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Agrochemicals in freshwater systems and their potential as endocrine disrupting chemicals: A South African context Full text
2021
Horak, Ilzé | Horn, Suranie | Pieters, Rialet
South Africa is the largest agrochemical user in sub-Saharan Africa, with over 3000 registered pesticide products. Although they reduce crop losses, these chemicals reach non-target aquatic environments via leaching, spray drift or run-off. In this review, attention is paid to legacy and current-use pesticides reported in literature for the freshwater environment of South Africa and to the extent these are linked to endocrine disruption. Although banned, residues of many legacy organochlorine pesticides (endosulfan and dichlorodiphenyltrichloroethane (DDT)) are still detected in South African watercourses and wildlife. Several current-use pesticides (triazine herbicides, glyphosate-based herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D) and chlorpyrifos) have also been reported. Agrochemicals can interfere with normal hormone function of non-target organism leading to various endocrine disrupting (ED) effects: intersex, reduced spermatogenesis, asymmetric urogenital papillae, testicular lesions and infertile eggs. Although studies investigating the occurrence of agrochemicals and/or ED effects in freshwater aquatic environments in South Africa have increased, few studies determined both the levels of agricultural pesticides present and associated ED effects. The majority of studies conducted are either laboratory-based employing in vitro or in vivo bioassays to determine ED effects of agrochemicals or studies that investigate environmental concentrations of pesticides. However, a combined approach of bioassays and chemical screening will provide a more comprehensive overview of agrochemical pollution of water systems in South Africa and the risks associated with long-term chronic exposure.
Show more [+] Less [-]Nationwide levels and distribution of endosulfan in air, soil, water, and sediment in South Korea Full text
2020
Kim, Leesun | Jeon, Jin-Woo | Son, Ji-Young | Kim, Chul-Su | Ye, Jin | Kim, Ho-Joong | Lee, Chang-Ho | Hwang, Seung-Man | Choi, Sung-Deuk
We investigated the levels and distribution patterns of α- and β-endosulfan and endosulfan sulfate in air, soil, water, and sediment samples collected from the South Korean persistent organic pollutants (POPs) monitoring networks. In the air samples, the highest concentrations of the total (Σ₃) endosulfan (50.3–611 pg/m³, mean: 274 pg/m³) were observed during summer. Spearman analysis revealed a good correlation between agricultural land area and atmospheric concentrations of Σ₃ endosulfan except during winter. Regardless of the season, the ratio of the two isomers (α/β) was 3.6–4.9 in the air samples, higher than that observed in technical mixtures (2.0–2.3), possibly due to the higher volatility of α-endosulfan, compared to β-endosulfan. Concentrations of Σ₃ endosulfan in the soil samples (n.d.−13.4 ng/g, mean: 0.8 ng/g) were not significantly different except at some stations adjacent to large areas of farmland. The average levels of Σ₃ endosulfan in the water and sediment samples were 2.1 ng/L and 0.1 ng/g dw, respectively. In analyzing the four largest rivers, it was observed that a few water stations during spring and fall and sediment stations in fall had high concentrations of the two isomers and endosulfan sulfate, particularly around the Yeoungsan and Nakdong Rivers near large areas of agricultural land. Endosulfan sulfate was dominant at most water and sediment sampling stations. This study demonstrates that the endosulfan found in most environmental compartments most probably derives from agricultural areas despite its ban as a pesticide. On the other hand, given that it was also detected in industrial and urban areas, in which pesticide application does not occur, it can be conjectured that endosulfan is aerially transported at higher temperatures and continuously circulates within the environment.
