济南市背景区域大气PM2.5污染特征及其对能见度的影响

为研究背景地区大气PM_(2. 5)化学组分季节变化特征及对能见度的影响,本研究于2016年春、夏、秋、冬在济南市七星台采集大气PM_(2. 5)样品,分析其中水溶性离子组分及OC、EC的污染特征并研究其区域传输贡献.结果表明,NH_4~+、SO_4~(2-)和NO_3~-三者之和占年均离子总浓度的90. 24%,二次生成的水溶性无机离子污染较为严重. NO_3~-/SO_4~(2-)呈现出明显的冬高夏低的季节性变化特征.各季节的SO_4~(2-)和NH_4~+主要以(NH4)2SO4结合的形式存在. SOC/OC的范围是21. 17%～54. 21%,表明该地区存在较为严重的二次有机污染.四季SOR值均大于0. 1,显示本区域四季均有SO_4~(2-)的二次生成,四季NOR的值均高于SOR,可知NO2的二次转化强于SO2的二次转化.大气消光系数(Bext)的范围是172. 68～320. 61 Mm-1,年均值为256. 48Mm-1,大气消光系数呈现明显的夏低冬高的季节性趋势.后推气流轨迹显示七星台地区春、夏季主要受长距离传输和海洋源的影响,秋、冬季主要受局地源的影响.对比2008年济南市大气PM_(2. 5)污染特征研究,结果显示机动车对大气环境影响显著提升.     

Interactions of fluoroquinolone antibiotics with sodium hypochlorite in bromide-containing synthetic water: Reaction kinetics and transformation pathways

Seven popular fluoroquinolone antibiotics (FQs) in synthetic marine aquaculture water were subject to sodium hypochlorite (NaClO) disinfection scenario to investigate their reaction kinetics and transformation during chlorination. Reactivity of each FQ to NaClO was following the order of ofloxacin (OFL) > enrofloxacin (ENR) > lomefloxacin (LOM) > ciprofloxacin (CIP) ~ norfloxacin (NOR) >> pipemedic acid (PIP), while flumequine did not exhibit reactivity. The coexisting chlorine ions and sulfate ions in the water slightly facilitated the oxidation of FQs by NaClO, while humic acid was inhibitable to their degradation. The bromide ions promoted degradation of CIP and LOM, but restrained oxidation of OFL and ENR. By analysis of liquid chromatography with tandem mass spectrometry (LC-MS/MS), eight kinds of emerging brominated disinfection byproducts (Br-DBPs) caused by FQ_S were primarily identified in the chlorinated synthetic marine culture water. Through density functional theory calculation, the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO) characteristic as well as the charge distribution of the FQs were obtained to clarify transformation mechanisms. Their formation involved decarboxylation, ring-opening/closure, dealkylation and halogenation. Chlorine substitution occurred on the ortho-position of FQs's N4 and bromine substitution occurred on C8 position. The piperazine ring containing tertiary amine was comparatively stable, while this moiety with a secondary amine structure would break down during chlorination. Additionally, logK_ow and logBAF of transformation products were calculated by EPI-Suite^TM to analyze their bioaccumulation. The values indicated that Br-DBPs are easier to accumulate in the aquatic organism relative to their chloro-analogues and parent compounds.     

