One interest of using biochar as soil amendment is to reduce pesticide adverse effects. In this paper, the sorption and degradation of thiacloprid (THI) in a black soil amended by various biochars ...were systematically investigated, and the mechanisms therein were explored by analyzing the changes in soil physicochemical properties, degrading enzymes and genes and microorganism community. Biochar amendment increased THI sorption in soil, which was associated with an increase in organic carbon and surface area and a decrease in H/C. Amendments of 300-PT (pyrolyzing temperature) biochar promoted the biodegradation of THI by increasing the microbe abundance and improving nitrile hydratase (NHase) activity. In contrast, 500- and 700-PT biochar amendments inhibited biodegradation by reducing THI availability and changing NHase activity and THI-degradative nth gene abundance, and instead promoted chemical degradation mainly through elevated pH, active groups on mineral surface and generation of •OH and other free radicals. Furthermore, THI shifted the soil microbial community, stimulated the NHase activity and elevated nth gene abundance. Biochar amendments also changed soil bacterial community by modulating soil pH, dissolved organic matter and nitrogen and phosphorus levels, which further influenced THI biodegradation. Therefore, the impact of biochars on the fate of a pesticide in soil depends greatly on their type and properties, which should be comprehensively examined when applying biochar to soil.
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•Biochar amendment increased the sorption of thiacloprid (THI) in soil.•Biochars promoted THI chemical degradation by elevated pH, active groups on mineral surface and generation of •OH.•High temperature biochars inhibited THI biodegradation by reducing their availability and decreased NHase activity.•Enhanced NHase activity and nth gene abundance improved THI degradation.•Biochar amendments changed soil bacterial community by altering soil properties and nutrients.
This paper systematically examined the sorption and degradation of THI in soil before and after biochar amendment and elucidated the mechanisms therein.
Microplastics (MPs) are a contaminant of increasing concern in the environment. However, the impacts of MPs on soil ecosystems and biogeochemical processes like nitrogen cycle have not been well ...elucidated. In this study, we designed an indoor microcosm experiment to investigate the effects of exposure to low density polyethylene (LDPE) MPs on soil bacterial community and nitrogen cycling function over a 90-day incubation. Next-generation sequencing of the 16S rRNA genes revealed that both 2% and 7% LDPE MPs exposure slightly affected the soil bacterial diversity. Further analysis at the genus level showed differential tolerance to LDPE MPs, the genera Pedomicrobium, Steroidobacter, Pseudonocardia, Nitrospira and Turicibacter were enriched in the soil with 2% (w/w) LDPE MPs amendment, while the genera Pedomicrobium, Mycobacterium and Hyphomicrobium were significantly enriched in the soil with 7% (w/w) LDPE MPs amendment on days 15 and 30. Co-occurrence network analysis further suggested that LDPE MPs changed bacterial network complexity and modularity and Acidobacteria formed intimate associations with each other in responding to LDPE MPs exposure. Additionally, LDPE MPs in soil increased the abundance of nifH, AOBamoA and nirK genes involved in nitrogen cycling in different incubation phases compared to the control. The abundance of AOAamoA genes decreased on day 15 and then increased. Conversely, the abundance of nirS genes increased during the first 15 days and then decreased. These results suggested that both 2% and 7% LDPE MPs impact soil bacterial network structure and alters functional groups involved in soil nitrogen cycling processing.
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•LDPE microplastics (MPs) had limited impact on the alpha diversity of soil bacteria.•The genera Pedomicrobium and Nocardia were significantly higher with LDPE MPs amendment.•LDPE MPs affected the network complexity and modularity of soil bacteria.•LDPE MPs stimulated the abundance of nifH, AOBamoA and nirK genes in the soil.
Dust is a fate of many contaminants and may be an important medium for the human exposure to these contaminants. Microplastics (MPs) have been observed in dust in previous studies. However, the mass ...concentrations of dominant MPs in dust and the exposure risk to human remain unclear. In this study, indoor and outdoor dust samples were collected from 39 major cities of China. The mass concentrations of polyethylene terephthalate (PET) and polycarbonate (PC) MPs were determined through alkali-assisted thermal depolymerization-liquid chromatography-tandem mass spectrometry, and the shape and component distribution of MPs were analyzed by optical microscopy and micro-Fourier transform infrared spectroscopy. PET MPs were detected in all the samples at high concentrations of 1550–120,000 mg/kg (indoor) and 212–9020 mg/kg (outdoor) and PC MPs were detected in approximately 70% of the samples, with median concentrations of 4.6 mg/kg (indoor) and 2.0 mg/kg (outdoor). Fiber was the main shape of suspected MPs, and polyester (including PET) was identified as an important component in MPs from dust. Indoor dust is a non-negligible source of human exposure to MPs, accounting for a geomean daily intake of 17,300 ng/kg-bw of PET MPs in children.
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•PET and PC microplastics (MPs) are widespread in dust.•PET MPs ranged from 1550 to 120,000 mg/kg in indoor dust.•μ-FTIR analysis indicated that polyester was an important type of MPs in dust.•Positive correlation was found between fiber abundance and PET concentrations in dust.•High daily intake of MPs through indoor dust was estimated.
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•6:2 Cl-PFAES and TFA are detected with high levels in serum, second to PFOA and PFOS.•A significant increase in 6:2 Cl-PFAES with age and BMI, and TFA with age are found.•Positive ...associations of several PFASs with fasting glucose and HbA1c are observed.
In recent years, the occurrence of novel per-/polyfluoroalkyl substances (PFASs) such as polyfluoroalkyl ether sulfonates (PFAESs) in human samples have aroused attention due to the change in PFASs production profile, however, the data are still lacking. Furthermore, epidemiological studies have examined the associations of PFAS exposure with glucose homeostasis, but with inconsistent results. Therefore, in this study, fasting serum samples from 252 participants with an age range from 19 to 87 years old were collected in Tianjin, China. A total of 21 target PFASs were determined to analyze the levels and distribution of novel and legacy PFASs in serum and to further evaluate the cross-sectional associations of serum PFAS concentrations with two glycemic biomarkers (i.e., fasting glucose and glycated hemoglobin (HbA1c)). 6:2 chlorinated PFAES (6:2 Cl-PFAES) and trifluoroacetic acid (TFA) were widely detected novel PFASs (greater than90%) with relatively high median concentrations (8.64 ng/mL and 8.46 ng/mL, respectively), which were second only to the two dominant legacy PFASs, i.e., perfluorooctanoic acid (PFOA, 14.83 ng/mL) and perfluorooctane sulfonic acid (14.24 ng/mL). The percentage contributions to the total known PFASs were separately 17.6% and 17.2% for 6:2 Cl-PFAES and TFA. The levels of 6:2 Cl-PFAES were significantly correlated with age and BMI, and the concentrations of TFA were also significantly correlated with age. Furthermore, 1% increase in serum PFOA and perfluorononanoic acid (PFNA) was separately significantly associated with 0.018% 95% confidence interval (CI): 0.004%, 0.033% and 0.022% (95% CI: 0.007%, 0.037%) increment in fasting glucose levels. Similarly, 1% increase in serum perfluorohexanoic acid, PFNA, and perfluorohexane sulfonic acid was significantly associated with 0.030% (95% CI: 0.010%, 0.051%), 0.018% (95% CI: 0.003%, 0.033%), 0.007% (95% CI: 0.003%, 0.011%) increment in HbA1c levels, respectively. These findings suggested that 6:2 Cl-PFAES and TFA showed greater contributions to PFASs in serum and supported an association of exposure to PFASs with fasting glucose and HbA1c.
Per- and polyfluoroalkyl substances (PFASs) contamination in the Bohai Sea and its surrounding rivers has attracted considerable attention in recent years. However, few studies have been conducted ...regarding the distribution of PFASs in multiple environmental media and their distributions between the suspended particles and dissolved phases. In this study, surface water, surface sediment, and air samples were collected at the Bohai Sea to investigate the concentration and distribution of 39 targeted PFASs. Moreover, river water samples from 35 river estuaries were collected to estimate PFAS discharge fluxes to the Bohai Sea. The results showed that total ionic compound (Σi-PFASs) concentrations ranged from 19.3 to 967 ng/L (mean 125 ± 152 ng/L) in the water and 0.70–4.13 ng/g dw (1.78 ± 0.76 ng/g) in surface sediment of the Bohai Sea, respectively. In the estuaries, Σi-PFAS concentrations were ranged from 10.5 to 13500 ng/L (882 ± 2410 ng/L). In the air, ΣPFAS (Σi-PFASs + Σn-PFASs) concentrations ranged from 199 to 678 pg/m3 (462 ± 166 pg/m3). Perfluorooctanoic acid (PFOA) was the predominant compound in the seawater, sediment, and river water; in the air, 8:2 fluorotelomer alcohol was predominant. Xiaoqing River discharged the largest Σi-PFAS flux to the Bohai Sea, which was estimated as 12,100 kg/y. Some alternatives, i.e., 6:2 fluorotelomer sulfonate acid (6:2 FTSA), hexafluoropropylene oxide dimer acid (HFPO-DA), and chlorinated 6:2 polyfluorinated ether sulfonic acid (Cl-6:2 PFESA), showed higher levels than or comparable concentrations to those of the C8 legacy PFASs in some sampling sites. The particle-derived distribution coefficient in seawater was higher than that in the river water. Using high resolution mass spectrometry, 29 nontarget emerging PFASs were found in 3 river water and 3 seawater samples. Further studies should be conducted to clarify the sources and ecotoxicological effects of these emerging PFASs in the Bohai Sea area.
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•Thirty-nine PFASs were quantified in water, sediment and air from the Bohai Sea and its rivers.•The Kd between dissolved and particle phases in seawater were higher than those in river water.•Discharge of total i-PFASs from 34 rivers was estimated to be 20.6 t/y.•Twenty-nine novel PFASs were screening in sea and river water by HRMS.
This paper revealed the levels and composition of legacy and emerging PFASs in multiple environmental media of the Bohai Sea.
Limited information exists on exposure to bisphenol A (BPA) by children, adults, and pregnant women in China. In the present study, we determined BPA concentrations in whole blood collected from 10 ...children (1-5 years), 40 women (30 pregnant and 10 nonpregnant), and 30 fetuses (i.e., cord blood). Further, to evaluate the relationship between urinary and blood BPA concentrations, paired specimens of blood and urine (n = 50 pairs) were collected from an adult population. BPA was found in 46% of all blood samples analyzed, with a geometric mean (GM) concentration of 0.19 ng/mL. BPA was found in 84% of urine samples from adults, with a GM concentration of 1.01 ng/mL 0.48 μg/g creatinine (Cr). Gender and age were not good predictors of blood BPA concentrations. However, we did find that the creatinine-adjusted urinary BPA concentrations in females were significantly higher (p < 0.05) than the concentrations found in males and that the blood BPA concentrations in children were significantly higher (p < 0.05) than the concentrations found in adults. Among all adults, unadjusted urinary BPA concentrations (i.e., volume-based) were inversely (r = -0.312, p < 0.05) correlated with age when an outlier value (8.70 ng/mL) was excluded from analysis. Concentrations of BPA in urine (creatinine-adjusted) and blood were significantly correlated (r = 0.571, p < 0.01), with concentrations measured in urine approximately an order of magnitude higher than the concentrations found in blood. The mean and GM values for ratios of concentration of BPA between blood and urine were 0.109 and 0.057, respectively. The ratio of mean concentrations of BPA between cord blood and maternal blood was 0.108. On the basis of urinary BPA levels, we estimated the total daily intake (EDI) of BPA by Chinese adults. The mean (range) EDIs of BPA by adult males and females in China were 0.041 (<0.005-0.224) and 0.048 (<0.005-0.151) ug/kg bw/day, respectively. The pregnant women who underwent intravenous drug administration immediately before delivery had significantly higher concentrations of BPA in their blood than did those who did not receive intravenous drug administration. This is the first study to document the occurrence of and human exposure to BPA by pregnant women and fetuses from China.
