铅同位素示踪技术在重金属污染研究中的应用

重金属通过在生态环境和生物中的迁移、转化和富集已对环境质量和人类健康构成了严重威胁.概述了重金属元素在地表环境中的迁移方式和在土壤-植物系统中的聚积形态,以及重金属污染治理的研究现状.针对以往研究工作的不足和在研项目特点,重点提出了土壤和茶叶中铅同位素组成的测试技术,综述了铅同位素示踪技术在重金属污染研究中的应用,并指出了今后研究重金属污染的重点.     

Tracing diffuse anthropogenic Pb sources in rural soils by means of Pb isotope analysis

Knowledge of the cause and source of Pb pollution is important to abate environmental Pb pollution by taking source-related actions. Lead isotope analysis is a potentially powerful tool to identify anthropogenic Pb and its sources in the environment. Spatial information on the variation of anthropogenic Pb content and anthropogenic Pb sources in rural topsoils is remarkably limited. This study presents results of a survey of approximately 350 topsoil samples from rural locations covering the entire Netherlands, for which the bulk geochemical and Pb isotope compositions were determined. The specific aim of this study is to determine the anthropogenic Pb sources in the topsoils from rural areas in The Netherlands. The spatial distribution of anthropogenic Pb in soils in The Netherlands will be explained in terms of land use and pollution sources.Nearly all studied topsoils display Pb contents that exceed the amount expected based on the soil lithology. The range in Pb isotope ratios of the additional Pb fraction in rural Dutch topsoils is established at 1.056–1.199, 2.336–2.486 and 0.452–0.490 for ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁷Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁸Pb, respectively. Five land use types are distinguished (forest, open nature, moor, arable land and grassland) with distinct isotopic compositions for added Pb. Additional Pb in soils of natural areas (forest, open nature and moor) has on average lower ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios than the agricultural soils (arable land and grassland). Additional Pb in both natural area soils and agricultural soils is interpreted to be of anthropogenic origin: most likely a mixture of coal/galena, incinerator ashes and gasoline Pb. The dominant sources of additional Pb in the topsoil of open nature areas are most likely incinerator ash and gasoline Pb. In contrast, the on average higher ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios of additional Pb in agricultural soils are most likely caused by the presence of animal manure and N–P fertilizers.Several areas are observed with notably high additional Pb contents (26–211 mg/kg on an organic matter-free basis) in the topsoil. The largest area is the Randstad area, which has the highest population and traffic density, and hosts a considerable fraction of the Dutch chemical industry. Two other areas with high additional Pb contents in the topsoil are located near the Dutch borders and are most likely influenced by German and Belgian chemical industries. The topsoils in the coastal dunes and southern, central and northern forests are characterized by relatively low additional Pb contents (<10 mg/kg on an organic matter-free basis). The population, traffic and chemical industry density is low in these areas and no fertilizers are applied.     

伟晶岩中不同副矿物U-Pb同位素定年和示踪的问题与应用

定年和示踪一直是伟晶岩成岩成矿过程和稀有金属富集机制研究的关键问题。副矿物不仅是伟晶岩中稀有稀土元素的重要载体,还蕴含丰富的微量元素并常常具有较高的U- Th含量,是研究伟晶岩年代学、成岩成矿过程和物质源区的“理想探针”。伟晶岩中常用的适合于U- Pb同位素定年的副矿物有锆石、铌钽铁矿、独居石、锡石、榍石、褐帘石、磷钇矿和磷灰石等。由于封闭温度、矿物学特性和不同性质流体中元素行为的差异,伟晶岩中不同副矿物的U- Pb系统常表现出复杂的年龄谱系,可能记录了伟晶岩中潜在的后期地质过程,如：自交代、后期变质与流体改造等。因此,基于前期光学显微镜、扫描电镜、冷阴极发光、激光拉曼光谱分析等矿物微观结构研究,对不同期次或世代的副矿物进行原位微区U- Pb定年及主微量元素和同位素地球化学分析,对于全面认知多期地质事件和伟晶岩成岩成矿过程演化历史,进而更准确地构建其构造- 岩浆- 热液- 成矿作用时空框架具有重要的科学意义。     

