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Suspect and non-targeted screening-based human biomonitoring identified 74 biomarkers of exposure in urine of Slovenian children
2022
Tkalec, Žiga | Codling, Garry | Tratnik, Janja Snoj | Mazej, Darja | Klánová, Jana | Horvat, Milena | Kosjek, Tina
Human exposure to organic contaminants is widespread. Many of these contaminants show adverse health effects on human population. Human biomonitoring (HBM) follows the levels and the distribution of biomarkers of exposure (BoE), but it is usually done in a targeted manner. Suspect and non-targeted screening (SS/NTS) tend to find BoE in an agnostic way, without preselection of compounds, and include finding evidence of exposure to predicted, unpredicted known and unknown chemicals. This study describes the application of high-resolution mass spectrometry (HRMS)-based SS/NTS workflow for revealing organic contaminants in urine of a cohort of 200 children from Slovenia, aged 6–9 years. The children originated from two regions, urban and rural, and the latter were sampled in two time periods, summer and winter. We tentatively identified 74 BoE at the confidence levels of 2 and 3. These BoE belong to several classes of pharmaceuticals, personal care products, plasticizers and plastic related products, volatile organic compounds, nicotine, caffeine and pesticides. The risk of three pesticides, atrazine, amitraz and diazinon is of particular concern since their use was limited in the EU. Among BoE we tentatively identified compounds that have not yet been monitored in HBM schemes and demonstrate limited exposure data, such as bisphenol G, polyethylene glycols and their ethers. Furthermore, 7 compounds with unknown use and sources of exposure were tentatively identified, either indicating the entry of new chemicals into the market, or their metabolites and transformation products. Interestingly, several BoE showed location and time dependency. Globally, this study presents high-throughput approach to SS/NTS for HBM. The results shed a light on the exposure of Slovenian children and raise questions on potential adverse health effects of such mixtures on this vulnerable population.
Show more [+] Less [-]Spatial distribution, ecological and health risk assessment of organophosphorus pesticides identified in the water of Naseri artificial wetland, Iran
2022
Zarei-Choghan, Mohammad | Jorfi, Sahand | Saki, Amal | Jaafarzadeh, Neamatollah
Agricultural development is inevitable to meet the growing need for food. But along with this development, there are unintended and undesirable consequences for human life and the environment that need, found a solution and corrected. One of the most important adverse consequences of agricultural development is the pollution of surface and groundwater resources, which results from various factors such as soil erosion and improper use of different pesticides. This study aimed to conduct an environmental monitoring program in Naseri wetland to determine the concentrations of organophosphorus pesticides (OPPₛ) in water samples and also to evaluate the potential risks (ecological and health risk assessment) of these pesticides. The salting-out assisted liquid-liquid extraction method was used to extract pesticides. The residual concentrations of OPPₛ evaluated by gas chromatography/mass spectrometry (GC/MS). In this study, the ecological risk of OPPₛ calculated for wetland ecosystem, based on the acute risk quotient (RQᵢ) formula with maximum (RQₘₐₓ), mean (RQₘₑₐₙ), and mixture (RQₘᵢₓ) concentrations of organophosphorus pesticides in the wetland water. Also, to assess the health risk of consuming contaminated fish with organophosphate pesticides, the potential non-carcinogenic and carcinogenic risks were determined by the hazard quotient (Index) (HQ, HI) and incremental lifetime cancer risk (ILCR) indices, respectively. The mean ± SD concentration of OPPₛ (Chlorpyrifos, Malathion, Ethion, Dichlorvos, Trifluralin and Diazinon) in samples of wetland water ranged from 0.14 ± 0.08 to 0.35 ± 0.12 and 0.054 ± 0.06 to 0.2 ± 0.1 (μg/L) in summer and autumn, respectively. The mean ± SD of OPPₛ in fish varied from 0.68 ± 0.86 to 3.94 ± 2.7 (μg/kg). Overall, the concentrations of pesticides in all water and fish samples were below the maximum residue limit (30 μg/kg) during the study period, according to the Environmental Protection Agency (EPA) and the World Health Organization (WHO). The results of acute risk quotient were in summer (RQₘₐₓ = 3.49E-4 to 0.067, RQₘₑₐₙ = 5.8E-5 to 0.029, RQₘᵢₓ = 0.139-0.026, 0.018-3.42E-3) and autumn (RQₘₐₓ = 8E-4 to 0.051, RQₘₑₐₙ = 7.74E-6 to 0.018 RQₘᵢₓ = 0.1–0.013, 6E-3- 1.5E-3). The non-carcinogenic and carcinogenic risk indexes due to fish consumption for adults and children were (HQ = 0.026-4.68E-4, HI = 0.041, ILCR = 1.7E-7) and (HQ = 1.85E-3-1.3E-5, HI = 0.041, ILCR = 5.55E-8), respectively. The risk of OPPₛ was generally low. But cumulative risk (pesticide mixtures), should not be ignored.
