Quantification of octacalcium phosphate, authigenic apatite and detrital apatite in coastal sediments using differential dissolution and standard addition

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

Authigenic apatite and octacalcium phosphate formation due to adsorption–precipitation switching across estuarine salinity gradients

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 (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

Depth distribution of soil water sourced by plants at the global scale : a new direct inference approach

Funding Information Fondazione Cassa di Risparmio di Padova e Rovigo. Grant Number: Bando Starting Grants 2015Peer reviewedPostprin

Appendix S4: Sample collection information for all specimens

To examine N-isotope ratios (15N/14N) in tissues and shell organic matrix of bivalves as a proxy for natural and anthropogenic nutrient fluxes in coastal environments, Pinctada imbricata, Isognomon alatus, and Brachidontes exustusbivalves were live-collected and analyzed from eight sites in Bocas del Toro, Panama. Sites represent a variety of coastal environments, including more urbanized, uninhabited, riverine, and oceanic sites. Growth under differing environmental conditions is confirmed by δ18O values, with open ocean Escudo de Veraguas shells yielding the highest average δ18O (−1.0‰) value and freshwater endmember Rio Guarumo the lowest (−1.7‰). At all sites there is no single dominant source of organic matter contributing to bivalve δ15N and δ13C values. Bivalve δ15N and δ13C values likely represent a mixture of mangrove and seagrass N and C, although terrestrial sources cannot be ruled out. Despite hydrographic differences between end-members, we see minimal δ15N and δ13C difference between bivalves from the river-influenced Rio Guarumo site and those from the oceanic Escudo de Veraguas site, with no evidence for N from open-ocean phytoplankton in the latter. Populated sites yield relative 15N enrichments suggestive of anthropogenic nutrient input, but low δ15N values overall make this interpretation equivocal. Lastly, δ15N values of tissue and shell organic matrix correlate significantly for pterioideans P. imbricata and I. alatus. Thus for these species, N isotope studies of historical and fossil shells should provide records of ecology of past environments

Illuminating hydrological processes at the soil-vegetation-atmosphere interface with water stable isotopes

Funded by DFG research project “From Catchments as Organised Systems to Models based on Functional Units” (FOR 1Peer reviewedPublisher PDFPublisher PD

Response of Cocoa Trees (Theobroma cacao) to a 13-month Dessication Period in Sulawesi, Indonesia

In South-east Asia, ENSO-related droughts represent irregularly occuring hazards for agroforestry systems containing cocoa which are predicted to increase in severity with expected climate warming. To characterize the drought response of mature cocoa tree, we conducted the Sulawesi Throughfall Displacement Experiment in a shaded (Gliricidia sepium) cocoa agroforestry system in Central Sulawesi, Indonesia. Three large sub-canopy roofs were installed to reduce throughfall by about 80% over a 13-month period to test the hypotheses that (i) cocoa trees are sensitive to drought due to their shallow fine root system, and (ii)bean yield is more sensitive to drought than leaf or stem growth. As 83% of fine root (diameter 2mm) was located in the upper 40 cm of the soil, the cocoa tree examined had a very shallow root system. Cocoa and Gliricidia differed in their vertical rooting patterns, thereby reducing competition for water. Despite being exposed for several mnths to soil water contents close to the conventional wilting point, cocoa trees showed no significant decreases in leaf biomass, stem and branch wood production or fine root biomass. Possible causes are active osmotic adjusment in roots, mitigation of drought stress by shading from Gliricidia or other factors. By contrast, production of cocoa bean

The physiological responses of cacao to the environment and the implications for climate change resilience. A review

Cacao (Theobroma cacao L.) is a tropical perennial crop which is of great economic importance to the confectionary industry and to the economies of many countries of the humid tropics where it is grown. Some recent studies have suggested climate change could severely impact cacao production in West Africa. It is essential to incorporate our understanding of the physiology and genetic variation within cacao germplasm when discussing the implications of climate change on cacao productivity and developing strategies for climate resilience in cacao production. Here we review the current research on the physiological responses of cacao to various climate factors. Our main findings are 1) water limitation causes significant yield reduction in cacao but genotypic variation in sensitivity is evident, 2) in the field cacao experiences higher temperatures than is often reported in the literature, 3) the complexity of the cacao/ shade tree interaction can lead to contradictory results, 4) elevated CO2 may alleviate some negative effects of climate change 5) implementation of mitigation strategies can help reduce environmental stress, 6) significant gaps in the research need addressing to accelerate the development of climate resilience. Harnessing the significant genetic variation apparent within cacao germplasm is essential to develop modern varieties capable of high yields in non-optimal conditions. Mitigation strategies will also be essential but to use shading to best effect shade tree selection is crucial to avoid resource competition. Cacao is often described as being sensitive to climate change but genetic variation, adaptive responses, appropriate mitigation strategies and interactive climate effects should all be considered when predicting the future of cacao production. Incorporating these physiological responses to various environmental conditions and developing a deeper understanding of the processes underlying these responses will help to accelerate the development of a more resource use efficient tree ensuring sustainable production into the future