skip to main content


Title: Trace elements in mollusc shells and benthic foraminifera
Throughout the course of an organism’s life, the chemical signatures of environment, food consumption, and weather are recorded into their carbonate structures; these signatures can be directly linked to a time-resolved lifespan. Here we present trace element data from benthic foraminifera and tropical molluscs determined using an ESI NWR193UC excimer laser coupled with an Agilent 8900 triple quadrupole mass spectrometer in the MicroAnalytical Geochemistry and Isotope Characterization (MAGIC) Laboratory at the University of Maine. Benthic foraminifera are protists that live on the sea floor and produce calcite shells, progressively adding chambers. Changes in Mg/Ca in foraminifera are used as a proxy for ocean temperature. Laser ablation ICP-MS data for 18 trace elements were collected in individual growth chambers in foraminifera of the genus Uvigerina from the Bay of Plenty. Line scans were performed within thin (~10 µm) chamber walls using a spot size of 8 µm, beam energy density of 3 J/cm2, repetition rate of 12 Hz, and scan speeds of 2-3 µm/s. Concentrations were determined relative to the NIST610 glass. Ratios of Mg/Ca and other trace elements record the same range of values as those determined via bulk wet chemistry analysis of ~10 foraminifera for a given population, which suggests that LA-ICP-MS may be a viable alternative to wet chemistry. Trace element data were collected across shells of the warm-tropical mollusc species Chione subrugosa from the Ostra Base Camp area, Peru (78°37’22”W, 8°54’46”S). Previous studies of the area have suggested that a large climate transition occurred, transforming a warm water tropical bay into a desert surrounded by a coastal stand with cool waters. This area was occupied by humans at 6250-5450 radiocarbon years BP. This study examines Chione subrugosa, which were found in the living position at the fossilized Ostra Beach and are thought to have been the final living warm-tropical molluscs in the bay. Studies of modern molluscs have revealed that molluscs record massive climatic changes, such as El Niño, in their chemistry. Laser ablation provides a unique opportunity to examine chemical changes directly related to the changing coastal environment. Line scans transverse growth bands along the length of the shell, providing a high resolution record of daily variation in trace element chemistry over the lifespan of the mollusc. Eleven elements were analysed with a beam energy density of 2.4 J/cm2, repetition rate of 15 Hz, spot size of 5 x 25 µm, and a scan speed of 5 µm/s. Preliminary data suggest the preservation of yearly oscillations in trace elements, with high concentrations of La, Ce, U, and Pb during early shell growth. Continued study will examine catastrophic mollusc life events in an effort to link these with environmental climate changes over daily timescales.  more » « less
Award ID(s):
1727460
NSF-PAR ID:
10108902
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
North American Workshop on Laser Ablation 2019 Abstracts
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Precisely targeted measurements of trace elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) reveal inter-chamber heterogeneities in specimens of the planktic foraminiferTrilobatus (Globigerinoides) sacculifer. We find that Mg/Ca ratios in the final growth chamber are generally lower compared to previous growth chambers, but final chamber Mg/Ca is elevated in one of thirteen sample intervals. Differences in distributions of Mg/Ca values from separate growth chambers are observed, occurring most often at lower Mg/Ca values, suggesting that single-chamber measurements may not be reflective of the specimen’s integrated Mg/Ca. We compared LA-ICPMS Mg/Ca values to paired, same-individual Mg/Ca measured via inductively coupled plasma optical emission spectrometry (ICP-OES) to assess their correspondence. Paired LA-ICPMS and ICP-OES Mg/Ca show a maximum correlation coefficient of R = 0.92 (p < 0.05) achieved by applying a weighted average of the last and penultimate growth chambers. Population distributions of paired Mg/Ca values are identical under this weighting. These findings demonstrate that multi-chamber LA-ICPMS measurements can approximate entire specimen Mg/Ca, and is thus representative of the integrated conditions experienced during the specimen’s lifespan. This correspondence between LA-ICPMS and ICP-OES data links these methods and demonstrates that both generate Mg/Ca values suitable for individual foraminifera palaeoceanographic reconstructions.

