基于拉曼光谱的铅致肝细胞生物分子变化研究

利用拉曼光谱技术采集不同铅离子暴露时间(0.5,1.5,3,6,12,24h)、暴露浓度(0.05,0.1,0.5,1,5mg/L)下HepG2细胞的光谱数据,欲探究在不同铅暴露条件下肝细胞的分子变化及其相关机制.研究结果发现,在不同条件下各组细胞的光谱形态基本相同,但部分特征峰的吸光度强度存在差异.经多元统计分析发现,除6h外,同一暴露时间下不同暴露浓度细胞的光谱数据在LD1上均存在离散趋势,并在暴露24h时最明显.细胞内蛋白质、脂质、核酸、类胡萝卜素、碳水化合物等生物分子的特征峰表现出明显差异,但不同类型生物分子发生显著变化的时间并不相同.由此可见铅暴露可损伤肝细胞蛋白质、脂质、核酸、类胡萝卜素的结构并影响其正常功能,这种毒性效应呈剂量-效应关系,且随暴露时间的增加而增加.本研究说明拉曼光谱可以实现铅对肝细胞生物分子变化的相关检测,这不仅为之后的细胞毒理研究提供了新的思路,同时也为环境污染物的安全评价提供了理论依据.     

Management of used lead acid battery in China: Secondary lead industry progress,policies and problems

The amount of used lead acid batteries rises along with the rapid development of battery manufacture in China. The battery manufacture and recycling industry has developed sharply in these recent 5 years. The annual production of secondary lead from used lead acid batteries in China increased rapidly to 1.5 million tonnes (MT) in 2013, making china the world's largest secondary lead producer. Secondary lead enterprises are mainly located in the middle and eastern regions of China, with a legal production capacity of 3 MT/year. Environmental pollution problems began to happen frequently from 2009. After 2011, the government began to put in efforts to promote pollution control, eliminate outdated production capacity, support advanced production and technology innovation research, and has achieved remarkable results. However, the main existing problems are that the proportion of secondary lead production is only 30% of the total lead production, no formal recycling network has been established and the overall level of industrial technology and equipment is outdated. Compared with developed countries, this paper predicts that, secondary proportion will reach 44% in 2015 and 60% in 2028. Finally some countermeasures are given to the recycling mode and technology promotion.     

江苏省铅蓄电池行业环保现状及对策

近年来铅蓄电池行业血铅污染事件引发了社会各界群众的高度关注,国家和地方也陆续颁布和实施了一系列控制重金属污染的法规政策,将铅蓄电池行业推向了改革的风口浪尖。经过几年的初步改革,虽然相关企业的环保行为有所提升,但与国家和地方的要求仍存在不小差距。以江苏省现有规模以上铅蓄电池生产企业为研究对象,深入剖析各企业在环境保护方面存在的突出问题,有针对性的提出环保发展对策,为全省乃至全国铅蓄电池行业的综合整治和产业升级指明方向,具有重要的现实意义。     

EDTA reduces lead accumulation in Symphytum officinale L. (comfrey) roots

The addition of EDTA in phytoextraction studies has been reported to increase heavy metal accumulation in above-ground parts or to have no negative impact on the overall (root/shoot) accumulation levels in terrestrial plants. At a purely quantitative level, this study assessed the phytoextraction potential of a previously untested high-biomass terrestrial plant, Symphytum officinale L. (comfrey), in the presence of Pb and EDTA. In this hydroponic-based study, we report a small increase in shoot accumulation of Pb with EDTA but, conversely, the presence of EDTA in the nutrient medium markedly reduced the overall quantity of Pb in the plant root by at least 80%. The loss does not appear to be explained by EDTA acting alone, increased transport of Pb to the shoots, or anionic charge repulsion of the [PbEDTA]^2? complex. The elusive action and negative effect of EDTA on Pb accumulation in S. officinale provides additional reasons towards a growing trend away from the use of EDTA as a chelating agent in phytoextraction.     

