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1.
Environ Sci Technol ; 58(9): 4392-4403, 2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38362876

RESUMEN

Unraveling the mysterious pathways of pollutants to the deepest oceanic realms holds critical importance for assessing the integrity of remote marine ecosystems. This study tracks the transport of pollutants into the depths of the oceans, a key step in protecting the sanctity of these least explored ecosystems. By analyzing hadal trench samples from the Mariana, Mussau, and New Britain trenches, we found the widespread distribution of organophosphate ester (OPE) flame retardants but a complex transport pattern for the OPE in these regions. In the Mariana Trench seawater column, OPE concentrations range between 17.4 and 102 ng L-1, with peaks at depths of 500 and 4000 m, which may be linked to Equatorial Undercurrent and topographic Rossby waves, respectively. Sediments, particularly in Mariana (422 ng g-1 dw), showed high OPE affinity, likely due to organic matter serving as a transport medium, influenced by "solvent switching", "solvent depletion", and "filtering processes". Amphipods in the three trenches had consistent OPE levels (29.1-215 ng g-1 lipid weight), independent of the sediment pollution patterns. The OPEs in these amphipods appeared more linked to surface-dwelling organisms, suggesting the influence of "solvent depletion". This study highlights the need for an improved understanding of deep-sea pollutant sources and transport, urging the establishment of protective measures for these remote marine habitats.


Asunto(s)
Anfípodos , Contaminantes Ambientales , Retardadores de Llama , Animales , Ecosistema , Organofosfatos , Ésteres , Solventes
2.
Environ Sci Technol ; 55(1): 788-796, 2021 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-33275416

RESUMEN

Elaborating the spatiotemporal variations and dynamic mechanisms of black carbon (BC) in coastal seas, the geographically pivotal intermediate zones that link the terrestrial and open oceanic ecosystems, will contribute significantly to refine the regional and global BC geochemistry. In this study, we implemented a large spatial-scale and multiseason and -layer seawater sampling campaign in high BC emission influenced coastal China seas (Bohai Sea and Northern Yellow Sea) and quantified the thermal/optical reflectance-based particulate BC (PBC) and benzene polycarboxylic acids-based dissolved BC (DBC). We found that the climate and its associated hydrological effects (including the intensive resuspension and coastal current transport) largely regulate both PBC and DBC spatiotemporal variations and dynamics. In combination with previous work on upstream rivers and downstream open ocean, a significant and continuous decrease in the DBC aromatic condensation was observed along the river-to-ocean continuum, probably due to the increment of the photochemical degradation during the waterborne transport. Based on our DBC methodological development, i.e., the determination and subsequent inclusion of the nitrated BC molecular markers, the magnitudes of the current global DBC fluxes and pools were updated. After the update, the DBC fluxes from atmospheric deposition and riverine delivery were estimated at rates of 4.3 and 66.3 Tg yr-1, respectively, and the global oceanic DBC pool was approximately 36 Gt. This update will greatly assist in constructing a more robust regional and global DBC and BC cycling and budgets.


Asunto(s)
Ecosistema , Hollín , Carbono/análisis , China , Monitoreo del Ambiente , Océanos y Mares
3.
J Environ Sci Health B ; 55(2): 91-102, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-31524045

RESUMEN

Information regarding the enantioselective endocrine disruption of chiral herbicides is scarce. This study assessed the disrupting effects of eight typical chiral herbicides on corticosteroids (including glucocorticoids and mineralocorticoids). Enantioselectivity of eight chiral herbicides were evaluated for their agonistic/antagonistic effects on glucocorticoid receptor (GR) and mineralocorticoid receptor (MR) with CHOK1 cell line using reporter gene assay. Their influence on the production of corticosteroids were further investigated in H295R cell line using enzyme-linked immunosorbent assay (ELISA). None of the racemates or enantiomers of eight chiral herbicides exhibited GR or MR agonistic activity at non-cytotoxic concentrations. However, rac-propisochlor and S-imazamox antagonized cortisol-induced transactivation of GR by 21.79% and 38.73% at the concentration of 1.0 × 10-7 M and 1.0 × 10-6 M, respectively, and R-napropamide remarkably attenuated aldosterone-induced MR transactivation by 68.78% at 1.0 × 10-6 M. The secretion of cortisol was significantly restrained after treated with 1.0 × 10-6 M rac-propisochlor and rac-/R-napropamide at the concentration of 1.0 × 10-6 M by 26.49%, 30.10% and 35.27%, respectively, while this glucocorticoid was remarkably induced by 1.0 × 10-5 M rac-diclofop-methyl and its two enantiomers at the concentration of 1.0 × 10-5 M by 75.60%, 100.1% and 68.78%, respectively. Exposure to rac-propisochlor (1.0 × 10-6 M), S-diclofop-methyl (1.0 × 10-5 M) or rac-/S-/R- acetochlor (1.0 × 10-6 M) and rac-/S-/R-lactofen (1.0 × 10-6 M) inhibited the secretion of aldosterone by approximately 40%. Our findings suggested that chiral herbicides disrupted corticosteroid homeostasis in an enantioselective way. Therefore, more comprehensive screening is required to better understand the ecological and health risks of chiral pesticides.


