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USGS1987

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.

Geochimica et Cosmochimica Acta↗

USGS1992

Rare earth, major, and trace element composition of Monterey and DSDP chert and associated host sediment: Assessing the influence of chemical fractionation during diagenesis

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO 2 concentration in chert, often with final SiO 2 ≥ 98 wt%. This contrast in SiO 2 (and Si Al "> SiAl ) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO 2 concentrations and Si Al "> SiAl ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO 2 , construct a chert composition which is essentially identical to observed SiO 2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO 2 concentration contrast seems caused by biogenic SiO 2 dissolution and transport from the local adjacent host sediment and subsequent SiO 2 reprecipitation in the chert. Along with SiO 2 , other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO 2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO 2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO Al 2 O 3 "> MnOAl2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce Ce ∗ "> CeCe* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu Eu ∗ "> EuEu* decreases slightly during formation of DSDP chert. La n Yb n "> LanYbn is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE Al "> REEAl ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.

Geochimica et Cosmochimica Acta↗

USGS1986

A boundary element-Random walk model of mass transport in groundwater

A boundary element solution to the convective mass transport in groundwater is presented. This solution produces a continuous velocity field and reduces the amount of data preparation time and bookkeeping. By combining this solution and the random walk procedure, a convective-dispersive mass transport model is obtained. This model may be easily used to simulate groundwater contamination problems. The accuracy of the boundary element model has been verified by reproducing the analytical solution to a two-dimensional convective mass transport problem. The method was also used to simulate a convective-dispersive problem.

Journal of Hydrology↗

USGS1988

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P 2 O 5 "> REEP2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 × 10 −3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment.

Marine Geology↗

USGS1979

The petrogenesis and trace-element geochemistry of intermediate lavas from Humphreys Peak, San Francisco volcanic field, Arizona

The San Francisco Mountain lavas exposed in the upper portion of the southeast slope of Humphreys Peak are composed of three petrographically distinct types: (1) a lower series of hornblende pyroxene andesites; (2) a group of hypersthene dacites; and (3) an upper series of olivine andesites. These rocks have been shown to be related by crystallization differentiation through comparison of groundmass and bulk rock-chemical data. The major and trace elements from rocks representative of the volcanic field form continuous trends, an indication of differentiation rather than separate and discrete magma sources. Xenoliths found in the volcanic field are composed of the proper major and trace element contents to allow their extraction from a primary melt to form residual melts of more silicic lavas. The alkali olivine basalts, probably formed by partial melting of the mantle at a depth of 35-60 km, may well have differentiated to the alkali-rich highalumina basalts at depths of 15-35 km (the lower crust of the Colorado Plateau) by removal of olivine and clinopyroxene. Some of both lava types erupted periodically onto the surface while others continued to differentiate. Removal of plagioclase, with more minor amounts of olivine and pyroxenes (of less mafic composition than those above), from the high-alumina basalts eventually may have resulted in magmas similar in composition to the intermediate and more silicic rocks. The intermediate and silicic magmas contain hornblende and probably formed between 5 and 8 km. This places a minimum depth of penetration by the normal faults, such as the Mesa Butte fault, along which many silicic centers are aligned, at a depth of 5-8 km. Because of the continuous linear trends of the chemical data and the repetition over the past 6 m.y. of most of the rock types, the mantle beneath this southwestern margin of the Colorado Plateau apparently has not changed significantly during the past 6 m.y., nor is it likely to be very heterogeneous.

Arizona↗

USGS1988

Trace element residues in bluegills and common carp from the lower San Joaquin River, California, and its tributaries

Whole-body samples of bluegills (Lepomis macrochirus) and common carp (Cyprinus carpio) from the San Joaquin River and two tributaries (Merced River and Salt Slough) were analyzed to determine if the concentrations of any of nine elements were elevated as a result of exposure of the fish to agricultural subsurface (tile) drainage water. Highest concentrations (μg/g dry weight) detected were as follows (first number in each pair applies to bluegills and the second to carp): arsenic (As), 0.97 and 1.5; boron (B), 14 and 20; cadmium (Cd), 0.14 and 0.27; chromium (Cr), 2.7 and 2.2; mercury (hg), 3.3 and 2.9; molybdenum (Mo), 2.8 and 3.6; nickel (Ni), 0.87 and 2.2; lead (Pb), 0.26 and 2.3; and selenium (Se), 3.2 and 5.5. The lowest concentrations were below the levels of detection, except for Hg (0.15 in bluegills and 0.12 in carp) and Se (0.43 and 0.56). As judged by comparisons with data from the National Contaminant Biomonitoring Program and other published surveys, the concentrations of B, Hg, Mo, and Se were moderately elevated in fish from several sites in the San Joaquin Valley. However, only the Se concentrations were positively correlated with water quality variables (e.g., total alkalinity, conductivity, and turbidity) known to be influenced by irrigation return flows. Historical data from one site (Salt Slough), where trace elements in whole fish have been measured since 1969, indicated that Se concentrations increased more than twofold between 1973 and 1977, but thereafter remained near 3.0 μg g−1 (dry weight basis), presumably due to the continuing practice of disposing seleniferous tile drainage water into the most convenient stream channel.

