Distribution of the CO2 partial pressure along an Atlantic meridional transect

Atmospheric and oceanic pCO₂ were measured continuously along an Atlantic Meridional transect (50°N–50°S) in September–October 1995 and 1996 (U.K. to the Falklands Islands) and in April–May 1996 (Falklands Islands to the UK). The Atlantic ocean was a net sink for atmospheric CO₂ for all 3 transects. The largest sinks were located at high latitudes, in regions of high wind speed, where strong CO₂ undersaturations, associated with high biological activity, were observed. In these regions the partial pressure difference between the ocean and the atmosphere reached −110 μatm. A CO₂ source occurred in the equatorial region between 0° and 10°S, where ΔpCO₂ of up to 40 μatm was found. Another source was in the northern subtropical gyre where its extension varied according to the season. Along the whole transect the October cruises exhibited similar pCO₂ distributions suggesting a dominance of the seasonal variability and small year to year changes.     

Fluid inclusion and microfabric studies on Zechstein carbonates (Ca2) and related fracture mineralizations – New insights on gas migration in the Lower Saxony Basin (Germany)

New petrographic and fluid inclusion data from core samples of Upper Permian dolomitic limestone (Hauptdolomit, Zechstein group, Stassfurt carbonate sequence) from a gas field located at the northern border of the Lower Saxony Basin (LSB) essentially improve the understanding of the basin development. The gas production at the locality is characterized by very high CO₂ concentrations of 75–100% (with CH₄ and N₂).Samples consist of fine grained, mostly laminated and sometimes brecciated dolomitic limestone (mudstone/wackestone) from the transition zone between the shallow water zone (platform) and the upper slope. The study focuses on migration fluids, entrapped as fluid inclusions in diagenetic anhydrite, calcite, and fluorite, and in syn-diagenetic microfractures, as well as on the geochemistry of fluorite fracture mineralizations, obtained by LA-ICP-MS analysis. Fluid inclusion studies show that the diagenetic fluid was rich in H₂ONaClCaCl₂. Recrystallized anhydrite contains aqueous inclusions with homogenization temperatures (T_h) of ca. 123 °C, but somewhat higher T_h of ca. 142 °C was found for calcite cement followed by early Fluorite A with T_h of 147 °C. A later Fluorite B preserves gas inclusions and brines with maximum T_h of 156 °C. Fluorite B crystallized in fractures during the mobilization of CO₂-bearing brines. Crossing isochores for co-genetic aqueous-carbonic and carbonic inclusions indicate fluid trapping conditions of 180–200 °C and 900–1000 bars. δ¹³C-isotopic ratios of gas trapped in fluid inclusions suggest an organic origin for CH₄, while the CO₂ is likely of inorganic origin.Basin modelling (1D) shows that the fault block structure of the respective reservoir has experienced an uplift of >1000 m since Late Cretaceous times.The fluid inclusion study allows us to, 1) model the evolution of the LSB and fluid evolution by distinguishing different fluid systems, 2) determine the appearance of CO₂ in the geological record and, 3) more accurately estimate burial and uplift events in individual parts of the LSB.     

