Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

The Political Economy of Climate Adaptation and Environmental Health: The Case of Ethiopia

The environment affects our health, livelihoods, and the social and political institutions within which we interact. Indeed, nearly a quarter of the global disease burden is attributed to environmental factors, and many of these factors are exacerbated by global climate change. Thus, the central research question of this dissertation is: How do people cope with and adapt to uncertainty, complexity, and change of environmental and health conditions? Specifically, I ask how institutional factors, risk aversion, and behaviors affect environmental health outcomes. I further assess the role of social capital in climate adaptation, and specifically compare individual and collective adaptation. I then analyze how policy develops accounting for both adaptation to the effects of climate and mitigation of climate-changing emissions. In order to empirically test the relationships between these variables at multiple levels, I combine multiple methods, including semi-structured interviews, surveys, and field experiments, along with health and water quality data. This dissertation uses the case of Ethiopia, Africa’s second-most populous nation, which has a large rural population and is considered very vulnerable to climate change. My fieldwork included interviews and institutional data collection at the national level, and a three-year study (2012-2014) of approximately 400 households in 20 villages in the Ethiopian Rift Valley. I evaluate the theoretical relationships between households, communities, and government in the process of adaptation to environmental stresses. Through my analyses, I demonstrate that water source choice varies by individual risk aversion and institutional context, which ultimately has implications for environmental health outcomes. I show that qualitative measures of trust predict cooperation in adaptation, consistent with social capital theory, but that measures of trust are negatively related with private adaptation by the individual. Finally, I describe how Ethiopia had some unique characteristics, significantly reinforced by international actors, that led to the development of an extensive climate policy, and yet with some challenges remaining for implementation. These results suggest a potential for adaptation through the interactions among individuals, communities, and government in the search for transformative processes when confronting environmental threats and climate change.

(Table 1) Uranium at DSDP Hole 69-504B pore water

Measurements of U concentration and 234U/238U ratio were made in five water samples from Deep Sea Drilling Project Hole 504B.The results indicate that a loss of U had occurred either during sampling or during the storage of the samples, probably as a result of adsorption by rust particles or by the walls of the sampling system. Within analytical uncertainty, the 234U/238U ratios in the samples were identical to those in unreacted seawater. Thus, it is not possible to detect any U exchange that may have occurred during the reaction of the solutions with the basement formation. Improvement in sampling technique is a necessity for future studies of uranium and probably other trace elements in drill hole water samples.

Relative abundance of anaerobic methanotrophic archaea in bacterial mat Cascadia margin off Oregon

The microbially mediated anaerobic oxidation of methane (AOM) is the major biological sink of the greenhouse gas methane in marine sediments (doi:10.1007/978-94-009-0213-8_44) and serves as an important control for emission of methane into the hydrosphere. The AOM metabolic process is assumed to be a reversal of methanogenesis coupled to the reduction of sulfate to sulfide involving methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB) as syntrophic partners which were describes amongst others in Boetius et al. (2000; doi:10.1038/35036572). In this study, 16S rRNA-based methods were used to investigate the distribution and biomass of archaea in samples from sediments above outcropping methane hydrate at Hydrate Ridge (Cascadia margin off Oregon) and (ii) massive microbial mats enclosing carbonate reefs (Crimea area, Black Sea). Sediment samples from Hydrate Ridge were obtained during R/V SONNE cruises SO143-2 in August 1999 and SO148-1 in August 2000 at the crest of southern Hydrate Ridge at the Cascadia convergent margin off the coast of Oregon. The second study area is located in the Black Sea and represents a field in which there is active seepage of free gas on the slope of the northwestern Crimea area. Here, a field of conspicuous microbial reefs forming chimney-like structures was discovered at a water depth of 230 m in anoxic waters. The microbial mats were sampled by using the manned submersible JAGO during the R/V Prof. LOGACHEV cruise in July 2001. At Hydrate Ridge the surface sediments were dominated by aggregates consisting of ANME-2 and members of the Desulfosarcina-Desulfococcus branch (DSS) (ANME-2/DSS aggregates), which accounted for >90% of the total cell biomass. The numbers of ANME-1 cells increased strongly with depth; these cells accounted 1% of all single cells at the surface and more than 30% of all single cells (5% of the total cells) in 7- to 10-cm sediment horizons that were directly above layers of gas hydrate. In the Black Sea microbial mats ANME-1 accounted for about 50% of all cells. ANME-2/DSS aggregates occurred in microenvironments within the mat but accounted for only 1% of the total cells. FISH probes for the ANME-2a and ANME-2c subclusters were designed based on a comparative 16S rRNA analysis. In Hydrate Ridge sediments ANME-2a/DSS and ANME-2c/DSS aggregates differed significantly in morphology and abundance. The relative abundance values for these subgroups were remarkably different at Beggiatoa sites (80% ANME-2a, 20% ANME-2c) and Calyptogena sites (20% ANME-2a, 80% ANME-2c), indicating that there was preferential selection of the groups in the two habitats.

