Mineralogical characteristics and photocatalytic properties of natural sphalerite from China

Different natural sphalerites have a range of photocatalytic properties that can potentially be exploited for environmental remediation purposes. To develop value in the exploitation of sphalerite, samples were collected from 19 ore deposits in China and characterized for their mineralogical and photocatalytic properties. X-ray diffraction (XRD) and electron probe micro analysis (EPMA) measurements indicated that all the natural sphalerites from various localities crystallized in cubic phases with various chemical compositions. The substitution of Fe for Zn ranged from 0.235% to 14.826% by weight, Mn from 0.004% to 4.868%, Cu from 0.009% to 5.529% and Cd from 0.133% to 1.576%. As Fe became more abundant, the color of natural sphalerite darkened, becoming almost black; and higher Fe content was associated with stronger visible light absorption. Photoluminescence spectra showed emission mainly related to S-vacancies and progressively decreasing fluorescence intensity with increasing Fe content. Tests of the photocatalytic degradation of methyl orange indicated that the sample with the highest Cd content but moderate Fe content had the highest photocatalytic activity. Specifically, the degradation of Methyl Orange (30 mg/L) attained 82.11% efficiency under visible light irradiation for 4 hr of natural sphalerite with 4.262% Fe and 1.576% Cd. Overall, the Fe content in sphalerite was found to contribute to the visible light absorption ability and the recombination rate of photo-generated electrons and holes, while substitution by Cd was observed to have a greater effect on the photocatalytic properties. These findings provide a scientific basis for the profitable utilization of base metal resources like sphalerite.     

Carbon reduction potential and cost evaluation of different mitigation approaches in China's coal to olefin Industry

Coal-based olefin (CTO) industry as a complement of traditional petrochemical industry plays vital role in China's national economic development. However, high CO₂ emission in CTO industry is one of the fatal problems to hinder its development. In this work, the carbon emission and mitigation potentials by different reduction pathways are evaluated. The economic cost is analyzed and compared as well. According to the industry development plan, the carbon emissions from China's CTO industry will attain 189.43 million ton CO₂ (MtCO₂) and 314.11 MtCO₂ in 2020 and 2030, respectively. With the advanced technology level, the maximal carbon mitigation potential could be attained to 15.3% and 21.9% in 2020 and 2030. If the other optional mitigation ways are combined together, the carbon emission could further reduce to some extent. In general, the order of mitigation potential is followed as: feedstock alteration by natural gas > CO₂ hydrogenation with renewable electricity applied > CCS technology. The mitigation cost analysis indicates that on the basis of 2015 situation, the economic penalty for feedstock alteration is the lowest, ranged between 186 and 451 CNY/tCO₂, and the cost from CCS technology is ranged between 404 and 562 CNY/tCO₂, which is acceptable if the CO₂ enhanced oil recovery and carbon tax are considered. However, for the CO₂ hydrogenation technology, the cost is extremely high and there is almost no application possibility at present.     

Seasonal variation and sources of derivatized phenols in atmospheric fine particulate matter in North China Plain

Qualitative and quantitative analyses of derivatized phenols in Beijing and in Xinglong were performed from 2016 to 2017 using gas chromatography-mass spectrometry.The results showed substantially more severe pollution in Beijing.Of the 14 compounds detected,the total average concentration was 100 ng/m~3 in Beijing,compared with 11.6 ng/m~3 in Xinglong.More specifically,concentration of nitro-aromatic compounds(NACs)(81.9 ng/m~3 in Beijing and 8.49 ng/m3 in Xinglong) was the highest,followed by aromatic acids(14.6 ng/m~3 in Beijing and 2.42 ng/m~3 in Xinglong) and aromatic aldehydes(3.62 ng/m~3 in Beijing and 0.681 ng/m~3 in Xinglong).In terms of seasonal variation,the highest concentrations were found for 4-nitrocatechol in winter in Beijing(79.1±63.9 ng/m~3) and 4-nitrophenol in winter in Xinglong(9.72±8.94 ng/m~3).The analysis also revealed diurnal variations across different seasons.Most compounds presented higher concentrations at night in winter because of the decreased boundary layer height and increased heating intensity.While some presented higher levels during the day,which attributed to the photo-oxidation process for summer and more biomass burning activities for autumn.Higher concentrations appeared in winter and autumn than in spring and summer,which resulted from more coal combustions and adverse meteorological conditions.The significant correlations among NACs indicated similar sources of pollution.Higher correlations presented within each subgroup than those between the subgroups.Good correlations between levoglucosan and nitrophenols,nitrocatechols,nitro salicylic acids,with correlation coefficients(r) of 0.66,0.69 and 0.69,respectively,indicating an important role of biomass burning among primary sources.     