A seasonal carbon budget for the sub-Antarctic Ocean, South of Australia

Changes from winter (July) to summer (February) in mixed layer carbon tracers and nutrients measured in the sub-Antarctic zone (SAZ), south of Australia, were used to derive a seasonal carbon budget. The region showed a strong winter to summer decrease in dissolved inorganic carbon (DIC;  45 µmol/kg) and fugacity of carbon dioxide (fCO₂;  25 µatm), and an increase in stable carbon isotopic composition of DIC (δ¹³C_DIC;  0.5‰), based on data collected between November 1997 and July 1999.The observed mixed layer changes are due to a combination of ocean mixing, air–sea exchange of CO₂, and biological carbon production and export. After correction for mixing, we find that DIC decreases by up to 42 ± 3 µmol/kg from winter (July) to summer (February), with δ¹³C_DIC enriched by up to 0.45 ± 0.05‰ for the same period. The enrichment of δ¹³C_DIC between winter and summer is due to the preferential uptake of ¹²CO₂ by marine phytoplankton during photosynthesis. Biological processes dominate the seasonal carbon budget (≈ 80%), while air–sea exchange of CO₂ (≈ 10%) and mixing (≈ 10%) have smaller effects. We found the seasonal amplitude of fCO₂ to be about half that of a study undertaken during 1991–1995 [Metzl, N., Tilbrook, B. and Poisson, A., 1999. The annual fCO₂ cycle and the air–sea CO₂ flux in the sub-Antarctic Ocean. Tellus Series B—Chemical and Physical Meteorology, 51(4): 849–861.] for the same region, indicating that SAZ may undergo significant inter-annual variations in surface fCO₂. The seasonal DIC depletion implies a minimum biological carbon export of 3400 mmol C/ m² from July to February. A comparison with nutrient changes indicates that organic carbon export occurs close to Redfield values (ΔP:ΔN:ΔC = 1:16:119). Extrapolating our estimates to the circumpolar sub-Antarctic Ocean implies a minimum organic carbon export of 0.65 GtC from the July to February period, about 5–7% of estimates of global export flux. Our estimate for biological carbon export is an order of magnitude greater than anthropogenic CO₂ uptake in the same region and suggests that changes in biological export in the region may have large implications for future CO₂ uptake by the ocean.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Formation of saddle dolomites in Upper Cambrian carbonates, western Tarim Basin (northwest China): Implications for fault-related fluid flow

The saddle dolomites occur more intensely in cores closely to fault than that in cores far away from the fault in Upper Cambrian carbonate of western Tarim basin, suggesting that formation of the saddle dolomites is likely related to fault-controlled fluid flow. They partially fill in fractures and vugs of replacement dolomite. The saddle dolomites exhibit complex internal textures, commonly consisting of core and cortex. In comparison with the matrix dolomites, the saddle dolomites show lower Sr-content and ⁸⁷Sr/⁸⁶Sr ratios, higher Fe- and Mn-content, and more negative δ¹⁸O values. Combined with high Th (100–130 °C) of primary fluid inclusions, it is suggested that the saddle dolomites precipitated from hydrothermal fluid derived from the deep evaporite-bearing Middle Cambrian strata, and the magnesium source may be due to dissolution of host dolomite during hydrothermal fluid migration. Fault activity resulted in petrographic and geochemical difference of the core and cortex of the saddle dolomites. The cores precipitated from the formation water mixed by deep brines at the early stage of fault activity, and the cortexes precipitated from the deep fluid with higher temperatures through the Middle Cambrian later. In summary, the formation of the saddle dolomites implies a hydrothermal fluid event related to fault activity, which also resulted in high porosity in Upper Cambrian carbonate in western Tarim Basin.     

Alkalinity changes in the Sargasso Sea: geochemical evidence of calcification?

Strong seasonal patterns in upper ocean total carbon dioxide (TCO₂), alkalinity (TA) and calculated pCO₂ were observed in a time series of water column measurements collected at the US Joint Global Ocean Flux Study (JGOFS) BATS site (31 °50′N, 64 °10′W) in the Sargasso Sea. TA distribution was a conservative function of salinity. However, in February 1992, a non-conservative decrease in TA was observed, with maximum depletion of 25–30 μmoles kg⁻¹ occuring in the surface layer and at the depth of the chlorophyll maximum (˜ 80–100 m). Mixed-layer TCO₂ also decreased, while surface pCO₂ increased by 25–30 μatm. We suggest these changes in carbon dioxide species resulted from open-ocean calcification by carbonate-secreting organisms rather than physical processes. Coccolithophore calcification is the most likely cause of this event although calcification by foraminifera or pteropods cannot be ruled out. Due to the transient increase in surface pCO₂, the net annual transfer of CO₂ into the ocean at BATS was reduced. These observations demonstrate the potential importance of open-ocean calcification and biological community structure in the biogeochemical cycling of carbon.     