Asunto(s)
Corticoesteroides/metabolismo , Herbicidas/química , Herbicidas/toxicidad , Aldosterona/metabolismo , Animales , Células CHO , Línea Celular , Cricetulus , Disruptores Endocrinos/química , Disruptores Endocrinos/toxicidad , Humanos , Hidrocortisona/metabolismo , Antagonistas de Receptores de Mineralocorticoides/química , Antagonistas de Receptores de Mineralocorticoides/toxicidad , Receptores de Glucocorticoides/agonistas , Receptores de Glucocorticoides/antagonistas & inhibidores , Receptores de Glucocorticoides/genética , Receptores de Glucocorticoides/metabolismo , Receptores de Mineralocorticoides/agonistas , Receptores de Mineralocorticoides/genética , Receptores de Mineralocorticoides/metabolismo , Estereoisomerismo
4.
Chirality ; 31(7): 492-501, 2019 07.
Artículo en Inglés | MEDLINE | ID: mdl-31111586

RESUMEN

The electronic absorption (UV) to circular dichroism (CD) signal ratio can be used for enantiomeric excess (ee) analysis within linear range. However, CD detection often requires a high sample concentration where deviations from Beer's law may occur. Individual enantiomers of four chiral compounds were separated from commercial racemates by semipreparative high-performance liquid chromatography (HPLC) with chiral columns. They were used to trace possible deviations in both UV and CD detection on achiral HPLC with a photodiode array detector and a CD detector. The CD/UV ratios for samples with the same ee value decreased by up to 7.8 to 52% when the injection volume increased, indicating that the linear standard curve of ee versus CD/UV is only valid within a narrow range. To extend the sample amount to a wider range, a data-processing method was developed based on two second-order polynomial functions, which were constructed to fit the relationship between the intensities of the UV and CD signals for two enantiomers. Moreover, a more simplified method based on a third-order polynomial function was established to calculate the ee values. The variations between the predicted and experimental ee values were within ±0.08 for both methods. To our knowledge, this is the first study that the deviations from Beer's law are considered in both UV and CD detection for ee analysis.

5.
Chirality ; 30(5): 661-669, 2018 05.
Artículo en Inglés | MEDLINE | ID: mdl-29675850

RESUMEN

Supercritical fluid chromatography (SFC) is already used for enantioseparation in the pharmaceutical industry, but it is rarely used for the separation of chiral pesticides. Comparing with high performence liquid chromatography, SFC uses much more environmnetal friendly and economic mobile phase, supercritical CO2 . In our work, the enantioseparation of an amide herbicide, napropamide, using three different polysaccharide-type chiral stationary phases (CSPs) in SFC was investigated. By studying the effect of different CSPs, organic modifiers, temperature, back-pressure regulator pressures, and flow rates for the enantioseparation of napropamide, we established a rapid and green method for enantioseparation that takes less than 2 minutes: The column was CEL2, the mobile phase was CO2 with 20% 2-propanol, and the flow rate was 2.0 mL/min. We found that CEL2 demonstrated the strongest resolution capability. Acetonitrile was favored over alcoholic solvents when the CSP was amylose and 2-propanol was the best choice when using cellulose. When the concentration of the modifiers or the flow rate was decreased, resolutions and analysis times increased concurrently. The temperature and back-pressure regulator pressure exhibited only minor influences on the resolution and analysis time of the napropamide enantioseparations with these chiral columns. The molecular docking analysis provided a deeper insight into the interactions between the enantiomers and the CSPs at the atomic level and partly explained the reason for the different elution orders using the different chiral columns.

