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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.
Afficher plus [+] Moins [-]Neonicotinoids residues in the honey circulating in Chinese market and health risk on honey bees and human
2022
Han, Minghui | Wang, Yuanping | Yang, Zichen | Wang, Yi | Huang, Min | Luo, Baozhang | Wang, Hexing | Chen, Yue | Jiang, Qingwu
China is the largest beekeeping and honey consumption country globally. Neonicotinoids in honey can pose adverse effects on honey bees and human, but data on neonicotinoids residues in honey and its health risk remain limited in China. A total of 94 honey samples were selected from Chinese market based on production region and sale volume in 2020. Eight neonicotinoids and four metabolites were determined by liquid chromatography coupled to mass spectrometry. Health risk of neonicotinoids in honey on honey bees and human was assessed by hazard quotient (HQ) and hazard index (HI). Neonicotinoids and their metabolites were overall detected in 97.9% of honey samples. Acetamiprid, thiamethoxam, and imidacloprid were top three dominant neonicotinoids in honey with the detection frequencies of 92.6%, 90.4%, and 73.4%, respectively. For honey bees, 78.7% of honey samples had a HI larger than one based on the safety threshold value of sublethal effects. Top three neonicotinoids with the highest percent proportion of HQ larger than one for honey bees were acetamiprid (43.6%), imidacloprid (31.9%), and thiamethoxam (24.5%) and their maximum HQs were 420, 210, and 41, respectively. Based on oral median lethal doses for honey bees, both HQ and HI were lower than one in all honey samples. For human, both HQ and HI were lower than one based on acceptable daily intakes in all honey samples. Neonicotinoids concentrations and detection frequencies in honey samples and its health risk varied with production region, commercial value of nectariferous plants, number of nectariferous plants, and sale price. The results suggested extensive residues of neonicotinoids in honey in Chinese market with a variation by the characteristics of honey. The residues were likely to affect the health of honey bees, but showed no detectable effect on human health.
Afficher plus [+] Moins [-]Restriction of biosolids returning to land: Fate of antibiotic resistance genes in soils after long-term biosolids application
2022
Qin, Xuechao | Zhai, Limei | Khoshnevisan, Benyamin | Pan, Junting | Liu, Hongbin
Although the utilization of biosolids in agricultural lands is widely considered as an effective way to improve resource reuse, the presence of antibiotic resistance genes (ARGs) severely restricts biosolids returning to fields. A 12-year long-term experiment with different biosolids application rates (from 0 to 36 t ha⁻¹ yr⁻¹) was conducted to study the effect of biosolids application on shaping ARGs in soil. Biosolids application significantly increased ARGs abundance in the soil, except for MBS treatment (9 t ha⁻¹ yr⁻¹ biosolids application). The abundance of ARGs in soil did not increase linearly with the dose of biosolids applied, but they were significantly (P < 0.05) positively correlated. A total of 173 subtypes were detected, among them mobile genetic elements (MGEs), aminoglycoside, and multidrug resistance genes were the most dominant types. Except for MBS treatment, most of the ARGs detected were enriched in amended soils after long-term continuous biosolids application. Specifically, tetPA, sul1, mefA, and IS6100 were highly enriched in all amended soils. In addition, biosolids application increased soil nutrients and heavy metals, and changed the soil microbial community, all of which affected ARGs formation. But MGEs may be a greater factor for shaping ARGs profiles than soil properties. Overall, controlling the rate of biosolid application is the key to reducing the accumulation and horizontal transfer of ARGs in soils.
