The solubility of CaCO3 in seawater at 2°C based upon in-situ sampled pore water composition

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.     

The dissociation constants of carbonic acid in seawater at salinities 5 to 45 and temperatures 0 to 45°C

The pK₁^* and pK₂^* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK₁^* have been determined from emf measurements for the cell:

Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag

where X is the mole fraction of CO₂ in the gas. The values of pK₂^* have been determined from emf measurements on the cell:

Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag

The results have been fitted to the equations:

lnK^*₁ = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S^0.5 + 0.08468345S − 0.00654208S¹

InK^*₂ = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S^0.5 + 0.1130822S − 0.00846934S^1.5

where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK₁^* and σ = 0.0070 in lnK₂^*.Our new results are in good agreement at S = 35 (±0.002 in pK₁^*and ±0.005 in pK₂^*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H₂|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.     

The solubility of calcite in seawater at atmospheric pressure and 35%permil; salinity

The apparent (stoichiometric) solubility product of calcite in artificial seawater of salinity 35‰ was measured by a saturometer technique. The value of the apparent solubility product was found to be (4·59 ± 0·05) × 10⁻⁷ moles/(kilogram of seawater)² at 25°C with a temperature coefficient of −0·0108 × 10⁻⁷/°C between 2 and 25°C. These values are significantly smaller than those found by MacIntyre (1965) and other workers. The effect of these results on the saturation of the oceans with respect to calcite is examined.     

Hydrogen ion exchange on amorphous silica in seawater

The amount of hydrogen ion exchange on the surface of amorphous silica in seawater was measured as a function of pH at 2 and 25°C. Hydrogen ion exchange with the cations present in seawater is pH dependent and at 25°C the fraction of the surface in the cation form increases from 9% at pH 7 to 22% at pH 8. The exchange is temperature dependent and at 2°C and pH 8, 14% of the exchange sites are occupied by cations, as opposed to 22% of the exchange sites at 25°C. These results were used to calculate the buffer capacity of a model sediment consisting of pore water and amorphous silica. For a sediment of 70% porosity, pH 7.7, and 25°C, the buffer capacity of sediment plus pore water is 67 times the buffer capacity of pure seawater.     

The solubility of aragonite in seawater at 25.0°C and 32.62‰ salinity

The apparent solubility product of aragonite in 32‰ seawater at 25.0°C is reported as K′_sp = (0.869±0.049) × 10^?6(mol²kgseawater^?2) thus confirming the value of R.A. Berner, 1976 (Am. J. Sci., 276: 713–730). The apparent solubility product ratio for aragonite and calcite is reported as $\text{K′}{}_{\mathrm{aragonite}}\text{K′}{}_{\mathrm{calcite}}\text{= 2.05}$ The deviation of this value from the thermodynamic ratio is atttributed to the formation of a stable low Mg-calcite coating on pure calcite in seawater measurements of solubility.     

Experimental determination of the silica solubility and of the H4SiO 4 0 activity ratio in standard and desalinated seawater

The solubility of amorphous silica was studied in mixtures of riverine and marine waters simulating the water composition at the river-sea geochemical barrier. The value of the thermodynamical equilibrium constant was determined for the reaction of silicon solubility as K _r ⁰ = (1.71 ± 0.01) × 10^?3 at 22°C. A near-linear dependence was found for the activity ratio of the H₄SiO ₄ ⁰ and the salinity with the increase of this ratio from 1.00 in the riverine to 1.15 in the standard seawater.     