Show more [+] Less [-]Air monitoring of new and legacy POPs in the Group of Latin America and Caribbean (GRULAC) region Full text
2018
Rauert, Cassandra | Harner, Tom | Schuster, Jasmin K. | Eng, Anita | Fillmann, Gilberto | Castillo, Luisa Eugenia | Fentanes, Oscar | Ibarra, Martín Villa | Miglioranza, Karina S.B. | Rivadeneira, Isabel Moreno | Pozo, Karla | Aristizábal Zuluaga, Beatriz Helena
A special initiative in the Global Atmospheric Passive Sampling (GAPS) Network was implemented to provide information on new and emerging persistent organic pollutants (POPs) in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale atmospheric concentrations of the new and emerging POPs hexachlorobutadiene (HCBD), pentachloroanisole (PCA) and dicofol indicators (breakdown products) are reported for the first time. HCBD was detected in similar concentrations at all location types (<20–120 pg/m³). PCA had elevated concentrations at the urban site Concepción (Chile) of 49–222 pg/m³, with concentrations ranging <1–8.5 pg/m³ at the other sites in this study. Dicofol indicators were detected at the agricultural site of Sonora (Mexico) at concentrations ranging 30–117 pg/m³. Legacy POPs, including a range of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were also monitored to compare regional atmospheric concentrations over a decade of monitoring under the GAPS Network. γ-hexachlorocyclohexane (HCH) and the endosulfans significantly decreased (p < 0.05) from 2005 to 2015, suggesting regional levels are decreasing. However, there were no significant changes for the other legacy POPs monitored, likely a reflection of the persistency and slow decline of environmental levels of these POPs. For the more volatile OCs, atmospheric concentrations derived from polyurethane foam (PUF) (acting as an equilibrium sampler) and sorbent impregnated PUF (SIP) (acting as a linear phase sampler), were compared. The complimentary methods show a good agreement of within a factor of 2–3, and areas for future studies to improve this agreement are further discussed.
Show more [+] Less [-]Air contamination by legacy and current-use pesticides in Brazilian mountains: An overview of national regulations by monitoring pollutant presence in pristine areas Full text
2018
Guida, Yago de Souza | Meire, Rodrigo Ornellas | Torres, João Paulo Machado | Malm, Olaf
In the last decades, research regarding the dynamics of pesticides has grown, even in remote regions. Due to long-range atmospheric transport, environmental persistence and toxicological potential of organochlorine pesticides (OCPs), similar characteristics of current-use pesticides (CUPs) and their massive use in Brazil, these contaminants have become a major concern for environmental and human life. Thus, this study aimed to evaluate subgroups or individual chemicals of OCPs and CUPs, which could have travelled over two Conservation Unit sites in the Rio de Janeiro state. The study was carried out for 24 months, (2013–2015), in Itatiaia National Park (INP) and in the Serra dos Órgãos National Park (SONP), at ∼2400 and ∼2200 meters above sea level, respectively. The study was based on atmospheric passive sampling (polyurethane foam disks). Target pesticides were detected by means of gas chromatography device coupled with mass spectrometry (GC-MS). Significantly higher concentrations were measured in SONP when compared to INP. However, in broad terms, the contamination profile was quite similar for both national parks: The highest concentrations of endosulfan (INP - 1275 pg m⁻³ and SONP - 3202 pg m⁻³) were followed by cypermethrin (INP - 148 pg m⁻³ and SONP - 881 pg m⁻³) and chlorpyrifos (INP - 67 pg m⁻³ and SONP - 270 pg m⁻³). In agreement with previous studies, the atmospheric concentrations of legacy OCPs showed background air levels. The decrease of endosulfan over the years was highlighted with a parallel increase of chlorpyrifos, suggesting a collateral effect of the national bias of permissive and massive use of agrochemicals. CUPs seemed to behave like pseudo-persistent pollutants (pseudo-POPs). This is the first report of atmospheric concentrations of pyrethroids in Brazilian mountain regions, and possibly the first to investigate them in the air in South America or in any mountain region in the world.
Show more [+] Less [-]Endosulfan induces autophagy and endothelial dysfunction via the AMPK/mTOR signaling pathway triggered by oxidative stress Full text
2017
Zhang, Lianshuang | Wei, Jialiu | Ren, Lihua | Zhang, Jin | Wang, Ji | Jing, Li | Yang, Man | Yu, Yang | Sun, Zhiwei | Zhou, Xianqing
Cardiovascular diseases is related to environmental pollution. Endosulfan is an organochlorine pesticide and its toxicity has been reported. However, the relationship between oxidative stress and autophagy induced by endosulfan and its underlying mechanism remain confusing. In this study, human umbilical vein endothelial cells (HUVECs) were chosen to explore the toxicity mechanism and were treated with 0, 1, 6, 12 μg/mL−1 endosulfan for 24 h, respectively. The present results showed that autophagy could be induced by endosulfan, which was verified by the monodansylcadaverine staining, autophagic ultrastructural observation, and LC3-I/LC3-II conversion. In addition, the levels of adenosine triphosphate (ATP), the mitochondria membrane potential (MMP) were significantly decreased in a dose-dependent way. The expression of proinflammatory cytokines (tumor necrosis factor α, interleukin-1β, and interleukin-6) were significantly elevated, and the index of endothelial function such as monocyte chemotactic protein 1 (MCP-1), intercellular cell adhesion molecule-1 (ICAM-1) increased. Moreover, endosulfan had an activation effect on the 5′AMP-activated protein kinase (AMPK)/rapamycin (mTOR) signaling pathway. Our findings demonstrated that endosulfan could induce oxidative stress and mitochondria injury, activate autophagy, induce inflammatory response, and eventually lead to endothelial dysfunction via the AMPK/mTOR pathway. This indicates that exposure to endosulfan is a potential risk factor for cardiovascular diseases.
