Nighttime dissolution in a temperate coastal ocean ecosystem increases under acidification

Anthropogenic emissions of carbon dioxide (CO2) are causing ocean acidification, lowering seawater aragonite (CaCO3) saturation state (Omega arag), with potentially substantial impacts on marine ecosystems over the 21st Century. Calcifying organisms have exhibited reduced calcification under lower saturation state conditions in aquaria. However, the in situ sensitivity of calcifying ecosystems to future ocean acidification remains unknown. Here we assess the community level sensitivity of calcification to local CO2-induced acidification caused by natural respiration in an unperturbed, biodiverse, temperate intertidal ecosystem. We find that on hourly timescales nighttime community calcification is strongly influenced by Omega arag, with greater net calcium carbonate dissolution under more acidic conditions. Daytime calcification however, is not detectably affected by Omega arag. If the short-term sensitivity of community calcification to Omega arag is representative of the long-term sensitivity to ocean acidification, nighttime dissolution in these intertidal ecosystems could more than double by 2050, with significant ecological and economic consequences.

Impact of atmospheric pCO2, seawater temperature, and calcification rate on the delta 18O and delta 13C composition of echinoid calcite (Echinometra viridis)

The tropical echinoid Echinometra viridis was reared in controlled laboratory experiments at temperatures of approximately 20°C and 30°C to mimic winter and summer temperatures and at carbon dioxide (CO2) partial pressures of approximately 487 ppm-v and 805 ppm-v to simulate current and predicted-end-of-century levels. Spine material produced during the experimental period and dissolved inorganic carbon (DIC) of the corresponding culture solutions were then analyzed for stable oxygen (delta 18Oe, delta 18ODIC) and carbon (The tropical echinoid Echinometra viridis was reared in controlled laboratory experiments at temperatures of approximately 20°C and 30°C to mimic winter and summer temperatures and at carbon dioxide (CO2) partial pressures of approximately 487 ppm-v and 805 ppm-v to simulate current and predicted-end-of-century levels. Spine material produced during the experimental period and dissolved inorganic carbon (DIC) of the corresponding culture solutions were then analyzed for stable oxygen (delta18Oe, delta18ODIC) and carbon (delta13Ce, delta13CDIC) isotopic composition. Fractionation of oxygen stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta18O = delta18Oe - delta18ODIC) was significantly inversely correlated with seawater temperature but not significantly correlated with atmospheric pCO2. Fractionation of carbon stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (Delta delta13C = delta13Ce - delta13CDIC) was significantly positively correlated with pCO2 and significantly inversely correlated with temperature, with pCO2 functioning as the primary factor and temperature moderating the pCO2-delta13C relationship. Echinoid calcification rate was significantly inversely correlated with both delta18O and delta13C, both within treatments (i.e., pCO2 and temperature fixed) and across treatments (i.e., with effects of pCO2 and temperature controlled for through ANOVA). Therefore, calcification rate and potentially the rate of co-occurring dissolution appear to be important drivers of the kinetic isotope effects observed in the echinoid spines. Study results suggest that echinoid delta18O monitors seawater temperature, but not atmospheric pCO2, and that echinoid delta13C monitors atmospheric pCO2, with temperature moderating this relationship. These findings, coupled with echinoids' long and generally high-quality fossil record, supports prior assertions that fossil echinoid delta18O is a viable archive of paleo-seawater temperature throughout Phanerozoic time, and that delta13C merits further investigation as a potential proxy of paleo-atmospheric pCO2. However, the apparent impact of calcification rate on echinoid delta18O and delta13C suggests that paleoceanographic reconstructions derived from these proxies in fossil echinoids could be improved by incorporating the effects of growth rate.13Ce, delta13CDIC) isotopic composition. Fractionation of oxygen stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta18O = delta18Oe - delta18ODIC) was significantly inversely correlated with seawater temperature but not significantly correlated with atmospheric pCO2. Fractionation of carbon stable isotopes between the echinoid spines and DIC of their corresponding culture solutions (delta13C = delta13Ce - delta13CDIC) was significantly positively correlated with pCO2 and significantly inversely correlated with temperature, with pCO2 functioning as the primary factor and temperature moderating the pCO2-delta13C relationship. Echinoid calcification rate was significantly inversely correlated with both delta18O and delta13C, both within treatments (i.e., pCO2 and temperature fixed) and across treatments (i.e., with effects of pCO2 and temperature controlled for through ANOVA). Therefore, calcification rate and potentially the rate of co-occurring dissolution appear to be important drivers of the kinetic isotope effects observed in the echinoid spines. Study results suggest that echinoid delta18O monitors seawater temperature, but not atmospheric pCO2, and that echinoid delta13C monitors atmospheric pCO2, with temperature moderating this relationship. These findings, coupled with echinoids' long and generally high-quality fossil record, supports prior assertions that fossil echinoid delta18O is a viable archive of paleo-seawater temperature throughout Phanerozoic time, and that delta13C merits further investigation as a potential proxy of paleo-atmospheric pCO2. However, the apparent impact of calcification rate on echinoid delta18O and delta13C suggests that paleoceanographic reconstructions derived from these proxies in fossil echinoids could be improved by incorporating the effects of growth rate.

