环境中溴系阻燃剂六溴环十二烷的水平及分析进展

六溴环十二烷(HBCDs)是一种添加型溴系阻燃剂,被广泛应用于建筑隔热材料、纺织用品及少量电子产品中。2006年欧盟、国际公约等组织相继停止生产和使用多溴联苯醚后,HBCDs也曾在某些用途中作为替代品使用。在各环境介质中,空气和水体是HBCDs的主要释放空间。点源附近的环境介质中通常能够检测出较高浓度的HBCDs,远高于没有明显点源的地区。工业合成的HBCDs以γ-HBCD异构体为主,大多数生物体内的HBCDs以α-HBCD所占比例最大,可能与化合物结构、环境条件及生物代谢过程等均有关。气相色谱-质谱分析技术对HBCDs有较高的检测灵敏度,但由于HBCDs存在热重排、热降解等现象,使得化合物的异构体分析受限。液相色谱-质谱分析技术弥补了上述缺陷,不但可以区分HBCDs化合物的对映与非对映异构体结构,还可以借助串联质谱(MS/MS)联用技术降低化合物的检出限。文章综述了环境中HBCDs的水平及分析进展,认为在HBCDs的立体结构以及各异构体之间的转化过程和转化条件等方面有很大的探索空间,指出在环境背景区开展HBCDs的环境行为、演变趋势、控制措施及替代技术研究,是今后应该深入研究的领域。     

持久性卤代有机污染物(PHCs)在食物网中的生物放大研究进展

持久性卤代有机污染物(PHCs)具有持久性、生物富集性和毒性,是对生态环境和人类健康有严重威胁的污染物。PHCs浓度会沿食物链在生物中逐营养级放大,对高等生物及人体产生毒性。本文综述了PHCs在食物网中生物放大的特征,总结了国内外对食物网中PHCs的营养级放大因子研究进展,探讨了生态和化学因素对PHCs沿食物链传递过程的影响。目前的研究多集中于水生生态系统中传统PHCs的生物放大,对PHCs的生物差异性代谢缺乏足够的了解,难以说明不同生态系统中复杂的气候、地理、生物种群特征对PHCs生物放大的影响,也给准确评估PHCs的生态风险带来了困难。PHCs的生物放大研究需要引入更多先进地球化学手段和准确构建不同生态系统的野生食物网,阐明PHCs的生物放大机制和影响因素。     

2010—2018年北京市人体中六溴环十二烷的残留特征与风险评估

六溴环十二烷(HBCDs)作为一种持久性有机污染物,具有生物累积性及多种生物毒性,以母乳、血清、头发及脂肪组织为介质,评价人体HBCDs的残留特征和健康风险受到广泛关注。本文以北京地区为研究区域,连续采集和分析2010—2018年母乳样品中的HBCDs,探究北京人体中HBCDs的残留特征与变化趋势,同时评估婴幼儿通过母乳喂养摄入HBCDs是否存在健康风险。研究共招募85名志愿者采集233份母乳样品,采用液液萃取-多级净化法进行样品处理,高效液相色谱-串联质谱法(LC-MS/MS)测定样品中HBCDs及其异构体含量。样品的测定结果显示：(1) HBCDs的检出率为100%,浓度范围为0.46～93.5ng/g lw(脂重),均值和中值分别为7.27ng/g lw和5.77ng/g lw,高端暴露量第95百分位值为15.6ng/g lw;(2)α-HBCD为主要异构体,3种非对映异构体的含量占比大小为：α-HBCD>γ-HBCD>β-HBCD;(3)婴幼儿HBCDs的每日估计摄入量EDI中值为20.5ng/kg bw/day,第95百分位值为71.4ng/kg bw/day,高...     

莱州湾河流表层沉积物中六溴环十二烷的含量水平、分布及组成特征

从莱州湾附近河流采集了36个表层沉积物样品,采用高效液相色谱耦合三重四极杆串联质谱的分析方法对沉积物中的六溴环十二烷（HBCDsl3种异构体进行了测定,目的是表征研究区域内HBCDs的污染水平和组成特征,并探讨其分布、来源及影响因素。结果表明,莱州湾河流沉积物中ZHBCDs的含量范围为0．03～20．17ng／gdw（均值是2．14ng／gdw）：较国内外其他河流,该研究区域HBCDs含量水平较低。HBCDs异构体组成各不相同,除1个站位外,其他站位样品中7-HBCD占主导地位（52．3％～97．3％,均值72．4％）,但是在农业区a-HBCD相对丰度较高。对HBCDs的分布特征及来源分析得出,含量较高的站点多集中在工业区,呈现出明显的点源特征：而远离工业区的采样点,HBCDs可能主要来自大气的传输和沉降,且HBCDs的含量与TOC含量呈现出较好的相关性,表明TOC是非工业区分布的一个控制因素。     