Increase of anthropogenic CO2 in the Pacific Ocean over the last two decades

The multiple-parameter linear regression method (Monitoring global ocean carbon inventories. Ocean Observing System Development Panel, Texas A&M University, College Station, TX, 1995, 54pp; Global Biogeochem. Cycles 13 (1999) 179) is used to compare inorganic carbon data from the GEOSECS CO₂ survey in the Pacific Ocean in 1973 to the WOCE/JGOFS global CO₂ survey in the 1990s. A model of total dissolved inorganic carbon (DIC) as a function of five variables (AOU, θ, S, Si, and PO₄) has been developed from the recent CO₂ survey data (namely CGC91 and CGC96) in the Pacific Ocean. After correcting for a systematic DIC offset of −30.3±7 μmol kg⁻¹ from the GEOSECS data, the residual DIC based on this model as computed from GEOSECS data has been used to estimate the anthropogenic CO₂ penetration in the Pacific Ocean. In the Northeast Pacific, we obtained an increase of CO₂ of 21.3±7.9 mol m⁻² over the period from GEOSECS in 1973 to CGC91 in 1991. This gives a mean anthropogenic CO₂ uptake rate of 1.3±0.5 mol m⁻² yr⁻¹ over this 17 year time period. In the South Pacific, north of 50°S between 180° and 120°W region, the integrated anthropogenic CO₂ inventory is estimated to be 19.7±5.7 mol m⁻² over the period from GEOSECS in 1974 to CGC96 in 1996. The equivalent mean CO₂ uptake rate is estimated to be 0.9±0.3 mol m⁻² yr⁻¹ over the 22 years. These results are compared with the isopycnal method (Nature 396 (1998) 560) to estimate the anthropogenic CO₂ signal in the Northeast Pacific (30°N, 152°W) at the crossover region between CGC91 and GEOSECS. The results of the isopycnal method are consistent with those derived from the MLR method. Both methods show an increase in anthropogenic CO₂ inventory in the ocean over two decades that is consistent with the increase expected if the ocean uptake has kept pace with the atmospheric CO₂ increase.     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.     

The carbonic system distribution and fluxes in the NE Atlantic during Spring 1991

The potential of the North Atlantic as a sink for atmospheric CO₂ was investigated by studying the carbonic system using data obtained during the spring of 1991. The air-sea flux of CO₂ was related to chlorophyll and other environmental variables, and the regeneration of carbon in the mid-ocean studied by examining vertical sections representative of the study area.Poor correlations were found between pCO₂ and chlorophyll throughout much of the study area, although a good correlation was found along 16°W. The highest air-sea fluxes of CO₂ were calculated for areas where chlorophyll was highest (45°13′N, 16°04′W), and where the greatest wind speeds occurred (47°51′N, 28°18′W). The mean CO₂ flux from the atmosphere to the ocean during the study period (May) was calculated as 0.65mmol m⁻²d⁻¹, which compares well with other studies. Regression equations were developed to predict total inorganic carbon from nutrients; errors were typically less than 1 μmol kg⁻¹. Regeneration of carbon in the mid-ocean occurred in two principal stages: 0–1000m and>2300m. Regeneration in the upper zone was dominated by soft tissue carbon (86%), with skeletal carbon (calcite) contributing only 14%. The fraction of regenerated carbon of skeletal origin increased to 51% in the>2300m zone.     

Surface water carbon dioxide in the southwest Indian sector of the Southern Ocean: a highly variable CO2 source/sink region in summer

Measurements of partial pressure of carbon dioxide (pCO₂), total dissolved inorganic carbon (TCO₂), total alkalinity (TA) and chlorophyll a (Chl a) have been made in surface water in the southwestern Indian sector of the Southern Ocean (20–85°E) in the austral summer (INDIVAT V cruise, January-February 1987). Between Antarctica and Africa, pCO₂ distribution was linked to the oceanic frontal zones and Chi a variations. The pCO₂ spatial structure was very close to that explored in summer 1967 in the same region but the pCO₂ differences between the ocean and the atmosphere were smaller in 1987 than 20 years ago. At all latitudes we found strongly contrasting surface pCO₂ characteristics between eastern (around 80°E) and western (around 25°E) regions; C02 sources were mainly in the west and CO₂ sinks in the east. South of 60°S, the contrast could be due to biological activity. Between 60°S and the Antarctic Polar Front, intensification of upwelling might be responsible for the higher _pCO₂ values in the west.     

