Optimizing the ratio of the spike to sample for isotope dilution analysis:a case study with selenium isotopes

Isotope dilution(ID)method has been widely applied to studies of elemental speciation and certification of the concentrations of geological reference materials.One of the key factors restricting the application of the ID method is the difficulty in identifying the optimal ratios of the isotope tracer(spike)to sample(S/N)and in estimating the error propagation.Here,using Se isotope as an example and employing a Monte Carlo method,we found that the optimal choice of spike and S/N are^(77)Se(spike)and 0.7,respectively.The S/N in the range from 0.1 to 4 can produce sufficiently low errors(<0.4%).Extending this method to other elements such as Cr,Fe,Ni,Sr,Cd and etc.,their optimal spike and S/N were also presented.According to the optimized parameters of Se,we determined the Se concentrations of geological reference materials(GRMs)by thiol cotton fiber(TCF)-hydride generation ID-MC-ICP-MS.The relative standard deviation is<5%,and the detection limit is reduced to0.1 ng/g.Most of the measured concentrations are consistent with those recommended by IGGE or reported previously.For some GRMs,discrepancies(e.g.6.90%for GSS-5)exist between our measurements and previous ones,which can be explained by the inhomogeneity of GRMs and/or the different digestion,purification and measurement methods among laboratories.

Cadmium isotope compositions of Fe-Mn nodules and surrounding soils: Implications for tracing Cd sources

Cadmium (Cd) pollution in agricultural soils has become a severe threat to food security and human health in recent years. Stable Cd isotopes are a potentially powerful tool for identifying the sources of Cd in soils. However, many Earth surface processes, including adsorption, leaching, and biogeochemical cycles in plants, may generate Cd isotope fractionation, which can complicate the potential application of Cd isotopes in tracing the sources of Cd pollution in soils. In this work, the Cd isotope compositions of typical Fe-Mn nodules (FMNs) and surrounding soils in two different soil profiles are investigated. Our results show that the FMNs in lower layers (i.e., C and W horizons) are isotopically lighter than the surrounding soils by –0.114‰ to –0.156‰ (Δ114/110CdFMN-soil). We interpret this fractionation as the result of preferential adsorption of isotopically light Cd onto the surface of goethite. In the upper layers (i.e., P and A horizons), the Δ114/110CdFMN-soil values are more negative in the P horizon (–0.213‰ to –0.388‰) but more positive in the A horizon (0.061‰ to 0.204‰). We interpret these fractionations as the result of natural biogeochemical processes (i.e., leaching and biological cycling) during soil development. Soil leaching preferentially releases isotopically heavy Cd into the underlying soil (i.e., P horizon), shifting the topsoil towards lower δ114/110Cd values but the underlying soils towards higher δ114/110Cd values. Moreover, biological cycling contributes isotopically heavy Cd to the topsoil, probably shifting the topsoil towards higher δ114/110Cd values. Our study demonstrates that the formation of Fe oxyhydroxides, leaching, and biological cycling can considerably modify the soil Cd isotope signature, highlighting the need to consider natural biogeochemical processes when using Cd isotopes to trace heavy metal pollution in soils.