圆盘固相萃取富集-气相色谱法测定地表水中有机氯和有机磷农药

采用环境友好的圆盘固相萃取新技术富集水体中有机氯农药和有机磷农药,分别用微池电子捕获检测器(μECD)和火焰光度检测器(FPD)气相色谱法检测,实现了水中有机氯和有机磷农药残留物的测定。结果表明,16种有机氯农药的平均回收率为64.7%~102%,精密度(RSD,n=6)为2.9%~15%;13种有机磷农药的平均回收率为65.9%~104%,精密度(RSD,n=6)为1.7%~17%。方法快速、灵敏、低污染,可用于水体中多种有机氯农药和有机磷农药的残留分析。     

气相色谱法测定地下水中六六六结果的不确定度评定

依照《测量不确定度评定与表示》,对气相色谱法测定地下水中六六六(HCH)四种单体结果进行了不确定度评定。分析了测量过程中引入的不确定度来源,包括提取液体积的量取、样品提取溶液的定容体积、分析仪器的进样量、标准系列溶液的测量以及仪器重复测定等分量引入不确定度及其各参数的采集和计算方法,最后合成标准不确定度,通过乘以95%概率下的扩展因子2,获得测量结果的扩展不确定度。     

Zircon U–Pb and Hf isotopic study of gneissic rocks from the Chinese Altai: Progressive accretionary history in the early to middle Palaeozoic

Gneissic rocks in the Chinese Altai Mountains have been interpreted as either Paleozoic metasedimentary rocks or Precambrian basement. This study reports geochemical and geochronological data for banded paragneisses and associated gneissic granitoids collected along a NE–SW traverse in the northwestern Chinese Altai. Petrological and geochemical data suggest that the protoliths of the banded gneisses were possibly immature sediments with significant volcanic input and that the gneissic granitoids were derived from I-type granites formed in a subduction environment. Three types of morphological features can be recognized in zircons from the banded gneisses and are interpreted to correlate with different sources. Zircons from five samples of banded paragneiss cluster predominantly between 466 and 528 Ma, some give Neoproterozoic ages, and a few yield discordant Paleoproterozoic to Archean ages. Zircon Hf isotopic compositions indicate that both juvenile/mantle and crust materials were involved in the generation of the source rocks from which these zircons were derived. In contrast, zircons occur ubiquitously as elongated euhedral prismatic crystals in the four samples of the gneissic granitoids, and define single populations for each sample with mean ages between 380 and 453 Ma. The general absence of Precambrian inheritance and positive zircon ?Hf values for these granitoids suggest insignificant crustal contribution to the generation of the precursor magmas. Our data can be interpreted in terms of a progressive accretionary history in early to middle Palaeozoic times, and the Chinese Altai may possibly represent a magmatic arc built on a continental margin dominated by Neoproterozoic rocks.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

Atmospheric mercury near Salmon Falls Creek Reservoir in southern Idaho

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured over 2-week seasonal field campaigns near Salmon Falls Creek Reservoir in south-central Idaho from the summer of 2005 through the fall of 2006 and over the entire summer of 2006 using automated Tekran Hg analyzers. GEM, RGM, and particulate Hg (HgP) were also measured at a secondary site 90 km to the west in southwestern Idaho during the summer of 2006. The study was performed to characterize Hg air concentrations in the southern Idaho area for the first time, estimate Hg dry deposition rates, and investigate the source of observed elevated concentrations. High seasonal variability was observed with the highest GEM (1.91 ± 0.9 ng m⁻³) and RGM (8.1 ± 5.6 pg m⁻³) concentrations occurring in the summer and lower values in the winter (1.32 ± 0.3 ng m⁻³, 3.2 ± 2.9 pg m⁻³ for GEM, RGM, respectively). The summer-average HgP concentrations were generally below detection limit (0.6 ± 1 pg m⁻³). Seasonally averaged deposition velocities calculated using a resistance model were 0.034 ± 0.032, 0.043 ± 0.040, 0.00084 ± 0.0017 and 0.00036 ± 0.0011 cm s⁻¹ for GEM (spring, summer, fall and winter, respectively) and 0.50 ± 0.39, 0.40 ± 0.31, 0.51 ± 0.43 and 0.76 ± 0.57 cm s⁻¹ for RGM. The total annual RGM + GEM dry deposition estimate was calculated to be 11.9 ± 3.3 μg m⁻², or about 2/3 of the total (wet + dry) deposition estimate for the area. Periodic elevated short-term GEM (2.2–12 ng m⁻³) and RGM (50–150 pg m⁻³) events were observed primarily during the warm seasons. Back-trajectory modeling and PSCF analysis indicate predominant source directions to the SE (western Utah, northeastern Nevada) and SW (north-central Nevada) with fewer inputs from the NW (southeastern Oregon and southwestern Idaho).     

新疆北部库尔提蛇绿岩中角闪片岩的原岩恢复及其成因

库尔提角闪片岩产于库尔提蛇绿岩南部岩片中,与斜长花岗岩呈互层产出。这套角闪片岩的不相容微量元素组分显示了大洋中脊和岛弧玄武岩的双重特征,主要表现为大离子亲石元素(LILE)富集,高场强元素(HFSE)亏损以及平坦到亏损的轻稀土(LREE)配分模式。原岩恢复的结果表明,该角闪片岩的原岩为亚碱性的拉斑玄武岩类。库尔提角闪片岩亏损的LREE、高ε_(Nd)(t),以及关键元素比值(Th/Nb,La/Yb和Th/Yb)呈正相关都表明,其源区可能以MORB地幔为主,同时还伴有少量弧组分。因此,我们认为其形成于弧后盆地环境,同时推断该区弧后盆地存在一个二阶段的熔融演化模式:第一阶段,大约在晚古生代早期,古亚洲洋向西伯利亚板块发生北向俯冲,在会聚板块边界,弧火山岩被从含水的地幔楔中提取出来,留下一个亏损地幔;第二阶段,随着古亚洲洋板块持续消减,在中-晚泥盆世形成了库尔提弧后盆地,下部的亏损地幔发生了小比例的部分熔融形成了这套角闪片岩的原岩。     

中祁连东段什川杂岩基的岩石化学特征及年代学研究

祁连造山带被托菜南山-了高山构造带及宗务隆山-贵得构造带分为北祁连、中祁连及南祁连构造带。什川岩基位于中祁连构造带东部,由闪长岩、斜长花岗岩、二长花岗岩组成;对二长花岗岩进行U-Pb单颗粒锆石微区LA-ICP-MS同位素测定,获得444.6Ma及414.3Ma两组加权平均年龄,前者代表岩石的形成年龄,后者代表构造热事件年龄。二长花岗岩主量元素W(SiO_2)=68.66%～80.77%,w(K_2O)/w(Na_2O)>1和A/CNK介于0.95～1.21间,总体为钾质钙碱性过铝质花岗岩。岩石富集LILE元素(K、Th、Rb、Ba等),亏损HFSE元素(Ta、Nb、Y等);稀土元素总量较高(∑REE多介于109.05×10~(-6)～322.66×10~(-6)),轻重稀土强烈分馏(∑LREE/∑HREE介于7.92～31.68),稀土元素分配模式为轻稀土富集型,具中等-强Eu负异常(δEu=0.26～0.58)。岩石矿物组合及岩石地球化学特征共同表明,什川岩基为中上地壳泥砂质岩石部分熔融而成,形成温度较低,为加厚地壳拆沉熔融成因。这为祁连造山带构造演化及其深部动力学机制研究提供了新的资料。     

浙江省长兴县煤山剖面二叠—三叠系过渡地层中的黑碳记录及其地质意义

首次报道了浙江煤山二叠-三叠系界线地层中黑碳的含量及其碳同住素的变化特征。黑碳含量在26层存在一个明显的峰值,含量高达0．51％。黑碳与总有机碳比值从25层底部开始持续升高,在26层达到最高,稳定在0．40以上。黑碳的碳同位素在24层和25层之间有一个陡然的降低,降低幅度达2‰,在25和26层中则存在一个幅度达3‰的缓慢降低,总降低幅度达5‰。黑碳是动植物和化石燃料燃烧的天然记录,浙江煤山二叠-三叠系界线附近黑碳特征反映了二叠纪末期陆地生态系统发生了突然的衰退,发生了强烈的天然大火。根据事件层大火燃烧的长期性或频繁的特征,以及黑碳同位素大幅度陡然降低和缓慢降低,认为燃烧源除了陆地植被外,还有其他富含轻碳的化石燃料,即大火的燃烧源除了植被外,还可能有煤和甲烷水合物等。浙江煤山剖面的黑碳记录,反映了二叠-三叠纪之交地球陆地环境的剧烈变化,有助于理解和揭示生物大灭绝的过程和原因。     

小波分析在天然伽玛测井地质解释中的应用

在分析天然伽玛测井数据的信息特点和小波多分辨率分析原理的基础上,用小波多分辨率分析天然伽玛测井数据,消除其中的统计涨落等噪声干扰及提取天然伽玛放射性强度在不同沉积岩地层中分界标志特征和不同岩性中的变化特征,以提高应用天然伽玛测井资料进行地层划分及岩性识别的准确性和有效性.     

贵州修文小山坝铝土矿中镓等伴生元素分布规律研究

通过ICP-MS等分析方法对贵州小山坝铝土矿中伴生元素的研究,发现该矿床TiO2、Ga、Ge、Sc、Nb、Li和REE等有用伴生元素在铝土矿矿体中均有较高富集,其含量大多接近或超过了工业综合利用标准,具有较大的经济价值,特别是矿区富铁铝土矿石中Ga和Sc等含量异常高.贵州铝土矿资源丰富,其伴生元素在铝土矿冶炼过程中所产生的赤泥中更为富集,因此,贵州铝土矿综合利用前景十分巨大,这些元素潜在的经济价值,在某种程度上,甚至会超过主导产品氧化铝的价值.开展铝土矿中镓等伴生有用元素的分布及赋存状态的研究,对于镓等稀散元素在特殊地质地球化学环境中超常富集机制、矿产资源综合价值的重新认识评估和矿产资源的综合利用将十分重要,不仅可为铝工业注入新的活力,增加新的经济增长点,而且还可以解决大量赤泥堆放和利用问题,同时获得较大的社会效益与环境效益.