碳酸盐岩对Fe2+生物氧化及铁矿物合成的影响

利用从高硫煤矸石堆场浸出液中培养驯化获得的氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans,A.f）,通过静态实验,探讨添加不同量的碳酸盐岩对酸性硫酸盐体系中Fe²⁺生物氧化速率及次生铁矿物合成的影响.结果表明：添加10 g和30 g碳酸盐岩不会对体系中pH、氧化还原电位（ORP）和Fe²⁺生物氧化速率产生明显影响,但总铁（TFe）的去除率可从37%分别提高到55%和62%,矿物生成量也从8.17 g·L^-1分别增加到12.03 g·L^-1和13.69 g·L^-1;同时,体系中合成的次生铁矿物相与不加碳酸盐岩时无明显变化,主要为黄铁矾和施氏矿物的混合物.随着碳酸盐岩添加量增至50、70和90 g时,体系pH快速上升,Fe²⁺生物氧化速率受到抑制,并产生大量结晶程度较好的硫酸钙,形成的铁矿物主要为纤铁矿或针铁矿.而适量的碳酸盐岩添加可使体系中产生Ca²⁺和Mg²⁺,从而影响次生铁矿物的合成.因此,在以碳酸盐岩为反应介质的酸性矿山废水处理工艺设计中,可通过添加A.f菌并控制碳酸盐岩投加量,强化系统中Fe²⁺生物氧化及次生矿物的合成,从而进一步提高反应系统对TFe的去除效果.     

Investigation of suitable precursors for manganese oxide catalysts in ethyl acetate oxidation

The control of ethyl acetate emissions from fermentation and extraction processes in the pharmaceutical industry is of great importance to the environment. We have developed three Mn₂O₃ catalysts by using different Mn precursors (MnCl₂, Mn(CH₃COO)₂, MnSO₄), named as Mn₂O₃-Cl, -Ac, -SO₄. The tested catalytic activity results showed a sequence with Mn precursors as: Mn₂O₃-Cl > Mn₂O₃-Ac > Mn₂O₃-SO₄. The Mn₂O₃-Cl catalyst reached a complete ethyl acetate conversion at 212℃ (75℃ lower than that of Mn₂O₃-SO₄), and this high activity 100% could be maintained high at 212℃ for at least 100 hr. The characterization data about the physical properties of catalysts did not show an obvious correlation between the structure and morphology of Mn₂O₃ catalysts and catalytic performance, neither was the surface area the determining factor for catalytic activity in the ethyl acetate oxidation. Here we firstly found there is a close linear relationship between the catalytic activity and the amount of lattice oxygen species in the ethyl acetate oxidation, indicating that lattice oxygen species were essential for excellent catalytic activity. Through H₂ temperature-programmed reduction (H₂-TPR) results, we found that the lowest initial reduction temperature over the Mn₂O₃-Cl had stronger oxygen mobility, thus more oxygen species participated in the oxidation reaction, resulting in the highest catalytic performance. With convenient preparation, high efficiency, and stability, Mn₂O₃ prepared with MnCl₂ will be a promising catalyst for removing ethyl acetate in practical application.     

An intercomparison of ozone taken from the Copernicus atmosphere monitoring service and the second Modern-Era retrospective analysis for research and applications over China during 2018 and 2019

Spatiotemporal variations of ozone (O₃) taken from the Copernicus Atmosphere Monitoring Service (CAMS) and the second Modern-Era Retrospective Analysis for Research and Applications (MERRA-2) were intercompared and evaluated with ground and ozone-sonde observations over China in 2018 and 2019. Intercomparison of the surface ozone from CAMS and MERRA-2 reanalysis showed significant negative bias (CAMS minus MERRA-2, same below) at Tibetan Plateau of up to 80 µg/m³, and the average R² was about 0.6 across China. Evaluated with the ground observations from China National Environmental Monitoring Center (CNEMC), we found that CAMS and MERRA-2 reanalysis were capable of capturing the key patterns of monthly and diurnal variations of surface ozone over China except for the western region, and MERRA-2 overestimated the observations compared to CAMS. Vertically, the CAMS profiles overestimated the ozone-sonde from the World Ozone and Ultraviolet Radiation Data Center (WOUDC) above 200 hPa with the magnitude reaching up to 150 µg/m³, while little bias was found between the reanalysis and observations below 200 hPa. Intercomparison drawn from the vertical distribution between CAMS and MERRA-2 reanalysis showed that the negative bias appeared throughout the troposphere over China, while the positive bias emerged in the upper troposphere and lower stratosphere (UTLS) with high order of magnitude exceeding 100 µg/m³, indicating large uncertainties at higher altitudes. In summary, we concluded that CAMS reanalysis showed better agreement with the observations in contrast to MERRA-2, and the large discrepancy especially at higher altitudes between these two reanalysis datasets could not be ignored.     