污水生物处理工艺低温下微生物种群结构

构建有针对性的运行控制策略是我国城市污水生物处理工艺冬季低水温条件下高效稳定运行的重要保证.以我国北方低温期（8~15℃）稳定运行的4个典型污水生物处理工艺为对象,利用高通量测序方法系统解析了活性污泥中的微生物群落及碳、氮、磷去除等关键功能种群结构,阐明了重要功能种群在低温影响下的动态变化及与污染物去除性能间关系,为控制策略的有效建立提供了坚实的科学数据基础.尽管存在着不同工艺形式,但结果表明低温期活性污泥均具有较为良好的种群丰富度,其中放线菌门（Actinobacteria）在低温期优势地位提升;关键功能种群中硝化种属Nitrosomonas受温度影响较大,而作为核心种群的反硝化种属则因分布广泛及多样性高,整体丰度受温度变化影响较小,工艺的反硝化性能仅与回流比具有相关性;Tetrasphaera在4个工艺中广泛存在但仅在厌氧/好氧交替条件下承担主要除磷功能;低温下4个工艺中多种丝状菌优势生长并诱发污泥膨胀,但对出水水质影响较小.     

海洋微生物胞外分泌物(EPS)对船用结构钢腐蚀行为的影响

目的研究微生物活性与船用钢DH32腐蚀行为之间的关系,并通过胞外分泌物的提取,研究分泌物浓度对材料腐蚀性能的影响。方法通过傅里叶红外光谱(FT–IR)分析胞外分泌物的组成,通过电感耦合等离子体发射光谱仪(ICP-OES)分析金属离子的含量,并使用用原子力显微镜(AFM)观测去除腐蚀产物后的表面形貌。结果通过电化学阻抗谱的拟合分析,短期内,EPS通过阻碍溶解氧的扩散抑制腐蚀速度,EPS浓度越高,效果越好,即实验初期试样腐蚀的速度与EPS浓度成反比。随着时间的延长,EPS浓度低的溶液中,其EPS络合金属离子的能力很快达到饱和,所以尽管其络合行为能促进试样的阳极溶解,但影响作用有限,此时起到主要影响的还是EPS抑制溶解氧扩散。对于浓度高的EPS溶液,其过量的EPS会促进EPS的官能团与材料表面更多的Fe~(2+)/Fe~(3+)离子键合,使得沉积的EPS保护层变得疏松失去隔离溶解氧的作用,进而加速试样腐蚀。结论海洋微生物胞外分泌物对船用钢腐蚀行为的影响与胞外分泌物的结构与浓度有关,随着浓度升高,EPS从抑制腐蚀变为加速腐蚀。     

Effect of sulfur source on photocatalytic degradation performance of CdS/MoS2 prepared with one-step hydrothermal synthesis

Cd S/Mo S_2,an extremely efficient photocatalyst,has been extensively used in hydrogen photoproduction and pollutant degradation.Cd S/Mo S_2can be synthesized by a facile one-step hydrothermal process.However,the effect of the sulfur source on the synthesis of Cd S/Mo S_2via one-step hydrothermal methods has seldom been investigated.We report herein a series of one-step hydrothermal preparations of Cd S/Mo S_2using three different sulfur sources:thioacetamide,L-cysteine,and thiourea.The results revealed that the sulfur source strongly affected the crystallization,morphology,elemental composition and ultraviolet(UV)–visible-light-absorption ability of the Cd S/Mo S_2.Among the investigated sulfur sources,thioacetamide provided the highest visible-light absorption ability for Cd S/Mo S_2,with the smallest average particle size and largest surface area,resulting in the highest efficiency in Methylene Blue(MB)degradation.The photocatalytic activity of Cd S/Mo S_2synthesized from the three sulfur sources can be arranged in the following order:thioacetamideL-cysteinethiourea.The reaction rate constants(k)for thioacetamide,L-cysteine,and thiourea were estimated to be 0.0197,0.0140,and 0.0084 min~(-1),respectively.However,thioacetamide may be limited in practical application in terms of its price and toxicity,while L-cysteine is relatively economical,less toxic and exhibited good photocatalytic degradation performance toward MB.     