(Table 1) Boron concentration and d11B values of interstitial water from IODP Holes 308-U1319A, U1320A, U1322B and U1324B

The Integrated Ocean Drilling Program Expedition 308 (IODP308) drilled normal-pressured sediments from the Brazos-Trinity Basin IV and over-pressured sediments from the Ursa Basin on the northern slope of the Gulf of Mexico. The interstitial water samples from the normal-pressured basin show B concentrations and B isotopic compositions ranging from 255 to 631 µM (0.6 to 1.5 times of seawater value) and from +29.1 to +42.7 per mil (relative to NIST SRM 951), respectively. A wider range is observed both for B concentrations (292 to 865 µM, 0.7 to 2.1 times of seawater value) and d11B values (+25.5 to +43.2 per mil) of the interstitial water in the over-pressured basin. The down-core distribution of B concentrations and d11B values in the interstitial waters are sensitive tracers for assessing various processes occurring in the sediment column, including boron adsorption/desorption reactions involving clay minerals and organic matter in sediments as well as fluid migration and mixing in certain horizons and in the sediment column. In the normal-pressured basin adsorption/desorption reactions in shallow sediments play the major role in controlling the B content and B isotopic composition of the interstitial water. In contrast, multiple processes affect the B content and d11B of the interstitial water in the over-pressured Ursa Basin. There, the stratigraphic level of the maxima of B and d11B correspond to seismic reflectors. The intruded fluids along the seismic reflector boundary from high to low-topography mix with local interstitial water. Fluid flow is inferred in the Blue Unit (a coarse sandstone layer, connecting the high- to low-pressured region) from the freshening of interstitial water in Ursa Basin Site U1322, and upward flow by the overpressure expels fluid from the overburden above the Blue Unit.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

(Table T1) Initial water quality conditions for bioassay experiments during Nathaniel B. Palmer cruise NBP09-01 in the Amundsen Sea

Nutrient addition experiments were performed during the austral summer in the Amundsen Sea (Southern Ocean) to investigate the availability of organically bound iron (Fe) to the phytoplankton communities, as well as assess their response to Fe amendment. Changes in autotrophic biomass, pigment concentration, maximum photochemical efficiency of photosystem II, and nutrient concentration were recorded in response to the addition of dissolved free Fe (DFe) and Fe bound to different model ligands. Analysis of pigment concentrations indicated that the autotrophic community was dominated by the prymnesiophyte Phaeocystis antarctica throughout most of the Amundsen Sea, although diatoms dominated in two experiments conducted in the marginal ice zone. Few significant differences in bulk community biomass (particulate organic carbon, nitrogen, and chlorophyll a) were observed, relative to the controls, in treatments with Fe added alone or bound to the ligand phytic acid. In contrast, when Fe was bound to the ligand desferrioxamine B (DFB), decreases in the bulk biomass indices were observed. The concentration of the diatom accessory pigment fucoxanthin showed little response to Fe additions, while the concentration of the P. antarctica-specific pigment, 19'-hexanoyloxyfucoxanthin (19'-hex), decreased when Fe was added alone or bound to the model ligands. Lastly, differences in the nitrate:phosphate (NO3- :PO4**3-) utilization ratio were observed between the Fe-amended treatments, with Fe bound to DFB resulting in the lowest NO3- :PO4**3- uptake ratios (~ 10) and the remaining Fe treatments having higher NO3- :PO4**3- uptake ratios (~ 17). The data are discussed with respect to glacial inputs of Fe in the Amundsen Sea and the bioavailability of Fe. We suggest that the previously observed high NO3- :PO4**3- utilization ratio of P. antarctica is a consequence of its production of dissolved organic matter that acts as ligands and increases the bioavailability of Fe, thereby stimulating the uptake of NO3-.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Stable oxygen isotope ratios of diatoms and relative species abundances in ODP Site 145-882

