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.     

Petroleum geochemistry of the Kimmeridge Clay of onshore Southern and Eastern England

The Kimmeridge Clay is considered a major oil source rock for the North Sea hydrocarbon province. The formation is also developed onshore in an organic-rich mudstone facies. This paper examines the possibility of onshore oil generation from the Kimmeridge Clay. Geochemically, onshore basin margin sediments contain rich, potential source horizons with mainly Type l/Type ll oil-prone kerogen, but are immature. Some deeper Cleveland Basin sediments have reached marginal maturity. Burial history reconstruction suggests significant formation palaeoburial depths in central areas of the Cleveland and Wessex Basins. Computed vitrinite isoreflectance contours show the Wealden and Isle of Wight Kimmeridge Clay to be thermally mature. Basin modelling suggests an early Palaeogene onset of oil generation in parts of the Cleveland Basin, while maximum oil generation could have been reached by the formation base in the Isle of Wight area during the late Cretaceous. Although basin subsidence ceased in the Neogene, in the Weald and Isle of Wight, where the formation is still deeply buried, oil generation probably continued for some time during uplift. Thus significant quantities of oil could have been generated. Whether or not this oil is present today however, would depend on the correct timing of suitable migration and trap structures.     

North Pacific Synthesis of the Joint Global Ocean Flux Study: Overview

This special issue is comprised of 13 papers, including this overview, and focuses on the synthesis of the Joint Global Ocean Flux Study (JGOFS) in the North Pacific which took place from 1997 through 2003. The effort was led by the JGOFS North Pacific Synthesis Group, with the aim of quantifying CO₂ drawdown by physical and biological pumps in the North Pacific by identifying and studying the regional, seasonal to inter-annual variations in the key processes, and understanding their regulating mechanisms. Emphasis was placed on the similarities and differences of the biogeochemical regimes in the eastern and western subarctic Pacific. Effort was also made to address the future research directions which arose from the scientific findings during the North Pacific JGOFS process study. A brief overview of the papers from view points of CO₂ drawdown by physical and biological pumps, spatial variability, and temporal variability from seasonal to decadal scales is made, followed by suggestions for the directions of future research. This revised version was published online in July 2006 with corrections to the Cover Date.     

The composition and distribution of saturated and aromatic hydrocarbons in nearshore sediments, river sediments, and coastal peat of the Alaskan Beaufort Sea: Implications for detecting anthropogenic hydrocarbon inputs

A 3-year program, to determine spatial and temporal trends in sediment concentrations of hydrocarbons and metals from oil and gas exploration and development activities, was conducted in the US Beaufort Sea. Concentrations of saturated and aromatic hydrocarbons in sediments from the Beaufort Sea were elevated in comparison to non-polluted shelf-sediments from other regions of the US coast. Potential natural sources for hydrocarbons that were examined included riverine sediments and coastal peat. Significant quantities of fossil hydrocarbons characterize the surface sediments from the entire region. Sediment inputs from river discharges appear to account for this observation. The use of source-diagnostic ratios has allowed the differentiation of various sources in an area with high naturally-occurring hydrocarbon concentrations where effects due to oil and gas exploration and development activities may be obscured.