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Pesticide residues in honey bees, pollen and beeswax: Assessing beehive exposure
2018
Calatayud-Vernich, Pau | Calatayud, Fernando | Simó, Enrique | Picó, Yolanda
In order to study the distribution of pesticide residues in beekeeping matrices, samples of live in-hive worker honey bees (Apis mellifera), fresh stored pollen and beeswax were collected during 2016–2017 from 45 apiaries located in different landscape contexts in Spain. A total of 133 samples were screened for 63 pesticides or their degradation products to estimate the pesticide exposure to honey bee health through the calculation of the hazard quotient (HQ). The influence of the surrounding environment on the content of pesticides in pollen was assessed by comparing the concentrations of pesticide residues found in apiaries from intensive farming landscapes to those found in apiaries located in mountainous, grassland and urban contexts. Beeswax revealed high levels of miticides used in beekeeping such as coumaphos, chlorfenvinphos, fluvalinate and acrinathrin, which were detected in more than 75% of samples. Pollen was predominantly contaminated by miticides but also by insecticides used in agriculture such as chlorpyrifos and acetamiprid, which showed concentrations significantly higher in apiaries located in intensive farming contexts. Pesticides residues were less frequent and at lower concentrations in live honey bees. Beeswax showed the highest average hazard scores (HQ > 5000) to honey bees. Pollen samples contained the largest number of pesticide residues and relevant hazard (HQ > 50) to bees. Acrinathrin was the most important contributor to the hazard quotient scores in wax and pollen samples. The contributions of the pesticides dimethoate and chlorpyrifos to HQ were considered relevant in samples.
Afficher plus [+] Moins [-]A review on the application of constructed wetlands for the removal of priority substances and contaminants of emerging concern listed in recently launched EU legislation
2017
Gorito, Ana M. | Ribeiro, Ana R. | Almeida, C.M.R. | Silva, Adrián M.T.
The presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L−1 and μg L−1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation.
Afficher plus [+] Moins [-]Interaction and coexistence characteristics of dissolved organic matter with toxic metals and pesticides in shallow groundwater
2020
He, Xiao-Song | Zhang, Ya-Li | Liu, Zhen-Hai | Wei, Dan | Liang, Gang | Liu, Hong-Tao | Xi, Bei-Dou | Huang, Zhan-Bin | Ma, Yan | Xing, Bao-Shan
The long-term and large-scale utilization of fertilizers and pesticides in facility agriculture leads to groundwater pollution. However, the coexistence and interactions between organic fertilizers (i.e., organic matter), toxic metals, and pesticides in shallow groundwater have seldom been studied. Thus, the study sought to characterize said interactions via fluorescence, ultraviolet–visible spectroscopy (UV–Vis), and Fourier-transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy and chemometric techniques. The results indicated that groundwater DOM was comprised of protein-, polysaccharide-, and lignin-like substances derived from organic fertilizers. Protein-like substances accounted for the binding of Co, Ni, and Fe, while polysaccharide- and lignin-like substances were mainly responsible for Cr and Mo complexation. Moreover, lignin- and polysaccharide-like substances played a key role in the binding of pesticides (i.e., dichlorodiphenyltrichloroethane [DDT], endosulfan, γ-hexachlorocyclohexane [γ-HCH], monocrotophos, chlorpyrifos, and chlorfenvinphos), rendering the conversion of γ-HCH to β-hexachlorocyclohexane (β-HCH) and the degradation of DDT to dichlorobenzene dichloroethylene (DDE) ineffective. However, the presence of protein-like substances in groundwater benefited the degradation and conversion of γ-HCH and α-endosulfan. Redundancy analyses showed that lignin- and polysaccharide-like matter had the most impacts on the coexistence of DOM with toxic metals and pesticides.