California↗

USGS1992

Selenium and other elements in freshwater fishes from the irrigated San Joaquin valley, California

Arsenic (As), chromium (Cr), mercury (Hg), and selenium (Se) were measured in composite whole-body samples of five fishes — bluegill ( Lepomis macrochirus ), common carp ( Cyprinus carpio ), mosquitofish ( Gambusia affinis ), largemouth bass ( Micropterus salmoides ), and Sacramento blackfish ( Orthodon microlepidotus ) — from the San Joaquin River system to determine if concentrations were elevated from exposure to agricultural subsurface (tile) drainage. Except for Cr, the concentrations of these elements in fishes from one or more sites were elevated; however, only Se approached concentrations that may adversely affect survival, growth, or reproduction in warm water fishes. Moreover, only Se among the four measured elements exhibited a geographic (spatial) pattern that coincided with known inflows of tile drainage to the San Joaquin River and its tributaries. Historical data from the Grassland Water District (Grasslands; a region exposed to concentrated tile drainage) suggested that concentrations of Se in fishes were at maximum during or shortly after 1984 and have been slightly lower since then. The recent decline of Se concentrations in fishes from the Grasslands could be temporary if additional acreages of irrigated lands in this portion of the San Joaquin Valley must be tile-drained to protect agricultural crops from rising groundwater tables

California↗

USGS1985

Simulation of steady-state flow in three-dimensional fracture networks using the boundary-element method

An efficient method for simulating steady-state flow in three-dimensional fracture networks is formulated with the use of the boundary-element method. The host rock is considered to be impervious, and the fractures can be of any orientation and areal extent. The fractures are treated as surfaces where fluid movement is essentially two-dimensional. Fracture intersections are regarded as one-dimensional fluid conduits. Hence, the three-dimensional geometric characteristics of the fracture geometry is retained in solutions of coupled sets of one- and two-dimentional equations. Use of the boundary-element method to evaluate the fluid responses in the fractures precludes the need to internally discretize the areal extent of the fractures.

Advances in Water Resources↗

USGS1990

Influence of climate and eolian dust on the major-element chemistry and clay mineralogy of soils in the northern Bighorn basin, U.S.A.

Soil chronosequences in the northern Bighorn basin permit the study of chronologic changes in the major-element chemistry and clay mineralogy of soils formed in different climates. Two chronosequences along Rock Creek in south-central Montana formed on granitic alluvium in humid and semiarid climates over the past two million years. A chronosequence at the Kane fans in north-central Wyoming formed on calcareous alluvium in an arid climate over the past 600,000 years. Detailed analyses of elemental chemistry indicate that the soils in all three areas gradually incorporated eolian dust that contained less zirconium, considered to be chemically immobile during weathering, than did the alluvium. B and C horizons of soils in the wettest of the chronosequences developed mainly at logarithmic rates, suggesting that leaching, initially rapid but decelerating, dominated the dust additions. In contrast, soils in the most arid of the chronosequences developed at linear rates that reflect progressive dust additions that were little affected by leaching. Both weathering and erosion may cause changes with time to appear logarithmic in A horizons of soils under the moist and semiarid climatic regimes. Clay minerals form with time in the basal B and C horizons and reflect climatic differences in the three areas. Vermiculite, mixed-layer illite-smectite, and smectite form in the soils of the moist-climate chronosequence; smectite forms in the semiarid-climate chronosequence; and smectite and palygorskite form in the arid-climate chronosequence. ?? 1990.

Catena↗

USGS1954

A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80·0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5·0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error.

Spectrochimica Acta↗

USGS1974

Movement of elements into the atmosphere from coniferous trees in subalpine forests of Colorado and Idaho

Exudates from conifer trees, presumably consisting largely of volatile materials, were sampled at 19 subalpine localitites in Colorado and Idaho where anomalous amounts of several metals were determined in vegetation and mull during previous geochemical testing. The trees sampled were lodgepole pine ( Pinus contorta ), Engelmann spruce ( Picea engelmannii ) and Douglas fir ( Pseudotsuga menziesii ). The condensed exudates were passed through No. 40 Whatman filters, and through 5-micron, 0.45-micron, and 0.05-micron average-pore-diameter membrane filters, evaporated to dryness, and each residue was ashed and analyzed by a semiquantitative spectrographic method. The ashed residues of the exudates contain lithium, beryllium, boron, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, strontium, yttrium, zirconium, molybdenum, silver, lead, bismuth, cadmium, tin, antimony, barium, and lanthanum. The presence of these elements suggests that volatile exudates from vegetation are a medium for the transport of elements in the biogeochemical cycle in subalpine environments. Thus, air sampling and analysis of aerosols derived from volatile exudates may be a useful tool in geochemical exploration.

