short extraction times, and high accuracy with less human error.


Assuntos
Praguicidas , Polímeros , Humanos , Polímeros/química , Praguicidas/análise , Adsorção , Extração em Fase Sólida/métodos , Estireno , Cromatografia Líquida de Alta Pressão/métodos
16.
Environ Geochem Health ; 46(4): 117, 2024 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-38478119

RESUMO

Continuous exposure to airborne pesticides causes their gradual accumulation in the human body, eventually posing a threat to human health. To the best of our knowledge, risk assessment study of pesticide non-occupational exposure to residents in agricultural areas has not been conducted in China. In this study, air samples (gas and dust) were collected from inside and outside residences of seven households and an area near the field in a grain-growing area (wheat and maize rotation) for eight months, and the pesticides present were examined both qualitatively and quantitatively. Using a 95% confidence interval, 9 out of 16 pesticides were detected, namely acetamiprid, acetochlor, atrazine, flucarbazone-sodium, imidacloprid, methyldisulfuron-methyl, nicosulfuron-methyl, pendimethalin, and beta-cyhalothrin, and their safety was subsequently evaluated. The results showed that the inhalation exposure of households to beta-cyhalothrin exceeded the acceptable range in the first residential, and the excess lifetime cancer risk of acetochlor inhalation exposure in six households and area around the field exceeds 1E-6, which highlights the need to strengthen preventive screening for cancer risk.


Assuntos
Neoplasias , Nitrilas , Praguicidas , Piretrinas , Toluidinas , Humanos , Praguicidas/toxicidade , Praguicidas/análise , Exposição Ambiental/análise , Medição de Risco
17.
Environ Geochem Health ; 46(4): 144, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38538830

RESUMO

Considering the extensive agricultural practices along the perennial rivers, viz. Periyar and Bharathappuzha of Kerala in the southwest coast of India, the first comprehensive surveillance of new and legacy organochlorine pesticides (OCPs) in surface sediment was conducted. Further, the sediment-water exchange fluxes have been elucidated. Mean concentrations of total HCH, DDT and endosulfan were 0.84 ng/g, 0.42 ng/g and 0.30 ng/g for Bharathappuzha Riverine sediment (BRS) and 1.08 ng/g, 0.39 ng/g and 0.35 ng/g for Periyar Riverine sediment (PRS). The dominance α-HCH and ß-HCH isomers in PRS and BRS reflect the ongoing use of technical HCH in Kerala. The calculated KSW in both rivers was very low in comparison with other Indian rivers. The average log K'OC for all the detected OCPs in both the rivers was lower than the predicted log KOC in equilibrium indicating the higher adherence of OCPs to sediment. Furthermore, fugacity fraction (fs/fw) was < 1.0 for all OCPs confirming the net deposition of OCPs into the sediment. Sediment concentrations for each of the OCPs in PRS and BRS did not surpass the threshold effect level and probable effect level as stipulated by the Canadian Council of Ministry of the Environment Guidelines. In addition, all the sites of both rivers had sediment quality guideline quotient (SQGQ) values below 0.1 indicating the absence of significant biological and ecological risks.


Assuntos
Hidrocarbonetos Clorados , Praguicidas , Poluentes Químicos da Água , Praguicidas/análise , Poluentes Orgânicos Persistentes , Água , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Sedimentos Geológicos , Canadá , Hidrocarbonetos Clorados/análise , Medição de Risco , Rios , China
18.
Biosens Bioelectron ; 253: 116143, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38452567