Afficher plus [+] Moins [-]Pesticides, nonylphenols and polybrominated diphenyl ethers in marine bivalves from France: A pilot study
2021
Lerebours, Adélaïde | Bathie, Marguerite | Receveur, Justine | Jézéquel, Ronan | Dubillot, Emmanuel | Brunello, Pascal | Barbier, Pierrick | Le Floch, Stéphane | Thomas, Hélène
The present pilot study aimed to provide an overview of organic contaminant concentration levels in the littoral ecosystems of the Pertuis seas. The study determined the concentrations of twenty-nine pesticides, six nonylphenols and seven polybrominated diphenyl ethers (PBDEs) in sediments, seawater, Pacific oysters and blue mussels. Oysters accumulated a higher number of pesticides than blue mussels. Indeed, alpha BHC (0.60–0.72 ng/g, ww), chlorfenvinphos (1.65–2.12 ng/g, ww), chlorpyrifos (0.79–0.93 ng/g, ww), chlortoluron (2.50–4.31 ng/g, ww), metolachlor (up to 0.38 ng/g, ww) and parathion (0.56–0.69 ng/g, ww) were quantified in oysters whereas only alpha BHC (0.24–0.31 ng/g, ww), was quantified in mussels. The present results also revealed that the POPs detected in water or sediments were not ultimately found accumulated in bivalves. Other molecules such as methylparathion and BDE47 were quantified in sediments. These molecules, BDE99 and one nonylphenol (OP2OE) were quantified in seawater. Finally, the comparison with the available environmental guidelines showed that the values measured were at concentrations not considered to cause adverse effects at the populations' level except for chlortoluron in seawater (15–50 ng/L).
Afficher plus [+] Moins [-]Valorization of Organic Wastes to Reduce the Movement of Priority Substances Through a Semiarid Soil
2017
Pérez-Lucas, Gabriel | Vela, Nuria | Escudero, José A. | Navarro, Ginés | Navarro, Simón
In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.
Afficher plus [+] Moins [-]Visible Light–Driven Advanced Oxidation Processes to Remove Emerging Contaminants from Water and Wastewater: a Review
2022
Zawadzki, Piotr
The scientific data review shows that advanced oxidation processes based on the hydroxyl or sulfate radicals are of great interest among the currently conventional water and wastewater treatment methods. Different advanced treatment processes such as photocatalysis, Fenton’s reagent, ozonation, and persulfate-based processes were investigated to degrade contaminants of emerging concern (CECs) such as pesticides, personal care products, pharmaceuticals, disinfectants, dyes, and estrogenic substances. This article presents a general overview of visible light–driven advanced oxidation processes for the removal of chlorfenvinphos (organophosphorus insecticide), methylene blue (azo dye), and diclofenac (non-steroidal anti-inflammatory drug). The following visible light–driven treatment methods were reviewed: photocatalysis, sulfate radical oxidation, and photoelectrocatalysis. Visible light, among other sources of energy, is a renewable energy source and an excellent substitute for ultraviolet radiation used in advanced oxidation processes. It creates a high application potential for solar-assisted advanced oxidation processes in water and wastewater technology. Despite numerous publications of advanced oxidation processes (AOPs), more extensive research is needed to investigate the mechanisms of contaminant degradation in the presence of visible light. Therefore, this paper provides an important source of information on the degradation mechanism of emerging contaminants. An important aspect in the work is the analysis of process parameters affecting the degradation process. The initial concentration of CECs, pH, reaction time, and catalyst dosage are discussed and analyzed. Based on a comprehensive survey of previous studies, opportunities for applications of AOPs are presented, highlighting the need for further efforts to address dominant barriers to knowledge acquisition.
