1988 COMPILATION REPORT ON TRACE ELEMENTS IN SIX ANRT ROCK REFERENCE SAMPLES: DIORITE DR-N, SERPENTINE UB-N, BAUXITE BX-N, DISTHENE DT-N, GRANITE GS-N AND POTASH FELDSPAR FK-N

The six ANRT rock reference samples (DR-N, UB-N, BX-N, DT-N, GS-N, FK-N) have been distributed as reference samples for nearly twenty years. All available data on trace elements in these samples are presented and evaluated. It has been possible to assign working values for nearly 40 trace elements. These samples prepared in 600 to 1300 kg quantities are expected to last for some decades to come.     

Sequential Inductively Coupled Plasma Determination Of Some Rare-Earth Elements in Five French Geostandards

Experimental data for eleven rare-earth elements (REE) obtained by inductively coupled plasma spectrometry (ICP) in five French geochemical reference standards (BE-N, BR, DR-N, GS-N and FK-N)are presented. The method is based on acid digestion of the sample and cation-exchange separation from matrix elements.
Together with these new determinations an updated compilation of these reference materials are presented. Good agreement between the present results and previously preferred and published values obtained by various analytical techniques is observed. The values obtained in the present work corroborate the validity of the outlined method.     

Neutron Activation Determination of Twenty-One Trace Clements, Including Rare - Earths, in Two ANRT Geochemical Reference Samples: Diorite DR-N And Granite GS-N

Results for twenty-one trace elements obtained by neutron activation analysis and high resolution Ge (Li) γ-ray spectrometry in two standard reference rocks - Diorite DR-N and Granite GS-N - distributed by the Association Rationale de la Recherche Technique (ANRT) are presented.     

SECOND REPORT (1993) ON THE FIRST THREE GIT-IWG ROCK REFERENCE SAMPLES: ANORTHOSITE FROM GREENLAND, AN-G; BASALTE D'ESSEY-LA-CÔTE, BE-N; GRANITE DE BEAUVOIR, MA-N

The first report (1980) on the three samples, Anorthosite AN-G, Basalt BE-N and Granite MA-N resulted in the chemical characterization of major, minor and 30 trace elements. The present report confirms the validity of a great majority of these working values, in addition to presenting working values for 20 more trace elements for each sample. Only compiled data on trace elements are presented, followed by Tables of statistical parameters used as a basis for their evaluation, both statistical and subjective. A plea is made to obtain more data on platinum group elements and on other "difficult" trace elements (Au, B, Bi, Se, Te, TI, …). The three samples have been processed in 900 kg amounts and, therefore, they are likely to remain available for some decades to come. As such, it is certainly worthwhile to take pains to characterize them well for even these difficult trace elements.     

Report (1967–1981) on Four ANRT Rock Reference Samples: Diorite DR-N, Serpentine UB-N, Bauxite BX-N and Disthene DT-N

All data reported by 200 analysts (106 laboratories) are presented for the four ANRT samples: Diorite DR-N, Serpentine UB-N, Bauxite BX-N and Disthène DT-N. Recommended values are given for the major and minor elements. As far as the as trace elements are concerned, DR-N has been characterized for 35 elements whereas the other three samples have been for only 20 elements. Wherever possible, brief comments have been inserted so as to explain our way of assigning recommended or proposed values.
After more than a decade of existence the total number of data reported for all the four samples reach only 3200 units which are not sufficient enough for a valid evaluation of compiled data. It is also pointed out that these samples are most likely to be available even during the next century as they have been prepared in large quantities of the order of one ton. A plea is therefore made for contribution of more data particularly for trace elements and for major elements which are present as trace elements in UB-N, BX-N and DT-N.     

Seasonal variability in response of estuarine phytoplankton communities to stress: Linkages between toxic trace elements and nutrient enrichment

