杭州湾北岸36种挥发性有机物污染特征及来源解析

为研究杭州湾北岸VOCs（挥发性有机物）的浓度水平、组成特征、反应活性和潜在来源,采用GC-FID在线监测系统对杭州湾北岸环境大气中的36种VOCs开展了为期1 a（2017年12月-2018年11月）的连续观测,采用LOH（VOCs的·OH消耗速率）和OFP（O₃生成潜势）2种方法估算了大气VOCs的反应活性,并利用PMF（正定矩阵因子分解）和CPF（条件概率函数）模型分析其来源.结果表明:①φ（VOCs）小时平均值在冬季（26.47×10-9）最高,夏季（9.76×10-9）最低;全年φ（VOCs）小时平均值为21.24×10-9,其中烷烃、烯烃+炔烃、芳香烃、卤代烃的贡献率分别为33.24%、34.13%、15.63%、17.00%;φ（烷烃）、φ（芳香烃）和φ（卤代烃）呈较明显的昼夜变化特征,φ（烯烃）和φ（炔烃）无明显昼夜变化趋势.②大气VOCs的总LOH和OFP分别为9.39 s-1和220.57 μg/m3,KOH（·OH反应速率常数）和MIR（最大增量反应活性）系数的平均值分别为17.34×10-12 cm3/（molecule·s）和3.31;KOH和MIR系数的平均值分别与间/对-二甲苯的KOH和乙苯的MIR系数接近,表明大气VOCs的化学反应活性较强;VOCs关键活性物种为异戊二烯、乙烯、丙烯、甲苯、二甲苯和顺-2-丁烯.③特征物种相关性分析表明,杭州湾北岸大气存在老化现象,异戊烷和正戊烷受煤燃烧源影响较大,二甲苯和乙苯受溶剂排放源影响较大,甲苯和苯除受机动车尾气影响外,还受其他排放源影响.④PMF和CPF模型来源分析表明,大气VOCs主要来自石化工业源、燃料挥发源、生物质燃烧和煤燃烧源、机动车排放源和溶剂使用源,其中,机动车排放源主要来自西北方向,其他源主要来自西北、西和西南方向.研究显示,杭州湾北岸大气VOCs来源复杂,受周边工业区的影响较大.      

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.     

纳米镍/铁和铜/铁双金属对四氯乙烯脱氯研究

以实验室合成的纳米双金属颗粒(Ni/Fe和Cu/Fe)为反应材料,对四氯乙烯(PCE)进行脱氯试验研究.纳米金属颗粒(直径范围在1～100nm)比表面积比微米级铁颗粒高数十倍.结果表明,纳米Ni/Fe和Cu/Fe对四氯乙烯有明显的脱氯作用,且脱氯反应符合准一级反应动力学方程;在作为还原剂的铁表面镀上一薄层起催化作用的金属Ni或Cu,催化剂的存在大大降低脱氯反应活化能,提高了脱氯速率,并减少氯代副产物的产量.与零价铁及微米级双金属系统(Ni/Fe,Cu/Fe)相比,纳米颗粒对PCE的脱氯速率有明显提高,尤其是纳米Ni/Fe,标准化反应速率常数KSA为4.283 mL·m-2·h-1,分别比零价铁和微米级Ni/Fe系统快33.23倍和11.59倍.纳米Cu/Fe标准化反应速率常数KSA为1.194 mL·m-2·h-1,分别比零价铁和微米级Cu/Fe双金属系统快9.26倍和5.24倍.在相同条件下,纳米Ni/Fe脱氯速率常数KSA是纳米Cu/Fe的3.59倍.     

基于白碳黑的水化硅酸钙制备及其磷回收特性简

以白碳黑、硅灰、硅藻土和硅胶筛选硅质原料,并与钙质原料电石渣制备了水化硅酸钙。借助XRF、BET、FTIR等表征手段,通过多次重复除磷实验,研究了硅质原料特性对水化硅酸钙回收磷性能的影响。结果表明,白碳黑具有极高的反应活性,因此可作为制备具有磷回收特性的水化硅酸钙的硅质原料。结合XRD等表征发现,白碳黑的有效利用率是影响水化硅酸钙回收磷性能的关键,该利用率取决于白碳黑与电石渣的摩尔配比以及水热反应温度。当电石渣与白碳黑的摩尔比为1.6：1,反应温度为170℃时,白碳黑具有最佳的利用效率。该条件制备的水化硅酸钙可作为晶种,在其表面结晶形成羟基磷灰石,从而达到磷回收的目的,磷回收后固体物质中的磷含量为19.05%。     

