Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

Removal of 2,4-dichlorophenol by suspended and immobilized Bacillus insolitus

In this experiment, Bacillus insolitus was isolated and selected from a mixed culture that have been acclimated to chlorophenols. Decomposition of chlorophenolic compounds will be studied using this pure culture in both suspended and immobilized form. The results are: at lower initial concentrations of 2,4-dichlorophenol (10-50 mg/l), immobilized Bacillus insolitus shows a higher removal of 2,4-dichlorophenol than Bacillus insolitus in suspended growth. When the 2,4-dichlorophenol concentration becomes higher (50-200 mg/l), both immobilized and suspended Bacillus insolitus have approximately the same efficiency for removal of 2,4-dichlorophenol. Higher concentrations of 2,4-dichlorophenol are inhibitive to the growth of either suspended or immobilized Bacillus insolitus. At lower concentrations of 2,4-dichlorophenol, immobilized mixed culture may have the same removal efficiency of 2,4-dichlorophenol as immobilized pure culture of Bacillus insolitus. But with regard to the overall 2,4-dichlorophenol removal efficiency, immobilized pure culture is considered to be superior to immobilized mixed culture.     

磷酸盐对硫化亚铁(FeS)吸附Sb(Ⅲ)的影响机理研究

还原环境(如湖泊、海洋沉积物)中,FeS是重金属的重要载体。在富营养化过程中,磷酸盐可能对重金属在FeS上的吸附行为产生重要影响。本文通过不同pH、磷酸盐浓度的批次试验,结合X射线衍射仪(XRD)和场发射透射电子电镜-能谱仪(TEM-EDS)固体分析手段,进行磷酸盐对FeS吸附Sb(Ⅲ)的影响研究。结果表明:酸性和中性条件下,磷酸盐会与FeS溶解释放的Fe(Ⅱ)反应生成磷酸亚铁沉淀,促进FeS溶解,同时释放出更多的H₂S(aq)/HS^-与Sb(Ⅲ)结合形成Sb₂S₃沉淀,从而促进溶液中Sb(Ⅲ)的吸附。碱性条件下,FeS对Sb(Ⅲ)只有吸附作用,而磷酸盐会占据FeS表面部分的吸附位点,与Sb(Ⅲ)形成竞争关系,进而抑制溶液中Sb(Ⅲ)的吸附。     

贾鲁河郑州段污染源与水质响应关系的模拟研究

以贾鲁河郑州段为研究对象,建立其污染源与水质响应关系的二维EFDC模型。首先,采用Delft3D针对贾鲁河郑州城区段建立了曲线正交网格,基于2014年上半年污染源流量数据和河流水文数据模拟该段河流流场,利用实测值率定河道糙率,采用2014年下半年数据对河流水动力模型进行验证;其次,在河流水动力模拟的基础上,以COD为主要指标构建水质模型,同样采用2014年上半年数据对模型进行率定,用2014年下半年数据进行模型验证;最后对模型建立结果进行了总结分析。     

低分子量有机酸提取土壤中部分重金属的拟合模型研究

为研究不同浓度低分子量有机酸与提取的土壤重金属含量之间的关系,本文以采自安徽省安庆市某铜矿区及其周围的土壤为例,通过浸提法,研究了不同浓度苹果酸、甲酸对采样点土壤中重金属Cu、Mn、Zn、Pb提取能力的影响并进行模型拟合.结果表明:不同浓度苹果酸和甲酸对采样点土壤中重金属的提取量不同,两种有机酸对低pH、高重金属含量采样点及其周围土壤中的重金属提取量较大,两种低分子量有机酸对S6采样点的重金属Mn的提取量最大,分别为322.5 mg·kg~(-1)和193.58 mg·kg~(-1),提取率达70.02%和42.03%,Zn、Pb次之,Cu最低;随着苹果酸、甲酸浓度的升高,土壤中重金属Cu、Mn、Zn、Pb的提取量增加,苹果酸对土壤中重金属的提取能力大于甲酸;拟合模型对于两种低分子量有机酸与其提取的土壤中部分重金属含量之间的关系,具有较好的拟合性,其决定系数R~2在0.8293～0.9990之间,都具有显著性(p0.05),该模型可以定量表征低分子量有机酸对土壤重金属的提取能力,此研究结果为土壤中重金属的固定化和增强植物修复受重金属污染的土壤提供了理论支持.     

