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Application of gas chromatographic retention times to determine physicochemical properties of nitrated, oxygenated, and parent polycyclic aromatic hydrocarbons
2022
Vuong, Quang Tran | Son, Ji-Min | Thang, Phan Quang | Ohura, Takeshi | Choi, Sung-Deuk
Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are receiving attention because of their high toxicity compared with parent PAHs. However, the experimental data of their physicochemical properties has been limited. This study proposed the gas chromatographic retention time (GC-RT) technique as an effective alternative one to determine octanol-air partition coefficients (KOA) and sub-cooled liquid vapor pressures (PL) for 11 NPAHs, 10 OPAHs, and 19 parent PAHs. The slopes and intercepts of the linear regressions between temperature versus KOA and PL were provided and can be used to estimate KOA and PL for the 40 targeted compounds at any temperature. The internal energies of phase transfer (ΔUOA) and enthalpies of vaporization (ΔHL) for all targeted compounds were also calculated using the GC-RT technique. High-molecular-weight compounds may release or absorb higher heat energy to transform between different phases. NPAHs and OPAHs had a non-ideal solution behavior with activity in octanol (γₒcₜ) in the range of 19–53 and 18–1,078, respectively, which is larger than the unity threshold. A comparison among four groups of PAH derivatives showed that a functional group (nitro-, oxygen-, chloro-, and bromo-) in PAH derivatives increased γₒcₜ for corresponding parent PAHs by tens (mono-group) to hundreds of times (di-group). This study suggests that the GC-RT method is applicable for indirectly measuring the physicochemical properties of various groups of organic compounds.
Afficher plus [+] Moins [-]The seasonal variations and potential sources of nitrous acid (HONO) in the rural North China Plain
2022
Song, Yifei | Zhang, Yuanyuan | Xue, Chaoyang | Liu, Pengfei | He, Xiaowei | Li, Xuran | Mu, Yujing
Nitrous acid (HONO), an essential precursor of hydroxyl radicals (OH) in the troposphere, plays an integral role in atmospheric photochemistry. However, potential HONO sources remain unclear, particularly in rural areas, where long-term (including seasonal) measurements are scarce. HONO and related parameters were measured at a rural site in the North China Plain (NCP) during the winter of 2017 and summer and autumn of 2020. The mean HONO level was higher in winter (1.79 ± 1.44 ppbv) than in summer (0.67 ± 0.50 ppbv) and autumn (0.83 ± 0.62 ppbv). Source analysis revealed that the heterogeneous conversion (including photo-enhanced conversion) of NO₂ on the ground surface dominated the daytime HONO production in the three seasons (43.1% in winter, 54.3% in summer, and 62.0% in autumn), and the homogeneous reaction of NO and OH contributed 37.8, 12.2, and 28.4% of the daytime HONO production during winter, summer, and autumn, respectively. In addition, the total contributions of other sources (direct vehicle emissions, particulate nitrate photolysis, NO₂ uptake and its photo-enhanced reaction on the aerosol surface) to daytime HONO production were less than 5% in summer and autumn and 12.0% in winter. Unlike winter and autumn, an additional HONO source was found in summer (0.45 ± 0.21 ppbv h⁻¹, 31.4% to the daytime HONO formation), which might be attributed to the HONO emission from the fertilized field. Among the primary radical sources (photolysis of HONO, O₃, and formaldehyde), HONO photolysis was dominant, with contributions of 82.6, 49.3, and 63.2% in winter, summer, and autumn, respectively. Our findings may aid in understanding HONO formation in different seasons in rural areas and may highlight the impact of HONO on atmospheric oxidation capacity.