6.
Chirality ; 30(4): 475-483, 2018 04.
Artículo en Inglés | MEDLINE | ID: mdl-29315818

RESUMEN

Polychlorinated biphenyls (PCBs) are harmful and persistent organic pollutants that have long been used in industrial manufacturing. Their persistence leads to accumulation in the food chain causing potential toxic effects. As 19 out of 78 of the chiral congeners have stable atropisomers at ambient temperature, we studied some typical enantiomers: PCB45, PCB95, PCB136, and PCB149. The chiral stationary phases OD-H and OJ-H were used for separation in analytic high-performance liquid chromatography (HPLC), as well as for collection in semi-preparative HPLC. The resolution was optimized with respect to n-hexane-based mobile phases, temperature, and flow rate. All pure enantiomers were recovered from semi-preparative HPLC within 15 minutes for practical purpose. Characterization of the absolute configurations were conducted with a combination of theoretical and experimental electronic circular dichroism measurements. The enantiomers of PCB45, PCB95, PCB136, and PCB149 proved to be eluted as R > S, S > R, R > S, and S > R, respectively. Molecular structures (eg, substituent groups) and properties (eg, bond lengths, bond angles, and dipole moments) were quantitatively analyzed to understand the toxicity effect of PCBs. In summary, we have developed a well-established methodology of collection and configuration identification for analogous PCB derivatives.

7.
Water Res ; 251: 121126, 2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38237461

RESUMEN

The "V"-shaped structure of hadal trenches acts as a natural collector of organic pollutants, drawing attention to the need for extensive research in these areas. Our review identifies significant concentrations of organic pollutants, including persistent organic pollutants, black carbon, antibiotic-resistant genes, and plastics, which often match those in industrialized regions. They may trace back to both human activities and natural sources, underscoring the trenches' critical role in ocean biogeochemical cycles. We highlight the complex lateral and vertical transport mechanisms within these zones. Advanced methodologies, including stable isotope analysis, biomarker identification, and chiral analysis within isotope-based mixing models, are crucial for discerning the origins and pathways of these pollutants. In forthcoming studies, we aim to explore advanced methods for precise pollutant tracing, develop predictive models to forecast the future distribution and impacts of pollutants in hadal zones and on the Earth's larger ecological systems.


Asunto(s)
Contaminantes Ambientales , Humanos , Ecosistema , Plásticos , Isótopos
8.
Mar Pollut Bull ; 196: 115587, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37797540

RESUMEN

Tuna and billfish are widely distributed in oceans worldwide. Their survival is relied on a decent share of essential and non-essential elements. We conducted a comprehensive evaluation of essential and non-essential elements in livers of tuna and billfish collected from global oceans. The individual element consistently shown similar orders of magnitude in both tuna and billfish, with essential elements generally being 1-3 orders of magnitude higher than non-essential elements. Various physicochemical properties and behaviors contributed to four distinct clusters of these elements. Also, element distribution pattern indicated the presence of four sample groups based on regions and categories. Nine elements served as characteristic indicators. Among them, fish category was the most important influencing factor. Hg, Fe, Tl, Co, and Se were influenced by body size, trophic level, and feeding habits. Ni was influenced by sampling regions, while Mg, Mn and As were influenced by body size and local primary production.


Asunto(s)
Mercurio , Atún , Animales , Océanos y Mares , Peces , Hígado
9.
J Hazard Mater ; 448: 130974, 2023 04 15.
Artículo en Inglés | MEDLINE | ID: mdl-36860051

RESUMEN

Organic anthropogenic pollutants reach even the deepest parts of the oceans, i.e., the hadal trenches. We here presented the concentrations, influencing factors, and potential sources of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in hadal sediments and amphipods from the Mariana, Mussau and New Britain trenches. Results showed that BDE 209 was the dominant PBDEs congener and DBDPE was the dominant NBFRs. No significant correlation was found between TOC contents and PBDEs or NBFRs levels in sediment. Lipid content and body length were the potential important factors affecting variation in pollutant concentrations in the carapace & muscle of amphipods, while the pollution levels of viscera were mainly affected by the sex and lipid content. PBDEs and NBFRs might reach trench surface seawater through long-range atmospheric transport and oceans currents but with little contribution from the Great Pacific Garbage Patch. Determination of carbon and nitrogen isotopes indicated that the pollutants were transported and accumulated in amphipods and sediment via different pathways. PBDEs and NBFRs in the hadal sediments were generally transported via the settling of sediment particles of either marine or terrigenous origin whereas in amphipods they accumulated via feeding on animal carrion through the food web. This is the first study reporting on BDE 209 and NBFR contaminations in hadal settings and provide new insight on influencing factors and sources of PBDEs and NBFRs in the deepest oceans.