闽江河口养殖塘水体溶存氧化亚氮浓度及扩散通量研究

水产养殖生态系统由于其高氮负荷而成为氧化亚氮(N_2O)的潜在释放源.本文以福建闽江河口养虾塘为研究对象,采用静态顶空-气相色谱法测定分析了表层水体溶存N_2O浓度和饱和度,基于薄边界层模型计算了水-气界面N_2O扩散通量,在此基础上结合气象要素与水环境因子分析其主要影响因素.结果表明,养殖塘水体溶存N_2O浓度和饱和度的均值分别为17.96 nmol·L~(-1)和198.03%,时间变化上表现为养殖中期显著高于养殖末期和初期,且具有一定的日变化特征.相关分析表明,N_2O浓度及饱和度与温度、水体NH~+_4-N和叶绿素a浓度呈显著正相关(p0.05),与气压、风速和水体pH值呈显著负相关(p0.05).LM86、W92和RC01模型估算的养殖塘水-气界面N_2O扩散通量的均值分别为20.80、183.75和298.52 nmol·m~(-2)·h~(-1),3种扩散通量均呈现出随着养殖时间推移显著增加的特征,风速和水体溶存N_2O是影响河口养殖塘N_2O扩散通量的重要因子.N_2O扩散通量与扩散系数的取值密切相关,但不同模型方程计算得出的扩散系数存在显著差异,比较发现,RC01模型更适合河口区养殖塘水-气界面N_2O扩散通量估算.本研究结果可为完善水产养殖生态系统的N_2O排放清单编制和近海水环境保护提供一定的科学依据.     

2022年北京市城区PM2.5水溶性离子含量及其变化特征

为探究北京市大气细颗粒物（PM_2.5）水溶性离子含量及其变化特征,有针对性地提出污染防治方案,对2022年全年PM_2.5水溶性离子、气态前体物（SO₂、NO₂）和气象因素（温度、RH）进行分析测定.结果表明,北京市城区PM_2.5中占比最高的水溶性离子为NO₃^-、NH₄⁺和SO₄^2-,占PM_2.5的52.7%,ρ（PM_2.5）（33.2 μg·m^-3）和ρ（SNA）（18.9 μg·m^-3）低于历史研究结果,但SNA占比（52.7%）、SOR（0.45）和NOR（0.15）高于历史研究结果,体现出北京市细颗粒物污染得到明显改善,但仍具有较强的二次污染特征.NO₃^-/SO₄^2-为2.2,高于历史及附近省市研究结果,反映出移动源的影响不断扩大.从季节变化上看,PM_2.5呈现秋高夏低的变化特征,秋、春、冬这3个季节NO₃^-的占比最高,夏季SO₄^2-占比最高,而NH₄⁺在各季节占比变化不大.NOR与SOR的季节变化规律几乎相反,反映出二者的转化形成因素存在差异.北京城区SNA的主要存在形式为NH₄NO₃和（NH₄）₂SO₄,其中冬季阴阳离子中和度最高,夏季阳离子NH₄⁺稍显不足,而春秋两季NH₄⁺处于过量状态,北京城区为富氨环境.从污染级别看,水溶性离子质量浓度均随污染加重有不同程度的增长,增长最快的是SNA,其在PM_2.5中占比出现先上升后稳定的变化特征.从空间分布特征来看,中心城区和东南西北部郊区的SNA质量浓度大小均为：NO₃^->SO₄^2->NH₄⁺,体现了以NO₃^-为主导的污染特征;SNA对PM_2.5的贡献率最高的区域发生在东部、中心城区和传输点,表明在中心城区和东部地区二次反应相对活跃,同时区域传输也是二次离子的重要来源.     

不同土地利用方式对城市土壤活性有机碳的影响——以开封市为例

以开封市为例,采集不同土地利用方式下城市表层土壤并测定其有机碳含量,进而探讨土地利用方式对城市土壤活性有机碳特性的影响。结果表明:土地利用方式对城市土壤活性有机碳的影响差异显著,其中易氧化态和水溶性有机碳含量依次为近郊蔬菜地>城区>近郊非农业区>远郊,微生物量有机碳含量则为近郊蔬菜地>近郊非农业区>城区>远郊,这与不同土地利用方式下土壤有机碳总量的变化情况不一样;土壤活性有机碳占总有机碳的比率也随土地利用方式的不同而变化,但其变化与土壤活性有机碳的变化情况不一致;土壤易氧化态、水溶性和微生物量有机碳之间有较强的相关性,其变化趋势在同一土地利用方式下近于一致。     