水生生态系统中汞-硒相互作用研究进展

甲基汞是汞存在于水生生态系统(水体、沉积物和水生生物)毒性最强的形态,并通过食物链的传递对生物体产生危害,因此有效控制汞的甲基化过程是汞环境化学和毒理学研究的重要课题。生物体内硒对汞的甲基化过程有明显的抑制作用,明确汞和硒在水生生态系统的形态特征以及汞-硒相互作用机制,有助于解决汞污染问题。汞在生物体内的毒性与生物体内硒含量紧密相关,汞与硒相之间的相互作用主要表现在生成不溶的化合物促使汞去甲基化或受生物体内硒相关酶抑制被直接排除于生物体外,从而抑制了汞的毒害作用。本文评述了汞、硒在水生生态系统中的形态特征,指出在水体中合理添加硒化合物可抑制无机汞在生物体内甲基化过程,深入研究生物体内汞和硒相互作用机制及其生理效应是该领域未来发展方向。     

湿地汞环境过程研究进展

汞在湿地生态系统中的环境过程是汞全球循环的组成部分,并与人类的健康有着密切关系。分析了湿地环境过程研究的重要意义,综述了国内外湿地汞环境过程研究的进展情况,包括在湿地汞来源、含量、赋存形态,迁移、转化、界面反应等方面。指出由于湿地独特的水文过程和环境条件,汞的累积、迁移与转化过程具有与其它生态系统不同的特点。湿地能吸收大气沉降和地表径流的汞,是汞的汇。汞在湿地生态系统中呈富集状态。湿地具有较高的汞累积速率和甲基汞生产能力,湿地的氧化-还原条件和丰富的有机碳有利于汞的甲基化。湿地甲基汞通过食物链的"生物放大",威胁人类的健康。全球气候变暖、酸雨和臭氧层耗竭可能增加湿地汞的生态环境风险。提出应开展湿地特定环境条件下汞的循环及其在汞全球循环中作用的研究,并关注湿地对全球环境变化的响应。     

武汉主要湖泊重金属污染的特点研究

对武汉主要类型湖泊环境的金属污染现状,进行了地球化学调查。探讨了重金属污染元素在湖泊环境体系各要素(水体、底泥、生物)间的地球化学行为——重金属污染元素在湖泊水体、底泥中的分布特点,指出重金属污染元素在湖泊底泥中,主要以铁锰氧化物相和有机相形式存在。水生植物藕带对重金属元素的吸收富集具有选择性。     

胶州湾水生系统中痕量金属组分场态特征

笔者利用宏量组分、微量组分、痕量金属组分的化学总量、环境因子等测试资料,深入讨论了胶州湾不同介质痕量金属的生物地球化学总体特征及各介质痕量金属组分在平面上的分布,揭示了胶州湾水生系统对陆源物质输入的响应。整个水生系统从垂向上看,表层沉积物是所有痕量金属组分的富集带;该系统中的生物相对于其所处水环境具有显著的富集痕量金属组分作用,生物体中Cu、Hg和As生物浓缩系数依次为1385、93和725。从横向上看,痕量金属组分化学场的研究揭示了痕量金属组分总量在底层水和沉积物介质中的分布主要受控于河口,即高值区分布于胶州湾的各个主要河口区,特别是沉积物中金属组分浓度的高值区主要集中分布于胶州湾的东部。而孔隙水中Cu的高值主要分布于水交替较弱的海域,如红岛前缘。但生物体中的痕量金属组分化学场空间分布规律与上述各介质的化学场均不吻合,亦即生物体中痕量金属组分的浓度与其所处环境中的同名金属组分浓度无关。生物对痕量金属组分的富集并不简单地取决于它所处环境介质中同名金属组分的总量,而存在形态上的选择性。并且通过回归分析揭示了底层水对生物体中Cu、Hg和As的富集贡献较大。     