Comparative study of carbonic anhydrase activity in waters among different geological eco-environments of Yangtze River basin and its ecological significance

This study provides the presence of carbonic anhydrase(CA) activity in waters of the Yangtze River basin, China, as well as the correlation of CA activity with HCO-3 concentration and CO_2 sink flux. Different degrees of CA activity could be detected in almost all of the water samples from different geological eco-environments in all four seasons. The CA activity of water samples from karst areas was significantly higher than from non-karst areas(PP3-concentration(r = 0.672, P2 sink flux(r = 0.602, P = 0.076) in karst areas. This suggests that CA in waters might have a promoting effect on carbon sinks for atmospheric CO_2 in karst river basins. In conditions of similar geological type, higher CA activity was generally detected in water samples taken from areas that exhibited better eco-environments, implying that the CA activity index of waters could be used as an indicator for monitoring ecological environments and protection of river basins. These findings suggest that the role of CA in waters in the karst carbon sink potential of river basins is worthy of further in-depth studies.     

Occupational exposure assessment of phthalate esters in indoor and outdoor microenvironments

Phthalate esters(PAEs) are widely used as plasticizers in consumer products. PAEs are a group of environmental hormone which disrupts human and animals' endocrine systems. Different occupational groups are exposed to various levels of PAEs. In the present study, four typical occupational groups were chosen, including doctors, college teachers, college students, and drivers who worked in public traffic system. In order to understand the exposure levels to PAEs via inhalation, air samples were collected from multiple microenvironments including indoor and outdoor in Hangzhou to measure the gas and particle concentrations of six PAEs, together with time spent in different microenvironments of these four groups. A comprehensive PAEs exposure model was built to estimate the daily PAEs exposure through inhalation, oral and dermal pathways. The Monte Carlo simulation results show that doctors were exposed to the highest level of PAEs, and consequently had the highest health risk among these four occupational groups. In contrast, college students had the lowest health risk. By setting the exposure level of staying in residences as the baseline, doctors and drivers were two occupations exposed to high PAEs health risk. Di-(2-ethylhexyl) phthalate(DEHP) was the largest contributor among the six phthalates, posing moderate health risk(10-5–10-6) to every occupation. For traffic microenvironments alone, the total exposure levels for different transportation modes were in the descending order of busses, cars, cabs, tubes, motor bikes, and walking.     

Spatial and temporal variation of haze in China from 1961 to 2012

The purpose of this study is to analyze the climatic characteristics and long-term spatial and temporal variations of haze occurrence in China. The impact factors of haze trends are also discussed. Meteorological data from 1961 to 2012 and daily PM₁₀ concentrations from 2003 to 2012 were employed in this study. The results indicate that the annual-average hazy days at all stations have been increasing rapidly from 4 days in 1961 to 18 days in 2012. The maximum number of haze days occur in winter (41.1%) while the minimum occur in summer (10.4%). During 1961-2012, the high occurrence areas of haze shifted from central to south and east regions of China. The Beijing-Tianjin-Hebei (Jing-Jin-Ji) region, Shanxi, Shaanxi, and Henan Province are the high occurrence areas for haze, while the Yangtze River Delta (YRD) and the Pearl River Delta (PRD) have become regions with high haze occurrences in the last 25 years. Temperature and pressure are positively correlated with the number of haze days. However, wind, relative humidity, precipitation, and sunshine duration are negatively correlated with the number of haze days. The key meteorological factors affecting the formation and dissipation of haze vary for high and low altitudes, and are closely related to anthropogenic activities. In recent years, anthropogenic activities have played a more important role in haze occurrences compared with meteorological factors.