Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Polycyclic aromatic hydrocarbons in benthos of the northern Bering Sea Shelf and Chukchi Sea Shelf

Eighteen polycyclic aromatic hydrocarbons (PAHs) were detected in benthos collected onboard the ‘Snow Dragon’ in the Northern Bering Sea Shelf and Chukchi Sea Shelf during the 6^th Chinese National Arctic Research Expedition (CHINARE 2014). Σ₁₈PAHs for all biota samples ranged from 34.2 to 128.1 ng/g dry weight (dw), with the highest concentration observed in fish muscle (Boreogadus saida) samples close to St. Lawrence Island. The PAH composition pattern was dominated by the presence of lighter 3 ring (57%) and 2 ring (28%) PAHs, indicating oil-related or petrogenic sources as important origins of PAH contamination. Concentrations of alkyl-PAHs (1-methylnaphthalene and 2-methylnaphthalene) were lower than their parent PAH (naphthalene) in all biological tissue, and their percentage also decreased significantly (p<0.05) compared with those in the corresponding sediment. There were no significant relationships between PAH concentrations and trophic levels, which is possibly due to the combined results of the complex benthic foodweb in the subarctic/Arctic shelf region, as well as a low assimilation/effective metabolism for PAHs. According to toxic potency evaluation results from TCDD toxic equivalents (TEQs) and BaP-equivalent (BaPE) values, whelk (Neptunea heros) and starfish (Ctenodiscus crispatus) are two macroinvertebrate species showing relatively higher dioxin-like toxicity and carcinogenic risk.     

固体样品六价铬的检测比对和验证

采用碱溶液提取/火焰原子吸收法(HJ 687—2014《固体废物六价铬的测定 碱消解/火焰原子吸收分光光度法》和HJ 1082—2019《土壤和沉积物 六价铬的测定 碱溶液提取-火焰原子吸收分光光度法》)测定了固体废物和土壤样品中六价铬含量,比对和验证了2种方法实验流程、分析方法性能及不确定度评定结果。结果表明:HJ 687—2014的方法检出限相对较高,不适合测定浓度较低的土壤;HJ 1082—2019要求按照试样制备的步骤配置工作曲线,考虑了基体干扰的影响。HJ 687—2014的检出限为0.28 mg/kg,相对标准偏差为0.69%~0.93%,样品加标回收率为95.7%~97.2%;HJ 1082—2019的检出限为0.17 mg/kg,相对标准偏差为0.6%~3.0%,样品加标回收率为76.0%~83.1%。对于同一实际样品,2种方法的测定结果相近,HJ 687—2014和HJ 1082—2019的测定结果分别为(48.1±4.2),(46.6±5.4) mg/kg。比对发现,影响HJ 687—2014和HJ 1082—2019不确定度的最主要环节分别为曲线拟合和样品消解。     

白洋淀流域地表水化学特征及控制因素

为探究半干旱区地表水化学特征及物质来源,以白洋淀流域为研究对象,利用Piper三线图和Gibbs水岩模型,对地表水的主要离子组成特征及其来源进行分析。结果表明:白洋淀流域地表水pH为7.56~8.23时,呈弱碱性,且溶解性总固体（TDS,100~650 mg/L）在流域的不同空间区域表现为淀区 > 下游 > 上游。白洋淀流域地表水阳离子以Na+和Ca2+为主,离子总量占比76.60%;阴离子以HCO₃-为主,约占阴离子总量61.52%。地表水的水化学类型为HCO₃-Ca型（上游水体）和HCO₃·SO₄·Cl-Na·Ca型（下游河流和淀区）。白洋淀水文地球化学过程受到人类活动和自然作用的双重控制;自然作用下,白洋淀流域地表水中的离子来源于岩石风化（碳酸盐岩及硅酸盐岩的风化溶解）,同时受到蒸发-结晶作用影响。     

全球海洋初级生产力与海洋环境要素时空关联模式挖掘分析

全球海洋初级生产力在海洋环境要素的驱动下呈现不同的时空分布特征,但在不同的海域两者之间的关联模式并不清晰。本文从地理时空规则挖掘的角度,利用1998年1月—2016年12月之间的序列多源遥感产品数据,探讨了全球海洋初级生产力和海洋表面温度、海面高度异常、海面降雨、混合层深度和ENSO（El Ni?o-Southern Oscillation）事件的时空关联模式。研究结果表明:1）在西赤道太平洋,海面高度异常降低、海面降雨异常降低和混合层深度异常升高会提升真光层营养盐供应,致使海洋初级生产力的异常升高。2）在中赤道太平洋,海面高度异常升高、海面降雨异常升高和混合层深度异常降低会抑制真光层营养盐供应,致使海洋初级生产力的异常降低。3）在东赤道太平洋,海面高度异常升高和海面降雨异常升高会抑制真光层营养盐供应、混合层深度异常升高降低了铁元素含量,从而导致海洋初级生产力的异常降低。4）在南太平洋,浮游植物丰度与营养盐呈负相关,海洋表面温度异常升高/异常降低会提升/抑制微生物光合作用效率、海面高度的异常升高/异常降低会抑制/提升真光层营养盐供应,致使海洋初级生产力的异常升高/异常降低。5）厄尔尼诺事件相较于拉尼娜事件更容易引起海洋初级生产力的异常变化。     