Recent research has increasingly advocated a role for the North Pacific Ocean in modulating global climatic changes over both the last glacial cycle and further back into the geological record. Here a diatom d18O record is presented from Ocean Drilling Program Site 882 over the Pliocene/Quaternary boundary from 2.73 Ma to 2.52 Ma (MIS G6-MIS 99). Large changes in d18Odiatom of c. 4 per mil from 2.73 Ma onwards are documented to occur on a timeframe broadly coinciding with glacial-interglacial cycles. These changes are primarily attributed to large scale inputs of meltwater from glacials surrounding the North Pacific Basin and the Bering Sea. Despite these inputs and associated change in surface water salinity, on the basis of existing opal and UK37 temperature data and new modelled water column densities, no evidence exists to suggests a removal of the halocline stratification or a resumption of the high productivity system similar to that which prevailed prior to 2.73 Ma. The permanence of the halocline suggests that the region played a key role in driving global climatic changes over the early glacial-interglacial cycles that followed the onset of major Northern Hemisphere Glaciation by inhibiting deep water upwelling and ventilation of CO2 to the atmosphere.

Relative abundance of diatom species in surface samples from the Southern Ocean, Tropical/Subtropical species

This paper gives a modern circumscription of Tropical/Subtropical diatoms regarding their relationship with sea-surface temperatures (SST) and sea ice cover. Diatoms from 228 core-top sediment samples collected from the Southern Ocean were studied to determine the geographic distribution of eight major diatom species/taxa preserved in surface sediments generally located north of the Subantarctic Front. The comparison of the relative contribution of diatom species with modern February SST and sea-ice cover reveals species-specific sedimentary distributions regulated both by water temperatures and sea ice conditions. Although selective preservation might have played some role, their presence in surface and downcore sediments from the Southern Ocean are reliable indicators of high SST and poleward transport of waters from the Tropical/Subtropical Atlantic. Our work supports the use of diatom remains to reconstruct past variations of these environmental parameters via qualitative and transfer function approaches.

Under-ice fauna, sea-ice concentration, sea-ice thickness and under-ice water parameters from the Eurasian central Arctic Ocean during POLARSTERN cruise ARK-XXVII/3 (PS80) in August-September 2012

Arctic sea-ice decline is expected to have a significant impact on Arctic marine ecosystems. Ice-associated fauna play a key role in this context because they constitute a unique part of Arctic biodiversity and transmit carbon from sea-ice algae into pelagic and benthic food webs. Our study presents the first regional-scale record of under-ice faunal distribution and the environmental characteristics of under-ice habitats throughout the Eurasian Basin. Sampling was conducted with a Surface and Under-Ice Trawl, equipped with a sensor array recording ice thickness and other physical parameters during trawling. We identified 2 environmental regimes, broadly coherent with the Nansen and Amundsen Basins. The Nansen Basin regime was distinguished from the Amundsen Basin regime by heavier sea-ice conditions, higher surface salinities and higher nitrate + nitrite concentrations. We found a diverse (28 species) under-ice community throughout the Eurasian Basin. Change in community structure reflected differences in the relative contribution of abundant species. Copepods (Calanus hyperboreus and C. glacialis) dominated in the Nansen Basin regime. In the Amundsen Basin regime, amphipods (Apherusa glacialis, Themisto libellula) dominated. Polar cod Boreogadus saida was present throughout the sampling area. Abrupt changes from a dominance of ice-associated amphipods at ice-covered stations to a dominance of pelagic amphipods (T. libellula) at nearby ice-free stations emphasised the decisive influence of sea ice on small-scale patterns in the surface-layer community. The observed response in community composition to different environmental regimes indicates potential long-term alterations in Arctic marine ecosystems as the Arctic Ocean continues to change.

