Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

气象因素对泉州臭氧的影响

利用泉州城区2017年全年连续观测的O_3和气象要素资料,统计了臭氧浓度的分布特征,分析了气象要素对O_3质量浓度的影响,对比了O_3超标日和非超标日的气象要素特征。结果表明:(1)泉州市O_3质量浓度月变化呈双峰形,春季最高,夏季最低;日变化呈单峰形,最大值出现在13:00—14:00,最小值出现在06:00—07:00,上下游站O_3浓度存在明显传输效应。(2)泉州O_3质量浓度与相对湿度呈负相关,其相关性最高;与风速呈正相关,其相关系数最低,且存在明显区位性差异;与气温的相关性比较复杂,既有正相关,也有负相关。(3)各站点O_3小时质量浓度超标时,均对应2个气象要素区间值。(4)对比污染日非污染日发现,污染日相对湿度较低(50%～60%),非污染日较高(70%～80%);污染日温度略低于非污染日;污染日风向总体为西南偏南,非污染日风向为西南-东南。     

Dibutyl phthalate adsorption characteristics using three common substrates in aqueous solutions

• DBP adsorption was tested using three kinds of substrates in constructed wetlands. • The DBP adsorption capacity followed the order: steel slag>gravel>shell sand. • High temperatures increased the DBP adsorption capacity in the substrates. • DOM consistently inhibited the DBP adsorption onto steel slag and gravel. In recent years, the presence and adverse impacts of phthalic acid esters in aquatic environments have gained increasing attention. This work investigated the adsorption behavior of a typical phthalic acid ester, dibutyl phthalate (DBP), onto steel slag, gravel, and shell sand (substrates commonly used in constructed wetlands). The influence of dissolved organic matter (DOM) on DBP adsorption was investigated using humic acid as a proxy for DOM. The results demonstrated that the adsorption of DBP to three substrates reached equilibrium within 96 h, and the adsorption kinetics were well fitted by a pseudo-second-order model. The DBP adsorption isotherms were best fitted by the Langmuir adsorption model. The DBP adsorption capacity decreased in the order of steel slag>gravel>shell sand, with values of 656 mg/kg, 598 mg/kg, and 6.62 mg/kg at 25°C, respectively. DBP adsorbed to the surface of all substrates in a monolayer via an endothermic process. The DBP adsorption capacities of steel slag and gravel decreased as the DOM content increased. The DBP adsorption mechanisms to steel slag and gravel mainly involved the surface coordination of DBP with –OH or –COOH groups and electrostatic interactions. The results of this work suggest that steel slag and gravel may be ideal substrates for use in constructed wetlands to treat wastewater polluted with DBP.     

铵盐气溶胶对烟气排放连续监测系统颗粒物比对监测的影响研究

利用拉曼光谱对采样后的滤筒进行分析,发现废气中的硫酸铵-硫酸氢铵气溶胶是造成成都市部分企业烟气排放连续监测系统(CEMS)颗粒物比对监测结果不合格的主要原因。通过比较分析得出:在对含硫酸铵-硫酸氢铵气溶胶废气进行颗粒物浓度比对监测时,参比方法(重量法)测定的颗粒物浓度是一定标干采样体积下废气中固体微粒和硫酸铵-硫酸氢铵液体微粒结晶后产生的晶体的总质量,基于光散射法的CEMS颗粒物浓度测试系统测定的颗粒物浓度只是一定标干采样体积下废气中固体微粒的质量,由此导致参比方法测出的颗粒物浓度远大于CEMS测出的浓度,造成比对误差远超出允许值范围。     

环境剂量磷酸三(1,3-二氯异丙基)酯多代暴露对斑马鱼子代仔鱼的神经发育毒性

为探究环境剂量磷酸三(1,3-二氯异丙基)酯(TDCIPP)多代暴露对生物体的影响,选取斑马鱼为模型,研究了斑马鱼暴露于0、3、30和300 ng·L~(-1)TDCIPP至3代后,对每一代子代5 dpf仔鱼神经发育的毒性效应。研究结果表明,F0代暴露于300ng·L~(-1)TDCIPP 120 d后所产F1代仔鱼的孵化率显著性下降,存活率显著性降低;但对F2代和F3代仔鱼的这些终点指标均无显著性影响。运动行为结果表明,F0代暴露于3和300 ng·L~(-1)TDCIPP 120 d会导致F1代仔鱼在光暗周期刺激下的游泳速度受到抑制,并伴随着神经元发育基因(ngn1)以及轴突生长标志基因(α1-tubulin、netrin1b和zn5)的显著性上调,相关性分析表明,游泳速度的抑制与ngn1、α1-tubulin和zn5这3个基因的表达显著相关。但对F2代仔鱼,仅300 ng·L~(-1)TDCIPP导致其游泳速度在黑暗刺激下显著性下降,且导致神经发育和再生相关基因(elavl3、gap43、gfap和shha)表达量显著性下降,但游泳速度的下降与基因表达无显著相关性。继续暴露至F3代仔鱼时,TDCIPP暴露对运动行为不再有显著影响。研究表明,环境剂量TDCIPP多代暴露对子代仔鱼具有神经发育毒性,表现为运动行为受损和神经发育相关基因表达量的改变,但毒性效应随着暴露代数的增加而减弱。     

