Statistical approaches to the discrimination of mantle- and crust-derived low-Cr garnets using major and trace element data

Diamond exploration focuses on geochemical analysis of indicator minerals that are more abundant than diamond itself. Among such indicators, low-Cr (Cr₂O₃ < 1 wt%) garnets from mantle eclogites are problematic since they overlap compositionally with many lower-crust-derived garnets also transported by kimberlite. Misclassification of these garnets may create “false positive” mantle signatures and possible misdirection of exploration efforts. Statistical solutions using major elements in low-Cr garnet (Hardman et al. in J Geochem Explor 186:24–35, 2018) provide improved error rates for the discrimination of low-Cr crustal and mantle garnets recovered from kimberlite. In this study we analysed a large suite of garnets (n = 571) from both crustal and mantle settings, already characterised for major elements, for a wide range of trace elements by laser ablation inductively-coupled plasma mass spectrometry and use these new data along with literature data (n = 169) to evaluate the effectiveness of adding trace elements to garnet-based diamond exploration programs. A new garnet classification scheme, initially using a major-element based filter, uses garnet Sr contents and Eu anomalies to help identify low-Cr garnets that are misclassified using major element methods. Combined with existing methods, our new trace element classifiers offer improvement in classification error rates for low-Cr, crustal and mantle garnets to as low as 4.7% for calibration data.

     

Determination of major and trace elements in sphalerite using laser ablation double focusing sector field ICP-MS

The analytical performance of laser ablation (LA) for the determination of Co, Fe, Cd, Ag, Mn, Cu and S in sphalerite was evaluated using double focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). Samples were collected from Zinkgruvan, situated in the south central Sweden. The use of Zn for internal standardisation, together with correction for FeS impurities in sphalerite, allows straightforward quantification without using external methods for the determination of the actual Zn content. LA–ICP-SFMS results were compared with data obtained by conventional pneumatic nebulisation introduction of sample solutions following acid digestion. Good agreement between the two methods was obtained for homogeneously distributed elements. For the majority of the elements under consideration, LA–ICP-SFMS precision was better than 10% RSD.     

Composition of estuarine colloidal material: major and trace elements

Colloidal-sized material from the Patuxent River estuary, Maryland, was analyzed for more than 30 elements by instrumental neutron activation analysis. Sample data from stations ranging in salinity from 0.04 g/kg to 12 g/kg indicate that the winter colloidal material is dominated upstream by poorly crystallized clay minerals and iron oxide, but above a salinity of 10 g/kg, it consists primarily of carbonaceous material. Winter colloidal material decreases non-conservatively seaward from 29 to 0.6 mg/l. The summer colloidal material, however, is carbon-rich throughout the estuary and the amount of colloidal material in the upper water column does not change appreciably with increasing salinity. Many trace elements (Cs, Hf, Rb, Se, Th, V and the REE) covary with Al and probably are associated with the clay component. Other elements (As, Ba, Sb, Se, U and Zn) are considerably enriched relative to Al and may covary with the organic component. The results suggest that the freshwater winter colloidal system is a product of continental weathering processes, whereas the summer colloidal material is derived primarily from estuarine biological processes.     

Baseline models of trace elements in major aquifers of the United States

Trace-element concentrations in baseline samples from a survey of aquifers used as potable-water supplies in the United States are summarized using methods appropriate for data with multiple detection limits. The resulting statistical distribution models are used to develop summary statistics and estimate probabilities of exceeding water-quality standards.The models are based on data from the major aquifer studies of the USGS National Water Quality Assessment (NAWQA) Program. These data were produced with a nationally-consistent sampling and analytical framework specifically designed to determine the quality of the most important potable groundwater resources during the years 1991–2001.The analytical data for all elements surveyed contain values that were below several detection limits. Such datasets are referred to as multiply-censored data. To address this issue, a robust semi-parametric statistical method called regression on order statistics (ROS) is employed.Utilizing the 90th–95th percentile as an arbitrary range for the upper limits of expected baseline concentrations, the models show that baseline concentrations of dissolved Ba and Zn are below 500 μg/L. For the same percentile range, dissolved As, Cu and Mo concentrations are below 10 μg/L, and dissolved Ag, Be, Cd, Co, Cr, Ni, Pb, Sb and Se are below 1–5 μg/L.These models are also used to determine the probabilities that potable ground waters exceed drinking water standards. For dissolved Ba, Cr, Cu, Pb, Ni, Mo and Se, the likelihood of exceeding the US Environmental Protection Agency standards at the well-head is less than 1–1.5%. A notable exception is As, which has approximately a 7% chance of exceeding the maximum contaminant level (10 μg/L) at the well head.     

