Precise determination of lithium isotopic composition in low concentration natural samples

Abstract

An improved procedure for lithium isotope analysis using Li 3PO 4 as the ion source has been investigated for application to geological samples. The 7Li/ 6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li + ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li 2BO 2 + method while maintaining a comparable precision of better than 1‰ (1σ). Replicate analyses of the NBS L-SVEC Li 2CO 3 standard yielded a mean value of 12.1047 ± 0.0043 ( n = 21), which is close to the reported absolute value of 12.02 ± 0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li 3PO 4 and Li 2BO 2 + techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.