原子吸收光谱法测定茶叶中微量元素

采用火焰原子吸收光谱法对江西庐山"云雾"茶叶中的铜、锌、锰、铁四种元素进行了含量测定,详细地研究了消解酸的种类、HNO3和HF的比例、消解酸的体积及消解时间对测定结果的影响.用HNO3-HF-HClO4处理样品,测定结果表明茶叶中含有丰富的人体必需的微量元素,采用此方法回收率为93.70%～102.40%,相对标准偏差小于10%.其方法简便、精密度和灵敏度高,结果令人满意.     

X射线荧光光谱法测定土壤和沉积物中的锰

X射线荧光光谱法(XRF)是测定土壤和沉积物中锰的重要方法,具有制样简单、非破坏性测定、检测速度快等优点。目前用于建立工作曲线的土壤和沉积物标准物质的锰含量最高为2490mg/kg,采用XRF法测定受污染土壤和沉积物中的锰含量时易超出工作曲线测定范围。本文将锰标准溶液定量加入到土壤标准物质中,制备锰含量更高的校准样品,工作曲线的测定上限范围由2490mg/kg提高至3780mg/kg。该方法测定不同含量标准物质中锰含量的结果均在认定值范围内,实际样品的加标回收率为97.8%～108.3%,高含量锰的实际样品测定值与电感耦合等离子体发射光谱法测定值的相对偏差小于5.7%,相对标准偏差(RSD)小于0.4%(n=7)。实验结果表明该法测定锰含量高的土壤和沉积物的准确度和精密度良好。     

电感耦合等离子体发射光谱法多向观测同时测定碳酸盐中常量和微量元素

采用偏硼酸锂熔矿分解试样,稀盐酸提取,电感耦合等离子体发射法同时测定碳酸盐中二氧化硅、氧化钙、氧化镁、三氧化二铝、三氧化二铁、氧化钾、氧化钠、氧化锰、二氧化钛、五氧化二磷、三氧化硫等多种常量和微量组分。各元素选择光谱干扰少、准确度高的多向观测方式(轴向、径向衰减),改善方法的检出限和精密度。方法回收率为94.7%~104.6%,相对标准偏差(RSD,n=10)低于3.0%。方法经国家一级标准物质验证,测定值与标准值基本相符。     

电感耦合等离子体发射光谱法同时测定卤水中锂钠钾钙镁硼硫氯

建立了电感耦合等离子体发射光谱法(ICP-AES)同时测定碳酸盐型、硫酸盐型、氯化物型三种类型卤水中Li、Na、K、Ca、Mg、B、S、Cl等高低含量元素的分析方法。选择仪器最佳的工作条件为射频功率1400W,炬管位置位于-3,载气流量0.60 L/min。确定了各元素测定谱线,使用ICP-AES的双向观测模式、轴向观测模式测定Li、Ca、B、S、Cl以及低含量的K、Mg,径向观测模式测定高含量的Na、K、Mg,可确保卤水中不同含量的元素同时检出。Li、Na、K、Ca、Mg、B、S的检测下限为0.07～3.00 mg/L,Cl的测定下限为165mg/L。方法精密度(RSD,n=10)均小于5%,回收率为92.4%～109.7%。其中Na、K、Mg、S、Cl测定结果与传统方法测定结果基本吻合。     

四酸敞口溶解-电感耦合等离子体发射光谱法测定土壤中的硫

当前土壤中硫元素的测定方法主要是X射线荧光光谱法和燃烧法,上述两种方法分析速度慢,对高、低含量样品的分析精度较差,难以满足大批量样品快速、准确分析的要求。为提高分析速度和结果的准确度,本文建立了用盐酸-硝酸-氢氟酸-高氯酸(四酸)溶解土壤样品,电感耦合离子体发射光谱法测定硫的方法。通过考察王水消解、王水水浴消解和四酸消解的溶样效果,测定结果表明采用四酸能更好地溶解土壤样品中的硫。方法检出限为10μg/g,测量范围为33.3~50000μg/g,相对标准偏差为0.47%~4.05%。本方法简单快速,准确度高,已经过数千件实际样品验证,在不增加分析成本的情况下,一份溶液还可以同时测定钾钠钙镁铁锰铍锂镧铈钪钒钴镍钛等元素,适合在地质行业推广应用。     

