Platinum-group elements (Ir,Pd, Pt and Rh) in road-deposited sediments in two urban watersheds,Hawaii

This study represents the first detailed investigation of platinum-group elements (PGEs) in road-deposited sediment (RDS) in Hawaii, USA. Thirty-three sample locations, in two urban watersheds in Honolulu, Oahu, Hawaii were sampled. The <63 μm fraction of RDS was digested with aqua regia, followed by matrix separation with Dowex AG50-X8 cation exchange resin. PGEs were analyzed with inductively coupled plasma-mass spectrometry (ICP-MS) equipped with a desolvating nebulizer. Concentrations of Rh, Pd and Pt in residential streets reached 64, 105 and 506 ng/g, respectively. Maximum enrichment ratios, computed as RDS concentrations relative to baseline values, exceeded 400, indicating a significant anthropogenic signal with the sequence Rh > Pt > Pd. Iridium concentrations were uniformly low <1 ng/g, and enrichment ratios support a geogenic source. Significant interelement PGE correlations (Pd–Pt–Rh), combined with the magnitude of PGE pair-wise ratios (Pt/Pd, Pt/Rh and Pd/Rh), and relative percentages comparable to European RDS and roadside soil in Indiana, USA all suggest an automobile source. Attrition of PGE-loaded automobile catalytic converters and subsequent loss to the environment by exhaust emissions explains the significant environmental signal of PGEs in road environments of Hawaii. Further PGE work is required to quantify urban transport paths as PGEs are known to bioaccumulate, cause cellular damage and may have detrimental human health effects.     

西天山喇嘛苏铜矿成矿斑岩的岩石学、地球化学特征及成因探讨

位于西天山别珍套-科古琴晚古生代岛弧西段的喇嘛苏铜矿床是区内最大的铜矿床,与成矿作用有着密切关系的斑岩体为英云闪长斑岩、花岗闪长斑岩,是同源岩浆分异演化的产物,且花岗闪长斑岩可能属于岩浆演化晚期的产物。本区成矿斑岩的主量、微量元素和Sr-Nd同位素地球化学特征表明,其富集大离子亲石元素,而相对亏损高场强元素,出现了较为明显的Ta、Nb负异常,初始锶同位素ISr和εNd(t=390Ma)值分别为0.7072～0.7076和-0.32～0.17,显示壳幔混合源的特征,利用Sr和Nd同位素估算其源区物质约有50%来源于地壳。岩石地球化学特征指示了其为典型钙碱性火山弧花岗岩,暗示其形成于大陆弧环境。结合区域地质背景,推测本区成矿斑岩是在洋壳俯冲作用下发生部分熔融,交代原先的地幔楔,并混合了部分下地壳的物质,经历分离结晶作用的产物,其形成可能与晚古生代准噶尔洋板块向南的俯冲作用有关。结合东西天山的成矿斑岩的地球化学特征对比研究,岩浆源区的差别可能导致不同类型斑岩型矿床的形成,斑岩型铜矿床的形成较斑岩型钼矿床可能有更少的地壳物质贡献。     

Combined Sr isotope and trace element analysis of melt inclusions at sub-ng levels using micro-milling, TIMS and ICPMS