Show more [+] Less [-]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 Full text
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.
Show more [+] Less [-]Spatial distribution, transport dynamics, and health risks of endosulfan at a contaminated site Full text
2016
Fang, Yanyan | Nie, Zhiqiang | Die, Qingqi | Tian, Yajun | Liu, Feng | He, Jie | Huang, Qifei
We analyzed concentrations, distribution characteristics, and health risks of endosulfan (α and β isomers, and endosulfan sulfate) in soils (top soils and soil profiles) and air, at and around a typical endosulfan production site in Jiangsu, China. The air–soil surface exchange flux is calculated to investigate transport dynamics of endosulfan. Concentrations at the production site ranged from 0.01 to 114 mg/kg d.w. in soil and 4.81–289 ng/m3 in air, with very high concentrations occurring at the location of endosulfan emulsion workshop. In the surrounding area, endosulfan was detected in all samples, with concentrations ranging from 1.37–415 ng/g d.w. in soil and 0.89–10.4 ng/m3 in air. In the contaminated site, endosulfan concentrations fluctuated with depth in the upper soil layers, then decreased below 120 cm. Soil and air within a distance of 2.0 km appear to be affected by endosulfan originating from the site. Even the health risk at the location of the endosulfan emulsifiable solution workshop was over seven times the acceptable value, the risk to nearby adults and children was low.
Show more [+] Less [-]Endosulfan inhibits proliferation through the Notch signaling pathway in human umbilical vein endothelial cells Full text
2016
Wei, Jialiu | Zhang, Lianshuang | Ren, Lihua | Zhang, Jin | Yu, Yang | Wang, Ji | Duan, Junchao | Peng, Cheng | Sun, Zhiwei | Zhou, Xianqing
Our previous research showed that endosulfan triggers the extrinsic coagulation pathway by damaging endothelial cells and causes hypercoagulation of blood. To identify the mechanism of endosulfan-impaired endothelial cells, we treated human umbilical vein endothelial cells (HUVECs) with different concentrations of endosulfan, with and without an inhibitor for Notch, N-[N-(3, 5-difluorophenacetyl)-1-alanyl]S-Phenylglycinet-butylester (DAPT, 20 μM), or a reactive oxygen species (ROS) scavenger, N-Acetyl-l-cysteine (NAC, 3 mM), for 24 h. The results showed that endosulfan could inhibit cell viability/proliferation by increasing the release of lactate dehydrogenase (LDH), arresting the cell cycle in both S and G2/M phases, and inducing apoptosis in HUVECs. We also found that endosulfan can damage microfilaments, microtubules, and nuclei; arrest mitosis; remarkably increase the expressions of Dll4, Notch1, Cleaved-Notch1, Jagged1, Notch4, Hes1, and p21; and significantly induce ROS and malondialdehyde production in HUVECs. The presence of DAPT antagonized the above changes of cycle arrest, proliferation inhibition, and expressions of Dll4, Notch1, Cleaved-Notch1, Hes1, and p21 caused by endosulfan; however, NAC could attenuate LDH release; ROS and malondialdehyde production; apoptosis; and the expression levels of Dll4, Notch1, Cleaved-Notch1, Notch4, and Hes1 induced by endosulfan. These results demonstrated that endosulfan inhibited proliferation through the Notch signaling pathway as a result of oxidative stress. In addition, endosulfan can damage the cytoskeleton and block mitosis, which may add another layer of toxic effects on endothelial cells.