Afficher plus [+] Moins [-]Soil dust as a potential bridge from biogenic volatile organic compounds to secondary organic aerosol in a rural environment
2022
He, Dong-Yi | Huang, Xiao Feng | Wei, Jing | Wei, Feng-Hua | Zhu, Bo | Cao, Li-Ming | He, Ling-Yan
The role of coarse particles has recently been proven to be underestimated in the atmosphere and can strongly influence clouds, ecosystems and climate. However, previous studies on atmospheric chemistry of volatile organic compounds (VOCs) have mostly focused on the products in fine particles, it remains less understood how coarse particles promote secondary organic aerosol (SOA) formation. In this study, we investigated water-soluble compounds of size-segregated aerosol samples (0.056 to >18 μm) collected at a coastal rural site in southern China during late summer and found that oxygenated organic matter was abundant in the coarse mode. Comprehensive source apportionment based on mass spectrum and ¹⁴C analysis indicated that different from fossil fuel SOA, biogenic SOA existed more in the coarse mode than in the fine mode. The SOA in the coarse mode showed a unique correlation with biogenic VOCs. ¹³C and elemental composition strongly suggested a pathway of heterogeneous reactions on coarse particles, which had an abundant low-acidic aqueous environment with soil dust to possibly initiate iron-catalytic oxidation reactions to form SOA. This potential pathway might complement understanding of both formation of biogenic SOA and sink of biogenic VOCs in global biogeochemical cycles, warrantying future relevant studies.
Afficher plus [+] Moins [-]Spatial and sex differences in mercury contamination of skuas in the Southern Ocean
2022
Mills, William F. | Ibañez, Andrés E. | Bustamante, Paco | Carneiro, Ana P.B. | Bearhop, Stuart | Cherel, Yves | Mariano-Jelicich, Rocío | McGill, Rona A.R. | Montalti, D. (Diego) | Votier, Stephen C. | Phillips, Richard A.
Antarctic marine ecosystems are often considered to be pristine environments, yet wildlife in the polar regions may still be exposed to high levels of environmental contaminants. Here, we measured total mercury (THg) concentrations in blood samples from adult brown skuas Stercorarius antarcticus lonnbergi (n = 82) from three breeding colonies south of the Antarctic Polar Front in the Southern Ocean (southwest Atlantic region): (i) Bahía Esperanza/Hope Bay, Antarctic Peninsula; (ii) Signy Island, South Orkney Islands; and, (iii) Bird Island, South Georgia. Blood THg concentrations increased from the Antarctic Peninsula towards the Antarctic Polar Front, such that Hg contamination was lowest at Bahía Esperanza/Hope Bay (mean ± SD, 0.95 ± 0.45 μg g⁻¹ dw), intermediate at Signy Island (3.42 ± 2.29 μg g⁻¹ dw) and highest at Bird Island (4.47 ± 1.10 μg g⁻¹ dw). Blood THg concentrations also showed a weak positive correlation with δ¹⁵N values, likely reflecting the biomagnification process. Males had higher Hg burdens than females, which may reflect deposition of Hg into eggs by females or potentially differences in their trophic ecology. These data provide important insights into intraspecific variation in contamination and the geographic transfer of Hg to seabirds in the Southern Ocean.
Afficher plus [+] Moins [-]Exposure to perfluoroalkyl substances and neonatal immunoglobulin profiles in the upstate KIDS study (2008–2010)
2022
Jones, Laura E. | Ghassabian, Akhgar | Lawrence, David A. | Sundaram, Rajeshwari | Yeung, Edwina | Kannan, Kurunthachalam | Bell, Erin M.
