TY - JOUR
T1 - Effect of organic matrices on the determination of the trace element chemistry (Mg, Sr, Mg/Ca, Sr/Ca) of aragonitic bivalve shells (Arctica islandica) - Comparison of ICP-OES and LA-ICP-MS data
AU - Schöne, Bernd R.
AU - Zhang, Zengjie
AU - Jacob, Dorrit
AU - Gillikin, David P.
AU - Tütken, Thomas
AU - Garbe-Schönberg, Dieter
AU - McConnaughey, Ted
AU - Soldati, Analía
PY - 2010
Y1 - 2010
N2 - The element chemistry of biogenic carbonates can provide important data on past environments. However, the Sr/Ca and Mg/Ca ratios as well as the Mg and Sr concentrations of biological carbonates, especially aragonitic bivalves often depart from apparent thermodynamic equilibrium. When measured in situ by means of LA-ICP-MS, the Mg concentration is often substantially enriched (two-to threefold) near the organic-rich, annual growth lines. To test the hypothesis that some organic components exert a major influence on the skeletal metal content, the element chemistry of different shell components (insoluble organic matrix, IOM; dissolved CaCO3 and soluble organics, SOM) of Arctica islandica was measured by means of ICP-OES and LA-ICP-MS. The ICP-OES data indicate that the IOM is strongly enriched in Mg (130 ppm) and depleted in Sr and Ca (10 ppm and 0.22 wt%, respectively) when compared to the whole biomineral (Mg: 68 to 99 ppm, Sr: 860 to 1, 060 ppm, Ca: ∼35.72 wt%). Although the average relative abundance of the IOM barely exceeds 0.46 wt%, its chemical composition in combination with its heterogeneous distribution across the shell can significantly increase estimates of the Mg concentration if measured in situ by LA-ICP-MS. Depending on the distribution of the IOM, the Ca concentration may be significantly lower locally than the average Ca concentration of the whole shell (35.72 wt%). If this remains undetected, the Mg concentration of shell portions with higher than average IOM content is overestimated by LA-ICP-MS and, conversely, the Mg concentration is underestimated in shell portions with lower than average IOM content. Removal of the IOM prior to the chemical analysis by LA-ICP-MS or mathematical correction for the IOM-derived magnesium concentrations is therefore strongly advised. The different chemistry of the IOM may also exert a major control on the trace element to calcium ratios. Shell portions enriched in IOM will show up to 200 times higher Mg/Ca and up to two times higher Sr/Ca ratios than the average shell of A. islandica. Without removal of the IOM prior to the analysis, Mg/Ca and Sr/Ca ratios of shell portions with higher IOM content cannot be used as paleothermometers. Because it is currently impossible to remove the IOM prior to chemical analyses by LA-ICP-MS, we recommend the use of wet chemical techniques (= possibility to separate and measure individual shell components) such as ICP-OES at the expense of lower sampling resolution. The results of this study will significantly improve our understanding of shellbased climate and environmental proxies.
AB - The element chemistry of biogenic carbonates can provide important data on past environments. However, the Sr/Ca and Mg/Ca ratios as well as the Mg and Sr concentrations of biological carbonates, especially aragonitic bivalves often depart from apparent thermodynamic equilibrium. When measured in situ by means of LA-ICP-MS, the Mg concentration is often substantially enriched (two-to threefold) near the organic-rich, annual growth lines. To test the hypothesis that some organic components exert a major influence on the skeletal metal content, the element chemistry of different shell components (insoluble organic matrix, IOM; dissolved CaCO3 and soluble organics, SOM) of Arctica islandica was measured by means of ICP-OES and LA-ICP-MS. The ICP-OES data indicate that the IOM is strongly enriched in Mg (130 ppm) and depleted in Sr and Ca (10 ppm and 0.22 wt%, respectively) when compared to the whole biomineral (Mg: 68 to 99 ppm, Sr: 860 to 1, 060 ppm, Ca: ∼35.72 wt%). Although the average relative abundance of the IOM barely exceeds 0.46 wt%, its chemical composition in combination with its heterogeneous distribution across the shell can significantly increase estimates of the Mg concentration if measured in situ by LA-ICP-MS. Depending on the distribution of the IOM, the Ca concentration may be significantly lower locally than the average Ca concentration of the whole shell (35.72 wt%). If this remains undetected, the Mg concentration of shell portions with higher than average IOM content is overestimated by LA-ICP-MS and, conversely, the Mg concentration is underestimated in shell portions with lower than average IOM content. Removal of the IOM prior to the chemical analysis by LA-ICP-MS or mathematical correction for the IOM-derived magnesium concentrations is therefore strongly advised. The different chemistry of the IOM may also exert a major control on the trace element to calcium ratios. Shell portions enriched in IOM will show up to 200 times higher Mg/Ca and up to two times higher Sr/Ca ratios than the average shell of A. islandica. Without removal of the IOM prior to the analysis, Mg/Ca and Sr/Ca ratios of shell portions with higher IOM content cannot be used as paleothermometers. Because it is currently impossible to remove the IOM prior to chemical analyses by LA-ICP-MS, we recommend the use of wet chemical techniques (= possibility to separate and measure individual shell components) such as ICP-OES at the expense of lower sampling resolution. The results of this study will significantly improve our understanding of shellbased climate and environmental proxies.
KW - Bivalve shell
KW - ICP-OES
KW - LA-ICP-MS
KW - Organics
KW - Sclerochronology
KW - Trace elements
UR - http://www.scopus.com/inward/record.url?scp=79951813664&partnerID=8YFLogxK
U2 - 10.2343/geochemj.1.0045
DO - 10.2343/geochemj.1.0045
M3 - Article
SN - 0016-7002
VL - 44
SP - 23
EP - 37
JO - Geochemical Journal
JF - Geochemical Journal
IS - 1
ER -