电感耦合等离子体发射光谱法多向观测同时测定锑矿石中锑砷铜铅锌

采用王水溶矿方法分解试样,在15％的王水介质中,建立了电感耦合等离子体发射光谱法测定锑矿石中锑、砷、铜、铅和锌的方法.通过选择光谱干扰少的分析线,结合径向衰减或径向观测方式,可减小样品稀释倍数,准确测量高含量的锑、砷;结合轴向观测方式,可准确测量低含量的铜、铅、锌.方法的检出限为:锑5.0 μg/g,砷5.0μg/g,铜0.5 μg/g,铅1.0 μg/g,锌0.5μg/g.建立的方法改善了测定的准确度,相对标准偏差( RSD,n=12)小于2.8％,方法回收率为97.5％ ～ 102.5％.建立的方法经锑矿石国家一级标准物质验证,测定结果与标准值吻合,具有测定含量范围宽、分析简便快速、结果准确等优点.     

电感耦合等离子体发射光谱法测定铅锌矿中15个主次量元素

铅锌矿多元素同时测定中,样品预处理过程受多种不同因素的影响,单因素试验往往无法同时为多因素实验提供合理的优化方案。本文采用盐酸-硝酸溶矿,考察了样品预处理过程中混合酸配比、混合酸体积、消解时间及消解温度对消解效果的影响,利用正交试验设计及极差分析确定了最优消解条件:盐酸-硝酸混合酸配比3∶1,混合酸体积10 m L,消解时间120 min,消解温度90℃,用电感耦合等离子体发射光谱法同时测定铅锌矿中15个主次量元素(铅锌铜锰砷银铋镉钴镍镓铟钼锗锑)的含量。在最优条件下,用富铅锌矿石国家标准物质(GBW 07165)进行试验,大多数元素的精密度(RSD,n=12)和准确度小于5%,方法检出限为0.0019~0.048μg/g。基于铅锌矿主要是以硫化物形式存在,采用一系列硫化物国家标准物质验证方法的准确度及可行性,检测结果基本都在标准值的误差范围内。应用该方法分析湖南某矿区中大批量铅锌矿样品,标样质量统计合格率为100%,密码质量统计合格率大于97%。     

微波消解-高分辨电感耦合等离子体质谱法测定土壤中8种金属元素

微波消解结合电感耦合等离子体质谱(ICP-MS)是土壤样品中金属元素测定的常用方法,其前处理可以采用不同的消解体系,但是消解体系对分析结果的准确性影响较大。此外,应用ICP-MS测定某些元素时干扰的存在会影响结果的准确性。基于上述问题,本文优选三个酸体系微波消解溶样,采用高分辨电感耦合等离子体质谱(HR-ICP-MS)测定土壤样品中8种金属元素(Cr、Co、Ni、Cu、Zn、Pb、Cd和U)的含量,对比研究了由不同用量硝酸、盐酸、氢氟酸混合组成的三个酸消解体系对国家土壤标准物质的消解效果,确定了最优前处理方法。结果表明：经国家土壤标准物质验证,采用HR-ICP-MS检测,在不需要干扰校正的情况下,酸体系Ⅰ(6mL硝酸+3mL盐酸+3mL氢氟酸)和酸体系Ⅱ(2mL硝酸+6mL盐酸+1mL氢氟酸)的测定值与标准值相吻合,方法检出限为0.001～0.715μg/g,精密度(RSD,n=6)小于7.0%。从消解情况、准确度和精密度比较,酸体系Ⅰ稍优于酸体系Ⅱ;从酸用量比较,酸体系Ⅱ酸用量最少。两种酸体系的样品处理方法均具有较高的适用性和可靠性,都可用于土壤样品中8种金属元素含量的直接测定。     

粉末压片制样-X射线荧光光谱法测定铁矿石中锌砷锰

应用X射线荧光光谱仪测定铁矿石中的锌、砷、锰含量,采用粉末压片法制样,并研究了制样的条件,确定了仪器最佳参数,建立了标准曲线。经国家实物标准铁矿石样品验证,测定值与标准值吻合,三元素的偏差均小于±0.007%;精密度试验表明相对标准偏差(n=10)均小于2.80%。大量实验数据表明,压片制样-X射线荧光光谱法测定锌、砷、锰元素的精密度高,准确可靠。该方法在检测准确度和分析速度上可以满足钢厂生产要求。     

密闭溶样-电感耦合等离子体质谱法测定煅烧高岭土中微量重金属元素

建立了密闭溶样-电感耦合等离子体质谱法同时测定煅烧高岭土中铜、铅、锌、铬、镉和锰等6个微量重金属元素的有效方法。实验中对仪器的最佳工作参数进行了优化,选择适当的同位素,并用铑作内标元素,有效地抑制了分析信号的漂移以及分子和多原子离子的质谱干扰;探讨了混合酸消解体系、消解液用量、密闭溶样的时间对测定结果的影响。以硝酸-氢氟酸作为消化试剂,在180℃下溶解4 h能完全消解样品。在选定的实验条件下,对煅烧高岭土样品进行了精密度和回收率试验,方法相对标准偏差(RSD,n=9)为0.96%~2.22%,加标回收率为98.0%~101.5%。     

Influences of the unsaturated,saturated, and riparian zones on the transport of nitrate near the Merced River,California, USA

Transport and transformation of nitrate was evaluated along a 1-km groundwater transect from an almond orchard to the Merced River, California, USA, within an irrigated agricultural setting. As indicated by measurements of pore-water nitrate and modeling using the root zone water quality model, about 63% of the applied nitrogen was transported through a 6.5-m unsaturated zone. Transport times from recharge locations to the edge of a riparian zone ranged from approximately 6 months to greater than 100 years. This allowed for partial denitrification in horizons having mildly reducing conditions, and essentially no denitrification in horizons with oxidizing conditions. Transport times across a 50–100-m-wide riparian zone of less than a year to over 6 years and more strongly reducing conditions resulted in greater rates of denitrification. Isotopic measurements and concentrations of excess N₂ in water were indicative of denitrification with the highest rates below the Merced River. Discharge of water and nitrate into the river was dependent on gradients driven by irrigation or river stage. The results suggest that the assimilative capacity for nitrate of the groundwater system, and particularly the riverbed, is limiting the nitrate load to the Merced River in the study area.     

山西五台山区滹沱群变质玄武岩岩石学、地球化学特征及其成因意义

在野外地质调查的基础上,选取滹沱群豆村亚群底部四集庄组玄武岩、顶部青石村组玄武岩和东冶亚群中下部河边村组玄武岩,进行岩石学和地球化学研究。分析结果表明：玄武岩主量元素高TiO2、TFeO,低MgO,具有演化的基性岩浆的特征。稀土元素含量相对较高,具有弱—中等程度的轻稀土元素富集,中等程度的轻重稀土元素分异,轻微的Eu异常;玄武岩中Cr、Ni含量变化较大,但与Mg#具有很好的正相关性。微量元素配分图解中具有明显的Sr负异常,部分样品具有Nb、Ta和Ti负异常,无Zr、Hf负异常,与岛弧火山岩不同;同时Nb、Ta无分异,Zr/Hf值较高,具有板内玄武岩浆的特征。综合分析认为,滹沱群玄武岩可能形成于板内裂谷环境。在岩浆上升过程中发生橄榄石与尖晶石的分离结晶作用,同时不同程度地受到地壳的混染。     

贵州岑巩羊桥罗家塘杷榔动物群的发现及其后生动物早期演化的意义

岑巩县羊桥乡罗家塘杷榔组仅出露中-上部地层,岩性单一,均为青灰、灰绿色粉砂质泥、页岩.在其上部层位发现了俞氏贵州始海百合(Guizhoueocrinus yui Zhao,Parsley et Peng,2007),计有棘皮动物始海百合、腕足动物、软体动物-软舌螺、节肢动物-三叶虫等8属9种,包括了2个未定名的新种和1...     