Asunto(s)
Anfípodos , Contaminantes Ambientales , Retardadores de Llama , Animales , Éteres Difenilos Halogenados , Lípidos
10.
Environ Int ; 179: 108163, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37619253

RESUMEN

Squid is traded globally as an important food resource. However, the occurrence of carcinogenic halogenated polycyclic aromatic hydrocarbons (HPAHs) in squid and the risk of their transfer through trade is little understood or recognized. Here, we comprehensively evaluated the occurrence and risk transfer by quantifying the congener-specific concentrations of HPAHs in 121 squid samples collected from the Pacific, Atlantic and Indian oceans. This was the first time that nine of the 36 target chlorinated and brominated PAH congeners had been detected in squid. The HPAHs exhibited growth-dilution effects in the squid. The lipid content of squid was the most significant factor influencing HPAH bioaccumulation, while differences in squid growth and local ocean contamination influenced by geographical distribution also affected HPAH bioaccumulation. The redistribution and risk transfers of HPAHs in squid as a food could be affected by international trading. The cancer risks from squid consumption in China and Mexico were increased by 50 % and 30 %, respectively, because of international squid trading.


Asunto(s)
Hidrocarburos Policíclicos Aromáticos , Alimentos Marinos , Animales , Bioacumulación , Decapodiformes
11.
Sci Total Environ ; 899: 166426, 2023 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-37598971

RESUMEN

Halogenated organic pollutants (HOPs) represent hazardous and persistent compounds characterized by their capacity to accumulate within organisms and endure in the environment. These substances are frequently transmitted through aquatic food webs, engendering potential hazards to ecosystems and human well-being. The trophodynamics of HOPs in aquatic food webs has garnered worldwide attention within the scientific community. Despite comprehensive research endeavors, the prevailing trajectory of HOPs, whether inclined toward biomagnification or biodilution within global aquatic food webs, remains unresolved. Furthermore, while numerous studies have probed the variables influencing the trophic magnification factor (TMF), the paramount determinant remains elusive. Collating a compendium of pertinent literature encompassing TMFs from the Web of Science between 1994 and 2023, our analysis underscores the disparities in attention accorded to legacy HOPs compared to emerging counterparts. A discernible pattern of biomagnification characterizes the behavior of HOPs within aquatic food webs. Geographically, the northern hemisphere, including Asia, Europe, and North America, has demonstrated greater biomagnification than its southern hemisphere counterparts. Utilizing a boosted regression tree (BRT) approach, we reveal that the food web length and type emerge as pivotal determinants influencing TMFs. This review provides a valuable basis for gauging ecological and health risks, thereby facilitating the formulation of robust standards for managing aquatic environments.


Asunto(s)
Contaminantes Ambientales , Cadena Alimentaria , Humanos , Ecosistema , Asia , Bioacumulación
12.
J Hazard Mater ; 426: 128115, 2022 03 15.
Artículo en Inglés | MEDLINE | ID: mdl-34959217

RESUMEN

Accumulation of organochlorine pesticides (OCPs) in Antarctic krill (Euphausia superba), a keystone species in the Southern Ocean, is potentially harmful to the Antarctic ecosystem and human health. In the current study, we collected E. superba specimens (including muscle and carapace tissues) from Bransfield Strait in northern Antarctic Peninsula and South Georgia to analyze the profile, influencing factors and mechanisms of OCPs bioaccumulation in them. Results indicated that the biological traits (δ13C, δ15N and lipid contents) of krill were significantly affected by habitat. There may exist growth dilution of OCPs in Antarctic krill and no fresh OCPs input in Antarctica, except for endosulfan I. Based on lipid-normalized concentrations, no significant differences were observed between the two regions at most sampling sites. However, OCP levels showed tissue and sex dependence. Boosted regression trees (BRTs) and partial least squares structural equation models (PLS-SEMs) were built to better investigate the main factors affecting the bioaccumulation of OCPs. Lipid content, negatively correlated with OCP levels, was the main factor. In vitro silicon modeling indicated that CYP3A4 metabolism capacity in krill contributed to the OCP residues except for endosulfan I. The results of this study expand current knowledge of OCPs in Antarctic marine biota, as well as their influencing factors and potential mechanisms.


