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Organic aerosol compositions and source estimation by molecular tracers in Dushanbe, Tajikistan
2022
Chen, Pengfei | Kang, Shichang | Zhang, Lanxin | Abdullaev, Sabur F. | Wan, Xin | Zheng, Huijun | Maslov, Vladimir A. | Abdyzhapar uulu, Salamat | Safarov, Mustafo S. | Tripathee, Lekhendra | Li, Yizhong
To elucidate the molecular composition and sources of organic aerosols in Central Asia, carbonaceous compounds, major ions, and 15 organic molecular tracers of total suspended particulates (TSP) were analyzed from September 2018 to August 2019 in Dushanbe, Tajikistan. Extremely high TSP concentrations (annual mean ± std: 211 ± 131 μg m⁻³) were observed, particularly during summer (seasonal mean ± std: 333 ± 183 μg m⁻³). Organic carbon (OC: 11.9 ± 7.0 μg m⁻³) and elemental carbon (EC: 5.1 ± 2.2 μg m⁻³) exhibited distinct seasonal variations from TSP, with the highest values occurring in winter. A high concentration of Ca²⁺ was observed (11.9 ± 9.2 μg m⁻³), accounting for 50.8% of the total ions and reflecting the considerable influence of dust on aerosols. Among the measured organic molecular tracers, levoglucosan was the predominant compound (632 ± 770 ng m⁻³), and its concentration correlated significantly with OC and EC during the study period. These findings highlight biomass burning (BB) as an important contributor to the particulate air pollution in Dushanbe. High ratios of levoglucosan to mannosan, and syringic acid to vanillic acid suggest that mixed hardwood and herbaceous plants were the main burning materials in the area, with softwood being a minor one. According to the diagnostic tracer ratio, OC derived from BB constituted a large fraction of the primary OC (POC) in ambient aerosols, accounting for an annual mean of nearly 30% and reaching 63% in winter. The annual contribution of fungal spores to POC was 10%, with a maximum of 16% in spring. Measurements of plant debris, accounting for 3% of POC, divulged that these have the same variation as fungal spores.
Show more [+] Less [-]Concentration and leachability of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD) and its quinone transformation product (6PPD-Q) in road dust collected in Tokyo, Japan
2022
Hiki, Kyoshiro | Yamamoto, Hiroshi
A recently identified chemical, 2-((4-Methylpentan-2-yl)amino)-5-(phenylamino)cyclohexa-2,5-diene-1,4-dione (6PPD-quinone; 6PPD-Q), is a transformation product of an additive used in the manufacture of tire rubber and causes acute lethality in coho salmon (Oncorhynchus kisutch) in urban watersheds. Despite its potential presence and ecotoxicity in receiving waters worldwide, information on the occurrence and fate of 6PPD-Q is limited. Here, we investigated the concentrations of 6PPD-Q and its parent chemical, 6PPD, in road dust collected from arterial and residential roads in Tokyo, Japan from May to October 2021. 6PPD-Q concentrations were highest from May to June, when atmospheric ozone concentrations are the highest in Japan; a correlation between 6PPD-Q and photochemical oxidants, as an alternative to ozone, corroborated this finding. We also found that 6PPD-Q concentrations at photochemical oxidant concentrations ranging from 35 to 47 ppbv were higher in dust collected from roads with high traffic volumes (i.e., arterial roads; median: 8.6 μg/g-OC) than in dust collected from roads with lower traffic volumes (i.e., residential roads; median: 6.3 μg/g-OC), indicating that 6PPD-Q is generated from traffic-related sources. We also found that 6PPD-Q was leached from dust particles within a few hours, with a log partitioning coefficient between organic carbon and water (KOC) of 3.2–3.5. The present results will help to understand the environmental occurrence, fate, and behavior of 6PPD-Q.
Show more [+] Less [-]Investigation of water-soluble organic constituents and their spatio-temporal heterogeneity over the Tibetan Plateau
2022
Niu, Hewen | Lu, Xixi | Zhang, Guotao | Sarangi, Chandan
Investigating the migration and transformation of carbonaceous and nitrogenous matter in the cryosphere areas is crucial for understanding global biogeochemical cycle and earth's climate system. However, water-soluble organic constituents and their transformation in multiple water bodies are barely investigated. Water-soluble organic carbon (WSOC) and organic nitrogen (WSON), and particulate black carbon (PBC) in multiple types of water bodies in eastern Tibetan Plateau (TP) cryosphere for the first time have been systematically investigated. Statistical results exhibited that from south to north and from east to west of this region, WSOC concentrations in alpine river runoff were gradually elevated. WSOC and nitrogenous matter in the alpine river runoff and precipitation in the glacier region presented distinct seasonal variations. WSON was the dominant component (63.4%) of water-soluble total nitrogen in precipitation over high-altitude southeastern TP cryosphere. Water-soluble carbonaceous matter dominated the carbon cycle in the TP cryosphere, but particulate carbonaceous matter in the alpine river runoff had a small fraction of the cryospheric carbon cycle. Analysis of optical properties illustrated that PBC had a much stronger light absorption ability (MAC-PBC: 2.28 ± 0.37 m² g⁻¹) than WSOC in the alpine river runoff (0.41 ± 0.26 m² g⁻¹). Ionic composition was dominated by SO₄²⁻, NO₃⁻, and NH₄⁺ (average: 45.13 ± 3.75%) in the snow of glaciers, implying important contribution of (fossil fuel) combustion sources over this region. The results of this study have essential implications for understanding the carbon and nitrogen cycles in high altitude cryosphere regions of the world. Future work should be performed based on more robust in-situ observations and measurements from multiple environmental medium over the cryosphere areas, to ensure ecological protection and high-quality development of the high mountain Asia.