Afficher plus [+] Moins [-]Co-application of biochar and nitrogen fertilizer promotes rice performance, decreases cadmium availability, and shapes rhizosphere bacterial community in paddy soil
2022
Zhang, Li | He, Yulei | Lin, Dasong | Yao, Yanpo | Song, Ningning | Wang, Fangli
Cadmium (Cd) contamination in soil has posed a great threat to crop safety and yield as well as soil quality. Biochar blended with nitrogen fertilizer have been reported to be effective in remediating Cd-contaminated soil. However, the influence of co-application of biochar and nitrogen fertilizer on the Cd bioavailability, rice yield and soil microbiome remains unclear. In this study, eight different treatments including control (CK), 5% biochar (B), 2.6, 3.5, 4.4 g/pot nitrogen fertilizers (N1, N2 and N3), and co-application of biochar and nitrogen fertilizers (BN1, BN2, BN3) were performed in a pot experiment with paddy soil for observations in an entire rice cycle growth period. Results showed single N increased soil available Cd content and Cd uptake in edible part of rice, while the soil available Cd content significantly decreased by 14.8% and 7.4%–11.1% under the B, BN treatments, and the Cd content in edible part of rice was significantly reduced by 35.1% and 18.5%–26.5%, respectively. Besides, B, N and BN treatments significantly increased the yield of rice by 14.3%–86.6% compared with CK, and the highest yield was gained under BN3 treatment. Soil bacterial diversity indices (Shannon, Chao1, observed species and PD whole tree index) under N2, N3 were generally improved. Cluster analysis indicated that bacterial community structures under BN treatments differed from those of CK and single N treatments. BN treatments enhanced the abundances of key bacterial phylum such as Acidobacteria, positively associated with yield, and increased the abundance of Spirochaetes, negatively correlated to soil available Cd and Cd uptake of rice. Furthermore, the regression path analysis (RPA) revealed that pH, organic matter (OM), alkaline hydrolysis of nitrogen (AHN) and available Cd were the major properties influencing Cd content in edible part of rice. Redundancy analysis (RDA) revealed that pH and available Cd played key role in shaping soil bacterial community. Thus, BN is a feasible practice for the improvements of rice growth and remediation of Cd-polluted soil.
Afficher plus [+] Moins [-]Assessing potential risks of aquatic polycyclic aromatic compounds via multiple approaches: A case study in Jialing and Yangtze Rivers in downtown Chongqing, China
2022
Zhu, Yunxi | Liang, Bo | Xia, Weiwei | Gao, Min | Zheng, Haojun | Chen, Jing | Chen, Yang | Tian, Mi
To better evaluate the potential risks of aquatic polycyclic aromatic compounds (PACs), multiple approaches have been implemented in this study to assess the human health and ecological risks of parent, nitrated and oxygenated polycyclic aromatic hydrocarbons (PAHs, NPAHs and OPAHs) in the surface water of Jialing and Yangtze Rivers in downtown Chongqing in southwestern China. The concentrations of ∑PAHs (334 ± 125 ng L⁻¹) were much higher than those of ∑OPAHs (20.2 ± 7.49 ng L⁻¹) in the two rivers, while NPAHs were barely detected. Concentrations of detected PACs were higher in wet season than dry season, probably resulted from the elevated particle input due to heavy rainfall in wet season. Concentrations of PAHs were higher in the particulate phase than dissolved phase, while OPAHs levels showed a reverse pattern. The partition coefficients (Kₚ) of PACs in the water-SPM (suspended particulate matter) system were mainly affected by SPM concentrations and octanol/water partition coefficients of specific PACs. Human health risks calculated from non-probabilistic risk assessment model and probabilistic risk assessment model based on Monte Carlo simulation showed similar data pattern with slight difference in absolute values. Both models revealed potential or even severe human health risks contributed mainly by dermal exposure to aquatic PACs in this study. Furthermore, these models also manifested that infant stage was highly sensitive for PAC exposure. Sensitivity analysis indicated that health risk results was most sensitive to Benzo[a]pyrene equivalent toxic concentration (BaPₑq), followed by showering time and daily water intake volume. Levels of ecological risks and contributions of individual PACs differed from models based on different quality values. The adequacy of toxicity data was crucial for the reliability of ecological risk assessment.
Afficher plus [+] Moins [-]Potential hot spots contaminated with exogenous, rare earth elements originating from e-waste dismantling and recycling
2022
Wang, Siyu | Xiong, Zhunan | Wang, Lingqing | Yang, Xiao | Yan, Xiulan | Li, You | Zhang, Chaosheng | Liang, Tao
Dismantling and recycling e-waste has been recognized as a potential emission source of rare earth elements (REEs). However, the presence of REEs in typical regional soils has yet to be studied. Given the potential health implications of such soil contamination, it is vital to study the characteristics, spatial distribution, and pollution level of REEs caused by e-waste dismantling as well as determine the influencing mechanism. This study focused on Guiyu Town as an example site, which is a typical e-waste dismantling base. From the site, 39 topsoil samples of different types were collected according to grid distribution points. Soil profiles were also collected in the dismantling and non-dismantling areas. The REE characteristic parameters showed that the REE distribution was abnormal and was affected by multiple factors. The results of the integrated pollution index showed that approximately 61.5% of soil samples were considered to be lightly polluted. Spatial distribution and correlation analysis showed that hot spots of REE-polluted soil coincided with known, main pollution sources. Moreover, there was a significant negative correlation (p ≤0.05) between the REE concentration and the distance from the pollution source. E-waste disassembly and recycling greatly affect the physical and chemical properties of the surrounding soil as well as downward migration areas. In the disassembly area, REE accumulated more easily in the surface layer (0–20 cm). Geographical detector results showed that distance factor was the main contribution factor for both light rare earth elements (LREE) and heavy rare earth element (HREE) (q = 34.59% and 53.33%, respectively). REE distribution in soil was nonlinear enhanced by different factors. Taken together, these results showed that e-waste disassembling and recycling not only directly affected the spatial distribution of REEs, but that their distribution was also affected by land use type and soil properties.
