Inter- and intra-chamber variability of trace elements in benthic foraminifera – potential and risks of LA-ICP-MS analyses

The Mg/Ca ratio of foraminiferal tests is widely used to reconstruct seawater temperature in past climates. With traditional methods (i.e. Inductively Coupled Plasma Optical Emission Spectrometry or ICP-OES), multiple tests have to be clustered together to attain enough material for analysis. The need for high amounts of carbonate can be problematic for shelf sediments if suitable foraminifera are scarce. As a consequence, grouping of different taxa into one bulk value or ‘sample grouping’ is applied, losing information on interspecific and intra-specimen geochemical variability. Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) solves this problem by targeting extremely small surfaces, e.g., single foraminifer tests or even single chambers. Nevertheless, understanding LA-ICP-MS-generated foraminiferal Mg/Ca records requires in-depth knowledge on the growth and reproductive cycle of extinct foraminiferal taxa, such as Cibicidoides sp. and Anomalinoides acutus from the Paleocene-Eocene transition and early Eocene. These species are commonly used for environmental reconstruction because they are thought to have incorporated the ocean water chemistry in equilibrium with their tests, yet not much is known about their life or precipitation cycle. The reproductive cycle of modern benthic foraminifera ranges from a few weeks to a year, depending on species and size, requiring about a single day to precipitate a new chamber. This implies a potential change in geochemistry from chamber to chamber. Hence, LA-ICP-MS hypothetically allows for an extremely high-resolution, in situ Mg/Ca record across a year, or a precipitation season, if sufficient snapshots of chamber calcification moments are incorporated. As a result, a comparison of cyclic temperature changes on both annual (seasonal variations across individual specimens of a sample) and sub-millennial (variations across closely spaced samples) scale could be feasible. However, the complex growth of the foraminiferal test (e.g. layering due to overgrowth of older chambers) likely also results in geochemical variability within chambers. Here we investigate the inter- and intra-chamber variability in Mg/Ca composition of extinct benthic foraminifera using LA-ICP-MS. We evaluate the resulting potential and risks stemming from inhomogeneous trace-element distribution in the tests. We utilize foraminiferal tests from shelves from the western North Atlantic and the North Sea Basin, covering a paleodepth transect (<150 m) during the early Eocene. The foraminiferal tests record not only the long-term global warming trend of the early Paleogene but also short temperature spikes during hyperthermals such as the Paleocene-Eocene Thermal Maximum.