Show more [+] Less [-]Quality of the surface water of a basin affected by the expansion of the agricultural frontier over the native forest in the Argentine Espinal region
2022
Van Opstal, Natalia Verónica | Seehaus, Mariela Soledad | Gabioud, Emmanuel Adrian | Wilson, Marcelo German | Galizzi, Flavio José | Pighini, Ramiro Joaquin | Repetti, Maria Rosa | Regaldo, Luciana María | Gagneten, Ana María | Sasal, María Carolina
Land use changes have led to the degradation of multiple ecosystem services and affected the quality of aquatic ecosystems. The aims of this study were (i) to assess the expansion of the agricultural border over the native forest of an Argentinean stream basin and (ii) to characterize the surface water quality, considering physicochemical parameters, and pesticide concentrations. The agricultural frontier expansion was estimated through the analysis of satellite image coverage. Samples of surface water were taken bimonthly for 2 years. The native forest cover decreased from 72% in 1987 to 60% in 2017 due to the sustained increase in agricultural activities. In surface water, the concentrations of cations decreased: Na > Ca > K > Mg, whereas those of anions decreased: HCO₃ > > Cl > SO₄ > PO₄. The 84 surface water samples analyzed revealed 25 pesticides, including herbicides (44%), insecticides (28%), and fungicides (28%). Herbicides were detected in more than 60% of the samples. 2,4-D, atrazine, cyproconazole, diazinon, glyphosate, AMPA, and metolachlor were detected in all the study sites and sometimes, 2,4-D, atrazine, dicamba, and metolachlor concentrations exceeded the guideline levels. The high sampling frequency of this study and the two annual cycles of crops in the basin enabled sensing of pesticide molecules and concentrations that had not been previously detected, indicating diffuse contamination. These findings signal an emergent challenge on the Espinal agro-ecosystem integrity due to changes in land use.
Show more [+] Less [-]Diazinon reduction in food products: a comprehensive review of conventional and emerging processing methods
2022
Nematollahi, Amene | Rezaei, Farahnaz | Afsharian, Zahra | Mollakhalili-Meybodi, Neda
Diazinon is known as one of the most commonly used organophosphorus pesticides which influence different pests through inactivating acetyl choline esterase enzymes. Despite diazinon applications, its toxicity to human health could result in a worldwide concern about its occurrence in foodstuffs. Malfunction of brain is considered as the main disorders induced by long time exposure to diazinon. Due to the degradation of diazinon in high temperatures and its susceptibility to oxidation as well as acidic and basic conditions, it could be degraded through several physical (9–94%) and chemical (19.3–100%) food processing procedures (both household and industrial methods). However, each of these methods has its advantages and disadvantages. Normally, the combination of these methods is more efficient in diazinon reduction. To this end, it is important to apply an effective method for diazinon reduction in the food products without affecting food quality or treating human health. It could be noticed that bioremediation by microorganisms such as probiotics could be a promising new method for diazinon’s reduction in several food products.