Asunto(s)
Euphausiacea , Plaguicidas , Animales , Regiones Antárticas , Bioacumulación , Ecosistema , Humanos
13.
J Hazard Mater ; 419: 126164, 2021 10 05.
Artículo en Inglés | MEDLINE | ID: mdl-34323730

RESUMEN

Halogenated polycyclic aromatic hydrocarbons (HPAHs) are high lipophilic and degradation-resistant, which have been detected in the air, water, sediment and biota. HPAHs tend to have strong adverse effects on animals and humans. Although we have realized HPAHs are emerging contaminants which needs to be paid attention, there is still a lack of their individual commercial standards. This makes it difficult for understanding HPAHs comprehensively. This review is devoted to collect all the results have reported, and give a systemic look of their global distributions, influence factors and sources. Compared with air, studies on other environmental matrices (water and sediment) are more limited. The researches on organisms are fewest. Comparing the studied congeners, there are more studies on ClPAHs than BrPAHs. Human activities contribute mostly to their occurrence. Further, we then also introduce the toxicity and analytical methods to better understand HPAHs. The future research directions are also provided. Through this review, we can conclude there is an urgent need to develop analysis methods and ecologic risk assessment for better exploring HPAHs. Effective methods should be done to control HPAHs. Therefore, this review can provide a good basis for researchers to understand and control global pollution.


Asunto(s)
Hidrocarburos Policíclicos Aromáticos , Animales , Monitoreo del Ambiente , Contaminación Ambiental , Humanos , Hidrocarburos Policíclicos Aromáticos/análisis , Hidrocarburos Policíclicos Aromáticos/toxicidad , Medición de Riesgo
14.
Mar Pollut Bull ; 173(Pt A): 112926, 2021 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-34536705

RESUMEN

Squids are globally distributed. Hg-contaminated squids may have high risks on humans. With abundant Se (antagonistic effect on Hg), the risks can be reduced. We collected squids around the world (Northwest Pacific Ocean, Southeast Pacific Ocean and Indian Ocean). Concentrations of Hg and Se were region-based and tissue-based. The higher content of Se were, the lower relative Hg levels were. The correlation between Se:Hg and Se was the strongest in the digestive gland. The values of Se:Hg and THQ all confirm that the health risk was lower in samples with higher concentrations of Se. Despite the risk assessment by Se:Hg, BRV and THQ analysis showed no risk when consumed in moderation, the maximum daily intake is provided based on Monte Carlo simulation. In future, when evaluating the risks cause by Hg exposure and providing the recommended daily amount, it may need to concurrent consideration of Se levels.


Asunto(s)
Mercurio , Selenio , Animales , Decapodiformes , Humanos , Océano Índico , Mercurio/análisis , Océano Pacífico , Selenio/análisis
15.
Environ Pollut ; 261: 114136, 2020 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-32066055

RESUMEN

Perfluorooctane sulfonates (PFOS) are one of the most prominent perfluoroalkyl contaminants in humans and wildlife. Currently, information regarding enantiomer-specific exposure to PFOS in humans through transplacental transfer is lacking. This study examined 32 matched maternal serum, cord serum and placenta samples collected from mother-infant pairs in Wuhan, China. The enantiomer fraction (EF) value of perfluoro-1-methylhptanesulfonate (1m-PFOS) was lower in cord sera (0.362 ± 0.062, n = 23) compared to maternal sera (0.422 ± 0.048, n = 21) and placenta (0.410 ± 0.060, n = 16). Evaluations of the difference between EF1m-PFOS suggested enantioselective transplacental transfer of 1m-PFOS. In silico evaluation of the binding affinity of 1m-PFOS to human serum albumin (HSA) showed that the two 1m-PFOS enantiomers enantioselectively interacted with the HSA. This result hints the enantioselective carrier protein affinity may be a key factor for stereoselective 1m-PFOS transplacental transfer. The percentage of branched PFOS (%br-PFOS) and EF1m-PFOS was correlated in maternal sera, but not in cord sera and placentas. These data indicated that %br-PFOS and EF1m-PFOS may be less reliable in identifying PreFOS exposure when it comes to complex biological processes, such as transplacental transport. This study could expand our understanding of stereoselective placental contaminant transfer in humans.