Optimal range of plug-in electric vehicles in Beijing and Shanghai

Both China’s national subsidy policies for plug-in electric vehicles (PEVs) purchasers and passenger cars corporate average fuel consumption and new vehicle credit regulation (dual-credit policy) favor long-range 300+ km battery electric vehicles (BEVs) and 80+ km plug-in hybrid electric vehicles (PHEVs). However, these electric vehicles tend to have lower energy efficiency and higher purchase and operation costs. Vehicle with larger batteries can also be less equitable because the subsidies are often provided to more expensive vehicles and wealthier owners. This study takes advantage of a novel dataset of daily driving data from 39,854 conventional gasoline vehicles in Beijing and 4999 PHEVs in Shanghai to determine the optimal range of BEVs and PHEVs within their respective cities. We simulate a model to explore ranges with which PEVs emit less GHGs than that of a baseline hybrid and conventional gasoline vehicle while ensuring that all daily travel demands are met. Our findings indicate that in both cities, the optimal ranges to balance cost and travel demand for BEVs are 350 km or less and for PHEVs are 60 km or less in Beijing and 80 km or less in Shanghai. We also find that to minimize carbon dioxide (CO₂) emissions, the ranges are even lower 10 km in Beijing and 30 km in Shanghai. Our study suggests that instead of encouraging long-range PEVs, governments should subsidize PEV models with shorter ranges. Parallel efforts should also be made to both increase renewable energy over fossil fuels and expand charging facilities. Although individual mobility demand varies, the government could reduce occasional long-distance driving by subsidizing alternative transportation choices. Providing week-long driving trials to consumers before their purchases may help decrease the demand of very long range PEVs by alleviating the range anxiety through a learning process.

     

Green innovation efficiency across China’s 30 provinces: estimate,comparison, and convergence

Mitigation and Adaptation Strategies for Global Change - Considering government and market failure of environmental regulation to combat increasing GHG (greenhouse gas) emissions, green innovation...     

南京八卦洲农用地表层土壤重金属分布特征及风险评价

为查明南京八卦洲土壤重金属污染物类型及其影响范围,于2017年12月在洲内采集了471个表层土壤样品,测定了pH及As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等8种重金属元素浓度,采用单因子指数法、内梅罗综合指数法和潜在生态危害指数法进行了污染风险评价。研究结果表明:As、Cd、Cr、Cu、Hg、Ni、Pb和Zn平均浓度分别为10.66、0.32、86.74、43.25、0.10、40.34、33.50和108.33 mg·kg-1,除As、Hg元素外,其余6种元素均超过南京市背景值,出现大范围的富集;Cd元素为研究区主要污染物,绝大部分为Ⅱ级轻微污染,均分布于八卦洲服务区附近的中、酸性土覆盖区,需做好安全利用措施。从全区来看研究区大部分农用地土壤处于安全生产级别,仅有少部分区域处于Ⅱ级和Ⅲ级风险水平,总体上潜在生态危害较低。     

南海浮游植物对沙尘和灰霾添加的响应

通过2016年5月~6月在南海3个站位开展的船基围隔培养实验,研究了沙尘和灰霾添加对南海浮游植物生长和群落结构变化的影响.结果发现,沙尘和灰霾添加由于提供了N、P等营养盐,整体上促进了浮游植物的生长,且促进程度与添加量密切相关.通过定量计算营养盐指数和叶绿素a累积浓度,发现培养期间叶绿素a累积浓度与沙尘添加浓度呈显著正相关关系（R²=0.87,P<0.01）;低浓度灰霾添加的作用与沙尘添加类似（R²=0.91,P<0.01）,但当灰霾浓度增大时,叶绿素a累积浓度的增加受到一定程度的抑制,这可能与灰霾中含有较高含量的毒性物质有关.各粒级浮游植物叶绿素a浓度的变化表明,沙尘和低浓度灰霾添加使浮游植物优势种群由超微型向小型和微型转变;在高浓度灰霾添加组,由于营养盐与毒性物质的综合作用,浮游植物粒级结构变化不明显.超微型浮游植物细胞丰度测定结果表明,沙尘对聚球藻、原绿球藻和超微型真核浮游植物均表现出促进作用,高浓度灰霾添加能够抑制聚球藻和超微型真核浮游植物的生长.