Infant exposure to per/polyfluoroalkyl compounds is associated with immune disruption. We examined associations between neonatal concentrations of perflurooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and immunoglobulin (Ig) isotype profiles in a prospective cohort of infants. We measured Ig isotypes, including IgA, IgE, IgM and the IgG subclasses IgG₁, IgG₂, IgG₃, and IgG₄, and PFOA and PFOS in newborn dried bloodspots from N = 3175 infants in the Upstate KIDS Study (2008–2010). We examined the association between newborn Ig isotype levels and individual PFOS and PFOA concentrations using mixed effects regression models with a random intercept to account for twins among study participants. We assessed the joint effect PFOA and PFOS with quantile-based g-computation on all singletons and one randomly selected twin (N = 2901), with Ig categorized as above or below median value. Models were adjusted for infant sex, and maternal pre-pregnancy body mass index, race, parity, age and infertility treatment. In adjusted models, PFOA was inversely associated with IgE (coefficient = −0.12 per unit increase in PFOA, 95% CI: −0.065, −0.17), whereas IgG₂, IgM, and IgA were positively associated with PFOA (coefficient for IgG₂ = 0.22, 95% CI: 0.15, 0.27; coefficient for IgM = 0.11, 95% CI: 0.08, 0.15; and coefficient for IgA = 0.15, 95% CI: 0.07, 0.18). There was no relation between PFOS and Ig isotypes. Analysis of the joint effect of PFOA and PFOS showed an OR of 1.2 (95% CI: 1.04, 1.36) for IgA and OR of 1.12 (95% CI: 1.00, 1.24) for IgG₂ levels above the median for every quartile increase. PFOA levels were significantly associated with elevated IgA, IgM, IgG₂, and reduced levels of IgE in single-pollutant models. A small but significant joint effect of PFOA and PFOS was observed. Our results suggest that early exposure to PFOA and PFOS may disrupt neonatal immunoglobulin levels.
Afficher plus [+] Moins [-]Stress responses in captive Crocodylus moreletii associated with metal exposure
2022
Romero-Calderón, A.G. | Alvarez-Legorreta, T. | Rendón von Osten, J. | González-Jáuregui, M. | Cedeño-Vázquez, J.R.
Environmental pollution by metals has repercussions on wildlife health. It is known that some metals can have an influence on the neuroendocrine stress response, and at the same time, metals have pro-oxidant effects that can overwhelm the antioxidant system and cause oxidative stress. This study evaluates the association of metals with neuroendocrine stress activity and biomarkers of oxidative stress in 42 captive female Morelet's crocodiles (Crocodylus moreletii). We measured five metals of ecotoxicological importance (Hg, Cd, Pb, Cu and Zn), and three biomarkers of the oxidative stress response in the liver: glutathione (GSH) and glutathione disulfide (GSSG) as markers for antioxidant system and thiobarbituric acid reactive substances (TBARS) for oxidative damage. We also measured one biomarker of the neuroendocrine response to stress: corticosterone (B) in blood plasma. The mean ± SD concentrations of metals in the liver expressed in μg/g (dw) were: Cd: 0.004 ± 0.003, Hg: 0.014 ± 0.019, Cu: 0.017 ± 0.013, Zn: 0.043 ± 0.035, Pb: 0.16 ± 0.256. The mean ± SD of GSH was 0.42 ± 0.35 nmol/mg protein, the mean ± SD of GSSG was 0.24 ± 0.20 nmol/mg protein, the mean ± SD concentrations of TBARS were 0.36 ± 0.21 nmol/mg protein, and the mean ± SD of B was 393.57 ± 405.14 pg/mL. Hg presented a significant negative relationship with corticosterone. Cd had a negative relationship with both GSH and GSSG; meanwhile, Zn showed a negative relationship with TBARS levels, could be a protective element against hepatic oxidative damage. Finally, B had negative relationship with oxidative damage. The connection found between Hg and the neuroendocrine stress response, as well as the correlations of Cd and Zn with oxidative damage and antioxidant activity should be studied further, given their toxicological importance and implications for the conservation of C. moreletii and other crocodilians.