扬子北缘马元铅锌矿床闪锌矿微量元素及S-Pb-He-Ar-C同位素地球化学研究

马元铅锌矿床是近年扬子陆块北缘铅锌找矿的新突破。矿体呈层状、似层状产于碑坝隆起翼部震旦系灯影组角砾状白云岩层间构造带中,围岩蚀变很弱。矿石中硫化物以闪锌矿、方铅矿为主,中粗粒晶质结构,充填于白云岩角砾间。闪锌矿富集Cd、Ge、Ag,贫In、Tl、Se,Ga/In为6~132,Ge/In多1000,成矿温度以中-低温为主。金属硫化物ε~(34)S值相对集中,为12.9‰~19.4‰,平均为17.4‰,来自于海相硫酸盐的还原。铅同位素组成稳定,~(206)Pb/~(204)Pb为17.858~17.918:~(207)Pb/~(204)Pb为15.603~15.694;~(208)Pb/~(204)Pb为37.756~38.046,具有造山带和上地壳铅的特征,震旦系可能提供了金属成矿物质。闪锌矿中流体包裹体的~3He/~4He为0.03Ra~1.05Ra,~(40)Ar/~(36)Ar为326.1~765.1,~(38)Ar/~(36)Ar为0.183~0.204,表明成矿流体主要为地壳流体和饱和大气水(大气降水或海水)的混合。闪锌矿内流体包裹体挥发分δ~(13)C_(CH_4)值为-36.01‰~-28.80‰,δ~(13)C_(C_2H_6)值为-27.72‰~-22.44‰,δ~(13)C_(CO_2)值为-23.24‰~-9.68‰,表明有机流体参与了成矿作用。石英、方解石的H-O同位素结果表明具有海水和有机水混合的特征。可见,成矿流体具有两种流体混合的特征,一为蒸发海水与围岩反应所形成的盆地卤水,二为有机流体。推测矿区可能存在一个古油气藏,由于TSR生成一高硫气藏,为区内还原性有机流体的主要来源。当富含Pb、Zn等成矿物质的成矿流体运移至富含CH_4和H_2S的还原性流体的矿区角砾岩带时,两种流体混合,Pb、Zn等遇到H_2S发生反应而沉淀成矿,并伴生热液白云石等,形成了马元铅锌矿床。综上所述,我们认为马元矿床属MVT型铅锌矿床。     

深港西部通道填海区地下水铜、钒、铊、镉、钨迁移的实验研究

填海工程使滨海地区的地下水物理化学条件改变,导致该区域地下水中重金属浓度升高。本文以深港西部通道填海区为例,采用实验室模拟填海条件的办法,初步探讨了影响填海区地下水重金属迁移的关键因素。模拟实验结果表明,填海区地下水中钨元素含量升高与地下水淡化、淤泥氧化过程以及填料风化有关;铜元素含量升高则与淤泥氧化过程以及填料风化有关;钒元素含量升高与地下水淡化和淤泥氧化过程有关,而其他元素含量升高则主要与填料风化释放有关。     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Geology, mineralogy, and PGE mineralization of the copper-nickel occurrences of the Kvinum ore field, Sredinny Range, Kamchatka