Description, geochemistry and growth rate of buried nodules from the Central Indian Basin

Buried nodules from siliceous sediments in the central Indian Basin are morphologically variable and mineralogically consist of d-MnO2 and incipient todorokite. Compositionally they are weakly diagenetic. The sediment coarse fractions (>63 µm) at different depths show variable abundances of micronodules, volcanic glass shards and biodebris. Dissolution of biodebris increases and abundance of micronodules decreases with increasing depth. Enrichment in Mn, Fe, Cu, Ni, Co, together with a decrease in organic carbon in the sediment column, may result from diagenetic metal remobilization. Diagenetically remobilized trace metals might have been utilized for the growth of micronodules over the buried nodules.

Dissolution of a spatially variable DNAPL (dense non aqueous phase liquid) source

Dissolution of non-aqueous phase liquids (NAPLs) or gases into groundwater is a key process, both for contamination problems originating from organic liquid sources, and for dissolution trapping in geological storage of CO2. Dissolution in natural systems typically will involve both high and low NAPL saturations and a wide range of pore water flow velocities within the same source zone for dissolution to groundwater. To correctly predict dissolution in such complex systems and as the NAPL saturations change over time, models must be capable of predicting dissolution under a range of saturations and flow conditions. To provide data to test and validate such models, an experiment was conducted in a two-dimensional sand tank, where the dissolution of a spatially variable, 5x5 cm**2 DNAPL tetrachloroethene source was carefully measured using x-ray attenuation techniques at a resolution of 0.2x0.2 cm**2. By continuously measuring the NAPL saturations, the temporal evolution of DNAPL mass loss by dissolution to groundwater could be measured at each pixel. Next, a general dissolution and solute transport code was written and several published rate-limited (RL) dissolution models and a local equilibrium (LE) approach were tested against the experimental data. It was found that none of the models could adequately predict the observed dissolution pattern, particularly in the zones of higher NAPL saturation. Combining these models with a model for NAPL pool dissolution produced qualitatively better agreement with experimental data, but the total matching error was not significantly improved. A sensitivity study of commonly used fitting parameters further showed that several combinations of these parameters could produce equally good fits to the experimental observations. The results indicate that common empirical model formulations for RL dissolution may be inadequate in complex, variable saturation NAPL source zones, and that further model developments and testing is desirable.

Seawater carbonate chemistry and calcification rate of eastern oyster Crassostrea virginica, 2011

Anthropogenic carbon dioxide (CO2) emissions reduce pH of marine waters due to the absorption of atmospheric CO2 and formation of carbonic acid. Estuarine waters are more susceptible to acidification because they are subject to multiple acid sources and are less buffered than marine waters. Consequently, estuarine shell forming species may experience acidification sooner than marine species although the tolerance of estuarine calcifiers to pH changes is poorly understood. We analyzed 23 years of Chesapeake Bay water quality monitoring data and found that daytime average pH significantly decreased across polyhaline waters although pH has not significantly changed across mesohaline waters. In some tributaries that once supported large oyster populations, pH is increasing. Current average conditions within some tributaries however correspond to values that we found in laboratory studies to reduce oyster biocalcification rates or resulted in net shell dissolution. Calcification rates of juvenile eastern oysters, Crassostrea virginica, were measured in laboratory studies in a three-way factorial design with 3 pH levels, two salinities, and two temperatures. Biocalcification declined significantly with a reduction of ~0.5 pH units and higher temperature and salinity mitigated the decrease in biocalcification.