Show more [+] Less [-]Contamination, dynamics, and health risk assessment of pesticides in seawater and marine samples from the Seto Inland Sea, Japan
2022
Chidya, Russel | Derbalah, Aly | Abdel-Dayem, Sherif | Kaonga, Chikumbusko | Tsuji, Hiroaki | Takeda, Kazuhiko | Sakugawa, Hiroshi
We assessed the contamination, dynamics, and health risks of the pesticides cyanazine, simetryn, fenarimol, isoprothiolane, diazinon, irgarol, fenitrothion, and diuron in marine samples (seawater, sediments, plankton, fish, and other edible organisms) at various locations in the Seto Inland Sea in Japan in 2016 and 2017. Pesticide concentrations were highest at sampling sites close to the coastline, and mean concentrations in seawater were slightly higher in surface water than in bottom water. All eight pesticides were detected in plankton. Diazinon concentrations (77–387 ng/g dw) were highest in sediments and cyanazine was the most frequently detected pesticide (88%, n = 17) in sediments. Only cyanazine (2.7–41.9 ng/g dw), simetryn (1.0–34.3 ng/g dw), and diazinon (6.3–308.8 ng/g dw) were detected in fish and other edible marine organisms. Based on the calculated bioconcentration factor, the results showed that plankton, fish, and marine animals bioaccumulated pesticides. The highest hazard quotients were calculated for diazinon in red seabream and greenling, indicating a possible risk to consumers. It is, therefore, imperative to promote strict implementation of pollution control, integrated pest management practices, and policy formulation on pesticides. Usage of diazinon must be controlled and monitored to ensure large residues do not reach aquatic ecosystems and marine coastlines.
Show more [+] Less [-]Investigation and probabilistic health risk assessment of pesticide residues in cucumber, tomato, and okra fruits from Khuzestan, Iran
2022
Khoshnam, Farzaneh | Ziaee, Masumeh | Daei, Mina | Mahdavi, Vahideh | Mousavi Khaneghah, Amin
In this study, 30 pesticide residues in 45 fresh-eating cucumber, tomato, and okra fruit samples collected from the Khuzestan province as the main agricultural products in Iran using the QuEChERS extraction method were analyzed. In addition, noncarcinogen and carcinogen health risk assessments were evaluated. Results indicated that 93% of cucumber samples had at least one pesticide, of course, less than the maximum residue limit (MRL). All tomato and okra fruit samples were contaminated by diazinon. All pesticides detected in tomato samples were below national MRL except for thiamethoxam in four samples. In okra fruit samples, all detected diazinon and malathion, but only tebuconazole fungicide exceeded MRL. In addition, the hazard index (HI) was 0.23 and 1.06 in cucumber samples, 0.33 and 1.51 in tomato samples, and 5.5E-03 and 0.025 in okra fruit samples in adults and children, respectively. The use of cucumber and tomato may have notable risks in the short term in children group age. Ranking based on total CR was 1.2E-05 in tomato, 7.7E-06 for cucumber, and in okra 9.1E-11 because of the difenoconazole residue. However, significant carcinogenic risk threatens cucumber and tomato consumers.