Assessing the factors impacting the bioaccessibility of mercury (Hg) in rice consumption by an in-vitro method

Mercury (Hg) in rice is drawing mounting concern since methylmercury (MeHg) was found capable of accumulating in rice. In-vitro bioaccessibility is a feasible and reliable method to assess the health effects of Hg in rice and has been utilized in a number of studies. This study was done to investigate the impact of cultivar, planting location, and cooking on the total mercury (THg) and MeHg bioaccessibility of rice, for which multiple statistical analysis methods were used to analyze the significance of their effects. The THg concentrations of rice samples taken from non-Hg contaminated areas of China were all below 15 ng/g and their MeHg concentrations were below 2 ng/g. Cooking could significantly reduce the MeHg bioaccessibility of rice because the MeHg was mainly combined with protein and the protein will be denatured during the cooking process, and then the denatured MeHg is difficult to be dissolved into the liquid phase. Indica- and japonica-type rice cultivars did not show significant differentiation in either the concentration of Hg or its bioaccessibility. However, the glutinous rice type differed significantly from the above rice types, and it showed greater bioaccessibility of THg and MeHg due to its distinct protein contents and starch properties. Planting location can affect the Hg concentration in rice and THg bioaccessibility but has a limited impact on MeHg bioaccessibility. Based on these results, two macro factors (rice cultivar, planting location) are presumed to impact Hg bioaccessibility by how they affect micro factors (i.e., Hg forms).     

Influence of dissolved organic matter on methylmercury transformation during aerobic composting of municipal sewage sludge under different C/N ratios

Current knowledge about the transformation of total mercury and methylmercury (MeHg) in aerobic composting process is limited. In this study, the composition and transformation of mercury and dissovled organic matter (DOM) in aerobic composting process of municipal sewage sludge were were comprehensively characterized, and the differences among the three C/N ratio (20, 26 and 30) were investigated. The main form of mercury in C/N 20 and 26 was organo-chelated Hg (F3, 46%-60%); while the main form of mercury in C/N 30 was mercuric sulfide (F5, 64%-70%). The main component of DOM in C/N 20 and 26 were tyrosine-like substance (C1, 53%-76%) while the main fractions in C/N 30 were tyrosine-like substance (C1, 28%-37%) and fulvic-like substance (C2, 17%-39%). The mercury and DOM varied significantly during the 9 days composting process. Compared to C/N 20 and 26, C/N 30 produced the less MeHg after aerobic composting process, with values of 658% (C/N 20), 1400% (C/N 26) and 139% (C/N 30) of the initial, respectively. Meanwhile, C/N 30 produced the best compost showed greater degree of DOM molecular condensation and humification. Hg fraction had been altered by DOM, as indicated by a significant correlation between mercury species and DOM components. Notably, C/N 30 should be used as an appropriate C/N ratio to control the methylation processes of mercury and degration of DOM.     

Migration and transformation of Sb are affected by Mn(III/IV) associated with lepidocrocite originating from Fe(II) oxidation