fCO2 variability at the CARIACO tropical coastal upwelling time series station

Monthly seawater pH and alkalinity measurements were collected between January 1996 and December 2000 at 10°30′N, 64°40′W as part of the CARIACO (CArbon Retention In A Colored Ocean) oceanographic time series. One key objective of CARIACO is to study temporal variability in Total CO₂ (TCO₂) concentrations and CO₂ fugacity (fCO₂) at this tropical coastal wind-driven upwelling site. Between 1996 and 2000, the difference between atmospheric and surface ocean CO₂ concentrations ranged from about − 64.3 to + 62.3 μatm. Physical and biochemical factors, specifically upwelling, temperature, primary production, and TCO₂ concentrations interacted to control temporal variations in fCO₂. Air–sea CO₂ fluxes were typically depressed (0 to + 10 mmol C m^{− 2} day^{− 1}) in the first few months of the year during upwelling. Fluxes were higher during June–November (+ 10 to 20 mmol C m^{− 2} day^{− 1}). Fluxes were generally independent of the slight changes in salinity normally seen at the station, but low positive flux values were seen in the second half of 1999 during a period of anomalously heavy rains and land-derived runoff. During the 5 years of monthly data examined, only two episodes of negative air–sea CO₂ flux were observed. These occurred during short but intense upwelling events in March 1997 (−10 mmol C m^{− 2} day^{− 1}) and March 1998 (− 50 mmol C m^{− 2} day^{− 1}). Therefore, the Cariaco Basin generally acted as a source of CO₂ to the atmosphere in spite of primary productivity in excess of between 300 and 600 g C m^{− 2} year^{− 1}.     

Seasonal and interannual variability of the air–sea CO2 flux in the Atlantic sector of the Barents Sea

The seasonal and interannual variability of the air–sea CO₂ flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO₂ (fCO₂^sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO₂^sw from phosphate (PO₄), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO₄ collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO₂^sw estimates were combined with data for the atmospheric mole fraction of CO₂, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO₂. The monthly mean uptake increases nearly monotonically from 0.101 mol C m^− 2 in midwinter to 0.656 mol C m^− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m^− 2 month^− 1. The variability is controlled mainly through combined variation of fCO₂^sw and wind speed. The annual mean uptake of atmospheric CO₂ in the region was estimated to 4.27 ± 0.68 mol C m^− 2.     

Effect of oil and dispersants on the growth of Mussels

Mussels (Mytilus edulis L.) were exposed to North Sea crude oil, microencapsulated oil and dispersants, singly and in combination, and growth rates measured at 24–48 h intervals.Exposure to microencapsulated pure oil (2·0–2·1 mg litre⁻¹) and to microencapsulated mixtures of oil (2·2−2·5 mg litre^-1+5 % of the different dispersants (FINASOL OSR 5, COREXIT 9527, DISPOLENE 36 S) gave approximately the same reduction in growth rate (80–90%) within 170h.Oil chemically dispersed with DISPOLENE 36 S and a pure oil mechanically dispersed in water were significantly less toxic. In high concentrations (2 mg litre⁻¹) all disperants are toxic, DISPOLENE 36 S ssignificantly more than the others.Mussels exposed for 170 h to microencapsulated oil and to microencapsulated oil dispersant mixtures recovered to control growth within 300 h in clean seawater, while in those given pure oil-in-water suspension, the recovery was slower.It is concluded that the toxicity of oil is mainly related to size and concentration of oil particles, while the effect of 5% dispersants added is negligible.     