Contents of water, sulphur, total organic and inorganic carbon, XRF counts of Ti, S and Ca and radiocarbon ages of sediment core Co1008 from Skua Lake, Rauer Group, East Antarctica

Limited information on the East Antarctic Ice Sheet (EAIS) geometry during Marine Isotope Stage 3 (MIS 3; 60-25 ka) restricts our understanding of its behaviour during periods of climate and sea level change. Ice sheet models forced by global parameters suggest an expanded EAIS compared to the Holocene during MIS 3, but field evidence from East Antarctic coastal areas contradicts such modelling, and suggests that the ice sheet margins were no more advanced than at present. Here we present a new lake sediment record, and cosmogenic exposure results from bedrock, which confirm that Rauer Group (eastern Prydz Bay) was ice-free for much of MIS 3. We also refine the likely duration of the Last Glacial Maximum (LGM) glaciation in the region. Lacustrine and marine sediments from Rauer Group indicate the penultimate period of ice retreat predates 50 ka. The lacustrine record indicates a change from warmer/wetter conditions to cooler/drier conditions after ca. 35 ka. Substantive ice sheet re-advance, however, may not have occurred until much closer to 20 ka. Contemporary coastal areas were still connected to the sea during MIS 3, restricting the possible extent of grounded ice in Prydz Bay on the continental shelf. In contrast, relative sea levels (RSL) deduced from field evidence indicate an extra ice load averaging several hundred metres thicker ice across the Bay between 45 and 32 ka. Thus, ice must either have been thicker immediately inland (with a steeper ice profile), or there were additional ice domes on the shallow banks of the outer continental shelf. Further work is required to reconcile the differences between empirical evidence of past ice sheet histories, and the history predicted by ice sheet models from far-field temperature and sea level records.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Pore water measurements of sediment cores from the Helgoland mud area, North Sea

Iron reduction in subseafloor sulfate-depleted and methane-rich marine sediments is currently a subject of interest in subsurface geomicrobiology. While iron reduction and microorganisms involved have been well studied in marine surface sediments, little is known about microorganisms responsible for iron reduction in deep methanic sediments. Here, we used quantitative PCR (Q-PCR)-based 16S rRNA gene copy numbers and pyrosequencing-based relative abundances of bacteria and archaea to investigate covariance between distinct microbial populations and specific geochemical profiles in the top 5 m of sediment cores from the Helgoland mud area, North Sea. We found that gene copy numbers of bacteria and archaea were specifically higher around the peak of dissolved iron in the methanic zone (250-350 cm. The higher copy numbers at these depths were also reflected by the relative sequence abundances of members of the candidate division JS1, methanogenic and Methanohalobium/ANME-3 related archaea. The distribution of these populations was strongly correlated to the profile of pore-water Fe2+ while that of Desulfobacteraceae corresponded to the pore-water sulfate profile. Furthermore, specific JS1 populations also strongly co-varied with the distribution of Methanosaetaceae in the methanic zone. Our data suggest that the interplay among JS1 bacteria, methanogenic archaea and Methanohalobium/ANME-3-related archaea may be important for iron reduction and methane cycling in deep methanic sediments of the Helgoland mud area and perhaps in other methane-rich depositional environments. .

Boron isotope composition and seawater characteristics of cold water scleratinian corals

The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2 per mil to 28.7 per mil. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pH(cf)), being elevated by ~0.6-0.8 units (Delta pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5 per mil, with a corresponding lower Delta pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pH(T) and shows an approximate linear correlation with Delta pH(Desmo) = 6.43 - 0.71 pH(T) (r**2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where Delta pH(Desmo) = 1.09 - 0.14 Omega(arag) (r**2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pH(cf), and consequently Omega(cf), of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+ -ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium.