Journal of environmental sciences最新文献

The selective recovery of copper from strongly acidic wastewater containing mixed metal ions remains a significant challenge. In this study, a novel reagent zinc dimethyldithiocarbamate (Zn(DMDC)₂) was developed for the selective removal of Cu(II). The removal efficiency of Cu(II) reached 99.6% after 120 min reaction at 30°C when the mole ratio Zn(DMDC)₂/Cu(II) was 1:1. The mechanism investigation indicates that the Cu(DMDC)₂ products formed as a result of the displacement of Zn(II) from the added Zn(DMDC)₂ by Cu(II) in wastewater, due to the formation of stronger coordination bonds between Cu(II) and the dithiocarbamate groups of Zn(DMDC)₂. Subsequently, we put forward an innovative process of resource recovery for strongly acidic wastewater. Firstly, the selective removal of Cu(II) from actual wastewater using Zn(DMDC)₂, with a removal efficiency of 99.7%. Secondly, high-value CuO was recovered by calcining the Cu(DMDC)₂ at 800°C, with a copper recovery efficiency of 98.3%. Moreover, the residual As(III) and Cd(II) were removed by introducing H₂S gas, and the purified acidic wastewater was used to dissolve ZnO for preparation of valuable ZnSO₄·H₂O. The total economic benefit of resource recovery is estimated to be 11.54 $/m³. Accordingly, this study provides a new route for the resource recovery of the treatment of copper-containing acidic wastewater.

The retention and fate of Roxarsone (ROX) onto typical reactive soil minerals were crucial for evaluating its potential environmental risk. However, the behavior and molecular-level reaction mechanism of ROX and its substituents with iron (hydr)oxides remains unclear. Herein, the binding behavior of ROX on ferrihydrite (Fh) was investigated through batch experiments and in-situ ATR-FTIR techniques. Our results demonstrated that Fh is an effective geo-sorbent for the retention of ROX. The pseudo-second-order kinetic and the Langmuir model successfully described the sorption process. The driving force for the binding of ROX on Fh was ascribed to the chemical adsorption, and the rate-limiting step is simultaneously dominated by intraparticle and film diffusion. Isotherms results revealed that the sorption of ROX onto Fh appeared in uniformly distributed monolayer adsorption sites. The two-dimensional correlation spectroscopy and XPS results implied that the nitro, hydroxyl, and arsenate moiety of ROX molecules have participated in binding ROX onto Fh, signifying that the predominated mechanisms were attributed to the hydrogen bonding and surface complexation. Our results can help to better understand the ROX-mineral interactions at the molecular level and lay the foundation for exploring the degradation, transformation, and remediation technologies of ROX and structural analog pollutants in the environment.

Bisphenol A (BPA) has received increasing attention due to its long-term industrial application and persistence in environmental pollution. Iron-based carbon catalyst activation of peroxymonosulfate (PMS) shows a good prospect for effective elimination of recalcitrant contaminants in water. Herein, considering the problem about the leaching of iron ions and the optimization of heteroatoms doping, the iron, nitrogen and sulfur co-doped tremella-like carbon catalyst (Fe-NS@C) was rationally designed using very little iron, S-C₃N₄ and low-cost chitosan (CS) via the impregnation-calcination method. The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA (20 mg/L) by activating PMS with the high kinetic constant (1.492 min⁻¹) in 15 min. Besides, the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference, but also maintained an excellent degradation efficiency on different pollutants. Impressively, increased S-C₃N₄ doping amount modulated the contents of different N species in Fe-NS@C, and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing S-C₃N₄ contents, verifying pyridine N and Fe-N_x as main active sites in the system. Meanwhile, thiophene sulfur (C-S-C) as active sites played an auxiliary role. Furthermore, quenching experiment, EPR analysis and electrochemical test proved that surface-bound radicals (^·OH and SO₄^⋅−) and non-radical pathways worked in the BPA degradation (the former played a dominant role). Finally, possible BPA degradation route were proposed. This work provided a promising way to synthesize the novel Fe, N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.

Microplastic pollution has become one of the most concerned focuses in the world. Among many treatment methods, photocatalysis is considered to be one of the most environmentally friendly methods. In this work, the photodegradation behavior of polyamide microplastics is studied by using polyamide 6 PA6) as model microplastics and FeCl₃ as catalyst. It is hoped that the PA6 fiber can be effectively degraded by utilizing the strong oxidizing active species that can be produced after FeCl₃ is irradiated in water. The results shows that PA6 fiber can be almost completely degraded after 10 days of irradiation in FeCl₃ aqueous solution, indicating that it is promising to use this new method to solve the problem of PA6 type microplastics. In addition, the chain scission mechanism and degradation process of PA6 are analyzed in detail by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS), which provides a new insight for the study of polymer degradation mechanism.

Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed. The surface properties and structure of birnessite change with the changes in external environmental conditions, which also affects the fate of heavy metals. Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution. Therefore, the four transformation pathways of birnessite are summarized first in this review. Second, the relationship between transformation pathways and environmental conditions is proposed. These relevant environmental conditions include abiotic (e.g., co-existing ions, pH, oxygen pressure, temperature, electric field, light, aging, pressure) and biotic factors (e.g., microorganisms, biomolecules). The phase transformation is achieved by the key intermediate of Mn(III) through interlayer-condensation, folding, neutralization-disproportionation, and dissolution-recrystallization mechanisms. The AOS (average oxidation state) of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite. Last but not least, the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up. They involve isomorphous substitution, redox, complexation, hydration/dehydration, etc. The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.

Global environmental concern over organic contaminated sites has been progressively conspicuous during the process of urbanization and industrial restructuring. While traditional physical or chemical remediation technologies may significantly destroy the soil structure and function, coupling moderate chemical degradation with microbial remediation becomes a potential way for the green, economic, and efficient remediation of contaminated sites. Hence, this work systematically elucidates why and how to couple chemical technology with microbial remediation, mainly focused on the controllable redox reactions of organic contaminants. The rational design of materials structure, selective generation of reactive oxygen species, and estimation of degradation pathway are described for chemical oxidation. Meanwhile, current progress on efficient and selective reductions of organic contaminants (i.e., dechlorination, defluorination, -NO₂ reduction) is introduced. Combined with the microbial remediation of contaminated sites, several consideration factors of how to couple chemical and microbial remediation are proposed based on both fundamental and practical points of view. This review will advance the understanding and development of chemical-microbial coupled remediation for organic contaminated sites.

Soil acidifications become one of the main causes restricting the sustainable development of agriculture and causing issues of agricultural product safety. In order to explore the effect of different acidification on soil cadmium (Cd) availability, soil pot culture and hydroponic (soil potting solution extraction) were applied, and non-invasive micro-test technique (NMT) was combined. Here three different soil acidification processes were simulated, including direct acidification by adding sulfuric acid (AP1), acid rain acidification (AP2) by adding artificial simulated acid rain and excessive fertilization acidification by adding (NH₄)₂SO₄ (AP3). The results showed that for direct acidification (AP1), DTPA-Cd concentration in field soils in Liaoning (S1) and Zhejiang (S2) increased by 0.167 - 0.217 mg/kg and 0.181 - 0.346 mg/kg, respectively, compared with control group. When soil pH decreased by 0.45 units in S1, the Cd content of rice stems, leaves and roots increased by 0.48 to 6.04 mg/kg and 2.58 to 12.84 mg/kg, respectively, When the pH value of soil S1 and S2 decreased by 0.20 units, the average velocity of Cd²⁺ at 200 µm increased by 10.03 - 33.11 pmol/cm²/sec and 21.33 -52.86 pmol/cm²/sec, respectively, and followed the order of AP3 > AP2 > AP1. In summary, different acidification measures would improve the effectiveness of Cd, under the same pH reduction condition, fertilization acidification increased Cd availability most significantly.

