The effect of extraction techniques on calcium concentrations and isotope ratios of marine pore water.

Comparing two different techniques applied for the extraction of marine pore water samples from sediments, the well-established whole round (WR) method and the more recent Rhizon method, in terms of their effects on stable calcium isotope ratios in extracted pore waters, we recognize a systematic offset between the two sampling methods. Higher δ44/40Ca values are associated with lower Ca concentrations for the Rhizon sampling technique and lower δ44/40Ca values are associated with higher Ca concentrations for the corresponding WR-derived pore water samples. Models involving Rayleigh fractionation and mixing calculation suggest that the observed offset is most likely caused by a combined process of CaCO3 precipitation and ion exchange taking place during Rhizon sampling-induced CO2 degassing. Changing pressure, extraction time or extraction yield during WR pressing does not lead to a variation in δ44/40Ca, indicating that no Ca isotope fractionation takes place during the sampling of pore water. On the basis of analytical and modelling results, WR samples appear to provide δ44/40Ca values that are more representative of the 'true' pore water isotopic composition. While the difference between the sampling techniques is close to the present-day analytical precision of Ca isotope analysis, it may become more relevant with increasing analytical precision in the future.

Biological fractionation of stable Ca isotopes in Göttingen minipigs as a physiological model for Ca homeostasis in humans.

In order to investigate fractionation of calcium (Ca) isotopes in vertebrates as a diagnostic tool to detect Ca metabolism dysfunction we analyzed the Ca isotopic composition (δ(44/40)Ca = [((44)Ca/(40)Ca)sample/((44)Ca/(40)Ca)reference]-1) of diet, faeces, blood, bones and urine from Göttingen minipigs, an animal model for human physiology. Samples of three groups were investigated: 1. control group (Con), 2. group with glucocorticosteroid induced osteoporosis (GIO) and 3. group with Ca and vitamin D deficiency induced osteomalacia (-CaD). In contrast to Con and GIO whose average δ(44/40)Cafaeces values (0.39 ± 0.13‰ and 0.28 ± 0.08‰, respectively) tend to be lower than their diet (0.47 ± 0.02‰), δ(44/40)Cafaeces of -CaD (-0.27 ± 0.21‰) was significantly lower than their δ(44/40)Cadiet (0.37 ± 0.03‰), but also lower than δ(44/40)Cafaeces of Con and GIO. We suggest that the low δ(44/40)Cafaeces of -CaD might be due to the contribution of isotopically light Ca from gastrointestinal fluids during gut passage. Assuming that this endogenous Ca source is a common physiologic feature, a fractionation during Ca absorption is also required for explaining δ(44/40)Cafaeces of Con and GIO. The δ(44/40)Caurine of all groups are high (>2.0‰) reflecting preferential renal reabsorption of light Ca isotopes. In Göttingen minipigs we found a Ca isotope fractionation between blood and bones (Δ(44/40)Cablood-bone) of 0.68 ± 0.15‰.