Composition and variation of major and trace elements in Croatian bottled waters

Within the framework of the Pan-European project about the geochemistry of bottled mineral waters in Europe launched in 2007 by the European Geological Surveys (EGS) Geochemistry Expert Group fourteen brands of bottled natural waters from Croatia of both mineral and spring types were evaluated for getting more coherent spatial information about the natural variation of element concentration in bottled waters found at the European market. Results of chemical analysis show that not a single one out of fourteen analyzed bottled waters from Croatia exceeds the Croatian water standards sanctioning thereby their suitability for human consumption. Also, statistical tests performed for 41 analytes (including pH and EC) clearly show that the water chemistry is in a high degree of conformity with regional geology, depending on structural, stratigraphic and, above all, lithological diversity of aquifers. Thus Dinaric and Pannonian parts of Croatia differ largely with regard to their water types: Dinaric region is completely lacking mineral water types while, on the other side, in the Pannonian region even the spring waters show stronger mineralization in comparison with their Dinaric counterparts. Typically, all natural waters from Croatia bear the bicarbonate (HCO₃) signature. However, Ca–Mg cation pair combination is characteristic of spring waters while Na–K dominates in the mineral waters.     

Natural concentrations of major and trace elements in some Norwegian bedrock groundwaters

Twenty-eight groundwater samples have been collected from boreholes in bedrock aquifers in Nord Trøndelag (Central Norway), the Hvaler archipelago and other areas around Oslofjord (South-eastern Norway). A clear relationship is demonstrated between many chemical parameters and lithology or geographical location. The parameters electrical conductivity, Cl⁻, SO₄²⁻, F⁻, Na, Al, Fe, Be, Bi, Cd, Cu, La, Mo, Pb, Th, Tl, U, Y, Zn, Zr, B, Rn, and Si have generally higher values in the Iddefjord Granite of Hvaler, while pH, alkalinity, Ca, Mg, Cs, Rb, and Sr are highest in Trøndelag. Several parameters such as F⁻, Na, Fe, U, Rn and possibly Al exceed drinking water norms on Hvaler. Measured values of the analyzed parameters compare well (except F⁻) with the Dutch “A” (background) values, developed for assessment of anthropogenic contamination. The authors warn, however, against uncritical use of “norms” developed in countries with other dominant lithologies than Norway.     

高铝粉煤灰中部分主微量元素的分布规律研究

本文旨在研究部分主微量元素在高铝粉煤灰中的分布规律,从而为其资源化利用提供科学依据。首先根据高铝粉煤灰的物相组成特点采用新的分离方法将之分离为三个相(或相组合):铁质微珠、莫来石-刚玉相以及玻璃相;然后分别用化学分析和ICP-MS测试主微量元素在高铝粉煤灰、铁质微珠以及莫来石-刚玉相中的含量,并结合相关数据计算出这些元素在玻璃相中的含量。结果表明,除Al、Mn外,其他元素均在玻璃相中有不同程度的富集;除Al外,其他元素则在莫来石-刚玉相中有不同程度的贫化;除Ti以外的铁族元素以及除Ga、Pb以外的金属成矿元素均在铁质微珠中富集,其他元素则在其中贫化。     

低熟煤中的孢粉与常量元素和微量元素的相关性初探

运用电离耦合等离子体原子发射光谱(ICP-AES)和X射线荧光光谱分析(XRF),对新疆八道湾煤矿中侏罗统西山窑组煤中的孢粉角质层进行了分析,测定了煤中的常量和微量元素。并对煤中孢粉和共伴生元素进行了回归分析,探讨了微量和常量元素的煤岩学及孢粉学属性,在微量元素与孢粉的煤相学应用方面作了初步尝试。结果表明,成煤的蕨类植物孢子和裸子植物花粉与某些常量元素和微量元素有着很高的相关性;蕨类植物孢子和裸子植物花粉的相对含量在煤中具有互补性,决定了它们与微量元素的关系也具有一定的互补性。     

Geographical variations of trace elements in sediments of the major rivers in eastern China

 A total of 26 geographically and hydrologically diverse sediment samples were collected from 12 major rivers in eastern China. The <63-μm fraction of the sediments was analysed for both total concentrations of Cu, Zn, Pb and Cd, and their associations with various geochemical phases. The geographical variations of sediment-bound trace metals can be related to the bedrock types and weathering processes in the corresponding river basins. The rivers in southern China had notably higher concentrations of trace metals in sediments because of abundant non-ferrous mineral deposits and stronger weathering process in the region. A large proportion of trace metals in these sediments was associated with iron and manganese oxides and organic matter. Relative low levels of trace metals were found in river sediments in northern China, and a significant proportion of the metals was bound to organic matter, carbonates, and the residual fraction. The sediments in the Yellow River, originating from special loess, had the lowest concentrations of trace metals. Most of the trace metals were associated with the carbonates and residual phases. Received: 24 March 2000 · Accepted: 11 July 2000     