     
    more » « less
  2. Abstract Trace element changes in fluids associated with ore-forming events in sedimentary basins may be recorded by contemporaneous cements, especially zoned carbonate minerals (microstratigraphy). Cement analysis using advanced mapping and analytical techniques including scanning electron microscopy cathodoluminescence (SEM-CL), charge contrast imaging, high-resolution X-ray computed tomography (XCT), and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) documents geochemical changes associated with Mississippi Valley–type mineralization in solution-collapse breccias of the Cambrian–Ordovician Knox Group (Tennessee and Kentucky, USA). Dolomite cement zonation coincident with changes in Fe and Mn can be observed with optical microscope CL in bands as narrow as 5 µm, whereas panchromatic SEM-CL reveals microfractures and cement subzones coincident with changes in La and Ce concentrations in bands as narrow as 0.1 µm. XCT scans image a high-density (Fe-rich) dolomite zone at the onset of late sulfide precipitation. The transition from pre-ore to ore-stage cementation is marked by increased Fe, Mn, Zn, Cd, Ga, Pb, and Sr and decreased La and Ce concentrations. Fine-scale metal depletion cycles during this transition may record metal precipitation from brine in response to the availability of reduced sulfur. Except for Fe and Mn, post-ore dolomite zones generally have low metal concentrations. Thus, dolomite microstratigraphy tracks systematic changes in brine metal concentrations modified by episodes of localized sulfide mineral precipitation. 
    more » « less
  3. Titanite has the ability to incorporate significant amounts of common Pb, which leads to uncertainty when applying the U-Pb decay series for geochronology. The isobaric interference of 204Hg on 204Pb poses an additional complexity in applying common Pb corrections. Here we investigate the removal of 204Hg interferences during titanite U-Pb dating using reaction cell gas chemistry via triple quadrupole mass spectrometry. U-Pb dates were determined for the natural titanite reference materials MKED-1 and BLR1 using an ESI NWR193UC excimer laser coupled to an Agilent 8900 ‘triple quad’ mass spectrometer. The 8900 is equipped with an octopole collision/reaction cell, which enables online interference removal. Two experiments were run, one in which we collected data in NoGas mode, and one in which NH3 was used as a reaction cell gas in MS/MS mode, in order to assess the feasibility of determining U/Pb ratios with mass shifted isotopes. In all experiments, a signal smoothing device was placed inline just before the ICP-MS interface, downstream from the addition of the Ar nebulizer gas to the He carrier gas stream. For the NoGas experiment, titanite was ablated using a 25 µm spot, with a beam energy density of 3 J/cm2, and a pulse rate of 4 Hz. In NoGas mode, signal intensities for the isotopes 201Hg, 202Hg, 204Pb, 206Pb, 207Pb, 232Th, 235U, and 238U were counted. In MS/MS mode, titanite was ablated using a 40 µm spot, with a beam energy density of 5 J/cm2, and a pulse rate of 4 Hz. A larger spot size in this experiment was used to counteract the decrease in signal intensity due to use of the reaction cell. In MS/MS mode, NH3 was flowed through the reaction cell in order to enable a charge transfer reaction between NH3 and Hg+, effectively neutralizing Hg. The isotopes 201Hg, 202Hg, 204Pb, 206Pb, and 207Pb were measured on-mass, as the isotopes of Pb are not affected by the NH3 gas. Uranium and Th both exhibit partial reaction with NH3 gas; therefore, the isotopes 232Th, 235U, and 238U were measured mass-shifted up 15 mass units, at masses 247, 250, and 253 respectively. Ratios of 207Pb/235U, 206Pb/238U, and 207Pb/206Pb were determined using the UPbGeochron4 DRS in Iolite (v.3.71) with MKED-1 as the primary reference material. Dates were calculated using IsoplotR by applying the Stacey-Kramers correction for common Pb. All isotopes of Hg were effectively neutralized by the NH3 charge transfer reaction in MS/MS mode; zero counts were detected for Hg isotopes. Dates for the BLR-1 titanite were 1050.55 ± 2.72 (2σ, n=12) Ma in NoGas mode, and 1048 ± 1.88 (2σ, n=15) Ma in MS/MS mode. These dates are in excellent agreement with the TIMS 206Pb/238U date for the BLR-1 titanite of 1047.1 ± 0.4 Ma. This method has the potential to enable measurement of 204Pb without needing to correct for Hg interferences. 