A review of the effect of salts on the solubility of organic compounds in seawater

The presence of electrolytes (salts) in aqueous solution modifies the solubility and related properties of organic compounds in water. Reported data for salting-out constants (Setschenow constants) which relate solubility to the salt concentration of aromatic and alkane hydrocarbons, and their chlorinated derivatives, and some organic acids have been compiled for 25 aqueous salt solutions at 20–25 °C. The salting-out sequences for various electrolytes are discussed and it is shown that the salting-out effect is greater for organic solutes with large molar volumes. A compilation of salting-out constants for NaCl solutions and seawater (natural or synthetic) with a variety of solutes, shows that the Setschenow constants are similar for natural or artificial seawater (at salinity of 30–35%.) and NaCl solutions (at 3.0–3.5% or 0.5 M). A simple correlation is suggested for estimating the Setschenow constants for a variety of organic solutes in seawater which typically yields a reduction in solubility by a factor of 1.36. The hydrophobicity of organic solutes is therefore increased by this factor, as is the air-water partition coefficient, implying an increased partitioning from aqueous solution into air, organic carbon and lipid phases. The effect must be quantified when comparing the behavior of organic contaminants in freshwater and marine conditions.     

Dynamics of carbohydrates in the Norwegian Sea inferred from monthly profiles collected during 3 years at 66°N, 2°E

Water samples were collected monthly for 3 years at 66°N, 2°E in the Norwegian Sea, 250 nautical miles off the Norwegian coast. Concentrations of mono- and polysaccharides were measured with the 2,4,6-tripyridyl-s-triazine (TPTZ) spectroscopic method. Total dissolved carbohydrates varied from 3.4 to 28.2 μM C of all samples and the ratio of carbohydrate to dissolved organic C (DOC) varied from an average of 14% at 0–25 m depth to 11% at 800–2000 m depth. This indicates that dissolved carbohydrates were a significant constituent of DOC in the Norwegian Sea. Polysaccharides varied from 0.4 to 21.5 μM C and monosaccharides from 0.7 to 11.7 μM C at all depths. The level of monosaccharides was relatively constant at 2.8–3.2 μM C below the euphotic zone, whereas polysaccharides showed more varying concentrations. Dissolved carbohydrates accumulated during the productive season, reaching maximum concentrations during summer although interannual differences were observed. A significant positive correlation between Chl a and soluble carbohydrate was found in one growing season with nutrient analyses. Average values for total carbohydrates were highest in the surface – 0 to 25 m – with 13.3 μM C and decreased to 8.4 μM C at 800–2000 m depth. The ratio of monosaccharides to polysaccharides exhibited a marked seasonal variation, increased from January to a maximum in June of 1.1, and declined to 0.5 in July.     

The behaviour of dissolved Cd, Co, Zn, and Pb in North Atlantic near-surface waters (30°N/60°W–60°N/2°W)

In September 1993 (M26) and June/July 1996 (M36), a total of 239 surface samples (7 m depth) were collected on two transects across the open Atlantic Ocean (224 samples) and northwest European shelf edge area. We present an overview of the horizontal variability of dissolved Cd, Co, Zn, and Pb in between the northwest and northeast Atlantic Ocean in relation to salinity and the nutrients. Our data show a preferential incorporation of Cd relative to P in the particulate material of the surface ocean when related to previously published parallel measurements on suspended particulate matter from the same cruise. There is a good agreement with results recently estimated from a model by Elderfield and Rickaby (Nature 405 (2000) 305), who predict for the North Atlantic Ocean a best fit for α_Cd/P=[Cd/P]_POM/[Cd/P]_SW of 2.5, whereas the approach of our transect shows a α_Cd/P value of 2.6. The Co concentrations of our transects varied from <5 to 131 pmol kg⁻¹, with the lowest values in the subtropical gyre. There were pronounced elevations in the low-salinity ranges of the northwest Atlantic and towards the European shelf. The Co data are decoupled from the Mn distribution and support the hypothesis of marginal inputs as the dominant source. Zinc varied from a minimum of <0.07 nmol kg⁻¹ to a maximum of 1.2 and 4.8 nmol kg⁻¹ in regions influenced by Labrador shelf or European coastal waters, respectively. In subtropical and northeast Atlantic waters, the average Zn concentration was 0.16 nmol kg⁻¹. Zinc concentrations at nearly three quarters of the stations between 40°N and 60°N were <0.1 nmol kg⁻¹. This suggests that biological factors control Zn concentrations in large areas of the North Atlantic surface waters. The Pb data indicated that significant differences in concentration between the northwest and northeast Atlantic surface waters presently (1996) do not exist for this metal. The transects in 1993 and 1996 exhibited Pb concentrations in the northeast Atlantic surface waters of 30 to 40 pmol kg⁻¹, about a fifth to a quarter of the concentrations observed in 1981. This decline is supported by our particle flux measurements in deep waters of the same region.     