The geology and mineralogy of host metamorphic rocks, the mineralogy of sulfide ores, and the distribution of PGE mineralization were studied in detail for the Kvinum-1 and Kvinum-2 copper-nickel occurrences of the Kvinum ore field, which are the most promising targets for the copper-nickel-PGE mineralization of the Sredinny Range of Kamchatka. It was established that stringer-disseminated and massive copper-nickel ores are localized in amphibole peridotites, cortlandites, and form ore bodies varying from tens of centimeters to 5–20 m thick among the layered cortlandite-gabbroid massifs. The massive sulfide ores were found only at the bottom of cortlandite bodies and upsection grade into stringer-disseminated and disseminated ores. Pyrrhotite, chalcopyrite, and pentlandite are the major ore minerals with a sharply subordinate amount of pyrite, sphalerite, galena, arsenopyrite, and löllingite. Besides pentlandite, the Ni-bearing minerals include sulforasenides (gersdorffite), arsenides (nickeline), and tellurides (melonite) of nickel. It was found that PGE mineralization represented by antimonides (sudburyite) and tellurobismuthides (michenerite) of Pd with sharply subordinate platinum arsenide (sperrylite) is confined to the apical parts of massive sulfide zones and the transition zone to the stringer-disseminated ores. Ore intervals enriched in arsenides and tellurides of Ni, Pd, and Bi contain high-purity gold. In the central parts of the orebodies, the contents of PGE and native gold are insignificant. It is suggested that the contents of major sulfide minerals and the productivity of PGE mineralization in the cortlandites are defined by combined differentiation and sulfurization of ultramafic derivatives under the effect of fluids, which are accumulated at the crystallization front and cause layering of parental magmas with different sulfur contents. The fluid-assisted layering of mafic-ultramafic massifs resulted in the contrasting distribution of PGM in response to uneven distribution of sulfur (as well as As, Te, and Bi) during liquid immiscibility. The productivity of PGE mineralization significantly increases with increasing contents of S, As, Te, and Bi (elements to which Pt and, especially, Pd have high affinity) in fluids.     

西藏南木林县秦马弄地区二长花岗岩体岩石成因

以出露在西藏南木林县秦马弄地区二长花岗岩体为研究对象,从野外地质调查、岩石学、LA-ICP-MS锆石U-Pb定年、元素和Lu-Hf同位素地球化学等方面对其进行了分析研究。结果显示：秦马弄地区二长花岗岩体类似于A型花岗岩,形成于古近纪(E1),其LA-ICP-MS锆石U-Pb年龄为(62.0±0.5)~(63.0±0.5) Ma;岩体形成的温度较高(锆石饱和温度为745~805 ℃,平均766 ℃);岩石富SiO2(72.6%~75.0%)、Na2O(2.86%~3.59%)和K2O(4.12%~5.25%),贫CaO(0.72%~1.39%)和MgO(0.26%~0.36%),高FeOT/MgO值(7.26~10.3),属高钾钙碱性系列,弱过铝质;岩石具明显的负Eu异常(Eu/Eu*=0.40~0.70),普遍表现出Ba、Sr、P、Ti元素的亏损和Rb、Th、K、Zr、Hf元素的富集。εHf(t)值为-4.7~-1.8,其两阶段地壳Hf模式年龄tDM2为(1.1~1.3) Ga。秦马弄A型花岗岩体是冈底斯基底地壳物质部分熔融的岩浆产物,形成于古近纪印度板块与欧亚板块俯冲碰撞引起的总体为岛弧背景下的局部拉张构造环境。     

Depth of the base of the Jackson aquifer, based on geophysical exploration, southern Jackson Hole, Wyoming, USA

 A geophysical survey was conducted to determine the depth of the base of the water-table aquifer in the southern part of Jackson Hole, Wyoming, USA. Audio-magnetotellurics (AMT) measurements at 77 sites in the study area yielded electrical-resistivity logs of the subsurface, and these were used to infer lithologic changes with depth. A 100–600 ohm-m geoelectric layer, designated the Jackson aquifer, was used to represent surficial saturated, unconsolidated deposits of Quaternary age. The median depth of the base of the Jackson aquifer is estimated to be 200 ft (61 m), based on 62 sites that had sufficient resistivity data. AMT-measured values were kriged to predict the depth to the base of the aquifer throughout the southern part of Jackson Hole. Contour maps of the kriging predictions indicate that the depth of the base of the Jackson aquifer is shallow in the central part of the study area near the East and West Gros Ventre Buttes, deeper in the west near the Teton fault system, and shallow at the southern edge of Jackson Hole. Predicted, contoured depths range from 100 ft (30 m) in the south, near the confluences of Spring Creek and Flat Creek with the Snake River, to 700 ft (210 m) in the west, near the town of Wilson, Wyoming. Received, May 1997 · Revised, February 1998 · Accepted, April 1998