Description: Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In situ relationships between liquid-and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determining particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions, and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP〉 HAP〉 CFAP (4.5% CO3)〉 CFAP (3.4% CO3)〉 CFAP (2.2% CO3)〉 FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the coastal sediments analyzed, which supports the hypothesis of apatite formation by an OCP precursor mechanism.

Description: Mechanisms governing phosphorus (P) speciation in coastal sediments remain largely unknown due to the diversity of coastal environments and poor analytical specificity for P phases. We investigated P speciation across salinity gradients comprising diverse ecosystems in a P-enriched estuary. To determine P load effects on P speciation we compared the high P site with a low P site. Octacalcium phosphate (OCP), authigenic apatite (carbonate fluorapatite, CFAP) and detrital apatite (fluorapatite) were quantitated in addition to Al/Fe-bound P (Al/Fe-P) and Ca-bound P (Ca-P). Gradients in sediment pH strongly affected P fractions across ecosystems and independent of the site-specific total P status. We found a pronounced switch from adsorbed Al/Fe-P to mineral Ca-P with decreasing acidity from land to sea. This switch occurred at near-neutral sediment pH and has possibly been enhanced by redox-driven phosphate desorption from iron oxyhydroxides. The seaward decline in Al/Fe-P was counterbalanced by the precipitation of Ca-P. Correspondingly, two location-dependent accumulation mechanisms occurred at the high P site due to the switch, leading to elevated Al/Fe-P at pH 〈 6.6 (landward; adsorption) and elevated Ca-P at pH 〉 6.6 (seaward; precipitation). Enhanced Ca-P precipitation by increased P loads was also evident from disproportional accumulation of metastable Ca-P (Ca-Pmeta) at the high P site. Here, sediments contained on average 6-fold higher Ca-Pmeta levels compared with the low P site, although these sediments contained only 2-fold more total Ca-P than the low P sediments. Phosphorus species distributions indicated that these elevated Ca-Pmeta levels resulted from transformation of fertilizer-derived Al/Fe-P to OCP and CFAP in nearshore areas. Formation of CFAP as well as its precursor, OCP, results in P retention in coastal zones and can thus lead to substantial inorganic P accumulation in response to anthropogenic P input.

Description: X-ray absorption near edge structure (XANES) studies on calcium phosphate species (Ca-P) deal with marginal differences among subtle spectral features despite a hitherto missing systematic breakdown of these differences. Related fingerprinting approaches depend therefore on spectral libraries that are not validated against each other, incomplete and scattered among publications. This study compiled a comprehensive spectral library from published reference compound libraries in order to establish more clear-cut criteria for Ca-P determination by distinctive phosphorus K-edge XANES features. A specifically developed normalization method identified diagnostic spectral features within the compiled library, e.g. by uniform calculation of ratios between white-line and secondary peak heights. Post-processing of the spectra (n = 81) verified distinguishability among most but not all phases, which included hydroxylapatite (HAP), poorly crystalline HAP, amorphous HAP, fluorapatite, carbonate fluorapatite (CFAP), carbonate hydroxylapatite, β-tricalcium phosphate, octacalcium phosphate (OCP), brushite, monetite, monocalcium phosphate, amorphous calcium phosphate (ACP), anapaite, herderite, scholzite, messelite, whiteite and P on CaCO3. Particularly, peak height ratios significantly improved analyte specificity, e.g. by supplementary breakdown into OCP and ACP. The spectral analysis also revealed Ca-P standards that were rarely investigated or inappropriately synthesized, and thus provides a basis for standard selection and synthesis. The developed method and resulting breakdown by species were subsequently tested on Ca-P spectra from studies on bone and sediment. The test indicated that bone material likely comprises only poorly crystalline apatite, which implies direct nucleation of apatite in bone. This biological apatite formation is likely opposed to that of sedimentary apatite, which apparently forms by successive crystallization. Application of the method to μXANES spectra of sediment particles indicated authigenic apatite formation by an OCP precursor.

Description: Oceanic Anoxic Events (OAEs) document major perturbations of the global carbon cycle with repercussions on the Earth’s climate and ocean circulation that are relevant to understand future climate trends. Here, we compare sedimentation patterns, nutrient cycling, organic carbon accumulation and carbon isotope variability across Cretaceous Oceanic Anoxic Events OAE1a and OAE2 in two drill cores with unusually high sedimentation rates from the Vocontian Basin (southern France) and Tarfaya Basin (southern Morocco). OAE1a and OAE2 exhibit remarkable similarities in the evolution of their δ13C excursion with long-lasting negative carbon isotope excursions preceding the onset of both anoxic events, supporting the view that OAEs were triggered by massive emissions of volcanic CO2 into the atmosphere. Based on analysis of cyclic sediment variations, we estimated the duration of the individual phases within the carbon isotope excursions. For both events, we identify: (1) a precursor phase lasting ~ 430 kyr and ~ 130 kyr, (2) an onset phase of ~ 390 and ~ 70 kyr, (3) a peak phase of ~ 600 and ~ 90 kyr, (4) a plateau phase of ~ 1400 and ~ 200 kyr and (5) a recovery phase of ~ 630 and ~ 440 kyr, respectively. The total duration of the positive carbon isotope excursion is estimated as 3400 kyr and 790 kyr and that of the main carbon accumulation phase as 980 kyr and 180 kyr, for OAE1a and OAE 2 respectively. The extended duration of the peak, plateau and recovery phases requires fundamental changes in global nutrient cycles either (1) through excess nutrient inputs to the oceans by increasing continental weathering and river discharge or (2) through nutrient-recycling from the marine sediment reservoir. We investigated the role of phosphorus on the development of carbon accumulation by analysing phosphorus speciation across OAE2 and the mid-Cenomanian Event (MCE) in the Tarfaya Basin. The ratios of organic carbon and total nitrogen to reactive phosphorus (Corg/Preact and Ntotal/Preact) prior to OAE2 and the MCE hover close to or below the Redfield ratio characteristic of marine organic matter. Decreases in reactive phosphorus resulting in Corg/Preact and Ntotal/Preact above the Redfield ratio during the later phase of OAE2 and the MCE indicate leakage from the sedimentary column into the water column under the influence of intensified and expanded oxygen minimum zones. These results suggest that a positive feedback loop, rooted in the benthic phosphorus cycle, contributed to increased marine productivity and carbon burial over an extended period of time during OAEs.