高精度铅同位素比值MC-ICP-MS测试方法及岩石标样铅同位素组成

利用多接收电感耦合等离子体质谱仪（Neptune plus）建立了高精度铅同位素比值MC-ICP-MS测试方法。建立该方法的过程中,重点评估了加入的Tl标准溶液对铅同位素比值测试结果的影响,并最终确定Tl标准溶液的浓度为25 ng/mL,同时样品溶液Pb的浓度应该大于25 ng/mL（即Pb/Tl浓度比应大于1）。利用该方法对铅同位素标准物质SRM 981进行了长期监控（2020年7月—2021年6月）,测试结果为：206Pb/204Pb=16.9415±0.0010、207Pb/204Pb=15.4985±0.0009、208Pb/204Pb=36.7204±0.0023,与统计的文献报道值一致。长期监控的全流程空白均小于0.25 ng,能满足地质样品高精度铅同位素比值测试的需要。同时运用该方法,对4个元素含量标样（BCR-2、AGV-2、BHVO-2和BIR-1a）进行了铅同位素比值测试,测试结果与文献报道的测试结果和精度一致,表明建立的方法是准确、可靠的。     

长石中Pb同位素的LA-MC-ICPMS测定

单矿物的微区原位Pb同位素分析是微区原位分析技术一个重要的研究方向,能够得到矿物晶体间甚至晶体本身不同区域同位素组成的变化信息.本文采用LA-MC-ICPMS对三件标准样品和两件长石样品进行了微区原位测试,标准样品结果在误差范围内与推荐值一致,两件长石样品测试结果在误差范围内与溶液法测试结果一致,测试精度达到1‰以内.     

西藏轮郎铅锌矿床S、Pb同位素组成及对成矿物质来源的示踪

轮郎矽卡岩型铅锌矿床位于冈底斯斑岩铜矿带北侧的铅锌银成矿带。本文基于该矿床成矿地质条件,对矽卡岩型矿石中主要的金属矿物闪锌矿、方铅矿、磁黄铁矿和黄铁矿的S、Pb同位素特征进行研究,进一步探讨了矿床成矿物质来源,并与区域矿产特征进行对比。结果显示,矿石矿物的δ34S为-2.3‰~4.1‰,平均值为1.46‰,其频率直方图具有塔式分布特征,具幔源硫特征。矿石矿物的~(206)Pb/~(204)Pb为18.179~18.692,平均值为18.543;~(207)Pb/~(204)Pb为15.588~15.802,平均值为15.687;~(208)Pb/~(204)Pb为38.532~39.305,平均值为38.900;μ值在9.44~9.83之间,具有上地壳与地幔混合的造山带铅特征。轮郎矿床S、Pb同位素特征与冈底斯成矿带北亚带矽卡岩型矿床类似。成矿物质主要来源于念青唐古拉结晶基底片麻岩,部分来自造山带幔源物质。     

Pb isotope signatures of sediments from Guanabara Bay, SE Brazil: Evidence for multiple anthropogenic sources

Sediments from Guanabara Bay and two rivers were analyzed for Pb isotope composition. The results define linear groups interpreted as different sources of Pb. The samples from Iriri and Surui rivers present different Pb compositions probably resulting from two active pollutants which are transported in the waters to the Guanabara Bay, where they are mixed. The ²⁰⁶Pb/²⁰⁷Pb values of 1.151 and 1.091 presented here are in the range of Brazilian galena ore signature.     

Trace element and Pb isotope variability during rainy events in the NW Mediterranean: constraints on anthropogenic and natural sources

Rain samples collected over the period 1995–1999 on the French Mediterranean coast have been analyzed for their trace elements and Pb isotopic compositions, both in the dissolved and particulate loads. Our results show that metal Enrichment Factors (EF) relative to Upper Erodable Crust are high for Cu, Pb, Zn and Cd and comparable to values reported about 10 years ago for North Western Mediterranean rains. Overall unradiogenic Pb isotopic compositions indicate the still visible influence of French gasoline lead on both dissolved and particulate loads. This influence is also seen on aerosols, although more variable. The examination of air mass trajectories allows us to distinguih the Pb isotopic signatures of main sources, in particular Marseille/North Italy/North Africa. Rains collected and analyzed sequentially show intra-rain variations for metal contents, metal EF and Pb isotopes, which may also be related to the main paths and altitudes of the air masses. Metal EFs and Pb isotopic data on rains from Southern France in the late 1990s are similar to recent data published on French aerosols or sediments, which are interpreted as reflecting the phasing out of leaded gasoline in the atmosphere.     