Show more [+] Less [-]Effect of photooxidation on size distribution, light absorption, and molecular compositions of smoke particles from rice straw combustion
2022
Zhao, Ranran | Zhang, Qixing | Xu, Xuezhe | Wang, Wenjia | Zhao, Weixiong | Zhang, Weijun | Zhang, Yongming
Organic aerosol (OA) emitted from biomass burning (BB) impacts air quality and global radiation balance. However, the comprehensive characterization of OA remains poorly understood because of the complex evolutionary behavior of OA in atmospheric processes. In this work, smoke particles were generated from rice straw combustion. The effect of OH radicals photooxidation on size distribution, light absorption, and molecular compositions of smoke particles was systematically investigated. The results showed that the median diameters of smoke particles increased by a factor of approximately 1.2 after photooxidation. In the particle compositions, although both non-polar fractions (n-hexane-soluble organic carbon, HSOC) and polar fractions (water-soluble organic carbon, WSOC) underwent photobleaching after aging, the photobleaching properties of HSOC (1.87–2.19) was always higher than that of WSOC (1.52–1.33). Besides, the light-absorbing properties of HSOC were higher than that of WSOC, showing a factor of approximately 1.75 times for mass absorption efficiency at 365 nm (MAE₃₆₅). Consequently, the simple forcing efficiency (SFE) caused by absorption showed that HSOC has higher radiation effects than WSOC. After photooxidation, the concentration of 16 PAHs in HSOC fractions significantly decreased by 15.3%–72.5%. In WSOC fractions, the content of CHO, CHONS, and CHOS compounds decreased slightly, while the content of CHON compounds increased. Meantime, the variations in molecular properties supported the decrease in light absorption of WSOC fractions. These results reveal the aging behavior of smoke particles, then stress the importance of non-polar organic fractions in particles, providing new insights into understanding the atmospheric pollution caused by BB smoke particles.
Show more [+] Less [-]The leaching behaviour of herbicides in cropping soils amended with forestry biowastes
2022
James, Trevor K. | Ghanizadeh, Hossein | Harrington, Kerry C. | Bolan, Nanthi S.
Leaching of herbicides in cropping soils not only impacts the groundwater sources but also reduces their effect in controlling weeds. Leaching studies were carried out in two cropping soils and two forestry biowaste media, wood pulp and sawdust with two herbicides, atrazine and bromacil in a packed lysimeter with simulated rainfall. The hypothesis was that high organic matter forestry biowaste soil amendments reduce the leaching of herbicides through the soil profile. Results from the experimental setups varied due to the impact of the simulated rainfall on the surface structure of the media. Organic carbon content, pH and structure of the media were all factors which affected the leaching of the two herbicides. The hypothesis was true for wood pulp, but for sawdust, organic matter content had less bearing on the leaching of the herbicides than other over-riding factors, such as pH, that were media specific. In sawdust, its large particle size and related pore volume allowed preferential flow of herbicides. Overall, the data indicated that both forestry biowastes were retentive to herbicide leaching, but the effect was more pronounced with wood pulp than sawdust.