Distribution coefficient of Mg ions between calcite and solution at 10–50°C

The distribution coefficient (λ_Mg) of Mg²⁺ ions between calcite and solution was found to be 0.012 ± 0.001 (10°C), 0.014 ± 0.001 (15°C), 0.019 ± 0.001 (25°C), 0.024 ± 0.001 (30°C), 0.027 ± 0.001 (35°C) and 0.040 + 0.003 (50°C). This indicates a remarkable dependence on temperature. The effect of the Mg²⁺/Ca²⁺ molar ratio in a parent solution on λ_Mg for calcite is small, where the molar ratio lies in the range 0.04-2. However, the λ_Mg value for aragonite tends to decrease with increasing Mg²⁺/Ca²⁺ ratio in the parent solution. The largest Mg content of calcite in the Ca(HCO₃)₂-Mg²⁺ → calcite system is around 2 mol% in the temperature range 10–50°C. Neither homogeneous nor heterogeneous distribution laws hold for aragonite precipitation, and the temperature effect on the coprecipitation of Mg²⁺ ions with aragonite is very small.     

Surface salinity in the Atlantic Ocean (30°S–50°N)

Sea surface salinity (SSS) data in the Atlantic Ocean is investigated between 50°N and 30°S based on data collected mostly during the period 1977–2002. Monthly mapping of SSS is done to extract the large-scale variability. This mapped variability indicates fairly long (seasonal) time scales outside the equatorial region. The spatial scales of the seasonal anomalies are regional, but not basin-wide (typically 500–1000 km). These seasonal SSS anomalies are found to respond with a 1–2 month lag to freshwater flux anomalies at the air–sea interface or to the horizontal Ekman advection. This relation presents a seasonal cycle in the northern subtropics and north-east Atlantic indicating that the late-boreal spring/summer season is less active than the boreal winter/early-spring season in forcing the seasonal SSS variability. In the north-eastern mid-latitude Atlantic, SSS is positively correlated to SST, with SSS slightly lagging SST. There are noticeable long-lasting larger-scale signals overlaid on this regional variability. Part of it is related to known climate signals, for example ENSO and NAO. A linear trend is present during the first half of the period in some parts of the basin (usually towards increasing salinities, at least between 20°N and 45°N). Based on a linear regression analysis, these signals combined can locally represent up to 20% of SSS variance (in particular near 30°N/60°W or 40°N/10–30°W), but usually represent less than 10% of the variance.     

Longwaves and primary productivity variations in the equatorial pacific at 0°, 140dgW

High temporal resolution measurements of physical and bio-optical variables were made in the upper ocean using a mooring located at 0°, 140°W from 9 February 1992 to 15 March 1993 as part of the equatorial Pacific Ocean (EgPac) study. Chlorophyll and primary productivity time-series records were generated using the mooring data. Primary productivity varied by about 50% around the mean on time scales of weeks and by over a factor of four within our observational period. The mooring observations encompassed both El Niho and cool conditions. Kelvin waves were evident during the El Nifio phase, and tropical instability waves (TIWs) were dominant during the cool phase. The two extreme conditions also were observed concurrently with complementary ship-based measurements. In addition, bio-optical drifters provided simultaneous spatial data concerning net phytoplankton growth rates during passage of a TIW. The collective data sets have been used to examine the causes of the observed variability in phytoplankton biomass and productivity. Our joint results and analyses appear to support the hypothesis that the vertical transport of iron into the upper layer and primary production rates are modulated by variability of the depth of the Equatorial Undercurrent and by equatorial longwaves. In particular, our results are consonant with the suggestion of Barber et al. (1996) that passage of a TIW may be considered to be a natural analog of a small iron enrichment experiment. Predicting primary productivity and, thus, carbon flux in the equatorial Pacific requires continuous, long-term observations of a few physical, biological, and optical properties that can be used to parameterize the biological variability.     