High-precision Pb isotope analysis by multicollector-ICP-mass-spectrometry using 205Tl/203Tl normalization: Optimization and calibration of the method for the studies of Pb isotope variations

The development of the MC-ICP-MS method, which was launched about one decade ago and was largely stimulated by the need to solve geological problems, has opened a new avenue in isotope mass spectrometry. One of the advantages of this method is the possibility of applying a newly developed approach to the correction of analytical results for the effect of mass discrimination by normalizing the measured isotope ratios of an element to a reference (standard) isotope ratio of another element. This makes it possible to overcome the main disadvantage of conventional thermal ionization mass spectrometry (TIMS), in which the effect of mass discrimination cannot be fully taken into account during isotope analysis, and thus to implement a highly accurate method for the analysis of Pb-isotope composition. In application to the capability of the NEPTUNE MC-ICP mass spectrometer, we optimized and calibrated a method for high-accuracy Pb isotope analysis in solutions spiked with Tl, with all currently measured Pb-isotope ratios normalized to the standard ²⁰⁵Tl/²⁰³Tl ratio (TLN-MC-ICP-MS). The factors affecting the random and systematic analytical errors were examined, and the optimal operating regime and analytical conditions were determined. Much attention was paid to the correlation of the measurement results and the mass discrimination effect determined from the ²⁰⁵Tl/²⁰³Tl ratio. The value of the ²⁰⁵Tl/²⁰³Tl normalizing ratio was analytically determined through isotope analyses of the NIST SRM 981, and SRM 982 standard samples of Pb-isotope composition. The data obtained for two mixtures Tl + Pb (SRM 982) and Tl + Pb (SRM 981) in ten replicate analyses were 2.38898 ± 12 and 2.38883 ± 20, respectively. These results are in good mutual agreement, and their general mean ²⁰⁵Tl/²⁰³Tl = 2.3889 ± 1 coincides (within the error) with the recently published values of 2.3887 ± 7 [Collerson et al., 2002] and 2.3889 ± 1 [Thirlwall, 2002]. The precision of the method (±2SD), which was assayed by the long-term reproducibility of the results of replicate analyses of SRM 981 and seven galena samples (90 analyses) was 0.016–0.018% for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios and 0.005 and 0.009% for the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios, respectively. The precision of the isotope analysis of common Pb was significantly improved (by factors of 6–10 for various isotope ratios) compared with the precision of TIMS techniques acceptable in isotope studies during three decades. The described method was applied to examine the Pb-isotope composition of approximately 250 samples of galena, scheelite, and pyrite from a number of well known (including large) gold, sulfied, and base-metal deposits. The precision of the method (0.01–0.02%) makes it possible to study small inter-and intra-phase differences in Pb-isotope ratios in hydrothermal and magmatic rocks, to assay the scale of regional and variations in the isotope composition of ore Pb, and to correlate the Pb-isotope composition of rocks and ores and reveal its evolutionary trends.     

鄂尔多斯盆地北部延安组白色砂岩形成的稳定同位素示踪及其地质意义

鄂尔多斯盆地东北部延安组顶部存在大规模的白色砂岩,形成当地的大型高岭土矿床。该白色砂岩与东胜—杭锦旗一带发现的大型砂岩铀矿含矿层位直罗组相邻相近;研究表明白色化与铀矿的富集保存、控矿砂岩的绿色蚀变、碳酸盐化等空间关系密切,成因相似,均与盆地中部上古生界天然气向北运移耗散所导致的低温气-水热液流体中烃类还原的流-岩作用有关。文中重点从稳定同位素示踪白色砂岩形成的地球化学成因机制和过程,同时也指示了本区存在天然气耗散的动力学背景。高岭石氢氧同位素揭示白色化砂岩形成的高岭土矿床成因以低温热液作用为主,与东胜铀矿形成的低温热液作用为同一性质及事件;高岭石硅同位素与铀矿石中铀矿物铀石的硅同位素数据相近,而与成岩作用黏土的硅同位素特征相去甚远,进一步证明了白色砂岩与铀矿化是在同一低温热液事件作用下的产物。碳氧同位素说明白色砂岩形成的流体与有机质来源有关,结合东胜砂岩铀矿有机地球化学及本区天然气耗散地质事件的背景,认为该有机质来源于向北耗散的上古生界天然气。方解石包裹体氢氧同位素特征表明,流体中水的性质和来源为大气降水。系统总结和综合以上认识认为,本区白色砂岩的形成过程是,中部上古生界低温天然气向北运移耗散至浅部延安组—直罗组,与地下水一起构成低温"天然气-水"混合热液,该低温热液的烃类还原作用同时导致了本区延安组顶部白色砂岩的形成以及直罗组下部东胜铀矿的富集保存、砂岩的绿色化和碳酸盐化等蚀变现象,从而形成本区东胜超大型铀矿及大型高岭土矿床和相关的烃类还原蚀变现象,构成现今多种能源及相关资源同盆共存、共荣的局面。     

有效应力对裂缝型低渗透砂岩油藏压力响应的影响

为了研究裂缝孔隙型低渗油藏中流体在双重介质之间的渗流规律及其影响,建立了双重介质间流体窜流的数学模型,并利用拉氏变换数值反演方法给出近似解析解;通过数值计算,研究窜流压力的动态特征,分析储容系数及窜流系数对压力响应的影响;通过压敏试验研究了有效应力对双重介质低渗油藏渗流能力的影响。研究结果表明：储容系数主要决定双重介质之间发生窜流现象的早晚,储容系数越大,发生窜流的时间越晚;储容系数越小,发生窜流的时间越早。窜流系数主要决定双重介质之间发生窜流压力的大小,窜流系数越大,发生窜流的压力越小;窜流系数越小,发生窜流的压力越大。有效应力对裂缝型低渗透油藏的渗流能力影响很大,有效应力的增加能够大大降低裂缝型油藏渗透率和孔隙度,以致降低储层的储容系数和窜流系数,从而影响双重介质间窜流压力的动态特征。因此,在裂缝型低渗透砂岩油藏开采中,保持压力、防止储层伤害是非常重要的。     

Mantle components in Iceland and adjacent ridges investigated using double-spike Pb isotope ratios

High precision Sr-Nd isotope ratios together with Pb isotope ratios corrected for mass fractionation using a double spike are reported for an extensive suite of late Quaternary to Recent lavas of Iceland, the Kolbeinsey and Reykjanes Ridges, and a small number of basalts from further south on the Mid-Atlantic Ridge. Compared with global MORB, the Icelandic region is distinguished by having low ²⁰⁷Pb/²⁰⁴Pb for any given ²⁰⁶Pb/²⁰⁴Pb, expressed by negative Δ²⁰⁷Pb (−0.8 to −3.5) in all but four Icelandic samples. Most samples also have elevated ²⁰⁸Pb/²⁰⁴Pb (strongly positive Δ²⁰⁸Pb), which combined with their negative Δ²⁰⁷Pb is very unusual in MORB worldwide. The negative Δ²⁰⁷Pb is interpreted as a consequence of evolution in high-μ mantle sources for the last few hundred Ma. The region of negative Δ²⁰⁷Pb appears to correspond with the region of elevated ³He/⁴He, suggesting that both lithophile and volatile elements in melts from the whole region between 56 and 70°N are dominantly sourced in a plume that has incorporated recycled Palaeozoic ocean crust and unradiogenic He, probably from the deep mantle. At least four mantle components are recognized on Iceland, two with an enriched character, one depleted and one that shows some isotopic affinities to EM1 but is only sampled by highly incompatible-element-depleted lavas in this study. Within restricted areas of Iceland, these components contribute to local intermediate enriched and depleted components that display near binary mixing systematics. The major depleted Icelandic component is clearly distinct in Pb isotopes from worldwide MORB, but resembles the depleted mantle source supplying the bulk of the melt to the Kolbeinsey and southern Reykjanes Ridges. However, an additional depleted mantle source is tapped by the northern Reykjanes Ridge, which with very negative Δ²⁰⁷Pb and less positive Δ²⁰⁸Pb is distinct from all Icelandic compositions. These components must mostly mix at mantle depths because a uniform mixture of three Icelandic components is advected southward along the Reykjanes Ridge.Despite strong covariation with isotope ratios, incompatible trace element ratios of Icelandic magmas cannot be representative of old mantle sources. The observed parent-daughter ratios in depleted and enriched Icelandic lavas would yield homogeneous Sr, Nd, Hf and ²⁰⁶Pb isotope signatures ∼170 Ma ago if present in their sources. The heterogeneity in ²⁰⁷Pb/²⁰⁴Pb is not however significantly reduced at 170 Ma, and the negative present day Δ²⁰⁷Pb cannot be supported by the low μ observed in depleted lavas from Iceland or the adjacent ridges. Since μ is higher in melts than in their sources, it follows that all the depleted sources must be residues from <170 Ma partial melting events. These are thought to have strongly affected most incompatible trace element ratios.     

Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite–carbonate–chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ⁵⁶Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ⁵⁶Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ⁵⁶Fe end member values are 0.4‰ for siderite and −0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ³⁰Si values that range between −1.0‰ and −2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate–chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite–carbonate–chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF’s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.     

Mg同位素示踪中国东部中生代深部碳循环

地球深部碳循环对全球气候变化、生命探索和岩石圈演化的研究具有重要意义。中国东部岩石圈是地球深部碳循环的重要场所,其减薄与破坏与深部碳循环密切相关。中生代太平洋板块俯冲是制约中国东部岩石圈减薄与破坏的关键,对华北克拉通和华南板块的大规模金属成矿作用具有重要作用。笔者等系统阐述了Mg示踪地球深部碳循环原理,例举了镁同位素示踪中国东部深部碳循环的实例,论述了中生代俯冲的古太平洋板块所释放的碳酸盐熔体/流体与地幔相互作用,是造成中国东部地幔具有普遍的轻Mg同位素组成的重要原因。此外,指出轻镁同位素的多解性,提出多同位素联合示踪是未来研究地球深部碳循环的趋势。     

Mg同位素示踪中国东部中生代深部碳循环

地球深部碳循环对全球气候变化、生命探索和岩石圈演化的研究具有重要意义。中国东部岩石圈是地球深部碳循环的重要场所,其减薄与破坏与深部碳循环密切相关。中生代太平洋板块俯冲是制约中国东部岩石圈减薄与破坏的关键,对华北克拉通和华南板块的大规模金属成矿作用具有重要作用。笔者等系统阐述了Mg示踪地球深部碳循环原理,例举了镁同位素示踪中国东部深部碳循环的实例,论述了中生代俯冲的古太平洋板块所释放的碳酸盐熔体/流体与地幔相互作用,是造成中国东部地幔具有普遍的轻Mg同位素组成的重要原因。此外,指出轻镁同位素的多解性,提出多同位素联合示踪是未来研究地球深部碳循环的趋势。     

Application of Pb isotopic tracing technique to constraining the source of Pb in the West Lake Longjing tea

This paper dealt with the Pb contents and Pb isotopic composition of the West Lake Longjing tea. The results showed that in the tea leaves, from young leaf →old leaf →tea limb, the Pb contents tend to increase gradu-ally from 1.63 →4.84 →6.07×10-6, wich revealed that the Pb was accumulated gradually in the tea. After cleaned, the Pb contents of tea leaves were significantly reduced. This indicated that the deposits on the surface of tea leaves made a great contributuion to Pb contents. The survey results for soils in the relevant tea gardens showed that soil from the Longjing tea garden has higher Pb contents, with an average level of 49.6×10-6, two times those of common soils (24×10-6) in China. Results of the systematic analysis for tea, tea garden soil and the samples with the relevant background of the Pb isotopic composition displayed that the Pb isotopic ratio of tea is 206Pb/207Pb=1.164±0.005 (2σ). The ratio of 206Pb/207Pb for the soil gradually decreased from residue phase, soil dilute acid extract phase, and then to urban topsoil, i.e., 1.175 →1.171 →1.170. The 208Pb/(206Pb+207Pb) ratios also show a similar variation trend. 206Pb/207Pb ratios in the samples with the relevant background were: vehicle exhaust, 1.124; coal-combustion, 1.156; atmosphere, 1.168; and water, 1.166. Comparative studies have shown that Pb pollution is popular in the environ-mental media (soil, atmosphere, water) in Hangzhou. With the aggravation of Pb pollution, the Pb isotopic composi-tion gradually changed from the natural background (soil residues) to the direction of automobile exhaust. This phe-nomenon could illustrate that the pollution source was the vehicle exhaust, while the coal-combustion contributed little to environmental pollution in Hangzhou. The Pb of the Longjing tea came mostly from soluble phase Pb in the polluted soil. Moreover, secondary pollution was caused by vehicle exhaust.     