Show more [+] Less [-]Insights into variations on dissolved organic matter of bauxite residue during soil-formation processes following 2-year column simulation
2022
Xue, Shengguo | Liu, Zheng | Fan, Jiarong | Xue, Rui | Guo, Ying | Chen, Wei | Hartley, William | Zhu, Feng
Bauxite residue, an industrial alkaline solid waste, has a low organic carbon content which hinders plant growth. Dissolved organic matter (DOM) drives many biogeochemical processes including carbon storage and soil formation in soils. Input of exogenous organic materials may provide organic carbon and accelerate soil formation processes in bauxite residue. However, the potential effects of ameliorants on the quantity and quality of DOM in bauxite residue are still poorly understood. Here, the integration of ultraviolet–visible (UV–Vis) spectra, fluorescence spectra, and parallel factor (PARAFAC) analysis were used to investigate the vertical characteristics of DOM in bauxite residue treated by PV (the combined addition of 2% phosphogypsum and 4% vermicompost, w/w) and BS (6% w/w including 4% bagasse and 2% bran) with 2-year column experiments. The content of DOM in untreated residues ranged from 0.064 to 0.096 g/kg, whilst higher contents of DOM were observed in PV (0.13 g/kg) and BS (0.26 g/kg) treatment. Meanwhile, with the increase of residue depth, the aromaticity and hydrophobic components of DOM in residue decreased, which indicated that the degree of humification of the treated residues in the upper layer was higher than that in the lower layer. Compared with BR, BS and PV treatment accumulated the related content of fulvic acid-like substance from 36.14% to 71.33% and 74.86%, respectively. The incorporation of vermicompost and biosolids increased the content of humic-like substances, whilst decreasing the content of protein-like substances in the surface layer, which may be due to the enrichment of the microbial community. During soil formation processes, the application of organic amendments reduced both salinity and alkalinity, enhanced microbial community diversity, and changed the quantity and quality of DOM in bauxite residue. These findings improve our understanding of the dynamics of DOM and response of DOM to soil formation processes in bauxite residue.
Show more [+] Less [-]Quinolone distribution, trophodynamics, and human exposure risk in a transit-station lake for water diversion in east China
2022
Liu, Yuanyuan | Hua, Zulin | Lü, Ying | Gu, Li | Luan, Chengmei | Li, Xiaoqing | Wu, Jianyi | Chu, Kejian
Quinolone antibiotics (QNs) pollution in lake environments is increasingly raising public concern due to their potential combined toxicity and associated risks. However, the spatiotemporal distribution and trophodynamics of QNs in transit-station lakes for water diversion are not well documented or understood. In this study, a comprehensive investigation of QNs in water, sediment, and aquatic fauna, including norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENR), and ofloxacin (OFL), was conducted in Luoma Lake, a major transit station for the eastern route of the South-to-North Water Diversion Project in China. The target QNs were widely distributed in the water (∑QNs: 70.12 ± 62.79 ng/L) and sediment samples (∑QNs: 13.35 ± 10.78 ng/g dw) in both the non-diversion period (NDP) and the diversion period (DP), where NOR and ENR were predominant. All the QNs were detected in all biotic samples in DP (∑QNs: 80.04 ± 20.59 ng/g dw). The concentration of ∑QNs in the water in NDP was significantly higher than those in DP, whereas the concentration in the sediments in NDP was comparable to those in DP. ∑QNs in the water-sediment system exhibited decreasing trends from northwest (NW) to southeast (SE) in both periods; however, the Kₒc (organic carbon normalized partition coefficients) of individual QNs in DP sharply rose compared with those in NDP, which indicated that water diversion would alter the environmental fate of QNs in Luoma Lake. In DP, all QNs, excluding NOR, were all biodiluted across the food web; whereas their bioaccumulation potentials in the SE subregion were higher than those in the NW subregion, which was in contrast to the spatial distribution of their exposure concentrations. The estimated daily QN intakes via drinking water and aquatic products suggested that residents in the SE side were exposed to greater health risks, despite less aquatic pollution in the region.
Show more [+] Less [-]Polar organic aerosol tracers in two areas in Beijing-Tianjin-Hebei region: Concentration comparison before and in the sept. Third Parade and sources
2021
Li, Li | Wu, Di | Chang, Xing | Tang, Yi | Hua, Yang | Xu, Qingcheng | Deng, Shihuai | Wang, Shuxiao | Hao, Jiming
A total of 106 24-h PM₂.₅ aerosol samples were collected in an urban area (Shijiazhuang, SJZ) and a suburban area (Liulihe, LLH, Fangshan County, Beijing) in the Beijing-Tianjin-Hebei (BTH) region in 2 periods: the first is from 10 July to 10 August, which is before Sept. Third Parade (Period I); the second is from 20 Aug. to 6 Sept. 2015, which is during Sept. Third Parade (Period II). Polar organic tracers, including isoprene, α-pinene, β-caryophyllene and toluene oxidation products, as well as sugars and carboxylic acids were measured. In Period II, rigorous emission-reduction measures were taken in the BTH region. With the anthropogenic emission being cut down significantly, the average concentrations of isoprene, α-pinene, β-caryophyllene and toluene oxidation products and all carboxylic acids (except tetradecanoic, palmitic, and stearic acids), were lower in Period II than those in Period I in LLH, indicating that the SOA tracers were decreased with precursor emission volumes and yields in the atmosphere. Moreover, sugar compounds were shown with comparable levels during the two periods in LLH, suggesting that no measures were taken to reduce the intensities of the biogenic sources. On the contrary, tetradecanoic, palmitic, and stearic acids were shown with obviously higher concentrations in Period II than those in Period I, demonstrating that cooking fumes increased during Sept. Third Parade period.The positive matrix factorization (PMF) model combining with tracer-based method was applied to explore the sources of secondary organic carbon (SOC). It reveals that the sources of SOC include isoprene, α-pinene, β-caryophyllene and toluene oxidation products, fossil fuel combustion, cooking fumes and regionally transferred aged aerosols. These sources accounted for 11.3%, 9.0%, 15.5%, 10.9%, 29.2%, 2.9%, 21.1% of SOC for SJZ, and 12.7%, 11.2%, 9.7%, 14.4%, 25.3%, 0%, 26.7% of SOC for LLH, during the whole sampling periods respectively.