Pb2+对城市污水处理厂污泥中苏云金芽孢杆菌发酵的影响

以城市污水处理厂污泥为培养基,研究了添加Pb2+对Bt(Bacillus thuringiensis,苏云金芽孢杆菌)生长和晶体蛋白合成的影响,同时分析了Bt发酵过程中有效态Pb含量(以ρ计)的变化,并采用FTIR(傅立叶红外光谱)和XPS(X射线光电子能谱),初步探讨了Pb2+在Bt表面的作用机制.结果表明:污泥培养基在支持Bt生长代谢和降低重金属有效态含量方面均优于商用培养基,当初始ρ(Pb2+)高达400 mg/L时,与未添加Pb2+相比,污泥培养基中Bt活菌数与晶体蛋白产量约分别下降48%和54%,而商用培养基中约分别下降82%和75%,证实了污泥作为Bt发酵培养基的可行性;Bt对Pb2+有较好的耐受性,当ρ(有效态Pb)在80 mg/L以下时,Bt生长代谢不会受到显著影响.光谱学分析表明,Bt对Pb2+有少量吸附,从而降低Bt发酵过程中Pb的生物有效性,吸附位点主要为羟基,部分C O和S O也参与了吸附反应.     

La-PTFE共掺杂二氧化铅电极的制备及其性能研究

以Ti为基体,掺杂La2O3和聚四氟乙烯(PTFE),通过电沉积法制备了Ti/SnO2+Sb2O3/PTFE+La2O3+β-PbO2电极,并将所制备的电极应用于亚甲基蓝模拟染料废水的降解.结果发现,与常规的Ti/SnO2+Sb2O3/PTFE+β-PbO2电极相比,Ti/SnO2+Sb2O3/PTFE+La2O3+β-PbO2电极对亚甲基蓝及COD有较好的去除效果.含有La2O3活性层的Ti/SnO2+Sb2O3/PTFE+La2O3+β-PbO2电极在电解质浓度为0.15mol.L-1,电极极距为6.0cm的酸性条件下降解亚甲基蓝的效果最佳.降解3.0h后,对100mg.L-1亚甲基蓝的去除率可达到97.92%,对COD去除率为93.39%.SEM结果显示,Ti/SnO2+Sb2O3/PTFE+La2O3+β-PbO2电极表面颗粒鲜明,比表面积增大,改善了电极的微观结构和催化效果.电化学测试表明,La2O3的掺杂显著提高了二氧化铅电极的析氧过电位,显示出较好的应用前景.     

低剂量长期铅暴露对雄性黑斑蛙精巢组织关键酶活性的影响

在实验条件下,将健康的性成熟雄性黑斑蛙暴露于0.1、0.2、0.4、0.8和1.6mg·L-1的Pb2+溶液中30d,以Ca2+-ATP酶、Na+-K+-ATP酶、Ca2+-Mg2+-ATP酶、β-葡萄糖醛酸苷酶(β-DG)、乳酸脱氢酶(LDH)和酸性磷酸酶(ACP)活性为指标,进行了长期铅暴露对雄性黑斑蛙生殖毒性的研究.结果表明:随着铅染毒剂量的增加,Ca2+-ATP酶和Na+-K+-ATP酶活性被诱导,Ca2+-Mg2+-ATP酶活性被抑制,当Ca2+-Mg2+-ATP酶的抑制程度超过Ca2+-ATP酶和Na+-K+-ATP酶的代偿机制时,会抑制精子的发生,进而导致雄性生殖毒性;在1.6mg·L-1Pb2+处理下,ACP酶被显著抑制,提示支持细胞受损,精子总数受到影响;在0.4mg·L-1Pb2+处理下,LDH酶被显著抑制,提示生精细胞受损,精子质量受到影响.     

2015年调水调沙期间黄河悬浮颗粒Pb及其稳定同位素组成变化

通过对2015年黄河调水调沙期间利津水文站悬浮泥沙以及小浪底水库表层沉积物的分析,研究了调水调沙期间黄河入海泥沙中Pb元素的含量及同位素组成的变化特征,探讨了其物质来源及对调水调沙进程的响应.结果表明,调水调沙期间黄河入海泥沙Pb元素含量为18.09~28.35μg/g,平均为21.64μg/g,稳定同位素²⁰⁷Pb/²⁰⁶Pb为0.8367~0.8481,²⁰⁸Pb/²⁰⁶Pb为2.0839~2.0997,与黄土等物质较为接近.Pb含量及稳定同位素组成在调水调沙前、后期均较高,而在调水调沙中间主要时段则较低.利津站悬浮泥沙及小浪底水库沉积物中Pb同位素组成均符合黄河源Pb演化规律,但小浪底水库沉积物Pb元素含量较高,部分站位受到了人类活动的影响.调水调沙进程对该期间黄河入海泥沙Pb的变化及来源有着显著影响,在调水调沙前期和后期,水沙通量小,洪水对下游河床冲刷作用弱,Pb受到中上游沉积物来源影响,导致含量和同位素组成较高.在调水调沙中间的主要时段,利津悬浮泥沙与小浪底水库沉积物显著不同,Pb主要来自洪水对下游河床的冲刷,以自然来源为主,未受到人类活动影响.     