Ra–Po–Pb isotope systematics in waters of Sambhar Salt Lake,Rajasthan (India): geochemical characterization and particulate reactivity

The Sambhar Salt Lake hydrological system, including river waters, groundwaters, evaporating pans and sub-surface brines, has been analyzed for the salt content (TDS) and naturally occurring radionuclides (²¹⁰Po, ²¹⁰Pb and ^226,228Ra). The abundance of these radionuclides and their activity ratios show a wide variation in different hydrological regimes, which helps to geochemically characterize the lake system. A significantly lower Ra to total dissolved solids (TDS) ratio in the brines (by two to three orders of magnitude), when compared to the groundwaters and river waters, suggests removal of dissolved Ra by co-precipitation with Ca–Mg minerals at an early stage of the brine evolution. The concentration of Ra in evaporating lake/pan waters saturates at a value of about 35 Bq L⁻¹ over the salinity range of 100–370 g L⁻¹; attributable to its equilibration with the clay minerals. The two distinct regimes, saline lake system (lake water, evaporating pans and sub-surface brines) and groundwaters have been identified based on their differences in the distribution of ^226,228Ra isotopes. This observation points to the conclusion that the groundwaters and the lake brines are not intimately coupled in terms of their origin and evolution. The abundances of ²¹⁰Po and ²¹⁰Pb along with their activity ratios (²¹⁰Po/²¹⁰Pb) are markedly different among the surface lake waters/evaporating pans, sub-surface lake brines and groundwaters. These differences are explained in terms of different geochemical behaviour of these nuclides in presence of algae and organic matter present in these water regimes.     

三峡水库汞活化效应对鱼汞含量影响的预测

报道了三峡库区长江干流江段鱼体汞元素的含量范围为０．０４￣０．４２ｍｇ／ｋｇ（湿重）,高于长江水系鱼体汞含量水平。分析了三峡库区鱼体汞含量高的原因,指出三峡库区毗邻武陵山高汞背景区,主要受汞矿开发、高汞燃煤及城市废弃物排放的影响。利用水库汞活化指数模型,预测三峡水库蓄水后库区干流及４０条主要支流水域汞的活化效应将增强０．３５￣１．５倍,鱼体汞含量将是现在鱼汞含量的１．４￣２．５倍;并根据不同鱼种汞     

氧氟沙星敏化光解磺胺甲恶唑

抗生素是环境中广泛存在的一类新兴污染物,因其可诱导细菌抗药性及产生抗性基因而备受关注.本研究发现氟喹诺酮类抗生素具有的光化学活性,可能影响共存的磺胺类抗生素（SAs）的转化.系统考察了一种典型的氟喹诺酮类抗生素—氧氟沙星（OFLO）对磺胺甲恶唑（SMX）的光化学转化.结果表明,在365 nm紫外光照条件下,OFLO可以有效敏化光解SMX.激发三重态（³OFLO^*）是促进SMX光解的主要活性物质.密度泛函理论（DFT）计算结合高分辨率质谱（HRMS）分析表明,³OFLO^*将SMX分子中的氨基氮氧化成一个自由基阳离子（R-NH₂^?+）.该自由基阳离子可水解生成羟胺衍生物,并进一步氧化生成亚硝化和硝化产物.此外,它们也可以二聚生成偶氮产物.光反应过程中,敏化剂OFLO也发生了降解.但OFLO的光解产物均保留了核心喹诺酮结构,因此也保留了OFLO分子的光敏活性.该研究有助于进一步了解抗生素复合污染情况下的环境行为,具有重要的环境意义.     

深圳市工业区VOCs污染特征与臭氧生成敏感性

于2020年9~10月在深圳北部典型工业区开展在线观测以分析该地VOCs污染状况,并使用基于观测的模型(OBM)研究臭氧生成敏感性.观测期间VOCs的总浓度为48.5×10^-9,浓度水平上烷烃>含氧有机物(OVOCs)>卤代烃>芳香烃>烯烃>乙炔>乙腈.臭氧生成潜势(OFP)为320μg/m³,其中芳香烃、OVOCs以及烷烃贡献最大,这3类物种OFP贡献总和超过90%.乙烯与苯呈现“两峰一谷”的日变化特征,主要受到机动车排放的贡献.相对增量反应性(RIR)分析表明,削减人为源VOCs对控制当地臭氧生成最为有效,当中又应优先控制芳香烃;经典动力学曲线(EKMA)分析表明该片区臭氧生成处于过渡区,在开展VOCs区域联防联控的同时,需要在当地进行有力的NOx控制以强化该地区臭氧污染长期管控.     