Show more [+] Less [-]Polychlorinated biphenyls and organochlorine pesticides in River Brahmaputra from the outer Himalayan Range and River Hooghly emptying into the Bay of Bengal: Occurrence, sources and ecotoxicological risk assessment Full text
2016
Chakraborty, Paromita | Khuman, Sanjenbam Nirmala | Sakthivel, S. | Sampath, Srimurali | Devi, Ningombam Linthoingambi | Bang, John J. | Katsoyiannis, Athanasios
River Brahmaputra (RB) from the outer Himalayan Range and River Hooghly (RH), a distributary of River Ganga, are the two largest transboundary perennial rivers supplying freshwater to the northeastern and eastern states of India. Given the history of extensive usage of organochlorine pesticides and increasing industrialization along the banks of these rivers we investigated selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in the surface water of River Brahmaputra and River Hooghly. Geomean of ΣOCPs (53 ng L−1) and Σ19PCBs (108 ng L−1) was higher in RH compared with geomean of ΣOCPs (24 ng L−1) and Σ19PCBs (77 ng L−1) in RB. Among OCPs, γ-HCH showed maximum detection frequency in both the rivers reflecting ongoing lindane usage. DDT and endosulfan residues were observed at specific locations where past or ongoing sources exist. Elevated concentrations of heavier congeners (penta-hepta) were observed in those sites along RH where port and industrial activities were prevalent including informal electronic waste scrap processing units. Furthermore along River Hooghly PCB-126 was high in the suburban industrial belt of Howrah district. PCBs were found to be ubiquitously distributed in RB. Atmospheric transport of tri- and tetra-PCB congeners from the primary source regions might be a major contributor for PCBs in RB. Heavier congeners (penta-nona) in the urban centers of RB were likely due to industrial wastewater runoff from the oil refineries in the Brahmaputra valley. Σ19PCBs concentrations in this study exceeded the USEPA recommended limit for freshwater. Ecotoxicological risk assessment showed the possibility of adverse impact on the organisms in the lower trophic level due to DDT and lindane contamination. Impact of endosulfan on fishes might be of considerable concern for aquatic environment.
Show more [+] Less [-]Endosulfan, pentachlorobenzene and short-chain chlorinated paraffins in background soils from Western Europe Full text
2015
(Kevin C.),
Endosulfan, pentachlorobenzene and short-chain chlorinated paraffins in background soils from Western Europe Full text
2015
(Kevin C.),
Soils are major reservoirs for many persistent organic pollutants (POPs). In this study, “newly” regulated POPs i.e. Σendosulfans (α-endosulfan, β-endosulfan, endosulfan sulfate), pentachlorobenzene (PeCB), and short-chain chlorinated paraffins (SCCPs) were determined in background samples from woodland (WL) and grassland (GL) surface soil, collected along an existing latitudinal UK–Norway transect. Statistical analysis, complemented with plots showing the predicted equilibrium distribution and mobility potential, was then explored to discuss factors controlling their spatial distribution. SCCPs were detected with the highest average concentrations (35 ± 100 ng/g soil organic matter (SOM)), followed by Σendosulfans (3 ± 3 ng/g SOM) and PeCB (1 ± 1 ng/g SOM). PeCB and Σendosulfans share many similarities in their distribution in these background soils as well as with several legacy POPs. A steep decline in concentrations of SCCPs with increasing latitude indicates that their occurrence is dictated by proximity to source regions, while concentrations of Σendosulfans peaked in regions experiencing elevated precipitation rates.
Show more [+] Less [-]Endosulfan, pentachlorobenzene and short-chain chlorinated paraffins in background soils from Western Europe Full text
2015
Halse, Anne Karine | Schlabach, Martin | Schuster, Jasmin K | Jones, Kevin C | Steinnes, Eiliv | Breivik, Knut
Soils are major reservoirs for many persistent organic pollutants (POPs). In this study, “newly” regulated POPs i.e. sum endosulfans (a-endosulfan, b-endosulfan, endosulfan sulfate), pentachlorobenzene (PeCB), and short-chain chlorinated paraffins (SCCPs) were determined in background samples from woodland (WL) and grassland (GL) surface soil, collected along an existing latitudinal UK-Norway transect. Statistical analysis, complemented with plots showing the predicted equilibrium distribution and mobility potential, was then explored to discuss factors controlling their spatial distribution. SCCPs were detected with the highest average concentrations (35 ± 100 ng/g soil organic matter (SOM)), followed by sum endosulfans (3 ± 3 ng/g SOM) and PeCB (1 ± 1 ng/g SOM). PeCB and sum endosulfans share many similarities in their distribution in these background soils as well as with several legacy POPs. A steep decline in concentrations of SCCPs with increasing latitude indicates that their occurrence is dictated by proximity to source regions, while concentrations of Sendosulfans peaked in regions experiencing elevated precipitation rates. | acceptedVersion
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