This paper describes a technique, which allows precise and accurate Sr isotope measurement combined with trace element analysis of individual melt inclusions, of sample sizes  1 ng of Sr. The technique involves sampling by micro-milling, chemical dissolution, micro Sr column chemistry, TIMS, and ICPMS analyses. A 10% aliquot of each sample solution is used for trace element analysis by double focusing magnetic sector field ICPMS, while Sr is chemically separated from the remaining 90% and used for ⁸⁷Sr/⁸⁶Sr determinations by TIMS.During the development of the technique outlined above, we documented in detail the potential sources of blank contributions and their magnitude. The average size and Sr isotope composition of our laboratory total procedural blank during this study was 5.4 pg ± 0.3 pg Sr (n = 21) with an ⁸⁷Sr/⁸⁶Sr of 0.7111 ± 0.0002 (2SE, n = 3). The total procedural Rb blank was 1.9 ± 0.7 pg (n = 21). The total procedural blank was found to have minimal effect (< 150 ppm shift) on the ⁸⁷Sr/⁸⁶Sr of sample material containing down to  250 pg Sr. Applying a blank correction allows ‘in house’ standards of this size to be corrected back to within 175 ppm of their accepted values. By applying blank corrections we can confidently measure the Sr isotope composition on sample sizes down to  25 pg Sr to an accuracy better than 400 ppm.The utility of the technique is illustrated by application to a suite of melt inclusions from NW Iceland and their host olivines. It is shown that the effect of a small amount of entrainment of the host olivine during sampling of 50 μm melt inclusions has a negligible effect on the measured Sr isotope and trace element composition. Furthermore, where melt inclusions are < 50 μm it is possible to obtain Sr isotope and trace element data on multiple melt inclusions hosted in a single olivine. This provides similar information to that of the single melt inclusions.     

Compartmentalisation and groundwater–surface water interactions in a prospective shale gas basin: Assessment using variance analysis and multivariate statistics on water quality data

An environmental concern with hydraulic fracturing for shale gas is the risk of groundwater and surface water contamination. Assessing this risk partly involves the identification and understanding of groundwater–surface water interactions because potentially contaminating fluids could move from one water body to the other along hydraulic pathways. In this study, we use water quality data from a prospective shale gas basin to determine: if surface water sampling could identify groundwater compartmentalisation by low-permeability faults; and if surface waters interact with groundwater in underlying bedrock formations, thereby indicating hydraulic pathways. Variance analysis showed that bedrock geology was a significant factor influencing surface water quality, indicating regional-scale groundwater–surface water interactions despite the presence of an overlying region-wide layer of superficial deposits averaging 30–40 m thickness. We propose that surface waters interact with a weathered bedrock layer through the complex distribution of glaciofluvial sands and gravels. Principal component analysis showed that surface water compositions were constrained within groundwater end-member compositions. Surface water quality data showed no relationship with groundwater compartmentalisation known to be caused by a major basin fault. Therefore, there was no chemical evidence to suggest that deeper groundwater in this particular area of the prospective basin was reaching the surface in response to compartmentalisation. Consequently, in this case compartmentalisation does not appear to increase the risk of fracking-related contaminants reaching surface waters, although this may differ under different hydrogeological scenarios.     

Relationships between molecular bacterial diversity and chemistry of groundwater in the Wairarapa Valley,New Zealand

Groundwater plays an important role in New Zealand water supplies and hence monitoring activities are conducted regularly. Most monitoring programmes aim to evaluate groundwater chemistry and almost completely overlook the microbial component in this ecosystem. In our present study, the bacterial community structure of groundwater in the Wairarapa Valley was examined using the terminal restriction fragment length polymorphism (T-RFLP), and relationships between bacterial community structure and groundwater chemistry, aquifer confinement and groundwater usage were explored. In addition, the results from this study were compared with a previous T-RFLP survey of the same area in an attempt to detect changes in bacterial community structure over time. The data obtained suggested that bacterial community structure was related to groundwater chemistry, especially to redox conditions. Species composition showed minimal variation over time if groundwater chemistry remained unchanged. These findings reflect the potential of using bacterial communities as biological indicators to evaluate the health of groundwater ecosystems. We suggest that it is important to include this type of broad bacterial diversity assessment criteria into regular groundwater monitoring activities.     