Effect of low-molecular weight organic acids on phosphorus release and phytoavailabilty of phosphorus in phosphate rocks added to soils

Phosphorus (P) is critically needed to improve soil fertility in many parts of the world. The use of water-soluble P fertilizers, e.g., single super-phosphate and triple super-phosphate in developing countries to improve crop production has been limited primarily by their high cost. The presence of indigenous phosphate deposits in some countries provides an incentive for direct application or local chemical treatment at low cost to improve the solubility of low reactive phosphate rocks (PRs). The use of naturally occurring low-molecular weight organic acids (LMWOAs) that are produced in soil as microbial metabolites or plant exudates from dead or living cells represents a new perspective in PR research. The LMWOAs contain various functional groups that may play a significant role in PR dissolution. Little information is available, however, about the potential of LMWOAs in releasing P from PRs. This study reports P release from 12 PRs, four each of low, medium, and high reactivity, obtained from various deposits (Kodjari, Tahoua, North Carolina, Gafsa, Khouribga, Tilemsi Valley, Central Florida, Sechura, Minjingu, North Florida, Hahotoe, and Parc W) using nine LMWOAs containing mono-, di-, and tri-carboxylic groups and a mineral acid (H₂SO₄). Laboratory studies showed that the organic acids are effective in releasing P from low and medium reactive PRs, but very ineffective in releasing P from high reactive PRs. The average amounts of P released by all the organic acids from the three types of PRs were 65.5 mmol kg⁻¹ PR from the low reactive PRs, 55.1 mmol kg⁻¹ from the medium, and 11.1 mmol kg⁻¹ from the high; those released from across all the PRs were 21.9 by the mono-carboxylic acid group, 54.2 by the di-carboxylic acid group, and 57.0 mmol P kg⁻¹ by the tri-carboxylic acid group. The P released was negatively correlated with the equilibrium pH, but positively correlated with Ca released from the PRs. Laboratory incubation studies on the release of P from PRs added to soils with or without organic acids and incubated at 25 °C for 15, 30, and 45 days showed that the percentage of plant-available P released varied considerably from 0.95 in the Kodjari PR to 40.1% in the North Carolina PR and was related to PR reactivity. A greenhouse study with corn (Zea mays L.) grown for 60 days on soils treated with PRs or with PRs mixed with organic acids showed that corn response to addition of oxalic or citric acid varied with P rates and PR sources, suggesting that organic acids have potential as amendments for increasing plant-available P in PR-treated soils.     

Observation and analysis of atmospheric volatile organic compounds in a typical petrochemical area in Yangtze River Delta, China

Volatile organic compounds (VOCs) are a kind of important precursors for ozone photochemical formation. In this study, VOCs were measured from November 5th, 2013 to January 6th, 2014 at the Second Jinshan Industrial Area, Shanghai, China. The results showed that the measured VOCs were dominated by alkanes (41.8%), followed by aromatics (20.1%), alkenes (17.9%), and halo-hydrocarbons (12.5%). The daily trend of the VOC concentration showed a bimodal feature due to the rush-hour traffic in the morning and at nightfall. Based on the VOC concentration, a receptor model of Positive Matrix Factorization (PMF) coupled with the information related to VOC sources was applied to identify the major VOC emissions. The result showed five major VOC sources: solvent use and industrial processes were responsible for about 30% of the ambient VOCs, followed by rubber chemical industrial emissions (23%), refinery and petrochemical industrial emissions (21%), fuel evaporations (13%) and vehicular emissions (13%). The contribution of generalized industrial emissions was about 74% and significantly higher than that made by vehicle exhaust. Using a propylene-equivalent method, alkenes displayed the highest concentration, followed by aromatics and alkanes. Based on a maximum incremental reactivity (MIR) method, the average hourly ozone formation potential (OFP) of VOCs is 220.49?ppbv. The most significant source for ozone chemical formation was identified to be rubber chemical industrial emissions, following one by vehicular emission. The data shown herein may provide useful information to develop effective VOC pollution control strategies in industrialized area.