Show more [+] Less [-]Diazinon pesticide photocatalytic degradation in aqueous matrices based on reductive agent release in iodide exciting under UV Irradiation
2022
Azarpira, Hossein | Rasolevandi, Tayebeh | Mahvi, Amir Hossein | Karimy, Mahmood
Regarding the cost-effective degradation of diazinon (DIZ), the present study was conducted to develop and UV/iodide process in a photo catalyst reactor. CCD modeling applied and the results shows that the highest R-squared value (adjusted R-squared: 0.9987), the lowest P-value (2.842 e − 10), the lowest AIC (14.54), and the most insignificant lack-of-fit (0.73) belonged to the second-order model. Based on second-order model, the stationary points for time, iodide: DIZ (molar ratio %), DIZ concentration, and pH were 6.99 min, 80.15% iodide: DIZ (molar ratio %), 3.34, mg L⁻¹, and pH 7.34 (− log₁₀[H⁺]), respectively. The maximum reduction efficiency of 97.22% was obtained at the experimental conditions. The LC–MS analyses from optimal condition implied that all the DIZ molecules and its intermediates breaking to simple compounds during 15 min of processing. The data shown UI process reduced the BOD and COD levels by about 66% and 86.29% within 80 min of photoreaction, respectively. Furthermore, in kinetic investigation, with the increase in DIZ concentration, kₒbₛ and rₒbₛ increased and secondly, the conventional and PCBR reactor kₒbₛ increased by about respectively 17% and 50% with an increase in DIZ concentration from 5 to 15 mgL⁻¹. Additionally, when the DIZ concentration increase from 5 to 15 mg L⁻¹, rₒbₛ increased in the conventional and PCBR reactors respectively about 4.9 and 6 times. Figure-of-merit EEₒ changed from 12.66–17.41 to 7.26–10.15 kWhm³ for the conventional reactor, and 8.66–13.61 to 5.24–8.12 kWhm³ in PCBR, when the DIZ concentration increasing from 5 to 15 mg L⁻¹. Consequently, in the PCBR reactor, the energy consumption reduced by 14% at 5 mg L⁻¹ DIZ concentration and by 60% at 15 mg L⁻¹ DIZ concentration. Also, total cost of the system (TCS) decreases from 4.52 to 1.46 $ in conventional reactor and 1.47 to 0.42 $ in PCBR reactor when the DIZ concentration increase from 5 to 15 mg L⁻¹.
Show more [+] Less [-]Pesticide residues levels as hematological biomarkers—a case study, blood serum of greenhouse workers in the city of Hamadan, Iran
2022
Leili, Mostafa | Ghafiuri-Khosroshahi, Abolfazl | Poorolajal, Jalal | Samiee, Fateme | Smadi, Mohammad Taghi | Bahrami, Abdulrahman
The cultivation of greenhouse crops is the most severe form of crop production in Iran, and vast quantities of unreasonable pesticides are being utilized to control the pests. The residual level of blood pesticides and their correlation with multibiomarkers were determined to evaluate the adverse health consequences on greenhouse workers in the Hamadan, west of Iran. Participants were 180 adult males, including 90 greenhouse workers exposed to pesticides and 90 control individuals. Blood samples were taken from all subjects for pesticide residues analysis, and hematological and biochemical parameters. The blood pesticide residues were analyzed using gas chromatography (GC) with a flame ionization detector. Hematological and biochemical parameters were determined using hematology cell counter and auto analyze, respectively. Statistical analyses were done with STATA version 14.2 software. The multivariate regression was used for relationship between various pesticide concentrations in blood and changes in biomarkers in pesticide exposed group. The analyses revealed that 64 out of the 90 workers had residues of dichlorvos, diazinon, and chlorpyrifos in their blood serum, and 56.25% out of these workers were exposed for >15-year period. The residues of all three pesticides were higher than the no observable adverse effect level (NOAEL) in all the exposure duration categories. Comparisons of hematological parameters showed that mean monocyte (0.76±0.41, P < 0.001), lymphocyte (3.52±1.20, P < 0.001) and platelet counts (278.18±66.05, P=0.001), mean platelet volume (10.18±0.59, P=0.002), and plateletcrit (PCT) (0.275±0.05, P<0.001) were significantly higher in workers than the controls, whereas hemoglobin (HB) (14.61±1.28, P=0.028), mean corpuscular hemoglobin (MCH), and mean corpuscular hemoglobin concentrations (MCHC) (32.44±0.90, P<0.001) were lower in workers than controls. These results indicate that the exposed individuals have experienced significant hemotoxic effects during the pesticide exposure. The study also predicts the risk to exposed individuals in developing countries like Iran and demands realization of safety measures to prevent such dangerous effects of pesticide exposures.