Show more [+] Less [-]Integrated analysis of petroleum biomarkers and polycyclic aromatic compounds in lake sediment cores from an oil sands region
2021
Salat, Alexandre P.J. | Eickmeyer, David C. | Kimpe, Linda E. | Hall, Roland I. | Wolfe, Brent B. | Mundy, Lukas J. | Trudeau, Vance L. | Blais, Jules M.
We examined polycyclic aromatic compounds (PACs) and petroleum biomarkers (steranes, hopanes, and terpanes) in radiometrically-dated lake sediment cores from the Athabasca oil sands region (AOSR) and the Peace-Athabasca Delta (PAD) region in Alberta (Canada) to determine whether contributions from petroleum hydrocarbons have changed over time. Two floodplain lakes in the PAD (PAD 30, PAD 31) recorded increased flux of alkylated PACs and increased petrogenic (petroleum-derived) hydrocarbons after ∼1980, coincident with a decline of sediment organic carbon content and a rise of bulk sedimentation rate, likely due to increased Athabasca River flow. A large expansion of upstream oilsands mining, upgrading, and refining may also have contributed to the observed shift to more petrogenic hydrocarbons to sediments since the 1980s. Alkylated PAC flux increased in the floodplain lake analyzed within the AOSR (Saline Lake) since the 1970s–1980s, coincident with a sharp rise in sediment organic carbon content and increased contributions of petrogenic hydrocarbons. These changes identify increased supply of petrogenic PACs occurred as Athabasca River floodwaters waned, and may implicate aerial contributions of petrogenic hydrocarbons from oilsands activity. PACs and petroleum biomarkers (steranes, hopanes, and terpanes) in sediment cores from Saline Lake, PAD 30 and PAD 31 revealed a predominance of petrogenic hydrocarbons in these lakes. In contrast, we recorded minimal petrogenic hydrocarbons in the reference lakes outside the surface minable area of the AOSR and PAD (Mariana Lake and BM11), though we noted slight increases in petrogenic contributions to modern (2010–2016) sediments. We show how a combined analysis of PACs and petroleum biomarkers in sediments is useful to quantify petrogenic contributions to lakes with added confidence and highlight the potential for petroleum biomarkers in lake sediment cores as a novel and effective method to track petroleum hydrocarbons in lake sediment.
Show more [+] Less [-]Mercury vertical and horizontal concentrations in agricultural soils of a historically contaminated site: Role of soil properties, chemical loading, and cultivated plant species in driving its mobility
2021
Morosini, Cristiana | Terzaghi, Elisa | Raspa, Giuseppe | Zanardini, Elisabetta | Anelli, Simone | Armiraglio, Stefano | Petranich, Elisa | Covelli, Stefano | Di Guardo, Antonio
The long term vertical and horizontal mobility of mercury (Hg) in soils of agricultural areas of a historically contaminated Italian National Relevance Site (SIN Brescia-Caffaro) was investigated. The contamination resulted from the continuous discharge of Hg in irrigation waters by an industrial plant (Caffaro S.p.A), equipped with a mercury-cell chlor-alkali process. The contamination levels with depth ranged from about 20 mg/kg dry weight (d.w.) of soil in the top (plow) layer to less than 0.1 mg/kg d.w. at 1 m depth. The concentrations varied also spatially, up to one order of magnitude within the same field and showing a decreasing trend from the Hg source (i.e., irrigation ditches). The concentration profiles and gradients measured were explained considering Hg loading, soil properties, such as the texture, organic carbon content, pH and cation exchange capacity. A Selective Sequential Extraction (SSE) was also applied on soil samples from an ad hoc greenhouse experiment to investigate the role of different plant species in influencing Hg speciation in soils. Although most of the extracted Hg was included in scarcely mobile or immobile forms, some plant species (i.e., alfalfa) showed to importantly increase the soluble and exchangeable fractions with respect to the unplanted control soils, thus affecting mobility and potential bioavailability of Hg.
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