Afficher plus [+] Moins [-]Evaluation of pesticide residues in commercial Swiss beeswax collected in 2019 using ultra-high performance liquid chromatographic analysis
2022
Marti, Joshua N. G. | Kilchenmann, Verena | Kast, Christina
The aim of this study was to determine residue levels of pesticides in Swiss commercial beeswax. Foundation samples were collected in 2019 from nine commercial manufacturers for analysis of 21 pesticides using ultra-high performance liquid chromatography. Individual samples showed the variability and residue ranges and pooled samples represented the average annual residue values of the Swiss production. In total, 17 pesticides were identified and 13 pesticides were quantified. They included 13 acaricides and/or insecticides, two fungicides as well as a synergist and a repellent. The means calculated from individual samples were similar to the average annual residue values for most tested pesticides. Mean values of 401, 236, 106 and 3 μg·kg⁻¹ were obtained for the beekeeping-associated contaminants coumaphos, tau-fluvalinate, bromopropylate and N-(2,4-Dimethylphenyl)-formamide (DMF; breakdown product of amitraz), respectively. For the other pesticides, the mean values were 203 μg·kg⁻¹ (synergist piperonyl butoxide), 120 μg·kg⁻¹ (repellent N,N-Diethyl-3-methylbenzamide, DEET), 19 μg·kg⁻¹ (chlorfenvinphos) and 4 μg·kg⁻¹ ((E)-fenpyroximate), while the means for acrinathrin, azoxystrobin, bendiocarb, boscalid, chlorpyrifos, flumethrin, permethrin, propoxur and thiacloprid were below the limit of quantification (< LOQ). Individual samples contained from seven to 14 pesticides. The ranges of values for coumaphos and piperonyl butoxide (from 14 to 4270 μg·kg⁻¹; from 6 to 1555 μg·kg⁻¹, respectively) were larger as compared to the ranges of values for DEET and tau-fluvalinate (from < LOQ to 585 μg·kg⁻¹; from 16 to 572 μg·kg⁻¹, respectively). In conclusion, the most prominent contaminants were the pesticides coumaphos and tau-fluvalinate, which are both acaricides with previous authorization for beekeeping in Switzerland, followed by piperonyl butoxide, a synergist to enhance the effect of insecticides.
Afficher plus [+] Moins [-]A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry
2015
Terzopoulou, Evangelia | Voutsa, Dimitra | Kaklamanos, George
A multi-residue method, based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS), has been developed for the determination of 70 organic micropollutants from various chemical classes (organochlorinated, organophosphorous, triazines, carbamate and urea, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pharmaceuticals, phenols, etc.) in surface waters. A single-step SPE extraction using OASIS HLB cartridges was employed for the recovery of target micropollutants. The method has been validated according to monitoring performance criteria of the Water Framework Directive, taking into account the approved guidelines on quality assurance and quality control. The recoveries ranged from 60 to 110 %, the coefficient of variation from 0.84 to 27.4 %, and the uncertainty from 6 to 37 %. The LOD varied from 6.0 to 40 ng/L. The limits of quantification for the priority pollutants anthracene, alachlor, atrazine, benzo(a)pyrene, chlorfenvinphos, diuron, isoproturon, nonylphenol, simazine, and terbutryn fulfill the criterion of <30 % of the relevant environmental standards. The method was employed to investigate the water quality in the basin of a transboundary river, Strymonas, in NE Greece during three sampling campaigns conducted in the year 2013. Thirty-nine compounds were detected in the river water. Metolachlor, diuron, isoproturon, salicylic acid, chlorfenvinphos, 1,2-benzanthracene, pyrene, diflubenzuron, and carbaryl exhibited the highest detection frequencies.
Afficher plus [+] Moins [-]Biodegradation of pesticides using fungi species found in the aquatic environment
2015
Oliveira, B. R. | Penetra, A. | Cardoso, V. V. | Benoliel, M. J. | Barreto Crespo, M. T. | Samson, R. A. | Pereira, V. J.
Relatively limited attention has been given to the presence of fungi in the aquatic environment compared to their occurrence in other matrices. Taking advantage and recognizing the biodegradable capabilities of fungi is important, since these organisms may produce many potent enzymes capable of degrading toxic pollutants. Therefore, the aim of this study was to evaluate the potential ability of some species of filamentous fungi that occur in the aquatic environment to degrade pesticides in untreated surface water. Several laboratory-scale experiments were performed using the natural microbial population present in the aquatic environment as well as spiked fungi isolates that were found to occur in different water matrices, to test the ability of fungi to degrade several pesticides of current concern (atrazine, diuron, isoproturon and chlorfenvinphos). The results obtained in this study showed that, when spiked in sterile natural water, fungi were able to degrade chlorfenvinphos to levels below detection and unable to degrade atrazine, diuron and isoproturon. Penicillium citrinum, Aspergillus fumigatus, Aspergillus terreus and Trichoderma harzianum were found to be able to resist and degrade chlorfenvinphos. These fungi are therefore expected to play an important role in the degradation of this and other pollutants present in the aquatic environment.
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