Afficher plus [+] Moins [-]Plant nitrogen-use strategies and their responses to the urban elevation of atmospheric nitrogen deposition in southwestern China
2022
Hu, Chao-Chen | Liu, Xue-Yan
The elevation of nitrogen (N) deposition by urbanization profoundly impacts the structure and function of surrounding forest ecosystems. Plants are major biomass sinks of external N inputs into forests. Yet, the N-use strategies of forest plants in many areas remain unconstrained in city areas, so their responses and adapting mechanisms to the elevated N deposition are open questions. Here we investigated concentrations and N isotope (δ¹⁵N) of total N (TN) and nitrate (NO₃⁻) in leaves and roots of four plant species in subtropical shrubberies and pine forests under N deposition levels of 13 kg-N ha⁻¹ yr⁻¹ and 29 kg-N ha⁻¹ yr⁻¹ at the Guiyang area of southwestern China, respectively. The δ¹⁵N differences between plant NO₃⁻ and soil NO₃⁻ revealed a meager NO₃⁻ reduction in leaves but a preferentially high NO₃⁻ reduction in roots. δ¹⁵N mass-balance analyses between plant TN and soil dissolved N suggested that soil NO₃⁻ contributed more than reduced N, and dissolved organic N contributed comparably with ammonium to plant TN, and the study plants preferred NO₃⁻ over reduced N. The elevation of N deposition induced root but not leaf NO₃⁻ reduction and enhanced the contribution of soil NO₃⁻ to plant TN, but plant NO₃⁻ preference decreased due to much higher magnitudes of soil NO₃⁻ enrichment than plant NO₃⁻ utilization. We conclude that plants in subtropical forests of southwestern China preferred NO₃⁻ over reduced N, and NO₃⁻ was reduced more in roots than in leaves, anthropogenic N pollution enhanced soil NO₃⁻ enrichment and plant NO₃⁻ utilization but reduced plant NO₃⁻ preference.
Afficher plus [+] Moins [-]Molecularly imprinted polymers for sensing gaseous volatile organic compounds: opportunities and challenges
2022
Hua, Yongbiao | Ahmadi, Younes | Kim, Ki Hyun
Chemical sensors that can detect volatile organic compounds (VOCs) are the subject of extensive research efforts. Among various sensing technologies, molecularly imprinted polymers (MIPs) are regarded as a highly promising option for their detection with many advantageous properties, e.g., specific binding-site for template molecules, high recognition specificity, ease of preparation, and chemical stability. This review covers recent advances in the sensing application of MIPs toward various types of VOCs (e.g., aliphatic and aromatic compounds). Particular emphasis has been placed on multiple approaches to the synthesis of MIP-based VOC sensors in association with their performance and sensing mechanisms. Current challenges and opportunities for new VOC-sensing applications are also discussed based on MIP technology.
Afficher plus [+] Moins [-]Systematic development of extraction methods for quantitative microplastics analysis in soils using metal-doped plastics
2022
Tophinke, Alissa H. | Joshi, Akshay | Baier, Urs | Hufenus, Rudolf | Mitrano, Denise M.
The inconsistency of available methods and the lack of harmonization in current microplastics (MPs) analysis in soils demand approaches for extraction and quantification which can be utilized across a wide variety of soil types. To enable robust and accurate assessment of extraction workflows, PET MPs with an inorganic tracer (Indium, 0.2% wt) were spiked into individual soil subgroups and standard soils with varying compositions. Due to the selectivity of the metal tracer, MPs recovery rates could be quickly and quantitatively assessed using ICP-MS. The evaluation of different methods specifically adapted to the soil properties were assessed by isolating MPs from complex soil matrices by systematically investigating specific subgroups (sand, silt, clay, non-lignified and lignified organic matter) before applying the workflow to standard soils. Removal of recalcitrant organic matter is one of the major hurdles in isolating MPs for further size and chemical characterization, requiring novel approaches to remove lignocellulosic structures. Therefore, a new biotechnological method (3-F-Ultra) was developed which mimics natural degradation processes occurring in aerobic (Fenton) and anaerobic fungi (CAZymes). Finally, a Nile Red staining protocol was developed to evaluate the suitability of the workflow for non-metal-doped MPs, which requires a filter with minimal background residues for further chemical identification, e.g. by μFTIR spectroscopy. Image analysis was performed using a Deep Learning tool, allowing for discrimination between the number of residues in bright-field and MPs counted in fluorescence mode to calculate a Filter Clearness Index (FCI). To validate the workflow, three well-characterized standard soils were analyzed applying the final method, with recoveries of 88% for MPs fragments and 74% for MPs fibers with an average FCI of 0.75. Collectively, this workflow improves our current understanding of how to adapt extraction protocols according to the target soil composition, allowing for improved MPs analysis in environmental sampling campaigns.
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