气相色谱-质谱法分析某阻燃剂生产厂周边淡水鱼中的多溴联苯醚及其累积特征

近年来多溴联苯醚(PBDEs)的研究集中在电子行业发达地区、电子废物处置区、塑料制品生产区等重点污染区域。对阻燃剂生产厂周边PBDEs的研究有助于更好地理解PBDEs的累积特征和环境过程。本文选择江苏某PBDEs生产厂周边的淡水河流,采用气相色谱-质谱法(GC-MS)分析该河流5种淡水鱼中13种PBDEs同族体的浓度。结果显示,淡水鱼样品肌肉、肝脏和鱼卵组织中∑_(13)PBDEs(BDE17、28、71、47、66、100、99、85、154、153、138、183、190)的浓度平均值分别为34.5 ng/g.lip、41.5 ng/g.lip和18.2 ng/g.lip。研究水域不同种类淡水鱼的食性、习性和代谢能力等是影响鱼体中PBDEs浓度的主要因素。鱼体中BDE47是主要的同族体,但是与大多数已报道的研究数据相比,鱼体中含有的六溴(BDE153、154)和七溴同族体(BDE183)比例较高,这与河流附近工厂生产八溴联苯醚工业品(以六溴、七溴和八溴同族体为主)相符。工厂生产的八溴联苯醚工业品以及河流上游径流带来的其他区域生产和使用的多溴联苯醚工业品释放到环境中,被河流中的淡水鱼类选择性地积累和代谢,形成了本研究区淡水鱼体中PBDEs特殊的同族体分布。     

腈菌唑在茶园土壤中的对映体选择性降解与碳同位素分馏

运用对映体分馏分析(EFA)与单体同位素分析(CSIA)技术研究了三唑类杀菌剂腈菌唑在4种不同种植年限茶园土壤中的对映体选择性降解规律。腈菌唑的降解符合一级反应动力学方程,半衰期为28.4~70.5 d。4种茶园土壤中均表现为(+)腈菌唑优先降解,并均有碳同位素富集,表明发生了显著的微生物降解。腈菌唑在茶园土壤中的降解半衰期和对映体比在50年茶园土中最小,显著低于100年、20年和2年茶园土壤(P<0.05)。降解半衰期与砂粒含量显著相关(P<0.05),对映体选择性与粉粒含量显著相关(P<0.05)。运用Rayleigh方程计算各土壤中腈菌唑的碳同位素富集因子,并建立生物降解评估模型。应用两种方法评估生物降解所得结果与总降解率趋势相同。     

核废物处置安全评价的地质类比研究

本文简要论述了利用天然地质类似物（或类比体），类比评价核废物处置系统的安全性能。地质类比研究是安全评价核废物处置系统的重要方法之一，也是地质学科的新研究领域。目前已有的地质类比研究对象主要有火山玻璃，陨石玻璃，粘土矿物，铁陨石，铜矿床，铀矿床，含含Ｔｈ和ＲＥＥ的铁矿床，天然核反应堆（一种特殊的铀矿床）和火成岩接触带等。最后对我国今后从事同类研究提出了若干建议。     

用于裂变径迹技术刻度的铀标准玻璃的研制

监测中子积分通量是裂变径迹技术的重要组成部分。铀玻璃监测中子积分通量是国际裂变径迹定年标准化工作组推荐的重要方法之一，铀玻璃测定法还普遍用于测定样品中的铀含量及其空间分布。本文介绍的铀标准玻璃，经过多家实验室定值测定，表明其稳定性、均匀性均达到国家一级标准物质的要求，抗酸性能达到Ⅰ级光学玻璃水平，抗潮性能达到Ⅱ级光学玻璃水平。其它性能指标均达到或超过美国国家标准局的同类产品。     

The chemical and isotopic record of rock-water interaction in the Sherman Granite,Wyoming and Colorado

Chemical, isotopic, radiographic, and rock-leaching data are combined to describe the effects of rock-water interactions in core samples of petrographically fresh, 1.43 b.y.-old Sherman Granite. The data serve to identify sensitive indicators of incipient alteration and to estimate the degree, pathways, and timing of element mobilization. Unfractured core samples of Sherman Granite are remarkably fresh by most chemical or isotopic criteria, but incipient alteration is indicated by the abundance and distribution of uranium and the degree of radioactive equilibration of uranium with its decay products. Uranium abundances which are out of equilibrium with lead decay products indicate remobilization of a portion (3 to 60 percent) of original uranium in late Phanerozoic time. Association of uranium with minor but pervasive secondary alteration products also indicates some remobilization. The amount of apparent uranium mobility in unfractured Sherman Granite (3 to 60 percent) is small compared to the results of similar studies of Archean granites from nearby localities. Chemical and isotopic data evaluated as a function of core-sample depth suggest a uranium migrational pathway involving near-surface leaching and reconcentration at depth. Movement of solutions through the upper 200 ft (60 m) of Sherman Granite is fracture controlled, and brecciated granite shows more obvious petrographic, chemical, and isotopic evidence of alteration and multi-element redistribution. Laboratory experiments using freshly crushed Sherman Granite confirm that uranium is leached in preference to elements such as Si, Mg, Ca, and K, and that leachable uranium is situated close to the solid-liquid interface; perhaps as uranium along grain boundaries, in crystal defects, or on cleavage traces of minerals that exclude uranium from their structure.     