西藏多不杂铜矿床硫铅同位素地球化学示踪

多不杂铜矿床的发现是西藏地质找矿工作取得的重大突破,前人对其做了大量的研究,但始终未能合理解释该矿床的形成过程,究其原因主要是因为成矿物质和成矿流体来源认识上存在争议。本次研究指出了前人在多不杂铜矿床成因机制认识中存在的问题,并测试了岩矿石及单矿物的硫铅同位素组成。研究表明,矿床中硫主要来源于深源岩浆,幔源岩浆和流体在参与成岩成矿过程中伴随岩浆结晶成岩交代岩石而致自身流体性质演变,进而引发壳幔物质混染;铅同位素具有由岩浆作用形成的地壳与地幔混合的俯冲带铅的特征,伴随着含矿地幔流体的上升侵位,不可避免的混染了地壳铅,导致了多不杂铜矿床铅同位素组成的变化。综合分析认为该矿床的成矿物质和成矿流体主要来源于地幔,成矿动力主要来自深部地质过程,矿床的形成与地幔流体作用有关。     

Chlorine isotope evidence for the anthropogenic origin of tris-(4-chlorophenyl)methane

Compound-specific Cl-isotope analysis was performed on the persistent and bioaccumulating compound tris-(4-chlorophenyl)methane (4,4′,4″-TCPMe, referred to as TCPMe in this study) to elucidate whether its main source is natural or anthropogenic. Blubber from the Baltic grey seal (Halichoerus grypus) was extracted by continuous acetonitrile partitioning, and the TCPMe was isolated from the extract by preparative-capillary gas chromatography. Chlorine isotope analysis was subsequently performed by sealed-tube combustion in conjunction with thermal-ionization mass spectrometry (TIMS). The δ³⁷Cl of TCPMe was −3.5 ± 0.5‰, similar to the previously reported δ³⁷Cl of technical grade p,p′-DDT (referred to as DDT in this study). The data is not consistent with a putative marine natural source of TCPMe, as enzymatic (biotic) production is reported to give values of δ³⁷Cl < −10‰. The δ³⁷Cl–TCPMe data thus supports the hypothesis that TCPMe is produced as a byproduct during DDT synthesis and is released to the environment through the same pathways as DDT. It is also consistent with tris-(4-chlorophenyl)methanol as the primary biotransformation product of TCPMe.     

三轴应力下不同粒径破碎砂岩渗透特性试验

地下工程中破碎岩体往往处于三向应力状态,此类岩体具有孔隙率大、渗透性高等特点,在地应力与高水头作用下易发生渗流失稳破坏,诱发突水灾害。为研究三轴应力下破碎砂岩的渗透特性,运用自主研发的破碎岩石三轴渗流试验系统,采用稳态渗透法进行5种粒径破碎砂岩的渗流试验,得到了三轴应力下破碎砂岩渗透特性变化规律,推导了有效应力与渗流速度之间的关系。试验结果表明：三轴应力下破碎砂岩的有效应力与渗流速度呈线性关系,且轴向位移越大时,随有效应力的增加渗流速度减小的幅度越小;三轴应力下5种粒径破碎砂岩的孔压梯度与渗流速度服从Forchheimer关系,两者之间的相关系数达0.95以上;轴向位移恒定时,随着围压的增大,破碎砂岩渗透率k减小,非Darcy流β因子增大,各级轴向位移下,破碎砂岩的渗透率与围压之间呈指数函数关系;随着孔隙率的减小,5种粒径的破碎砂岩渗透率呈减小趋势,非Darcy流β因子整体增大,且渗透率量级为10-14～10-11 m2,非Darcy流β因子的量级为106～1012 m-1。