Afficher plus [+] Moins [-]Spatial characteristics of fine particulate matter in subway stations: Source apportionment and health risks
2022
Ji, Wenjing | Zhao, Kaijia | Liu, Chenghao | Li, Xiaofeng
Air in subway stations is typically more polluted than ambient air, and particulate matter concentrations and compositions can vary greatly by location, even within a subway station. However, it is not known how the sources of particulate matter vary between different areas within subway stations, and source-specific health risks in subway stations are unclear. We analyzed the spatial characteristics of particulate matter by source and calculated source-specific health risks on subway platforms and concourses and in station offices by integrating source apportionment with health risk assessments. A total of 182 samples were collected in three areas in six subway stations in Nanjing, China. Enrichment factors and the positive matrix factorization receptor model were used to identify major sources. The carcinogenic and non-carcinogenic health risks to subway workers and passengers were evaluated to determine control priorities. Seven sources of particulate matter were identified in each area, with a total of four subway sources and six outdoor sources over all the areas. The source contributions to total element mass differed significantly from the source contributions to human health risks. Overall, subway sources contributed 48% of total element mass in the station office and 75% and 60% on the concourse and platform, respectively. Subway-derived sources accounted for 54%, 81%, and 71% of non-carcinogenic health risks on station platforms, concourses, and office areas, respectively. The corresponding values for carcinogenic risks were 51%, 86%, and 86%. Among the elements, cobalt had the largest contributions to carcinogenic and non-carcinogenic risks, followed by manganese for non-carcinogenic risks and hexavalent chromium for carcinogenic risks. Reducing emissions from subway sources could effectively protect the health of subway workers and passengers.
Afficher plus [+] Moins [-]Comparative study on the potential risk of contaminated-rice straw, its derived biochar and phosphorus modified biochar as an amendment and their implication for environment
2022
Zong, Yutong | Chen, Han | Malik, Zaffar | Xiao, Qing | Lu, Shenggao
Direct application of contaminated-rice straw (CRS) to soil can cause the secondary pollution in agricultural land because of high content of Cd in rice straw. This study employed biochar or modified biochar technique to reduce the potential pollution risk of Cd in CRS. In the pot experiment, the CRS, straw biochar prepared at 300 °C (B300) and 500 °C (B500), and phosphorus modified biochar pyrolyzed at 300 °C (PB300) and 500 °C (PB500) were added at dosage of 5% into three typical paddy soils. The results showed that CRS and its derived biochar could enhance soil pH, EC, Eh, organic carbon, exchangeable base cations (K⁺, Na⁺, Ca²⁺ and Mg²⁺), and available phosphate. The application of CRS, biochar and phosphorus modified biochar significantly increased the contents of total Cd in soils relative to control soil. Compared to CRS, the biochar application (especially the PB500) decreased the contents of 0.01M CaCl₂-extractable Cd. The application of CRS significantly increased the content of exchangeable Cd fraction (F1), whereas biochar increased residual Cd content (F4). The biochar and phosphorous modified biochar significantly decreased the contents of bioavailable Cd in soils compared to CRS application. The increased soil pH and dissolve organic matter were found to be the main factors in reducing the release of Cd in biochar. The possible mechanisms of biochar in reducing bioavailability of Cd were to significantly increase soil pH, enhance the complexation of Cd ions, and promote the transformation of Cd from easily available to stable (residual) forms. It could conclude that conversion of contaminated rice straw into biochar was an efficient way to minimize Cd availability in soil and reduce the pollution risk of Cd in rice straw.