The distribution and preferential biological uptake of cadmium at 6°W in the Southern Ocean

The spatial and temporal distribution of cadmium (Cd) and phosphate in the Southern Ocean are related to biology and hydrography. During a period of 18 days between transects 5/6 and 11, a phytoplankton spring bloom developed in the Polar Frontal region. Upper water Cd concentrations were not depleted and ranged from 0.2 to 0.8 nM at about 10 m depth. These relatively high Cd concentrations are attributed to upwelling of Upper Circumpolar Deep Water (0.5–1.2 nM in the core) in combination with low biological productivity (0.2 to 0.3 mg m⁻³ chlorophyll-a, 0.3 g C m⁻² d⁻¹). Total particulate Cd concentrations at 40 m depth were between 0.02 and 0.14 nM with the maximum in concentration in the Polar Frontal region. Most of the particulate Cd at this depth (85–94%) was detected in the first phase of a sequential chemical leaching treatment which includes adsorbed Cd as well as Cd incorporated in algae. The Polar Frontal region was characterized by minima in Cd concentration and Cd/phosphate ratio of seawater at both transects; values were the lowest at transect 11 after development of the spring bloom which was dominated by diatoms. This decreasing Cd/phosphate ratio in seawater during spring bloom development was attributed to preferential Cd gross uptake which more than compensated the process of preferential Cd recycling. Within the Upper Circumpolar Deep Water, Cd showed a maximum in concentration similar to that of the major nutrients. Both the Cd concentration and the Cd/phosphate ratio of the deeper water increased in southern direction, from 0.4 to 0.7 nM and from 0.2 to 0.3 nM/μM, respectively. Antarctic Intermediate Water has a Cd concentration of 0.21 nM with a Cd/phosphate ratio of 0.10 nM/μM. In Antarctic Bottom Water, Cd concentrations ranged from 0.60 to 0.82 nM.     

The effect of pressure on the chemical potentials of seawater components,on ionic species in seawater,and on calcite saturation levels

The activities of most of the major seawater components at 1,001 bars have been estimated, and values for the ions deduced. Equations giving the effect of pressure on the activities of ionic species in seawater ($\text{S = 35‰}$) have been developed. The species covered are: NaSO₄^?, MgSO₄⁰, CaSO₄⁰, H⁺, the free base (NH₃), the HCO₃^?/CO₃² activity ratio and the ion activity product of calcium carbonate. Comparison of the latter with the “ideal” solubility of calcite (pure solid in equilibrium with a mixed electrolyte solution) indicates a degree of saturation compatible with the trends indicated by in situ measurements.     

Temporal and spatial variability of biogenic particles fluxes during the JGOFS northeast Atlantic process studies at 47°N, 20°W

Particle fluxes to 3100 m depth at 45°50′N, 19°30′W were measured using time-series sediment traps during a 17 month period encompassing 1989 and 1990 JGOFS spring bloom process studies in the northeast Atlantic. There was a marked intra-annual variability in fluxes of mass, particulate inorganic carbon (PIC), particulate organic carbon (POC) and opal, appearing as two major flux events in each year. In 1989, the first flux event represented the settlement of spring bloom-type material, whereas the second, in autumn, was heavily enriched in mucopolysaccharides. In 1990, in contrast, the two flux events comprised spring bloom-type material and arrived at depth at different times relative to the 1989 events. The intra- and interannual variability evident for all three biogenic components was most notable for POC: (i) the autumn 1989 event supplied twice as much POC to 3100 m as the earlier spring bloom settlement—a quite unexpected observation—and (ii) the annual average POC flux in 1989 was 3–4 times more than in 1990. A synthesis of process study datasets with sediment trap data enables an evaluation of the coupling of deep fluxes with surface-water events. Spatial variability of the 1989 deep flux events is assessed by comparing the sediment trap data reported here with those from a second site 100 km away (Honjo and Manganini,Deep-Sea Research II,40, 587–607, 1993). The timing and magnitude of the 1989 spring bloom settlement was indistinguishable in the two datasets, indicating no spatial variability in flux between these sites. In contrast, the autumn 1989 flux event was barely recorded at the second site. Given the biogeochemical importance of this latter event to deep waters, most notable in terms of its contribution to POC flux, this observation of deep-water mesoscale flux variability indicates a significant problem in determining regional carbon budgets. Construction of basin-scale budgets is a central goal of JGOFS and for this to be achieved further studies of mesoscale variability of particle flux are essential.     

