Calcium carbonate and organic carbon at DSDP Leg 62 Holes

Percent CaCO3 was determined in selected samples aboard the ship by the carbonate-bomb technique (Müller and Gastner, 1971). Results of these analyses are listed in Table 1 and plotted in Figures 1, 3, 4, and 5 as plus signs (+). Samples collected specifically for analyses of CaCO3 and organic carbon were analyzed at three shore-based laboratories. Concentrations of total carbon, organic carbon, and CaCO3 were determined in some samples at the DSDP sediment laboratory, using a Leco carbon analyzer, by personnel of the U.S. Geological Survey, under the supervision of T. L. Valuer. Most of these samples were collected from lithologic units containing relatively high concentrations of organic carbon. Sample procedures are outlined in Boyce and Bode (1972). Precision and accuracy are both ±0.3% absolute for total carbon, ±0.06% absolute for organic carbon, and ±3% absolute for CaCO3.

Sediment texture, carbonate content, and carbonate mineralogy of ODP Holes 182-1130A and 182-1132B

At Sites 1130 and 1132 of Ocean Drilling Program Leg 182 in the Great Australian Bight, we recovered an expanded Pleistocene section dominated by packstone and wackestone, deposited at unusually high rates of >20 cm/k.y. Shipboard observations detected an intermittent meter-scale alternation of light gray intervals with olive-gray intervals. Meter-scale samples were collected from the upper 250 m at both sites and decimeter-scale samples from four selected 2.5- to 4.0-m intervals in order to determine the texture and composition of sediments deposited along the upper slope throughout the Quaternary. Detailed textural and compositional data are presented from a total of 540 samples collected from both sites. Results indicate a general coarsening upward at both sites, with an accompanying upcore increase in high-Mg calcite (HMC) and aragonite and a decrease in low-Mg calcite (LMC). Samples collected at decimeter-scale intervals substantiate that the alternating light gray and olive-gray units detected on board ship are lithologically distinct. Light gray units consist of an LMC-rich silt, whereas olive-gray units consist of an aragonite and HMC-rich sand and silt. Sediment sources as well as timing and controls of this cyclic depositional pattern will be the subject of further investigations.

Carbonate concentrations of ODP Leg 115 samples

We measured carbonate concentrations in Pleistocene and Pliocene sediments deposited at Sites 709, 710, and 711. Carbonate concentrations exhibit low-amplitude, long-wave length (300-400 k.y. period) variations at the shallowest sites (709 and 710). Before 2.47 Ma, all three sites exhibit higher frequency (100 k.y. period) variations. The deepest site (711) exhibited low-amplitude variations and very low concentrations up to the Gauss/Matuyama magnetic reversal (2.47 Ma), then concentrations abruptly increased. After 2.47 Ma, carbonate concentrations at Site 711 exhibited the same periodic changes as at Site 709. Although a long wave-length periodicity (260-280 k.y.) occurs at these sites after 2.47 Ma, the 100 k.y. period is absent. The dominant periods observed in these data are those found in the eccentricity component of the earth's orbital geometry. Estimates of carbonate accumulation at Sites 709 and 710 document that surface-water productivity decreased near the Gauss/Matuyama magnetic reversal whereas accumulation at Site 711 increased. These results indicate that the rate of carbonate preservation in the deep Indian Ocean increased at that time. This increase in preservation may have re- sulted from a decrease in the production rate of carbonate in tropical oceans of the world. Carbonate accumulation esti- mated from sediments in shallow locations (~3000-3800 m) of the Atlantic and Pacific oceans also indicates that carbonate production decreased at this time. A consequence of lowered surface-water productivity is increased carbonate ion concentration of the deep ocean and better preservation of carbonate on the seafloor.

Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

Stable isotope ratios measured on carbonate tests from the Kara Sea

River discharge of Ob and Yenisei to the Kara Sea is highly variable on seasonal and interannual time scales. River water dominates the shallow bottom water near the river mouths, making it warmer and less saline but seasonally and interannually more changeable than bottom water on the deeper shelf. This hydrographic pattern shows up in measurements and modelling, and in stable isotope records (delta18O, delta13C) along the growth axis of bivalve shells and in multiple analyses of single benthic foraminiferal shells. Average isotope ratios increase, but sample-internal variability decreases with water depth and distance from river mouths. However, isotope records of bivalves and foraminifera of a sediment core from a former submarine channel of Yenisei River reveal a different pattern. The retreat of the river mouth from this site due to early Holocene sea level rise led to increasing average isotope values up core, but not to the expected decrease of the in-sample isotope variability. Southward advection of cold saline water along the palaeo-river channel probably obscured the hydrographic variability during the early Holocene. Later, when sediment filled the channel, the hydrographic variability at the core location remained low, because the shallowing proceeded synchronously with the retreat of the river mouth.