Antimony (Sb) is a recognized priority pollutant with toxicity that is influenced by its migration and transformation processes. Oxidation of Fe(II) to Fe(III) oxides, which is a common phenomenon in the environment, is often accompanied by the formation of Mn(III/IV) and might affect the fate of Sb. In this study, incorporated Mn(III) and sorbed/precipitated Mn(III/IV) associated with lepidocrocite were prepared by adding Mn(II) during and after Fe(II) oxidation, respectively, and the effects of these Mn species on Sb fate were investigated. Our results indicated that the association of these Mn species with lepidocrocite obviously enhanced Sb(III) oxidation to Sb(V), while concomitantly inhibiting Sb sorption due to the lower sorption capacity of lepidocrocite for Sb(V) than Sb(III). Additionally, Mn oxide equivalents increased in the presence of Sb, indicating that Sb oxidation by Mn(III/IV) associated with lepidocrocite was a continuous recycling process in which Mn(II) released from Mn(III/IV) reduction by Sb(III) could be oxidized to Mn(III/IV) again. This recycling process was favorable for effective Sb(III) oxidation. Moreover, Sb(V) generated from Sb(III) oxidation by Mn(III/IV) enhanced Mn(II) sorption at the beginning of the process, and thus favored Mn(III/IV) formation, which could further promote Sb(III) oxidation to Sb(V). Overall, this study elucidated the effects of Mn(III/IV) associated with lepidocrocite arisen from Fe(II) oxidation on Sb migration and transformation and revealed the underlying reaction mechanisms, contributing to a better understanding of the geochemical dynamics of Sb.     

Sulfur-driven methylmercury production in paddies continues following soil oxidation

Methylmercury (MeHg) production in paddy soils and its accumulation in rice raise global concerns since rice consumption has been identified as an important pathway of human exposure to MeHg. Sulfur (S) amendment via fertilization has been reported to facilitate Hg methylation in paddy soils under anaerobic conditions, while the dynamic of S-amendment induced MeHg production in soils with increasing redox potential remains unclear. This critical gap hinders a comprehensive understanding of Hg biogeochemistry in rice paddy system which is characterized by the fluctuation of redox potential. Here, we conducted soil incubation experiments to explore MeHg production in slow-oxidizing paddy soils amended with different species of S and doses of sulfate. Results show that the elevated redox potential (1) increased MeHg concentrations by 10.9%−35.2%, which were mainly attributed to the re-oxidation of other S species to sulfate and thus the elevated abundance of sulfate-reducing bacteria, and (2) increased MeHg phytoavailability by up to 75% due to the reductions in acid volatile sulfide (AVS) that strongly binds MeHg in soils. Results obtained from this study call for attention to the increased MeHg production and phytoavailability in paddy soils under elevated redox potentials due to water management, which might aggravate the MeHg production induced by S fertilization and thus enhance MeHg accumulation in rice.     

Understanding the risks of mercury sulfide nanoparticles in the environment: Formation, presence, and environmental behaviors

Mercury (Hg) could be microbially methylated to the bioaccumulative neurotoxin methylmercury (MeHg), raising health concerns. Understanding the methylation of various Hg species is thus critical in predicting the MeHg risk. Among the known Hg species, mercury sulfide (HgS) is the largest Hg reservoir in the lithosphere and has long been considered to be highly inert. However, with advances in the analytical methods of nanoparticles, HgS nanoparticles (HgS NPs) have recently been detected in various environmental matrices or organisms. Furthermore, pioneering laboratory studies have reported the high bioavailability of HgS NPs. The formation, presence, and transformation (e.g., methylation) of HgS NPs are intricately related to several environmental factors, especially dissolved organic matter (DOM). The complexity of the behavior of HgS NPs and the heterogeneity of DOM prevent us from comprehensively understanding and predicting the risk of HgS NPs. To reveal the role of HgS NPs in Hg biogeochemical cycling, research needs should focus on the following aspects: the formation pathways, the presence, and the environmental behaviors of HgS NPs impacted by the dominant influential factor of DOM. We thus summarized the latest progress in these aspects and proposed future research priorities, e.g., developing the detection techniques of HgS NPs and probing HgS NPs in various matrices, further exploring the interactions between DOM and HgS NPs. Besides, as most of the previous studies were conducted in laboratories, our current knowledge should be further refreshed through field observations, which would help to gain better insights into predicting the Hg risks in natural environment.