基于大田试验的铅镉复合污染土壤中甜糯玉米低积累特性

为筛选适合在铅（Pb）、镉（Cd）复合污染土壤种植的低积累特性甜糯玉米品种,选取39个玉米品种,通过大田试验,研究其籽粒和秸秆对Pb和Cd的富集特性和差异.将玉米产量、富集系数和基于土壤Pb和Cd风险阈值的方法作为筛选低积累玉米品种的评价指标.结果表明,不同品种玉米的产量、籽粒和秸秆的Pb和Cd含量之间存在显著差异（P<0.05）.籽粒对Pb和Cd的富集系数分别为0.00003~0.00230和0.01~0.15,秸秆对Pb和Cd的富集系数分别为0.003~0.065和0.64~4.28.通过对不同玉米富集系数的聚类分析,综合不同品种玉米的土壤Pb和Cd风险阈值得出,惠甜5号、新美甜818和玉糯9号可在Pb和Cd含量超风险管制值的耕地安全生产,天贵糯937和金萬糯2000可在Cd含量超风险筛选值的耕地安全生产.惠甜5号、新美甜818和玉糯9号作为Pb和Cd复合低积累品种,适宜在广西铅镉复合污染土壤上推广种植,天贵糯937和金萬糯2000作为籽粒低积累、秸秆Cd高积累品种,建议将其作为植物修复资源加以利用.     

Human teeth as historical biomonitors of environmental and dietary lead: some lessons from isotopic studies of 19th and 20th century archival material

The lead isotopic composition of various sections (crown, crown base, root) of teeth was determined in specimens collected from 19th century skulls preserved in museum collections and, upon extraction or exfoliation, from humans of known ages residing in Scotland in the 1990s. For most 20th century samples, calculation of accurate crown-complete or root-complete dates of tooth formation ranging from the 1920s to the 1990s enabled comparison of ²⁰⁶Pb/²⁰⁷Pb ratios for teeth sections (crown base root) with corresponding decadally averaged data for archival herbarium Sphagnum moss samples. This showed that the teeth sections had been significantly influenced by incorporation of non-contemporaneous (more recent) lead subsequent to the time of tooth formation, most probably via continuous uptake by dentine. This finding confirmed that separation of enamel from dentine is necessary for the potential of teeth sections as historical biomonitors of environmental (and dietary) lead exposure at the time of tooth formation to be realised. Nevertheless, the mean 19th century value of 1.172±0.007 for the ²⁰⁶Pb/²⁰⁷Pb ratio in teeth was very similar to the corresponding mean value of 1.173±0.004 for 19th century archival moss, although relative contributions from environmental sources – whether direct, by inhalation/ingestion of dust contaminated by local lead smelting (²⁰⁶Pb/²⁰⁷Pb~1.17) and coal combustion (²⁰⁶Pb/²⁰⁷Pb~1.18) emissions, or indirect, through ingestion of similarly contaminated food – and drinking/cooking water contaminated by lead pipes of local origin, cannot readily be determined. In the 20th century, however, the much lower values of the ²⁰⁶Pb/²⁰⁷Pb ratio (range 1.100–1.166, mean 1.126±0.013, median 1.124) for the teeth collected from various age groups in the 1990s reflect the significant influence of imported Australian lead of lower ²⁰⁶Pb/²⁰⁷Pb ratio (~1.04) and released to the environment most notably through car-exhaust emissions arising from the use of alkyl lead additives (²⁰⁶Pb/²⁰⁷Pb~1.06–1.09) in petrol in the U.K. from ca. 1930 until the end of the 20th century.