Afficher plus [+] Moins [-]Changes in the contour of karyology and histoarchitecture of the primary respiratory organ in the fish Oreochromis mossambicus (Peters, 1852) inhabiting the polluted estuarine ecosystem
2022
Punitha, Subramaniam | Krishnamurthy, Rajamanickkam | Elumalai, Kuppusamy | Mahboob, Shahid | Al-Ghanim, Khalid A. | Ahmed, Zubair | Mustafa, Ahmed | Govindarajan, Marimuthu
The wetland ecosystem (WE) is subject to pollution by many anthropogenic activities, including domestic and industrial effluents. These effluents may contain toxic heavy metals that can interact within the aquatic ecosystem and have a capacity to disturb the metabolic activities, histological profile, and genetic structure and functions in aquatic species inhabiting the environment. The present study observed the karyological and histological alterations in gills of the freshwater fish, Mozambique tilapia, Oreochromis mossambicus in two different sublethal concentrations (1% and 3%) of heavy metals in 7, 15, and 30 days of experimental periods. The heavy metals induced various structural damages such as ring chromosome, sister chromatid exchange, acrocentric association region, condensed chromosomal morphology, heterochromatin region, and nucleolar organizer region in the chromosomes of O. mossambicus treated with 1% and 3% sublethal concentrations of water sample collected from Pallikaranai wetland ecosystem. Gills exposed to 1% and 3% effluent exhibited several variations in the respiratory surfaces of gill arches or lamellae in the light and scanning microscopical study. The gills exposed to 1% concentration for 30 days showed marked necrosis, and the secondary lamellae showed the lamellar membrane's dissolution. Exposure of gills to raw effluent in the field condition was observed in the presence of Cd, Pb, Cr, Cu, and Zn. Thus, this present study shows the environmental deterioration by heavy metal pollution on the structure of the gills in tilapia.
Afficher plus [+] Moins [-]Response of soybean (Glycine max L.) seedlings to polystyrene nanoplastics: Physiological, biochemical, and molecular perspectives
2022
Surgun-Acar, Yonca
Micro and nanoplastics are new generation contaminants of global concern. It is important to evaluate the effects on edible products due to the presence of micro- and nano-sized plastics in the treated wastewater. A hydroponic experiment was carried out to explore the effect of polsytrene nanoplastics (PS-NPs; 20 nm) at different concentrations (0, 12.5, 25, and 50 mg L⁻¹) on Glycine max L. (soybean) seedlings for 7-days. In the current study, firstly the uptake of PS-NPs by Glycine max L. (soybean) roots were confirmed by laser confocal scanning microscope. Exposure to PS-NPs, negatively affected growth parameters and increased Fe, Zn and Mn contents in roots and leaves of soybean seedlings. PS-NPs treatments caused oxidative stress in soybean seedlings. The hydrogen peroxide and malondialdehyde contents, showed similar increase pattern in seedlings exposed to PS-NPs. Response to PS-NPs, the level of antioxidant enzymes (superoxide dismutase, catalase, ascorbate peroxidase, and guaiacol peroxidase) and proline content were generally enhanced in roots and leaves of soybean. The expression level of stress-related genes examined in the study included CSD5, FSD3, APX1, and POD up-regulated in PS-NPs treated-soybean seedlings in a tissue specific manner. The results of the present study showed the adverse effects of PS-NPs on soybean seedlings, which may have important implications for the risk assessment of NPs on crop production and environmental safety.
Afficher plus [+] Moins [-]Long-term trends of second generation anticoagulant rodenticides (SGARs) show widespread contamination of a bird-eating predator, the Eurasian Sparrowhawk (Accipiter nisus) in Britain
2022
Broughton, Richard K. | Searle, Kate R. | Walker, Lee A. | Potter, Elaine D. | Pereira, M Glória | Carter, Heather | Sleep, Darren | Noble, David G. | Butler, Adam | Johnson, Andrew C.
Second generation anticoagulant rodenticides (SGARs) are widely used to control rodents around the world. However, contamination by SGARs is detectable in many non-target species, particularly carnivorous mammals or birds-of-prey that hunt or scavenge on poisoned rodents. The SGAR trophic transfer pathway via rodents and their predators/scavengers appears widespread, but little is known of other pathways of SGAR contamination in non-target wildlife. This is despite the detection of SGARs in predators that do not eat rodents, such as specialist bird-eating hawks. We used a Bayesian modelling framework to examine the extent and spatio-temporal trends of SGAR contamination in the livers of 259 Eurasian Sparrowhawks, a specialist bird-eating raptor, in regions of Britain during 1995–2015. SGARs, predominantly difenacoum, were detected in 81% of birds, with highest concentrations in males and adults. SGAR concentrations in birds were lowest in Scotland and higher or increasing in other regions of Britain, which had a greater arable or urban land cover where SGARs may be widely deployed for rodent control. However, there was no overall trend for Britain, and 97% of SGAR residues in Eurasian Sparrowhawks were below 100 ng/g (wet weight), which is a potential threshold for lethal effects. The results have potential implications for the population decline of Eurasian Sparrowhawks in Britain. Fundamentally, the results indicate an extensive and persistent contamination of the avian trophic transfer pathway on a national scale, where bird-eating raptors and, by extension, their prey appear to be widely exposed to SGARs. Consequently, these findings have implications for wildlife contamination worldwide, wherever these common rodenticides are deployed, as widespread exposure of non-target species can apparently occur via multiple trophic transfer pathways involving birds as well as rodents.
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