We examined individual and interactive effects of two stressors—nutrients (nitrogen [N] and phosphorus [P]) and trace elements (a mix of arsenic [As], copper [Cu], and cadmium [Cd], and in a second experiment also zinc [Zn] and nickel [Ni])—on phytoplankton of the mesohaline Patuxent River, a tributary of Chesapeake Bay. Experiments were conducted in twenty 1-m³ mesocosms. Four mesocosm runs used two levels of nutrient loadings (0.7–1.0 × ambient N loading and enriched to 1.3–1.6 × ambient N loading) crossed with two levels of trace elements (ambient and enriched approximately 2–5 × higher than ambient concentrations) crossed with five progressive levels of ecosystem complexity. To examine seasonal patterns of responses to stressors, data from these experiments were combined with results of a similar experiment conducted during 1996 (Breitburg et al. 1999a). A second mesocosm experiment examined effects of individual and mixed trace elements, both alone and in combination with nutrients, to further examine which nutrient-trace element interactions were important. Nutrients consistently increased phytoplankton productivity and biomass. Most of the increased biomass was created by large centric diatoms, which increased the mean cell size of the phytoplankton community. Trace element additions decreased phytoplankton productivity and biomass, as well as the contribution of large centric diatoms to phytoplankton biomass. When both trace elements and nutrients were added, trace elements reduced nutrient stimulation. Although the magnitude of the response to nutrient additions tended to be somewhat greater in spring, the seasonal patterns of trace element effects, and nutrient-trace element interactions were far more striking with significant responses restricted to spring mesocosm runs. The second experiment indicated that both As and Cu were more inhibitory to phytoplankton in spring than in summer, but As was more inhibitory in the low nutrient treatments and Cu was more inhibitory in the nutrient enrichment treatments. The potential for strong seasonal patterns and high temporal variability in stressor effects and multiple stressor interactiosn will require close attention in the design and interpretation of management-relevant research and monitoring and may indicate the need for seasonally varying management strategies.     

鱼耳石微化学特征在湖库水质评价中的标型意义——以河北白洋淀和北京密云水库野生鲤鱼为例

对河北白洋淀和北京密云水库的野生鲤鱼耳石和水体中的微量元素进行了定量分析。白洋淀鱼耳石中诸微量元素含量均高于密云水库的鱼耳石,反映了白洋淀各水体较密云水库水体的环境复杂,污染程度高。统计分析结果表明,在鱼耳石中大致存在两类生物地球化学习性不同的元素,水体中第一类元素的变化不会引起耳石中相应元素的响应,如Au、K和Na;第二类元素的变化会引起耳石中相应元素的强烈响应,如As、Ba、Co、Cr、Fe、Sr和Zn。诸微量元素在耳石中富集的强弱顺序为,Zn>Sr>Se>Fe>As>Ba>K>Co>Au>Na>Cr。通过相关性分析发现,白洋淀和密云水库的鱼耳石和水体中对应微量元素平均含量的自然对数值之间均存在良好的线性关系。     

Neutron Activation Analysis of Seven B.C.S. Certified Reference Materials of Geological Interest

The concentrations of 26 elements have been investigated in seven BCS certified reference samples using three varieties of neutron activation analysis. The ANRT granite GS-N was used as the comparator reference material while the USGS basalt BHVO-1 and the GIT-IWG basalt BE-N were analysed concurrently to assess the analytical accuracy.     

The chemistry of gabbro/amphibolite transitions in South Norway

Trace element data are presented for sixteen gabbro (hyperite)/amphibolite pairs which were collected from geological situations where it seems clear that the amphibolite formed from material similar in composition to that of the adjacent hyperite. The metamorphism of hyperite to amphibolite was not isochemical with respect to some trace elements. Cl, V and Rb were increased, as possibly was Zr. S and Zn were diminished, as possibly was Co. Sr and Ba are rather constant in the hyperites and appear to have been irregularly dispersed during the amphibolitisation. The trace element movement patterns are consistent with the known changes in the major elements, which have been reported earlier (Elliott, 1973). The introduced material was added during metamorphism under amphibolite facies conditions, by upward migration from an originally subjacent granulite facies zone. The evidence supports a hydrous fluid diffusion process for the mechanism of transfer.     

Report (1984) on Two GIT-IWG Geochemical Reference Samples: Albite from Italy, AL-I And Iron Formation Sample from Greenland, IF-G

Two reference samples, Albite AL-I and Iron Formation sample IF-G were analysed for their chemical composition by the International Working Group "Analytical Standards of Minerals, Ores and Rocks" (GIT-IWG). AL-I was processed in 189 kg and IF-G and 760 kg. 103 GIT-IWG laboratories participated in this collaborative study along with 171 geoanalysts. This study lasted 15 months (September 1982 - December 1983) and is the second undertaken by the GIT-IWG. Over 2400 units of data were collated. As a result of this international study, the major and minor elements have been well characterized in both the samples; however, more data on trace elements will be very welcome for a better definition of trace elements, although working values have been proposed for about forty trace elements in each sample. The first and the second collaborative studies undertaken by GIT-IWG demonstrate well the immense analytical potential of the GIT-IWG.     