Biostratigraphy and average linear sedimentation rate and accumulation rate of ODP Site 159-959 (Table 1)

Reconstructing the long-term evolution of organic sedimentation in the eastern Equatorial Atlantic (ODP Leg 159) provides information about the history of the climate/ocean system, sediment accumulation, and deposition of hydrocarbon-prone rocks. The recovery of a continuous, 1200 m long sequence at ODP Site 959 covering sediments from Albian (?) to the present day (about 120 Ma) makes this position a key location to study these aspects in a tropical oceanic setting. New high resolution carbon and pyrolysis records identify three main periods of enhanced organic carbon accumulation in the eastern tropical Atlantic, i.e. the late Cretaceous, the Eocene-Oligocene, and the Pliocene-Pleistocene. Formation of Upper Cretaceous black shales off West Africa was closely related to the tectonosedimentary evolution of the semi-isolated Deep Ivorian Basin north of the Côte d'Ivoire-Ghana Transform Margin. Their deposition was confined to certain intervals of the last two Cretaceous anoxic events, the early Turonian OAE2 and the Coniacian-Santonian OAE3. Organic geochemical characteristics of laminated Coniacian-Santonian shales reveal peak organic carbon concentrations of up to 17% and kerogen type I/II organic matter, which qualify them as excellent hydrocarbon source rocks, similar to those reported from other marginal and deep sea basins. A middle to late Eocene high productivity period occurred off equatorial West Africa. Porcellanites deposited during that interval show enhanced total organic carbon (TOC) accumulation and a good hydrocarbon potential associated with oil-prone kerogen. Deposition of these TOC-rich beds was likely related to a reversal in the deep-water circulation in the adjacent Sierra Leone Basin. Accordingly, outflow of old deep waters of Southern Ocean origin from the Sierra Leone Basin into the northern Gulf of Guinea favored upwelling of nutrient-enriched waters and simultaneously enhanced the preservation potential of sedimentary organic matter along the West African continental margin. A pronounced cyclicity in the carbon record of Oligocene-lower Miocene diatomite-chalk interbeds indicates orbital forcing of paleoceanographic conditions in the eastern Equatorial Atlantic since the Oligocene-Miocene transition. A similar control may date back to the early Oligocene but has to be confirmed by further studies. Latest Miocene-early Pliocene organic carbon deposition was closely linked to the evolution of the African trade winds, continental upwelling in the eastern Equatorial Atlantic, ocean chemistry and eustatic sea level fluctuations. Reduction in carbonate carbon preservation associated with enhanced carbon dissolution is recorded in the uppermost Miocene (5.82-5.2 Ma) section and suggests that the latest Miocene carbon record of Site 959 documents the influence of corrosive deep waters which formed in response to the Messinian Salinity Crisis. Furthermore, sea level-related displacement of higher productive areas towards the West African shelf edge is indicated at 5.65, 5.6, 5.55, 5.2, 4.8 Ma. In view of humid conditions in tropical Africa and a strong West African monsoonal system around the Miocene-Pliocene transition, the onset of pronounced TOC cycles at about 5.6 Ma marks the first establishment of upwelling cycles in the northern Gulf of Guinea. An amplification in organic carbon deposition at 3.3 Ma and 2.45 Ma links organic sedimentation in the tropical eastern Equatorial Atlantic to the main steps of northern hemisphere glaciation and testifies to the late Pliocene transition from humid to arid conditions in central and western African climate. Aridification of central Africa around 2.8 Ma is not clearly recorded at Site 959. However, decreased and highly fluctuating carbonate carbon concentrations are observed from 2.85 Ma on that may relate to enhanced terrigenous (eolian) dilution from Africa.