Colorado, Idaho↗

USGS1982

An electric-analog simulation of elliptic partial differential equations using finite element theory

Elliptic partial differential equations can be solved using the Galerkin-finite element method to generate the approximating algebraic equations, and an electrical network to solve the resulting matrices. Some element configurations require the use of networks containing negative resistances which, while physically realizable, are more expensive and time-consuming to construct.

Mathematics and Computers in Simulation↗

USGS2005

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 ??g/L. For the same percentile range, dissolved As, Cu and Mo concentrations are below 10 ??g/L, and dissolved Ag, Be, Cd, Co, Cr, Ni, Pb, Sb and Se are below 1-5 ??g/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 ??g/L) at the well head.

Applied Geochemistry↗

USGS2009

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry↗

USGS2009

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Applied Geochemistry↗

USGS2023

Mechanisms of water-rock interaction and implications for remediating flooded mine workings elucidated from environmental tracers, stable isotopes, and rare earth elements

Contamination from acid mine drainage affects ecosystems and usability of groundwater for domestic and municipal purposes. The Captain Jack Superfund Site outside of Ward, Boulder County, Colorado, USA, hosts a draining mine adit that was remediated through emplacement of a hydraulic bulkhead to preclude acid mine drainage from entering nearby Lefthand Creek. During impoundment of water within the mine workings in 2020, a diverse and novel dataset of stable isotopes of water, sulfate, and carbon (δ 2 H, δ 18 O H2O , δ 18 O SO4 , δ 34 S, δ 13 C DIC ), rare earth elements, and environmental tracers (noble gases and tritium) were collected to understand groundwater recharge and mixing, mechanisms of sulfide oxidation and water-rock interaction, and the influence of remediation on the hydrologic and geochemical system. Water isotopes indicate that groundwater distal from the mine workings has seasonally variable recharge sources whereas water within the workings has a distinctive composition with minimal temporal variability. Sulfate isotopes indicate that sulfide oxidation occurs both within the mine workings and in adjacent igneous dikes, and that sulfide oxidation may occur under suboxic conditions with ferric iron as the oxidant. Carbon isotopes track the neutralization of acidic waters and the carbon mass budget of the system. Rare earth elements corroborate stable isotopes in indicating groundwater compartmentalization, and additionally illustrate enhanced mineral weathering in the mine workings. Environmental tracers indicate mixing of modern and pre-modern groundwater and inform timelines that active remediation may be needed. Together these datasets provide a useful template for similar investigations of abandoned mine sites where physical mixing processes, sources of solute loading, or remediation timeframes are of importance.

Colorado↗

USGS2010

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by 210 Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m −2 yr −1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m −2 yr −1 . The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m −2 yr −1 for preindustrial and 11.7 μg m −2 yr −1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m −2 yr −1 , which are lower than the modern sediment-based estimate of 11.7 μg m −2 yr −1 , perhaps owing to inputs of dry-deposited Hg to the lakes.

Atmospheric Environment↗

USGS2004

Improved 206Pb/238U microprobe geochronology by the monitoring of a trace-element-related matrix effect; SHRIMP, ID-TIMS, ELA-ICP-MS and oxygen isotope documentation for a series of zircon standards

Precise isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) documentation is given for two new Palaeozoic zircon standards (TEMORA 2 and R33). These data, in combination with results for previously documented standards (AS3, SL13, QGNG and TEMORA 1), provide the basis for a detailed investigation of inconsistencies in 206Pb/238U ages measured by microprobe. Although these ages are normally consistent between any two standards, their relative age offsets are often different from those established by ID-TIMS. This is true for both sensitive high-resolution ion-microprobe (SHRIMP) and excimer laser ablation-inductively coupled plasma-mass spectrometry (ELA-ICP-MS) dating, although the age offsets are in the opposite sense for the two techniques. Various factors have been investigated for possible correlations with age bias, in an attempt to resolve why the accuracy of the method is worse than the indicated precision. Crystallographic orientation, position on the grain-mount and oxygen isotopic composition are unrelated to the bias. There are, however, striking correlations between the 206Pb/238U age offsets and P, Sm and, most particularly, Nd abundances in the zircons. Although these are not believed to be the primary cause of this apparent matrix effect, they indicate that ionisation of 206Pb/238U is influenced, at least in part, by a combination of trace elements. Nd is sufficiently representative of the controlling trace elements that it provides a quantitative means of correcting for the microprobe age bias. This approach has the potential to reduce age biases associated with different techniques, different instrumentation and different standards within and between laboratories. Crown Copyright ?? 2004 Published by Elsevier B.V. All rights reserved.

Chemical Geology↗