河北开滦矿区煤洗选过程中 15种主要有害微量元素的迁移和分配特征

以河北开滦矿区晚古生代煤及其洗选产品为例,运用电感耦合等离子体质谱 (ICP-MS)和冷原子吸收光谱 (CV-AAS)方法对煤中主要微量有害元素 (包括 Be、 Cr、 Co、 Ni、 Cu、 Zn、 Ga、 As、 Se、 Mo、 Tl、 Pb、 Th、 U和 Hg)的含量及其在洗选过程中的迁移和分配特征进行了研究.通过对开滦矿区 10个矿井 47个煤层刻槽样品主要有害微量元素含量的统计,发现开滦矿区晚古生代煤中 Cr、 Ni、 Cu、 Zn、 Pb和 As富集.通过对原煤精煤中煤尾煤煤泥两套系列样品的分析,发现主要有害微量元素在精煤中都有不同程度的脱除,中煤中相对富集的元素有 Se和 Th,明显被脱除的元素有 Co和 Tl.除 Tl以外,尾煤中主要微量有害元素均有不同程度的富集,以 As的富集率最高,可达 34.4%, Hg的富集率最低,为 1.1%.煤泥中所有微量有害元素均相对富集,以 Hg的相对富集率最高,达 78.4%.因此,如果对尾煤和煤泥加以利用,需要特别关注 As和 Hg等微量有害元素对环境的影响.主要微量有害元素在洗选过程中的分配行为主要受控于它在煤中的赋存状态.     

Temporal and spatial patterns of trace elements in the Patuxent River: A whole watershed approach

Trace element distributions, partitioning, and speciation were examined at 15 sites in the Patuxent River watershed from May 1995 through October 1997 to determine possible sources of trace elements to the river and estuary, to examine the relationship of the trace element discharges to freshwater discharges as well as to land use and geographic region, to validate previous estimates of loadings to the river, and to provide baseline data for trace elements in the Patuxent River watershed and estuary. Six freshwater sites were examined, representing different basins and geographic provinces, and nine sites along the estuarine salinity gradient. Subregions within the watershed varied considerably in concentrations and areal yields for some elements. Concentrations of As, Cd, Ni, Pb, and Zn were elevated in the Coastal Plain sites compared to the Piedmont sites, while Cu and Hg were more evenly distributed. Cadmium, Cu, Hg, Ni, Pb, and Zn showed overall positive correlations with river flow while As and methylHg (meHg) showed negative correlations with river flow. Concentrations of trace elements in the estuarine portion of the river were generally low, and consistent with mixing between Patuxent River water with elevated concentrations and the lower concentrations of the Chesapeake Bay. Interesting features included a local Cd maximum in the low salinity region of the estuary, probably caused by desorption from suspended sediments, and a significant input of water containing high As concentrations from the Chesapeake Bay and from As being released from bottom sediments in summer. Comparisons between the estimated annual flux of trace elements and the estimates of suspected source terms (atmospheric deposition, urban runoff, and known point sources) suggest that, except for Hg, direct atmospheric deposition is small compared to fluvial loads. Current estimates of trace element inputs from point sources or from urban runoff are inadequate for comparison with other sources, because of inappropriate techniques and/or unacceptably high detection limits. A complete examination of trace element dynamics in the Patuxent River (and in other coastal systems) will require better data for these potential sources.     

A new way of interpreting trace element concentrations with respect to modes of mineral formation

The availability of multi-element analyses provides numerous data on trace elements. These data complete petrochemical analyses in general and are often reported as averages although they vary over many orders of magnitude. It can be shown that the variation of trace elements in ores is related to fundamental processes during ore formation. As examples the fractionation of the lanthanoids in Ca-minerals (fluorite, calcite, apatite, phosphorite, etc.), chalcophile elements in sphalerite and Ga, Sc, W, and Fe in cassiterite are discussed. Plotting of analytical data in variation diagrams (fractional index vs. chemical environmental index) help to decipher the mode of mineral formation.The information obtained from trace and minor element fractionation are discussed with respect to the probable origin of hydrothermal solutions.     

湘西南元古宙高涧群微量元素主成分分析

主成分分析法（PCA）是多元样本数据的数理统计方法。本文结合湘西南元古宙高涧群地层剖面等离子光谱分析所得Au、Ag、As、Sb、Cu、Pb、Zn、Sr、Ba、Mn、Co、Ti、Cr共13个微量元素的主成分计算结果和图解,解释了主成分参数和图解的地质含义。在C剖面和L剖面上,主成分F1具有相似的信息量,反映高涧群“原始”沉积物以铁镁矿物为主要特征。F2的信息量不同,在L剖面上,F1－F2图解可以将13个“原”变量分为5组“原”变量的组合：Co-Zn-Cu(Mn、Ba)、Ti-Cr、As-Pb、Au-Pb-Sr和Ag,Ag主要来自碎屑沉积物;在C剖面上,“原”变量的组合特征不明显,As、Cr、Sb、Ti与F2呈正相关,Sr与F2呈负相关。在L剖面上,Au主要受氧化条件制约;在C剖面上,海水较深,还原条件有利于Au、Ag的沉积。由于沉积环境不同,研究区的南部和北部一些微量元素存在明显的差异。根据（di^k)^2计算值,Ag、Pb的分布部分与后期构造破坏有关。     

Seasonal and spatial dynamics of trace elements in water and sediment from Pearl River Estuary, South China

In this study, spatial and seasonal dynamics of trace elements (Cu, Pb, Zn, Cd, As) in water and sediments were examined in the Pearl River Estuary (PRE), South China. The spatial variations of all the studied trace elements in sediments show the general decrease pattern from northwest to southeast side of the PRE, suggesting that the main sources of these trace elements may originate from terrestrial (rock and soil) weathering and human activities (e.g. agricultural, industrial and municipal wastewaters) via riverine inputs. The dissolved Cu, Pb, Cd, As, and Zn in PRE ranged from 0.34 to 3.26, 0.19 to 4.58, 0.0015 to 0.30, 0.16 to 8.18, 3.74 to 36.10 μg/L, respectively. There are obvious seasonal changes of dissolved trace elements in the PRE aquatic system. The maximum seasonal averages of all the dissolved trace elements excluding Zn were observed in summer, whereas dissolved Zn showed the minimum in this season. The overall spatial pattern of all the dissolved trace elements excluding Zn demonstrates decreasing trends from inshore to offshore, and the highest concentrations of dissolved Cu, Cd, As, and Zn appeared in the western part of PRE or the mouths of Pearl River, suggesting strong riverine and anthropogenic local inputs. PCA and correlation analysis show that the geochemical behavior of dissolved Cu and As are complicated and the dynamics of these two elements are controlled by various physicochemical parameters, whereas physicochemical parameters might play a relatively small role in the distributions of other studied trace elements.     

安山岩风化过程中元素行为——以豫西熊耳山地区为例

在风化过程中主量元素的风化行为可用风化指数来表征,但对在地球化学中更重要的微量元素的风化行为还缺少研究。本文研究了豫西熊耳山地区—安山岩风化剖面,发现花岗岩风化指数(WIG)也适用于安山岩风化过程的定量表征。基于上陆壳作标准绘制风化剖面样品稀土元素配分曲线时,发现风化过程稀土元素出现分馏现象,表现为富集中稀土;但基于球粒陨石作标准时,风化壳样品均具有相似的稀土配分曲线形态,即上陆壳是一种比球粒陨石更为敏感的稀土元素标准化标尺。牛头沟金矿区安山岩风化过程中部分微量表现出随风化程度增强而显著富集的特征,Au、Ag含量变化可达两个数量级以上,Pb、As、Hg可达一个数量级以上。     

Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

Distribution of selected trace elements in sediments of Pamlico river estuary,north Carolina

Sixty-eight samples of sediment collected on a variably-spaced grid pattern from Pamlico River Estuary of North Carolina were analyzed for As, Cd, Co, Cr, Cu, F, Ni, Pb, U, Zn, clay, and organic matter. The major objectives of the study were to determine background and anomalous levels of trace elements in the sediments, and the effects of human activities on concentration and distribution of trace elements in the sediments. Clay and organic matter are more concentrated near the center of the estuary. This causes the highest concentration of trace elements in the sediments to be located there also owing to their preferential uptake of these elements. Highest trace element concentrations were observed in clay and organic matter near industrial sites, housing developments, and tributary mouths that drain areas of human activity. The apparent increase in trace element contents of fine sediments in Pamlico River Estuary owing to human activities is 4 to 1,750 times normal background levels.