RESUMO

A modern agriculture uses alternative pest control methods to boost productivity, leading to an accumulation of organophosphorus (OPPs) congeners. This necessitates an intuitive and quick way to identify OPPs congeners. A colorimetric sensor for detecting OPPs congeners using a double-enzyme cascade reaction has been successfully designed and constructed in this study. The OPPs regulate the color changes induced by manganese dioxide nanoflowers (MnO2 NFs) and specific alkaline phosphatases (ALP) during the etching of gold nanopyramids (Au NBPs). The ascorbic acid (AA) produced by ALP hydrolysis inhibits Au NBPs etching by MnO2 NFs oxidized 3, 3', 5, 5'-tetramethylbenzidine (TMB). By inhibiting ALP catalytic activity, OPPs prevent AA formation. In this process, Au NBPs will undergo further etching, resulting in various colors so they can be analyzed semi-quantitatively with the naked eye. It has been found that different types of OPPs inhibit enzymes differently and therefore result in varying degrees of etching of Au NBPs. Principal Component Analysis (PCA) is performed by smart devices that convert R, G, and B signals into digital signals. This colorimetric array tests various foods (tea, apple, and cabbage). Colorimetric visualization sensors combined with data analysis will be used in real-life product development.


Assuntos
Técnicas Biossensoriais , Praguicidas , Praguicidas/toxicidade , Praguicidas/análise , Óxidos , Compostos Organofosforados , Compostos de Manganês , Colorimetria/métodos , Ácido Ascórbico , Fosfatase Alcalina
19.
Sci Rep ; 14(1): 6389, 2024 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-38493253

RESUMO

The present work aimed to predict the fate of two pesticides, copper (Cu) and glyphosate in a Mediterranean basin with an intermittent river and to assess the ecotoxicological risk related to their presence in water bodies coupling field measurements of streamflow and pesticide concentrations, and an eco-hydrological model. The Soil and Water Assessment Tool (SWAT) model was calibrated and, subsequently used to assess predicted environmental concentrations of pesticides in surface waters. The ecotoxicological risk related to the presence of Cu and glyphosate in surface water was assessed at the reach scale by using the Toxicity to Exposure Ratio approach (TER). Measurements of glyphosate concentrations (< 0.5 µg l-1) exceeded the maximum European threshold of environmental quality standards for pesticides (EQS) of 0.1 µg l-1. High concentrations of glyphosate were predicted in the wet season and in September, when glyphosate is mostly used in vineyards and olive grove productions. Acute risk (TER < 100) associated with the presence of glyphosate was detected for several reaches. High concentrations of Cu (< 6.5 µg l-1), mainly used as a fungicide in vineyards, were predicted in several river reaches. The results of the ecotoxicological risk assessment revealed that November and January were the critical months during which most of the river reaches showed a chronic risk associated with the presence of Cu.


Assuntos
Praguicidas , Poluentes Químicos da Água , Praguicidas/toxicidade , Praguicidas/análise , Rios , Solo , Água , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Medição de Risco
20.
Sci Total Environ ; 922: 171382, 2024 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-38432369

RESUMO

The present review addresses the significance of lowering pesticide residue levels in food items because of their harmful impacts on human health, wildlife populations, and the environment. It draws attention to the possible health risks-acute and chronic poisoning, cancer, unfavorable effects on reproduction, and harm to the brain or immunological systems-that come with pesticide exposure. Numerous traditional and cutting-edge methods, such as washing, blanching, peeling, thermal treatments, alkaline electrolyzed water washing, cold plasma, ultrasonic cleaning, ozone treatment, and enzymatic treatment, have been proposed to reduce pesticide residues in food products. It highlights the necessity of a paradigm change in crop protection and agri-food production on a global scale. It offers opportunities to guarantee food safety through the mitigation of pesticide residues in food. The review concludes that the first step in reducing worries about the negative effects of pesticides is to implement regulatory measures to regulate their use. In order to lower the exposure to dietary pesticides, the present review also emphasizes the significance of precision agricultural practices and integrated pest management techniques. The advanced approaches covered in this review present viable options along with traditional methods and possess the potential to lower pesticide residues in food items without sacrificing quality. It can be concluded from the present review that a paradigm shift towards sustainable agriculture and food production is essential to minimize pesticide residues in food, safeguarding human health, wildlife populations, and the environment. Furthermore, there is a need to refine the conventional methods of pesticide removal from food items along with the development of modern techniques.


Assuntos
Resíduos de Praguicidas , Praguicidas , Humanos , Resíduos de Praguicidas/análise , Contaminação de Alimentos/prevenção & controle , Contaminação de Alimentos/análise , Praguicidas/análise , Inocuidade dos Alimentos , Controle de Pragas
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