堆浸铀矿堆液体饱和渗流规律的研究

铀矿堆浸,溶浸液在铀矿堆中的渗流对浸出效果有非常重要的影响,研究堆浸铀矿堆的渗透特性,对改善铀矿堆浸效果具有重要的意义。采用取自我国南方某铀矿山的堆浸铀矿石,配制10组不同粒径分维数的试样,利用自制的饱和渗流试验装置,对其液体饱和渗流的规律进行试验研究,获得相应的渗透率和流态指数。利用试验结果,分析粒径分维数对渗透率的影响。采用支持向量机（SVM）模型,以粒径分维数和孔隙率作为输入量,建立渗透率和流态指数预测模型。结果表明,（1）在文中试验条件下,堆浸铀矿堆的液体饱和渗流遵循非Darcy指数定律,流态指数在1.1～1.5之间,且渗透率随着粒径分维数的增加而逐渐减小;（2）渗透率的SVM预测模型和流态指数的SVM 预测模型给出预测值的相对误差分别低于8%和7%,可以满足工程应用的要求。     

Preferential leaching and the age of radiation damage from alpha decay in minerals

Preferential release into solution of radionuclides that result from alpha decay is a contributor to natural isotopic disequilibrium. Such release is critical to geochemical understanding of alpha-decay products and would be an undesirable characteristic of solidified nuclear waste in deep geological formations. Spontaneous annealing of the radiation damage that is responsible for the preferential release is shown to diminish the effect in thorianite and uraninite which we have found to be 550 to 1000 M.y. old, respectively. Leaching experiments and measurements of the thorium and uranium isotopes show that there is strongly enhanced release of short-lived ²²⁸Th relative to ²³²Th, but only slight enhancement of long-lived ²³⁴U and ²³⁰Th relative to ²³⁸U and ²³²Th. These results are interpreted in terms of natural annealing of damage occurring on a time scale between the ~10 and 10⁵ years of the alpha-decay products. With a simple assumption actual times for the survival of the enhanced leaching in these minerals are ~ 15,000 years.     

Hydrothermal transformations in an aluminophosphate glass matrix containing simulators of high-level radioactive wastes

The interaction of aluminophosphate glass with water at 95°C for 35 days results in glass heterogenization and in the appearance of a gel layer and various phases. The leaching rate of elements is low owing to the formation of a protective layer on the glass surface. It is shown that over 80% of uranium leached from the glass matrix occurs as colloids below 450 nm in size characterized by high migration ability in the geological environment. To determine the composition of these colloids is a primary task for further studies. Water vapor is a crystallization factor for glasses. The conditions as such may appear even at early stages of glass storage because of the failure of seals on containers of high-level radioactive wastes. The examination of water resistance of crystallized matrices and determination of the fraction of radionuclide in colloids are also subjects for further studies.     

Evaluation of lead isotopic methods for uranium exploration, Koongarra Area, Northern Territory, Australia

Analysis of radioactive (²¹⁰Pb) and stable lead isotopes in near-surface samples has been tested as a method of uranium exploration in the Pine Creek Geosyncline, Northern Territory, Australia. The lead isotopes were extracted from the samples by a mild leaching agent and were measured by alpha spectrometry for ²¹⁰Pb and by mass spectrometry for stable lead isotopes. The results are compared with those obtained by conventional methods utilizing measurements of radioactivity and radon (Track Etch) in situ and ²²⁶Ra, ²²⁸Ra and U contents of soils. The major problems addressed were whether the lead isotopic methods are more sensitive than the conventional methods and whether they can discriminate “real” anomalies from the common barren anomalies found in black soils and swamps which contain radium in excess of the uranium present.Four test areas, representing a range of exploration problems, were chosen in the vicinity of the Koongarra uranium deposits and 25 samples from each area were analyzed. Most samples have more ²²⁶Ra than uranium. Radium analyses of several water samples show the source of this radium to be non-uraniferous rocks within the Kombolgie sandstone. The results for soil ²²⁶Ra, radon, scintillometry and ²¹⁹Pb were generally closely correlated, and as a result, the ²¹⁰Pb method was not considered to have any advantages over the conventional methods.At the Koongarra X prospect, which has a weak surface expression, the ratio gave the strongest indication of the underlying uranium mineralization with an anomaly to background ratio of 12.5. However, this ratio is correlated with uranium content and does not offer any particular advantages over uranium analyses alone. More subtle indications of uranium mineralization were found by relating the radiogenic lead (²⁰⁶Pb) and the thorium-derived lead (²⁰⁸Pb) to the common lead content (²⁰⁴Pb). A plot of versus (horizontal axis) is linear for country rock samples, irrespective of the amount of more recently introduced ²²⁶Ra. Samples above uranium mineralization lie off this trend, along a line of near-zero slope. By the use of this plot, indications were found of the Koongarra No. 2 orebody, which is concealed by about 40 m of barren overburden; none of the other techniques detected this mineralization.     