The reliability of the thermodynamic constants for the dissociation of carbonic acid in seawater

Laboratory measurements of all four CO₂ parameters [f_CO2 ( = fugacity of CO₂), pH, TCO₂ ( = total dissolved inorganic carbon), and TA ( = total alkalinity)] were made on the same sample of Gulf Stream seawater (S = 35) as a function of temperature (5–35 °C) and the ratio of TA/TCO₂ (X) (1.0–1.2). Overall the measurements were consistent to ±8 μ atm in f_CO2, ± 0.004 in pH, ± 3 μ mol kg⁻¹ in TCO₂, and ± 3 μ mol kg⁻¹ in TA with the thermodynamic constants of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). Deviations between the measured pH, TCO₂, TA and those calculated from various input combinations increase with increasing X when the same constants are used. This trend in the deviations indicates that the uncertainties in pK₂ become important with increasing X (surface waters), but are negligible for samples with the lower X (deep waters). This trend is < 5 μ mol kg⁻¹ when the pK₂ values of Lee and Millero (1995) are used.The overall probable error of the calculated f_CO2 due to uncertainties in the accuracy of the parameters (pH, TCO₂, TA, pK₀, pk₁, and pK₂) is ± 1.2%, which is similar to the differences between the measured values and those calculated using the thermodynamic constants of Millero (1995).The calculated values of pK₁, (from f_CO2-TCO₂-TA) agree to within ± 0.004 compared to the results of Dickson and Millero (1987), Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995) over the same experimental conditions. The calculated values of pK₂ (from pH-TCO₂-TA) are in good agreement (± 0.004) with the results of Lee and Millero (1995) and also in reasonable agreement (± 0.008) with the results of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). The salinity dependence of our derived values of pK₁ and pK₂, (S = 35) can be estimated using the equations determined by Millero (1995).     

Seasonal evolution of hydrographic properties in the Antarctic circumpolar current at 170°W during 1997–1998

This paper discusses the seasonal evolution of the hydrographic and biogeochemical properties in the Antarctic Circumpolar Current (ACC) during the US Joint Global Ocean Flux (JGOFS) Antarctic Environment and Southern Ocean Process Study (AESOPS) in 1997–1998. The location of the study region south of New Zealand along 170°W was selected based on the zonal orientation and meridional separation of the physical and chemical fronts found in that region. Here we endeavor to describe the seasonal changes of the macronutrients, fluorescence chlorophyll_, particulate organic carbon (POC), and carbon dioxide (CO₂) in the upper 400 m of the ACC during the evolution of the seasonal phytoplankton bloom found in this area. While the ACC has extreme variability in the meridional sense (due to fronts, etc.), it appears to be actually quite uniform in the zonal sense. This is reflected by the fact that a good deal of the seasonal zonal changes in nutrients distributions at 170°W follow a pattern that reflects what would be expected if the changes are associated with seasonal biological productivity. Also at 170°W, the productivity of the upper waters does not appear to be limited by availability of phosphate or nitrate. While there is a significant decrease (or uptake) of inorganic nitrogen, phosphate and silicate associated with the seasonal phytoplankton bloom, none of the nutrients, except perhaps silicate (north of the silicate front) are actually depleted within the euphotic zone. At the end of the growing season, nutrient concentrations rapidly approached their pre-bloom levels. Inspection of the ratios of apparent nutrient drawdown near 64°S suggests N/P apparent drawdowns to have a ratio of 10 and N/Si apparent drawdowns to have a ratio of >4. These ratios suggest a bloom that was dominated by Fe limited diatoms. In addition, the surface water in the Polar Front (PF) and the Antarctic Zone (AZ) just to the south of the PF take up atmospheric CO₂ at a rate 2–3 times as fast as the mean global ocean rate during the summer season but nearly zero during the rest of year. This represents an important process for the transport of atmospheric CO₂ into the deep ocean interior. Finally, the net CO₂ utilization or the net community production during the 2.5 growing months between the initiation of phytoplankton blooms and mid-January increase southward from 1.5 mol C m⁻² at 55°S to 2.2 mol C m⁻² to 65°S across the Polar Frontal Zone (PFZ) into the AZ.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

The contribution of atmospheric acid deposition to ocean acidification in the subtropical North Atlantic Ocean