Diffusion coupling between trace and major elements and a model for calculation of magma residence times using plagioclase

Residence times of plagioclase crystals in magma reservoirs can be determined by modeling the compositional zoning of trace elements in these crystals. We present a formulation to model diffusion of trace elements in plagioclase paying special attention to certain thermodynamic and kinetic aspects. In particular, we account for the compositional dependence on anorthite content of the chemical potential and diffusion coefficients of trace elements (e.g., Mg), the choice of suitable boundary conditions and potential effects of diffusion in more than one dimension. We show that contrary to intuition, diffusive fluxes of trace elements may be coupled to major element concentration gradients, and ignoring such coupling can lead to incorrect estimates of timescales. We illustrate application of the model using plagioclase crystals from a suite of gabbroic xenoliths from a Holocene dacitic lava flow of Volcán San Pedro (Chilean Andes, 36°S). The inferred timescale for metasomatism of the xenoliths by evolved liquids is on the order of 100 (30 to 148) yr and serves to illustrate how trace element zoning in plagioclase provides a window into timescales of magmatic processes inaccessible by isotopic or other methods.     

Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.     

Migration and contamination of major and trace elements in groundwater of Madras city,India

Groundwater samples collected from both open and bore wells in an area of about 270 km² from Madras City, India, have been analyzed for major ions (HCO₃, Cl, Si, Na, Ca, and Mg) and trace elements (As, Se, B, V, Cr, Fe, Co, Pb, Cu, Zn, Cd, Mn, Ni, Mo, and Ba). The study reveals that the quality of potable water has deteriorated to a large extent. Seawater intrusion into the aquifer has been observed in nearly 50 percent of the study area. The toxic elements (As and Se) have already exceeded the maximum permissible limits of drinking water in almost the entire city. A positive correlation of As and Se with other toxic metals such as V, Cr, Fe, B, etc., indicates that all these elements are anthropogenic in origin. Applying multivariate analysis, the source for trace elements in groundwater has been grouped into two major factors: pollution and mobilization factors. The groundwater in the study area is largely contaminated by organic effluents and reflects the intensity of pollution caused by the overlying soil sediment and rapid infiltration of the pollutants.     

Experimental constraints on major and trace element partitioning during partial melting of eclogite

Isobaric partial melting experiments were performed on an Fe-free synthetic composition to simulate partial melting of subducted oceanic crust. Nominally anhydrous experiments at 3.0 GPa yielded melts in equilibrium with garnet (13 to 16 mol.% grossular) and aluminous clinopyroxene (14 to 16 wt.% Al₂O₃). Melt compositions show decreasing Si and alkalis and increasing Ca, Mg, and Ti contents with increasing temperatures. Experiments at 1200 and 1300°C were rutile saturated, whereas experiments at 1400°C contained no residual rutile. We argue that during the initial stages of subduction, accessory rutile is likely to be stable in subsolidus eclogites of average midocean ridge basalt composition and that only large degrees of partial melting will eradicate rutile from an eclogitic source. At 3 GPa, any eclogites with a bulk TiO₂ content of ≥1.5 wt.% rutile will produce rutile-saturated partial melts, except at very high degrees of melting. At higher pressures, all bulk Ti may dissolve in clinopyroxene and garnet, leaving no accessory rutile.Trace element partition coefficients for 24 trace elements between clinopyroxene, garnet, and melt were determined by secondary-ion mass spectrometry analysis of experimental run products at 1400°C and 3 GPa. Partition coefficients for the rare earth elements agree well with previous studies and have been evaluated using the lattice strain model. Partitioning data for high-field strength elements indicate complementary D_Zr/D_Hf for clinopyroxene and garnet. Partial melting of an eclogitic component of different modal compositions may therefore explain both subchondritic and superchondritic Zr/Hf ratios. Superchondritic Zr/Hf has recently been observed in some ocean island basalts (OIB), and this may be taken as further evidence for components of recycled oceanic crust in OIB. The data also indicate slight Nb/Ta fractionation during partial melting of bimineralic eclogite, which is not, however, sufficient to explain some recently observed Nb/Ta fractionation in island arc rocks. Accessory rutile, however, can explain such fractionation.     

Use of major and selected trace elements to describe mixing processes in a water reservoir

Data on temperature, major constituents and some trace elements, measured in the dissolved and particulate phases, were used to identify the hydrodynamics of a reservoir (the Bicaz reservoir, Romania). Results revealed that the reservoir experiences two thermal stratifications per year (summer and winter). However, the summer stratification is delayed by the high river inflow of June–July. Two layers were identified, a surface and a deep layer, whose location and impact vary with time. The surface layer originates from the river inflow (intrusion layer) and the deep current is produced by the outflow (velocity current). According to season, the river inflow either supplies the deep current or remains recordable up to the dam. Consequently, the structure of the water column, and thus the biogeochemical processes within it, are governed both by thermal stratification and by these layers.     