CaO对钙矾石固化/稳定化重金属铅污染土的影响

为研究CaO的赋存形态及含量对钙矾石固化/稳定化重金属铅污染土效果的影响,采用高铝水泥提供AlO2-,纯石膏或磷石膏提供SO42-,高铝水泥、石膏、普通硅酸盐水泥或生石灰提供CaO,制备不同组分固化剂配比的固化土,测试试样强度和孔隙溶液pH值等宏观物理力学指标,通过醋酸缓冲溶液法测试试样的铅溶出量,对比分析不同固化剂固化土的矿物成分与微观结构特征。结果表明,钙矾石固化/稳定化重金属铅污染土效果显著;钙矾石对孔隙的填充作用带来的增强效果不能代替水化硅酸钙胶结土颗粒的胶结作用,普通硅酸盐水泥对试样的强度更有利,但其后期强度增幅不大,而生石灰有利于固化土强度的持续增长;生石灰较普通硅酸盐水泥对钙矾石的形成、稳定和重金属Pb2+的固化/稳定化更有利;磷石膏和纯石膏对试样的pH值、无侧限抗压强度及钙矾石固化/稳定化重金属Pb2+的效果影响较小;固化土体微观结构特征表明,CaO含量对钙矾石生成形态及作用效果影响显著。当CaO含量较低时,早期生成的钙矾石将向单硫型硫铝酸钙转化。研究成果可丰富重金属污染场地原位处理技术,具有重要的理论意义和工程应用价值。     

Methods of local analysis for study of carbon in silicates: Nuclear microprobe analysis and secondary ion mass spectrometry

New approaches are proposed to analyze the content, distribution, and diffusion of carbon in silicates using nuclear microprobe analysis and secondary-ion mass spectrometry (SIMS). Techniques based on the nuclear reaction ¹²C(d,p)¹³C were developed to determine the coefficients of radiation-enhanced carbon diffusion in olivine at 300–370 K and deuteron doses that are comparable in terms of defect formation with those of α-particles generated by the decay of uranium and thorium isotopes for ~400 Ma (olivine age). The coefficients of thermal (D _th) and radiation-enhanced (D _rad) carbon diffusion in synthetic forsterite were compared to those of natural olivines from alkaline basalt nodule (Shevaryn Tsaram volcano, Mongolia). It is demonstrated that the diffusion coefficients strongly depends on the migration mechanisms of carbon atoms in crystals. The developed techniques and software package for SIMS determination of carbon distribution in silicates allowed us to study simultaneously the carbon and hydrogen distribution in a glass vein of the Chelyabinsk meteorite. The possible presence of hydrocarbons in the studied silicate glass of meteorite is suggested.     

固化黄土的干湿循环特性研究

抗干湿循环能力是检验固化土耐久性能的重要指标,研究固化黄土的干湿循环特性具有较重要的意义。本文利用高分子材料SH固化剂对黄土进行固化改良,就固化黄土抗压和抗剪强度受干湿循环变化的影响开展室内模拟试验研究。试验结果表明:SH固化黄土试样经过干湿循环后,强度整体下降,但是仍远高于素黄土强度。随干湿循环次数的增大,抗压强度呈指数衰减,SH掺量增大,循环后的强度损失减小,质量损失率非常小,完整性良好。抗剪强度随干湿循环次数的增大而减小,干湿循环对SH固化黄土的黏聚力影响明显。不同掺量的SH固化黄土试件经3次干湿循环黏聚力下降,第4次循环后略有增大再下降,经多次循环下降平缓。经3～4次干湿循环的固化黄土试件的内摩擦角均有不同程度的降低,随后基本趋于稳定。由于增湿与脱湿过程中水分质量的变化,试样的质量和体积呈波状起伏变化。对掺量为10%的固化黄土应力应变关系分析得出其应变具有硬化特征。大于10%的SH固化黄土干湿循环之后仍然保持较高和较稳定的强度,能抵抗15次干湿循环,进一步说明了SH固化黄土的水稳性良好。SH固化剂在运用于黄土抗干湿循环方面具有明显的作用,因而具有较广阔的应用前景。