Lessening energy-related carbon emissions has become a crucial measure to achieve Chinese carbon neutrality. This study is the first to construct a Difference in Carbon pressures-adjusted Human Development Index (DCHDI) model for the purpose of exploring the coupling effect between carbon emissions and human development variety from 2000 to 2019 in Chinese provinces. We demonstrate the following. (1) The total energy-related carbon footprint of 30 provinces in China reached 10.2 billion tons in 2019, with an average annual growth rate of 6.93% over the past two decades; and the provinces with the highest carbon emissions per capita are InnerMongolia, Ningxia, and Shanxi. (2) At the provincial level, we observed that the Human Development Index (HDI), which includes life expectancy, education, and income, has been rising, while Beijing, Shanghai, and Tianjin entered the super-high HDI level before 2008. (3) The entire coupling effect of 30 Chinese provinces has been broadly fortified in the last 20 years, but the growth rate of DCHDI values in 2011–2019 has slowed down compared with that in 2000–2010; the clustering phenomenon demonstrated that this discovery is associated with historical peaks in total carbon emissions. (4) The coordination degree of carbon emissions per capita and HDI was verified, and 96% of the data points were found in the range of super high coupling coordination degree. Overall, this study provides the government with worthwhile guidance for decision-making and carbon reduction strategies for other countries struggling to advance human sustainable development.

Partial nitrification is a key aspect of efficient nitrogen removal, although practically it suffers from long start-up cycles and unstable long-term operational performance. To address these drawbacks, this study investigated the effect of low intensity ultrasound treatment combined with hydroxylamine (NH₂OH) on the performance of partial nitrification. Results show that compared with the control group, low-intensity ultrasound treatment (0.10 W/mL, 15 min) combined with NH₂OH (5 mg/L) reduced the time required for partial nitrification initiation by 6 days, increasing the nitrite accumulation rate (NAR) and ammonia nitrogen removal rate (NRR) by 20.4% and 6.7%, respectively, achieving 96.48% NRR. Mechanistic analysis showed that NH₂OH enhanced ammonia oxidation, inhibited nitrite-oxidizing bacteria (NOB) activity and shortened the time required for partial nitrification initiation. Furthermore, ultrasonication combined with NH₂OH dosing stimulated EPS (extracellular polymeric substances) secretion, increased carbonyl, hydroxyl and amine functional group abundances and enhanced mass transfer. In addition, 16S rRNA gene sequencing results showed that ultrasonication-sensitive Nitrospira disappeared from the ultrasound + NH₂OH system, while Nitrosomonas gradually became the dominant group. Collectively, the results of this study provide valuable insight into the enhancement of partial nitrification start-up during the process of wastewater nitrogen removal.

Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter, for which the reason have not been clearly elucidated. Here we measured carbonyl compounds and other trace gasses together with PM_2.5 over urban Jinan in North China Plain during the winter. Markedly higher carbonyl concentrations (average: 14.63 ± 4.21 ppbv) were found during wintertime haze pollution, about one to three-times relative to those on non-haze days, with slight difference in chemical composition except formaldehyde (HCHO). HCHO (3.68 ppbv), acetone (3.17 ppbv), and acetaldehyde (CH₃CHO) (2.83 ppbv) were the three most abundant species, accounting for ∼75% of the total carbonylson both haze and non-haze days. Results from observational-based model (OBM) with atmospheric oxidation capacity (AOC) indicated that AOC significantly increased with the increasing carbonyls during the winter haze events. Carbonyl photolysis have supplied key oxidants such as RO₂ and HO₂, and thereby enhancing the formation of fine particles and secondary organic aerosols, elucidating the observed haze-carbonyls inter-correlation. Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources. 1-butene was further confirmed to be the major precursor for HCHO. This study confirms the great contribution of carbonyls to AOC, and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.