南天山川乌鲁碱性杂岩体的岩石学和地球化学特征及其岩石成因

位于中国南天山西侧阔克萨彦岭一带的川乌鲁碱性杂岩体,与该区川乌鲁铜金多金属矿床有着直接的成因联系,该杂岩体由早期的辉长岩—闪长岩岩、主期的二长岩—正长岩和晚期的正长花岗斑岩脉组成,各期岩石在矿物组成和化学成分上有明显的变化。从早到晚,SiO2含量增加,变化范围是50.52%～70.64%;全碱含量先增后减,在SiO2含量小于61.69%时,随SiO2含量增加而增加,而当SiO2含量大于61.69%时,与SiO2含量负相关。在AR-SiO2图解上,大多样品落入碱性区间,在A/CNK-A/NK图解上表现出由准铝质向过碱性演化的趋势。微量元素表现为大离子亲石元素相对高场强元素富集,Rb、Ba、Th、Sr等元素的相对富集和Nb、Ta、P、Ti等元素的负异常。稀土元素表现为轻稀土相对富集的特征,其(La/Yb)N为14.13～25.09,具有Eu的正异常或极微弱的Eu负异常。一些元素比值的线性关系暗示了该杂岩体为岩浆混合成因,基性岩浆的源区为富水的岩石圈地幔,而酸性岩浆是中下地壳中性火成岩在含饱和水条件下部分熔融的产物。这些性质指示川乌鲁杂岩体是在后碰撞拉张环境中由岩石圈地幔熔融的基性岩浆的底侵作用导致地壳的熔融以及后期的岩浆混合作用有关。     

A Complex Petrogenesis for an Arc Magmatic Suite, St Kitts, Lesser Antilles

St Kitts forms one of the northern group of volcanic islandsin the Lesser Antilles arc. Eruptive products from the Mt Liamuigacentre are predominantly olivine + hypersthene-normative, low-Kbasalts through basaltic andesites to quartz-normative, low-Kandesites. Higher-Al and lower-Al groups can be distinguishedin the suite. Mineral assemblages include olivine, clinopyroxene,orthopyroxene, plagioclase and titanomagnetite with rarer amphibole,ilmenite and apatite. Eruptive temperatures of the andesitesare estimated as 963–950°C at fO₂ NNO + 1 (whereNNO is the nickel–nickel oxide buffer). Field and mineralchemical data provide evidence for magma mixing. Glass (melt)inclusions in the phenocrysts range in composition from andesiteto high-silica rhyolite. Compositional variations are broadlyconsistent with the evolution of more evolved magmas by crystalfractionation of basaltic parental magmas. The absence of anycovariation between ⁸⁷Sr/⁸⁶Sr or ¹⁴³Nd/¹⁴⁴Nd and SiO₂ rulesout assimilation of older silicic crust. However, positive correlationsbetween Ba/La, La/Sm and ²⁰⁸Pb/²⁰⁴Pb and between ²⁰⁸Pb/²⁰⁴Pband SiO₂ are consistent with assimilation of small amounts (<10%)of biogenic sediments. Trace element and Sr–Nd–Pbisotope data suggest derivation from a normal mid-ocean ridgebasalt (N-MORB)-type mantle source metasomatized by subductedsediment or sediment melt and fluid. The eruptive rocks arecharacterized by ²³⁸U excesses that indicate that fluid additionof U occurred <350 kyr ago; U–Th isotope data for mineralseparates are dominated by melt inclusions but would allow crystallizationages of 13–68 ka. However, plagioclase is consistentlydisplaced above these ‘isochrons’, with apparentages of 39–236 ka, and plagioclase crystal size distributionsare concave-upwards. These observations suggest that mixingprocesses are important. The presence of ²²⁶Ra excesses in twosamples indicates some fluid addition <8 kyr ago and thatthe magma residence times must also have been less than 8 kyr. KEY WORDS: Sr–Nd–Pb isotopes; U-series isotopes; crystal size distribution; petrogenesis     

Mixed fluid sources involved in diamond growth constrained by Sr–Nd–Pb–C–N isotopes and trace elements

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665–667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ～ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid–rock interaction and to immiscibility processes.Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.