Enhancement of nitric oxide decomposition efficiency achieved with lanthanum-based perovskite-type catalyst

Direct decompositions of nitric oxide (NO) by La_0.7Ce_0.3SrNiO₄, La_0.4Ba_0.4Ce_0.2SrNiO₄, and Pr_0.4Ba_0.4Ce_0.2SrNiO₄ are experimentally investigated, and the catalysts are tested with different operating parameters to evaluate their activities. Experimental results indicate that the physical and chemical properties of La_0.7Ce_0.3SrNiO₄ are significantly improved by doping with Ba and partial substitution with Pr. NO decomposition efficiencies achieved with La_0.4Ba_0.4Ce_0.2SrNiO₄ and Pr_0.4Ba_0.4Ce_0.2SrNiO₄ are 32% and 68%, respectively, at 400 °C with He as carrier gas. As the temperature is increased to 600 °C, NO decomposition efficiencies achieved with La_0.4Ba_0.4Ce_0.2SrNiO₄ and Pr_0.4Ba_0.4Ce_0.2SrNiO₄, respectively, reach 100% with the inlet NO concentration of 1000 ppm while the space velocity is fixed at 8000 hr^?1. Effects of O₂, H₂O_(g), and CO₂ contents and space velocity on NO decomposition are also explored. The results indicate that NO decomposition efficiencies achieved with La_0.4Ba_0.4Ce_0.2SrNiO₄ and Pr_0.4Ba_0.4Ce_0.2SrNiO₄, respectively, are slightly reduced as space velocity is increased from 8000 to 20,000 hr^?1 at 500 °C. In addition, the activities of both catalysts (La_0.4Ba_0.4Ce_0.2SrNiO₄ and Pr_0.4Ba_0.4Ce_0.2SrNiO₄) for NO decomposition are slightly reduced in the presence of 5% O₂, 5% CO₂, or 5% H₂O_(g). For durability test, with the space velocity of 8000 hr^?1 and operating temperature of 600 °C, high N₂ yield is maintained throughout the durability test of 60 hr, revealing the long-term stability of Pr_0.4Ba_0.4Ce_0.2SrNiO₄ for NO decomposition. Overall, Pr_0.4Ba_0.4Ce_0.2SrNiO₄ shows good catalytic activity for NO decomposition.

Implications: Nitrous oxide (NO) not only causes adverse environmental effects such as acid rain, photochemical smog, and deterioration of visibility and water quality, but also harms human lungs and respiratory system. Pervoskite-type catalysts, including La_0.7Ce_0.3SrNiO₄, La_0.4Ba_0.4Ce_0.2SrNiO₄, and Pr_0.4Ba_0.4Ce_0.2SrNiO₄, are applied for direct NO decomposition. The results show that NO decomposition can be enhanced as La_0.7Ce_0.3SrNiO₄ is substituted with Ba and/or Pr. At 600 °C, NO decomposition efficiencies achieved with La_0.4Ba_0.4Ce_0.2SrNiO₄ and Pr_0.4Ba_0.4Ce_0.2SrNiO₄ reach 100%, demonstrating high activity and good potential for direct NO decomposition. Effects of O₂, H₂O_(g), and CO₂ contents on catalytic activities are also evaluated and discussed.     

电絮凝对电厂循环冷却水中硬度的去除

以某电厂冷却塔循环冷却水为处理对象,利用电絮凝法,以铝板为牺牲阳极去除水中的Ca~(2+)和Mg~(2+),分别考察了电絮凝过程中不同电流密度、电解时间、溶液初始pH、阳极极板数量对总硬度去除率的影响。结果表明:增加电流密度、延长电解时间有利于Ca~(2+)和Mg~(2+)的去除;当电流密度为10 mA·cm~(-2),电解时间为90 min时,Ca~(2+)和Mg~(2+)去除率分别达到93.5%和95.8%,总硬度去除率为94.6%;相对于酸性和中性条件,碱性条件更有利于Ca~(2+)和Mg~(2+)的去除,当初始pH为10时,Ca~(2+)和Mg~(2+)去除率分别达到85.4%和97.7%,总硬度去除率为93.5%;随极板数量的增加,Ca~(2+)和总硬度去除率均有所提高;投加Na_2CO_3有利于Ca~(2+)和总硬度的去除。上述结果可为进一步提高电絮凝过程中总硬度的去除率提供参考。