To elucidate the sorption affinity of biochars for neonicotinoid pesticides and the influence of biochar structure on sorption mechanisms therein, 24 biochar samples were obtained by pyrolyzing maize ...straw and pig manure at pyrolyzing temperatures (PTs) of 200–700 °C and by further deashing them using acids, and the sorption of three typical neonicotinoids, imidacloprid, clothianidin and thiacloprid on untreated and acid-deashed biochars were evaluated. All the biochar samples could efficiently adsorb the three neonicotinoids and multiple mechanisms were involved in sorption. With the increasing PTs, hydrophobic partition sorption increased, but had a declined contribution to the total sorption as revealed by a dual-mode model. Besides hydrophobic partition, specific interactions like cation-π electron donor acceptor (EDA) interactions (only for protonated IMI and CLO) and hydrogen bond and contributed much to the sorption on low-PT (≤500 °C) biochars, while the sorption on those high-PT (>500 °C) biochars mainly depended on pore-filling strengthened by cation-π and p/π-π EDA interactions. Thiacloprid showed stronger sorption on untreated biochars compared to imidacloprid and clothianidin, due to its greater ability to form hydrogen bond and hydrophobic interactions. Acid-deashing treatments increased the relative percentage contents of organic carbon, bulk O, aromaticity and O-containing functional groups, surface area and pore volume of biochars. The ash can bind neonicotinoids by specific interactions but played a negative role in the whole sorption on high-PT biochars by covering the inner sorption sites of organic moieties and blocking the micropores in biochars. The results acquired in the present study will help us to get deep insight in the comprehensive sorption mechanisms of polar pesticides on biochar and the effects of biochar structure.
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•Untreated and deashed biochars all effectively absorbed neonicotinoids.•Hydrophobic partition and specific interactions contributed much to low-PT biochars.•High-PT biochars adsorbing neonicotinoids mainly depend on pore-filling strengthened by cation-π and p/π-π EDA.•Ash played a negative role on high-PT biochars and did not show obvious effects on low-PT biochars in neonicotinoid sorption.
This paper elucidated the sorption affinity of untreated and acid-treated biochars for neonicotinoids and the influence of biochar structure on sorption mechanisms.
A nationwide survey was conducted on per- and polyfluoroalkyl substances (PFASs) in precipitation across mainland China. Twenty-two PFASs, including precursors to perfluoroalkyl acids (pre-PFAAs), ...were investigated in thirty-nine precipitation samples collected from twenty-eight cities. Trifluoroacetate (TFA), perfluorooctanoic acid, and perfluorooctane sulfonic acid (PFOS) were ubiquitous in precipitation. TFA displayed the highest concentrations (8.8–1.8 × 103 ng/L), which were particularly elevated in coastal cities. 6:2 chlorinated polyfluorinated ether sulfonic acid, an alternative to PFOS, was detected for the first time in precipitation at a frequency of 43%. Polyfluoroalkyl phosphoric acid diesters and 6:2 fluorotelomer sulfonic acid were also occasionally detected. PFAS fluxes in the northeastern area (C4C12; 2.0 × 102–3.4 × 103 ng/m2/d) with major PFAS manufacturing facilities were higher than those in the southwestern area (63–1.7 × 103 ng/m2/d). Using total oxidizable precursor (TOP) assay, the occurrence of unknown pre-PFAAs was for the first time uncovered in precipitation with maximum estimated fluxes of C6 and C8 pre-PFAAs at 3.1 × 103 and 4.3 × 103 ng/m2/d, respectively. The relative contribution of ultrashort-chain PFCAs (C2C3) ranged from 22% to 91% of ∑PFASs, while unknown pre-PFAAs accounted for 6%–56% of the total molar concentrations of PFASs. This bears critical concerns on underestimation of PFAS mass load from precipitation to surface environment ascribed to monitoring data solely on known PFASs. Unknown precursors of PFAAs in the atmosphere are yet to be identified for their chemical structures and relevant environmental risks as well.
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•TFA, PFOA and PFOS were the predominant PFAAs in precipitation samples in China.•6:2 Cl-PFAES, 6:2 FTSA, 6:2 diPAP and 8:2 diPAP were detected in precipitation.•TFA and unknown PFAA precursors make a significant contribution to PFASs mass loading.•Unknown PFAA precursors can be scavenged effectively by wet deposition.
Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers in consumer products, which contributes to widespread exposure of humans. OPE diester metabolites in urine have been ...used as biomarkers of human exposure to these chemicals. Little is known, however, about occurrence and temporal variability in urinary concentrations of OPE metabolites in humans. In this study, 11 OPE metabolites were measured in 213 urine samples collected from 19 volunteers from Albany, New York, United States, at 3-day intervals for five weeks to investigate temporal variability in urinary concentrations. Diphenyl phosphate (DPHP) and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) were the major OPE metabolites, detected in all urine samples at specific gravity (SG)-adjusted concentrations (geometric mean, GM) of 1060 and 414 pg/mL and creatinine (Cr)-adjusted concentration (GM) of 404 and 156 ng/g, respectively. Inter-day variability in urinary OPE metabolite concentrations in 19 individuals was evaluated by intraclass correlation coefficients (ICCs). The inter-day variability in Cr-adjusted OPE metabolite concentrations (ICC: 0.31–0.67) was lower than those of SG-adjusted (ICC: 0.19–0.71) and unadjusted urinary concentrations (ICC: 0.24–0.74). BDCIPP (ICC: 0.68) and bis(2-chloroethyl) phosphate (BCEP) (ICC: 0.67) concentrations showed a moderate-to-high reliability over the sampling period, whereas the other nine OPE metabolites exhibited a moderate reliability (ICC: 0.31–0.55). Urine samples were further stratified by gender, age, ethnicity, and body mass index (BMI). The concentrations of BDCIPP and DPHP were significantly lower in males with normal BMI (BMI: 18.5–25 kg/m2) than in females and other BMI categories (p < 0.01). Relatively high ICCs, indicating low inter-day variability, were observed for males (ICC: 0.35–0.71) of 30–40 years of age (ICC: 0.34–0.87) with normal BMI (ICC: 0.28–0.64). The daily exposure doses to OPEs were estimated from urinary concentrations of corresponding OPE metabolites. The estimated doses of triphenyl phosphate (TPHP) and triethyl phosphate (TEP), based on median urinary concentrations of their metabolites, were 19.4 and 24.0 ng/kg bw/day, and the exposure dose to ∑OPEs was estimated at 65.3 ng/kg bw/day. Overall, our results indicate a high ICC for Cr-adjusted urinary concentrations of 11 OPE metabolites in urine.
•Interday variability in urinary concentrations of OPE metabolites was studied.•Diphenyl phosphate and bis(1,3-dichloro-2-propyl) phosphate were the major OPE metabolites in urine.•Urine collected longitudinally for five weeks from volunteers showed moderate variability.•Creatinine adjustment of urinary OPE metabolite levels improved ICC and increased reproducibility.•Age, gender, race and BMI had some effects on ICC.
Due to its high sorption capacity for different kinds of contaminants, biochar is advocated as a novel remediation strategy for contaminated soils. However, it is not clear how long this ...extraordinary sorption capacity will be maintained after the biochar is applied to the soil. In this study, a commercial biochar was applied to an agricultural soil, and the sorption of atrazine and phenanthrene on biochar amended soils with different aging periods ranging from 0 to 2 y was investigated. The application of fresh biochar in soil led to an obvious enhancement of the sorption coefficients (Kd) of atrazine and phenanthrene (by 3.13 and 2.93 times at Ce = 0.01 Sw, respectively) compared with the untreated soil. The surface area of biochar first increased and then decreased with aging time. Correspondingly, the sorption of atrazine and phenanthrene on the biochar amended soils first increased and then decreased markedly. Based on the changing trend of the Kd values with aging time, it could be predicted that the sorption capacity of biochar amended soils will decrease to the level of the untreated soil after 2.5 y.
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•The properties of biochar changed after being aged in a field soil.•The surface area of biochar first increased and then decreased with aging time.•The amendment of biochar enhanced soil sorption capacity for organic pollutants.•The high sorption capacity of biochar amended soil only maintained for up to 2.5 y.
The extraordinary sorption capacity of biochar over atrazine and phenanthrene lost completely after aging in soil for 2.5 y due to changes in its micro-structure.
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