Asunto(s)
Ácidos Alcanesulfónicos , Fluorocarburos , Animales , Monitoreo Biológico , China , Femenino , Humanos , Madres , Placenta , Embarazo , Estereoisomerismo
16.
Sci Total Environ ; 656: 1365-1372, 2019 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-30625665

RESUMEN

Echinochloa crus-galli is one of the most noxious weeds in the world and causes yield losses in a variety of different field crops. Napropamide and acetochlor are herbicides commonly employed to control this weed. Both compounds are chiral, with enantiomers displaying different activities. However, it is unclear how the enantiomers of these two chiral herbicides act on different tissues of E. crus-galli. The objective of this paper is to investigate the action mechanism of napropamide and acetochlor in the roots and shoots of E. crus-galli. R­enantiomers were found to be more active than either the racemates or S-enantiomers on the weed. The content of chlorophyll was not significantly affected by treatment with either enantiomer. The impacts on the activity for the oxidative stress enzymes, except catalase (CAT), showed that both napropamide and acetochlor enantiomers could induce oxidative stress. Furthermore, R­enantiomers caused greater oxidative damage. Enhanced glutathione-S-transferase (GST) activity and expression of GST genes suggested both EcGSTF1 and EcGSTZ1 were present in the roots and shoots, and this will be helpful for detoxification. The changes in both the roots and shoots revealed the two herbicides displayed tissue selectivity in E. crus-galli. These results enable a better understanding on the mechanism of action for napropamide and acetochlor enantiomers on different tissues, including the shoots and roots in E. crus-galli.


Asunto(s)
Echinochloa/efectos de los fármacos , Herbicidas/efectos adversos , Naftalenos/efectos adversos , Toluidinas/efectos adversos , Transcripción Genética/efectos de los fármacos , Echinochloa/genética , Echinochloa/fisiología , Raíces de Plantas/efectos de los fármacos , Raíces de Plantas/genética , Raíces de Plantas/fisiología , Brotes de la Planta/efectos de los fármacos , Brotes de la Planta/genética , Brotes de la Planta/fisiología , Estereoisomerismo
17.
Environ Pollut ; 246: 728-733, 2019 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-30623828

RESUMEN

Harmful algal blooms have emerged as a worldwide issue. After concentrations of herbicides entering water, herbicides in water may pose ecological effects on them. The present study investigates the toxicity and environmental behavior of the herbicides, napropamide and acetochlor as enantiomers and as racemates on Microcystis aeruginosa which is the main specie known to produce hepatotoxins. S-napropamide/acetochlor are degraded faster than their corresponding isomer R-napropamide/acetochlor, with the latter more prone to accumulate in algal cells. Moreover, all the enantiomers did not undergo measurable racemization in the medium and algal cells. S-napropamide/acetochlor exhibited much higher toxicity than R-napropamide/acetochlor, with the S-enantiomer inducing a much greater production of antioxidant defense enzymes (superoxide dismutase (SOD) and malondialdehyde (MDA)) and microcystins (MC). SOD and MC increased after treatment with the herbicides and these increases were dependent on the exposure time, whereas MDA showed no apparent change. The information provided in this work will be useful for understanding the toxicity mechanism and environmental behaviors of different amide herbicides (napropamide and acetochlor) in aquatic environments at the enantiomeric level. Additionally, analysis of chiral herbicides in aquatic system needs more attention to aide in the environmental assessment of chiral herbicides.


Asunto(s)
Antioxidantes/metabolismo , Floraciones de Algas Nocivas/efectos de los fármacos , Herbicidas/metabolismo , Microcistinas/metabolismo , Microcystis/metabolismo , Naftalenos/metabolismo , Estrés Oxidativo/efectos de los fármacos , Toluidinas/metabolismo , Naftalenos/toxicidad , Estereoisomerismo
18.
Sci Total Environ ; 690: 181-188, 2019 Nov 10.
Artículo en Inglés | MEDLINE | ID: mdl-31288109