2008—2018年黄山市酸雨污染特征变化趋势分析

采用2008—2018年黄山市酸雨监测数据,阐述了黄山市酸雨变化特征及成因。结果表明:黄山市降水pH在5.0左右徘徊；酸雨频率在2017年以前均处于高位,以2017年为拐点,下降到最低值(35.7%)。总体上,黄山市酸雨污染情况正在得到改善,但形势依然严峻。SO2-₄和NO-₃的当量浓度之比从2013年的4.09下降到2018年的1.10；SO₂和NO_x排放量逐年减少,但是幅度不同,NO_x排放量下降幅度不大,致使NO_x对酸雨的贡献有增加的趋势；酸雨类型由硫酸型转变为硫酸型和硝酸型并重,机动车排放对酸雨污染的贡献已不可忽视。对黄山市降水中的碱性离子中和能力进行分析发现,黄山市起主要中和作用的离子为NH⁺₄和Ca²⁺。将黄山市降水与其他地区降水进行对比发现,黄山市降水受到的中和作用强于东南地区,但弱于北方地区。     

在役悬索管道抗风性能研究及结构退化分析*

为提高在役成品油悬索跨越管道结构及性能的可靠性，保障长输油气管道生产运营的安全，建立某在役成品油悬索跨越管道的有限元力学仿真模型，研究风载荷对悬索跨越管道的影响作用，探讨主索、吊索等主要构件性能退化时对悬索管道安全性的影响规律。结果表明:通过有限元模拟可以得到管道失效风速为60 m/s，远大于极限风速，且涡激振动振幅很小；主索腐蚀、吊索断裂以及是否存在抗风索这3种情况均能影响结构的安全性。相关企业应当对结构的重要构件进行定期检修，以保障生产运营安全。     

Soils impacted by PAHs: Would the stabilized organic matter be a green tool for the immobilization of these noxious compounds?

The objective of this study was to investigate the role of stabilized organic matter (vermicompost) and tropical soils in the sorption of naphthalene, anthracene and benzo[a]pyrene. The results obtained for the three compounds were extrapolated for the priority polycyclic aromatic hydrocarbons (PAHs) pollutants according to Environmental Protection Agency (US EPA). To evaluate the sorption process, high performance liquid chromatography was employed and the data was fitted by Freundlich isotherms. The results suggest that the sorption effect generally increases with the number of benzene rings of the PAHs, and that the persistence of PAHs in the environment is possibly related to the number of benzene rings in the PAH molecule. In addition, the pH of the vermicompost can strongly affect the adsorption process in this matrix.     

Influence of thermal environment on metallographic structure characteristics of the electric arc bead pattern

Electrical apparatuses are prone to arc, which generally causes a fire, even an explosion hazard, when a flammable gas mixture is present, especially during industrial processes. Terrible fire scenes are challenging for fire investigations. In this work, by performing a simultaneous thermal analysis test we simulated a fire environment and found that as the oxygen concentration decreased, the oxidation/exothermic peak temperature of ‘cause’ bead became higher, but the melting temperature was unaffected. Results indicated that the bead pattern underwent oxidation at approximately 831 °C, melting initiated at approximately 1060 °C, and the pattern then disappeared. The melted pattern grain changes were divided into three critical temperature stages: Approximately 600 °C, the onset temperature at which the melted pattern grains began to be equiaxed; approximately 831 °C, at which the grains were interspersed with oxygen-containing material; and 831–1060 °C, when the grains disappeared, which is a criterion for identifying electrical fires. However, the boundaries remained throughout the thermal environment process. Moreover, the bead pattern demonstrated three metallographic regions: Deep layer (Region I), the intermediate layer (Region Ⅱ), and surface layer (Region Ⅲ). Region I was the most thermally sensitive, in which equiaxed crystals first appeared. Region Ⅲ was the thermal reaction lag zone, in which the typical branching crystals finally disappeared, and Region Ⅱ was intermediate between Regions I and Ⅲ. The results may help fire investigators determine the fire scene temperature stages and provide support for fire evidence extraction.     

速生杨木粉尘最小点火能的实验研究

为防止木材加工中木质粉尘燃爆事故的发生，以纤维板生产中常见的原材料速生杨木粉尘作为研究对象，在分析粉尘粒径分布、元素分析、工业分析及形貌特征的基础上，采用1.2 L哈特曼管对3种不同粒径（0~50，＞50~96，＞96~180 μm）速生杨木粉尘进行最小点火能实验，探究点火延迟时间、喷粉压力、质量浓度和粒径分布对速生杨木粉尘最小点火能的影响及变化规律。研究结果表明:在质量浓度为500 g/m3时，分别增加点火延迟时间和喷粉压力，最小点火能都先减小后增大；最佳点火延迟时间和最佳喷粉压力分别为120 ms和120 kPa；粒径对最佳点火延迟时间和最佳喷粉压力无显著影响。在点火延迟和喷粉压力分别为120 ms和120 kPa条件下，最小点火能随质量浓度的增加先减小后增大。粉尘粒径与最小点火能呈正相关性，3种样品的最小点火能分别为1~3，1~3和7~13 mJ，对应的敏感质量浓度分别为500 ，750和1 250 g/m3，属于特别着火敏感性粉尘。