Show more [+] Less [-]Photocatalytic removal of diazinon from aqueous solutions: a quantitative systematic review
2022
Barjasteh-Askari, Fateme | Nasseri, Simin | Nabizadeh, Ramin | Najafpoor, Aliasghar | Davoudi, Mojtaba | Mahvi, Amir-Hossein
Diazinon is a widely used pesticide that can be effectively degraded in aqueous solutions via photocatalytic oxidation. This quantitative systematic review was conducted to shed light on the various aspects of photocatalytic diazinon removal based on evidence. A systematic search was performed in Scopus, PubMed, Web of Science, Embase, and Ovid databases with keywords including diazinon, photocatalysis, and their equivalents. The search was limited to original articles in English published between January 1, 2010, and March 25, 2021. The results were expressed by descriptive statistics including mean, SD, median, and percentiles, among others. The initial electronic and manual search retrieved 777 articles, among which 41 studies comprising 49 trials were qualified for data synthesis. The reported diazinon degradation rate ranged from 2 to 100%, with a mean ± SD of 59.17 ± 28.03%. Besides, ZnO/UV, WO₃/UV, TiO₂/UV, and TiO₂/Vis, in sequence, were the most widely used processes with the highest efficacies. Solution pH in the range of 5–8, catalyst dose below 600 mg/L, diazinon initial concentration below 40 mg/L, and contact time of 20–140 min could be the optimum conditions. Diazinon degradation obeyed the first-order kinetic model with kₒbₛ between 0.0042 and 1.86 min⁻¹ and consumed energy of 38.93–350.36 kWh/m³. Diazoxon and IMP were the most detected by-products of diazinon degradation although bioassay data were scarce. Based on the results, photocatalytic processes are very efficient in removing diazinon from aqueous solutions although more elaborate studies are needed to assess the mineralization rate and effluent toxicity.
Show more [+] Less [-]The protective effects of erdosteine on subacute diazinon-induced oxidative stress and inflammation in rats
2022
Birdane, Yavuz Osman | Avci, Gulcan | Birdane, Fatih Mehmet | Turkmen, Ruhi | Atik, Orkun | Atik, Hulya
In today’s world, pesticides are commonly used to control pests and in advanced agriculture. As an organophosphorus insecticide (OPI), diazinon (DZN) is a commonly used substance. However, the widespread usage of DZN increases the probability of incidence of toxication. This toxication has been reported to be shaped not through cholinergic syndromes that are experienced as a result of acetylcholinesterase inhibition, which is the primary effect of these cases. It is rather shaped by the altering of the facilitation of oxidative stress and inflammatory response. In this study, the protective effect of administering erdosteine (ERDOS) subacute DZN exposure was investigated. A total of 24 male Wistar albino rats were separated into 4 groups (with 6 rats in each group), namely, the control, DZN (15 mg/kg/day), ERDOS (10 mg/kg/day), and DZN + ERDOS (15 mg/kg/day DZN + 10 mg/kg/day ERDOS) groups. These medications were given through oral gavage for 28 days. With the whole blood, plasma, and serum samples taken from the rats, oxidant-antioxidant parameters and cytokine levels were measured. The MDA and NOx levels and SOD and CAT enzyme activities of the DZN group were higher than those of the control group, while the GSH levels and TAC and GPx activities of the DZN group were lower than those of the control group (p < 0.05). It was also found that cytokine (IL-1β, IL-10, and TNF-α) levels in the DZN group were higher than those in the control group (p < 0.05). On the other hand, the ERDOS implementations were detected to ameliorate the harmful effects of DZN on the oxidant-antioxidant parameters and cytokine levels (p < 0.05). Conclusively, besides the known mucolytic efficacy of ERDOS, it may also be stated to display free radical scavenger, antioxidant, and anti-inflammatory characteristics to inhibit some proinflammatory cytokines that are specifically involved in oxidative stress. Additionally, the ameliorating property of ERDOS can be benefited from in possible DZN-induced toxication cases.
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