RESUMEN

Agricultural chemicals are normally used as mixtures of several isomers, e.g., enantiomers. In theory, in order to minimize the pesticides dose, it is desirable to use the most target-active isomer. Metolachlor is a typical multichiral herbicide belonging to amide herbicides. An asymmetric carbon atom and a chiral axis yield four stereoisomers. In this study, a novel laboratory method was developed to prepare the S-metolachlor and the four stereoisomers using high performance liquid chromatography. The separated isomers had a purity of >99%, with their absolute configurations assigned by electronic circular dichroism. The enantioseparation by ultra performance convergence chromatography tandem mass spectrometry was also performed for the rapid and sensitive detection of metolachlor stereoisomers. The enantioselective herbicidal activity toward the target weed (Echinochloa crusgalli) was systematically assessed for the first time by measuring the morphology of the weed after treatment with rac-, S-metolachlor and the four stereoisomers, respectively. Among the commercial pesticides, S-metolachlor was more effective in weed inhibition than rac-metolachlor, and to the four stereoisomers, the herbicidal activities were ranked as: SS > SR ≫ RS > RR, and the RR-isomer even had some stimulative effect to the weed growth at lower concentration (1 ppm). Thus, we concluded that in these cases, the chiral carbon feature played a major role in herbicidal activity rather than the chiral axis feature, and the higher bioactivity of the S-isomers was confirmed by more effective uptake and stronger interaction with target enzymes that were involved in the gibberellic acid biosynthesis. Although the SS-isomer shows the highest herbicidal activity, controlling the major chiral feature is still much easier and more economical than controlling two chiral features.


Asunto(s)
Acetamidas/toxicidad , Agroquímicos/toxicidad , Echinochloa/efectos de los fármacos , Herbicidas/toxicidad , Acetamidas/química , Agroquímicos/química , Relación Dosis-Respuesta a Droga , Herbicidas/química , Estereoisomerismo
19.
Sci Total Environ ; 682: 151-159, 2019 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-31112816

RESUMEN

Napropamide is a chiral acetamide herbicide commonly applied to control Echinochloa crus-galli in maize. The inhibition effect may be enantioselective for Echinochloa crus-galli and maize. It may also be affected by the potential allelopathy at field condition. To investigate this, we have examined the inhibition effect of napropamide on Echinochloa crus-galli mono-cultured or co-cultured with maize at field conditions. Our results on morphology, physiology, chlorophyll content and chlorophyll fluorescence suggest that R-napropamide has stronger inhibitory effect than Rac-napropamide and S-napropamide on Echinochloa crus-galli, while none of them affects maize. We found that both glutathione-S-transferase (GST) genes and oxidative enzymes (superoxide dismutase, malondialdehyde) played roles in the inhibition. Accumulations of napropamide in Echinochloa crus-galli were more prominent in roots than in shoots, and no enantioselectivity was found in medium dissipation. We have observed relative allelopathy when applying napropamide to Echinochloa crus-galli co-cultured with maize. The results warrant further field studies on the enantioselectivity and allelopathy of herbicides.


Asunto(s)
Alelopatía/fisiología , Echinochloa/efectos de los fármacos , Herbicidas/farmacología , Naftalenos/farmacología , Zea mays/efectos de los fármacos , Echinochloa/anatomía & histología , Echinochloa/genética , Echinochloa/fisiología , Herbicidas/toxicidad , Naftalenos/toxicidad , Estereoisomerismo , Zea mays/anatomía & histología , Zea mays/genética , Zea mays/fisiología
20.
Sci Total Environ ; 626: 860-866, 2018 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-29396347

RESUMEN

Amide herbicides, which are used extensively worldwide, are often chiral. Enantiomeric selectivity comes from the different effects of the enantiomers on target and non-target organisms. In this study, the enantiomers of three amide herbicides were purified by the semi-preparative column and were used to investigate the enantioselective effects on target Echinochloa crusgalli (lowland rice weeds), and non-target Microcystis aeruginosa, and the yeast transformed with the human TRß plasmid organisms. The results showed that (i) the R-enantiomers of the three amide herbicides exhibited the strongest activity toward weed inhibition and the lowest toxicity toward non-target organisms; (ii) napropamide was better suited for controlling root growth, while acetochlor and propisochlor were better for leaves control; (iii) herbicides at certain low concentrations (0.01 mg L-1 for acetochlor and propisochlor) could be utilized to promote plant growth. These findings encourage the use of R-amide herbicides instead of their racemates to increase the efficiency of weed control and reduce the risk to non-target organisms. On the other hand, the adverse effects are caused mostly by S-enantiomer, using R-enantiomer-enriched products may offer great environmental/ecological benefits.

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