The absorption of anthropogenic CO₂ and atmospheric deposition of acidity can both contribute to the acidification of the global ocean. Rainfall pH measurements and chemical compositions monitored on the island of Bermuda since 1980, and a long-term seawater CO₂ time-series (1983–2005) in the subtropical North Atlantic Ocean near Bermuda were used to evaluate the influence of acidic deposition on the acidification of oligotrophic waters of the North Atlantic Ocean and coastal waters of the coral reef ecosystem of Bermuda. Since the early 1980's, the average annual wet deposition of acidity at Bermuda was 15 ± 14 mmol m^− 2 year^− 1, while surface seawater pH decreased by 0.0017 ± 0.0001 pH units each year. The gradual acidification of subtropical gyre waters was primarily due to uptake of anthropogenic CO₂. We estimate that direct atmospheric acid deposition contributed 2% to the acidification of surface waters in the subtropical North Atlantic Ocean, although this value likely represents an upper limit. Acidifying deposition had negligible influence on seawater CO₂ chemistry of the Bermuda coral reef, with no evident impact on hard coral calcification.     

An improved model for the calculation of CO2 solubility in aqueous solutions containing Na, K, Ca, Mg, Cl, and SO4

An improved model is presented for the calculation of the solubility of carbon dioxide in aqueous solutions containing Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻ in a wide temperature–pressure–ionic strength range (from 273 to 533 K, from 0 to 2000 bar, and from 0 to 4.5 molality of salts) with experimental accuracy. The improvements over the previous model [Duan, Z. and Sun, R., 2003. An improved model calculating CO₂ solubility in pure water and aqueous NaCl solutions from 273 to 533K and from 0 to 2000 bar. Chemical Geology, 193: 257–271] include: (1) By developing a non-iterative equation to replace the original equation of state in the calculation of CO₂ fugacity coefficients, the new model is at least twenty times computationally faster and can be easily adapted to numerical reaction-flow simulator for such applications as CO₂ sequestration and (2) By fitting to the new solubility data, the new model improved the accuracy below 288 K from 6% to about 3% of uncertainty but still retains the high accuracy of the original model above 288 K. We comprehensively evaluate all experimental CO₂ solubility data. Compared with these data, this model not only reproduces all the reliable data used for the parameterization but also predicts the data that were not used in the parameterization. In order to facilitate the application to CO₂ sequestration, we also predicted CO₂ solubility in seawater at two-phase coexistence (vapor–liquid or liquid–liquid) and at three-phase coexistence (CO₂ hydrate–liquid water–vapor CO₂ [or liquid CO₂]). The improved model is programmed and can be downloaded from the website http://www.geochem-model.org/programs.htm.     

Carbon disulfide in the estuarine, coastal, and oceanic environments

The concentration of carbon disulfide (CS₂) in surface water and relevant hydrographic parameters were determined in coastal waters of the eastern USA (Delaware Bay and Chesapeake Bay, including the Potomac River; 7–11 September 1986). The CS₂ concentration varied extensively along the cruise track, from 4 to 510 pmol S(CS₂) l⁻¹ (n = 103). The average values in estuarine, shelf, and oceanic waters were found to be 118 ± 100 pmol S(CS₂) l⁻¹ (n = 54), 51 ± 34 pmol S(CS₂) l⁻¹ (n = 14), and 28 ± 12 pmol S(CS₂) l⁻¹ (n = 35), respectively. To help interpret the geochemical behavior of CS₂, we analyzed the depth distribution of CS₂ in the North Atlantic Ocean during an earlier cruise (23 April–2 May 1986). In most cases, these depth profiles show a near-surface maximum at about 10–20 m depth and a relatively steep gradient below this maximum. Based on the distribution pattern in the water column and evidence provided by earlier workers, we propose that diffusion of CS₂ from bottom sediments may contribute to CS₂ levels in surface seawater. The atmospheric concentration of CS₂ was also investigated at some locations during the September cruise. Except during periods when there was a significant anthropogenic input, the concentration of CS₂ in air was generally in the range of 4–15 pptv (parts per trillion by volume) with a mean of 10.4 ± 4.0 pptv (n = 10). The calculated sea-to-air emission rates of CS₂ at each of our sampling stations show a decreasing trend across estuarine, shelf, and oceanic areas, in agreement with the trend in surface water concentrations.