Determination of major and trace elements in European bottled mineral water — Analytical methods

A total of 1785 European bottled water samples were analyzed using standard laboratory methods. The bottled water samples were purchased in 2008 at supermarkets throughout 40 European countries. The samples were analyzed for 71 chemical parameters (As, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, Br⁻, HCO₃⁻, Cl⁻, F⁻, NH₄⁺, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻, SiO₂, pH, and EC) by quadrupole inductively coupled emission spectroscopy (ICP-QMS, trace elements), inductively coupled plasma atomic emission spectroscopy (ICP-AES, major elements), ion chromatography (IC, anions), atomic fluorescence spectrometry (AFS, Hg), titration (alkalinity), photometric methods (NH₄⁺), potentiometric methods (pH), and conductometric methods (specific electrical conductivity, EC). A very strict quality control procedure was followed by analysing blanks, international reference materials, an internal project standard, and duplicate analyses, as well as by analysing 23 elements by both ICP-QMS and ICP-AES. Analysis of marketed bottled water from springs, wells or boreholes, apart from the evaluation of its quality with respect to inorganic elements, it may provide a cheap alternative to obtain a first impression about groundwater chemistry at the European scale.     

Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

Geochemical factors controlling accumulation of major and trace elements in Greenland coastal and fjord sediments

 The major (Al, Ti, Ca, Mg, Fe, Mn, Si) and trace element (Cd, Cr, Cu, Hg, Li, Ni, Pb, V, Zn) concentrations in surficial (<20 cm) sediments from fjords and open coastal waters around Greenland have been determined. Regionally, high concentrations of Fe, Ti, Mg, Cr, Cu, Ni, and V occur in some west and east coast sediments, but they appear to be natural in origin, as there is no indication of anthropogenic influence. Chemical partition indicates that most of the heavy metals are structurally bound in various silicate, oxide, and sulfide minerals. These host minerals occur more or less equally in the coarse and fine sediment fractions (material >63 μm and <63 μm) and have accumulated at the same rate as other detrital clastic material. Provenance and glaciomarine deposition are the main factors controlling the abundance and distribution of the major and trace elements. The chemical composition reflects the mineralogical differences in the provenance of glacial marine material deposited by water and ice adjacent to Greenland. The main source of the sediments enriched in Ti, Fe, Mg, Cr, Cu, Ni, and V appears to be material derived from the volcanic rocks of the Mesozoic-Tertiary Provinces of Greenland by glacial erosion. Received: 26 June 1995 · Accepted: 11 August 1995     

Source/process apportionment of major and trace elements in sinking particles in the Sargasso sea

Elemental composition of the particle flux at the Oceanic Flux Program (OFP) time-series site off Bermuda was measured from January 2002 to March 2005. Eighteen elements (Mg, Al, Si, P, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sr, Cd, Ba and Pb) in sediment trap material from 500, 1500 and 3200 m depths were quantified using fusion-HR-ICPMS. Positive Matrix Factorization (PMF) was used to elucidate sources, elemental associations and processes that affect geochemical behavior in the water column.Results provide evidence for intense elemental cycling between the sinking flux material and the dissolved and suspended pools within mesopelagic and bathypelagic waters. Biological processing and remineralization rapidly deplete the sinking flux material in organic matter and associated elements (N, P, Cd, Zn) between 500 and 1500 m depth. Suspended particle aggregation, authigenic mineral precipitation, and chemical scavenging enriches the flux material in lithogenic minerals, barite and redox sensitive elements (Mn, Co, V, Fe). A large increase in the flux of lithogenic elements is observed with depth and confirms that the northeast Sargasso is a significant sink for advected continental materials, likely supplied via Gulf Stream circulation.PMF resolved major sources that contribute to sinking flux at all depths (carbonate, high-Mg carbonate, opal, organic matter, lithogenic material, and barite) as well as additional depth-specific elemental associations that contribute about half of the compositional variability in the flux. PMF solutions indicate close geochemical associations of barite-opal, Cd-P, Zn-Co, Zn-Pb and redox sensitive elements in the sinking flux material at 500 m depth. Major reorganizations of element associations occur as labile carrier phases break down and elements redistribute among new carrier phases deeper in the water column.Factor scores show strong covariation and similar temporal phasing among the three trap depths and indicate a tight coupling in particle flux compositional variability throughout the water column. Seasonality in flux composition is primarily driven by dilution of the lithogenic component with freshly-produced biogenic material during the late winter primary production maximum. Temporal trends in scores reveal subtle non-seasonal changes in flux composition occurring on month long timescales. This non-seasonal variability may be driven by changes in the biogeochemical properties of intermediate water masses that pass through the region and which affect rates of chemical scavenging and/or aggregation within the water column.