Upper ocean export of particulate organic carbon and biogenic silica in the Southern Ocean along 170°W

Upper-ocean fluxes of particulate organic carbon (POC) and biogenic silica (bSi) are calculated from four US JGOFS cruises along 170°W using a thorium-234 based approach. Both POC and bSi fluxes exhibit large variability vs. latitude during the seasonal progression of diatom dominated blooms. POC fluxes at 100 m of up to 50 mmol C m⁻² d⁻¹ are found late in the bloom, and farthest south near the Ross Sea Gyre. Biogenic Si fluxes also peak late in the bloom as high as 15 mmol Si m⁻² d⁻¹, but this flux peak occurs at a different latitude, just south of the Antarctic Polar Front (APF), which is centered around 60°S along this cruise track. The ratios of both POC and bSi export relative to their production rates are large, suggesting an efficient biological pump at these latitudes. The highest relative bSi/POC flux ratios at 100 m are found just south of the APF, coincident with a bSi/POC flux peak seen in 1000 m traps during this same program by Deep-Sea Research II (Honjo et al., Deep-Sea Research II 47, 3521–3548). These data suggest that efficient export at these latitudes can support the high accumulation rates of bSi found in the sediments under and south of the APF, despite the generally low biomass and productivity levels in this region.     

Association of picophytoplankton distribution with ENSO events in the equatorial Pacific between 145°E and 160°W

Climatological variability of picophytoplankton populations that consisted of >64% of total chlorophyll a concentrations was investigated in the equatorial Pacific. Flow cytometric analysis was conducted along the equator between 145°E and 160°W during three cruises in November–December 1999, January 2001, and January–February 2002. Those cruises were covering the La Niña (1999, 2001) and the pre-El Niño (2002) periods. According to the sea surface temperature (SST) and nitrate concentrations in the surface water, three regions were distinguished spatially, viz., the warm-water region with >28 °C SST and nitrate depletion (<0.1 μmol kg⁻¹), the upwelling region with <28 °C SST and high nitrate (>4 μmol kg⁻¹) water, and the in-between frontal zone with low nitrate (0.1–4 μmol kg⁻¹). Picophytoplankton identified as the groups of Prochlorococcus, Synechococcus and picoeukaryotes showed a distinct spatial heterogeneity in abundance corresponding to the watermass distribution. Prochlorococcus was most abundant in the warm-water region, especially in the nitrate-depleted water with >150×10³ cells ml⁻¹, Synechococcus in the frontal zone with >15×10³ cells ml⁻¹, and picoeukaryotes in the upwelling region with >8×10³ cells ml⁻¹. The warm-water region extended eastward with eastward shift of the frontal zone and the upwelling region during the pre-El Niño period. On the contrary, these regions distributed westward during the La Niña period. These climatological fluctuations of the watermass significantly influenced the distribution of picophytoplankton populations. The most abundant area of Prochlorococcus and Synechococcus extended eastward and picoeukaryotes developed westward during the pre-El Niño period. The spatial heterogeneity of each picophytoplankton group is discussed here in association with spatial variations in nitrate supply, ambient ammonium concentration, and light field.