    more » « less
  4. The U-Pb system in titanite has been shown to be reset during a variety of high-temperature processes including high-temperature deformation, but post-deformation modification and recovery of crystal-lattice strain have so far made U-Pb equilibration mechanism from deformed titanites equivocal. Microstructures, including mechanical twinning and subgrain rotation recrystallization are more likely to be preserved at low-temperatures, but the systematics of chemical equilibration have not been established for these conditions. This study identifies progressive crystallographic misorientation and deformation twins in titanite porphyroclasts from the Wasatch Fault Zone, Utah, USA. The microstructures, mapped using electron backscatter diffraction (EBSD), developed at ~11 km depth during 300–400 ºC crystal-plastic deformation within the ductile fault zone. These microstructural maps were used to guide laser ablation-split stream ICP-MS analysis: U-Pb isotopes measured in tandem with major and trace element contents. Despite the low temperature, U-Pb and trace element contents in titanite equilibrated, at least partially, during deformation. Both major and trace elements in titanite also likely partitioned with a fluid and in response to the (re)crystallization of other mineral phases in the fault zone. Chemical zoning and crystal lattice recovery suggestive of fluid-aided recrystallization are absent, and the main mechanism for this resetting may instead be an enhancement of element mobility along microstructure dislocations. These processes are interpreted to record complex open-system behavior of titanite caused by crystal-plastic deformation during the initiation of the WFZ. This presentation will summarize the comparative analysis of microstructure by EBSD and titanite chemistry by LASS-ICP-MS, and how it bears on the understanding of elemental mobility in titanite during low-temperature crystal-plastic deformation. 
    more » « less
  5. ABSTRACT The trace element composition of planktic foraminifera shells is influenced by both environmental and biological factors (‘vital effects’). As trace elements in individual foraminifera shells are increasingly used as paleoceanographic tools, understanding how trace element ratios vary between individuals, among species, and in response to high frequency environmental variability is of critical importance. Here, we present a three-year plankton tow record (2010–2012) of individual shell trace element (Mg, Sr, Ba, and Mn) to Ca ratios in the planktic species Globigerina ruber (pink), Orbulina universa, and Globorotalia menardii collected throughout the upper 100 m of Cariaco Basin. Plankton tows were paired with in situ measurements of water column chemistry and hydrography. The Mg/Ca ratio reflects different calcification temperatures in all three species when calculated using species-specific temperature relationships from single-species averages of Mg/Ca. However, individual shell Mg/Ca often results in unrealistic temperate estimates. The Sr/Ca ratios are relatively constant among the four species. Ratios of Mn/Ca and Ba/Ca are highest in G. menardii and are not reflective of elemental concentrations in open waters. The Mn/Ca ratio is elevated in all species during upwelling conditions, and a similar trend is demonstrated in Neogloboquadrina incompta shells from the California margin collected during upwelling periods. Together this suggests that elevated shell Mn/Ca may act as a tracer for upwelling of deeper water masses. Our results emphasize the large degree of trace element variability present among and within species living within a limited depth habitat and the roles of biology, calcification environment, and physical mixing in mediating how trace element geochemistry reflects environmental variability in the surface ocean. 
    more » « less