Cycling of dissolved and particulate nitrogen and carbon in the Framvaren Fjord, Norway: stable isotopic variations

The reaction pathways of nitrogen and carbon in the Framvaren Fjord (Norway) were studied through stable isotope analysis (δ¹⁵N and δ¹³C) of dissolved inorganic and particulate organic matter (POM). The variations in the isotopic compositions of the various C and N pools within the water column were use to evaluate the historical deposition of material to the sediments. The high δ¹⁵N-NH₄⁺ at the O₂/H₂S interface, as a consequence of microbial uptake between 19 and 25 m, results in extremely depleted δ¹⁵N-particulate nitrogen (PN) of approximately 1‰ within the particulate maximum at approximately 19 m. The carbon isotopic distribution of dissolved inorganic carbon (DIC) and particulate organic carbon (POC) within the interface suggests that the distinct microbial flora (Chromatium sp. and Chlorobium sp.) fractionate inorganic carbon to different degrees. The extremely light δ¹³C-POC within the interface (−31‰) appears to be a result of carbon uptake by Chromatium sp. while δ¹³C-POC of −12‰ is more indicative of Chlorobium sp. Nitrogen isotopic mass balance calculations suggested that approximately 75% of the material sinking to the sediments was derived from the dense particulate maximum between 19 and 25 m. The sediment distribution of nitrogen isotopes varied from 2‰ at the surface to approximately 6‰ at 30 cm. The nitrogen isotopic variations with depth may be an indicator of the depth or position of the O₂/H₂S interface in the fjord. Low sediment δ¹⁵N indicated that the interface was within the photic zone of the water column, while more enriched values suggested that the interface was lower in the water column potentially allowing for less fractionation during biological incorporation of dissolved inorganic nitrogen. Results indicate that the dense layers of photo-autotrophic bacteria in the upper water column impart unique carbon and nitrogen isotopic signals that help follow processes within the water column and deposition to the sediments.     

Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin, China: towards prediction of fatal H2S concentrations

New sour pools have recently found in the Lower Triassic Feixianguan Fm carbonate reservoirs in the East Sichuan Basin in China with H₂S up to 17.4% by volume. A recent blowout from a well drilled into this formation killed hundreds of people as a result of the percentage concentrations of H₂S. In order to assess the origin of fatal H₂S as well as the cause of petroleum alteration, H₂S concentrations and the isotopes, δ³⁴S and δ¹³C have been collected and measured in gas samples from reservoirs. Anhydrite, pyrite and elemental sulphur δ³⁴S values have been measured for comparison. The high concentrations of H₂S gas are found to occur at depths >3000 m (temperature now at 100 °C) in evaporated platform facies oolitic dolomite or limestone that contains anhydrite nodule occurrence within the reservoirs. Where H₂S concentrations are greater than 10% its δ³⁴S values lie between +12.0 and +13.2‰ CDT. This is within the range of anhydrite δ³⁴S values found within the Feixianguan Fm (+11.0 to +21.7‰; average 15.5±3.5‰ CDT). Thus H₂S must have been generated by thermochemical sulphate reduction (TSR) locally within the reservoirs. Burial history analysis and fluid inclusion data reveal that the temperature at which TSR occurred was greater than about 130–140 °C, suggesting that the present depth-temperature minimum is an artifact of post-TSR uplift. Both methane and ethane were actively involved in TSR since the petroleum became almost totally dry (no alkanes except methane) and methane δ¹³C values become significantly heavier as TSR proceeded. Methane δ¹³C difference thus reflects the extent of TSR. While it is tempting to use a present-day depth control (>3000 m) to predict the distribution of H₂S in the Feixianguan Fm, this is an invalid approach since TSR occurred when the formation was buried some 1000–2000 m deeper than it is at present. The likelihood of differential uplift across the basin means that it is important to develop a basinal understanding of the thermal history of the Feixianguan Fm so that it is possible to determine which parts of the basin have been hotter than 130–140 °C.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Formation of chemogenic calcite in super-anoxic seawater — Framvaren, southern Norway

Framvaren, a super-anoxic fjord in southern Norway, contains 7–8 mmoll⁻¹ of sulphide and a total carbonate concentration of 18.5 mmol kg⁻¹ in the bottom water. The chemistry of calcium has been studied, considering sources, biogenic and chemical processes and sedimentary sinks. Calcium associated with the bacteria biomass at the redox interface (18m depth) appears to be the primary source of dissolved calcium in the deep, anoxic water. Excess calcium and high total carbonate cause supersaturation of calcite, which is precipitated chemogenically. Calcite (and presumably some aragonite) is identified both in sediment trap material and the bottom sediments below the depth of supersaturation.     

Removal and bioaccumulation of anthropogenic, halogenated transient tracers in an anoxic fjord

The persistence of the anthropogenic halogenated tracers, CFC-11 (CCl₃F), CFC-12 (CCl₂F₂), CFC-113 (CCl₂FCClF₂), carbon tetrachloride (CCl₄) and methyl chloroform (CH₃CCl₃) in oxygen-depleted waters was investigated in the anoxic fjord Framvaren in southern Norway. A model for the ventilation of the water in the fjord was created based on tritium and CFC-12 profiles. The results suggest that CFC-12 is stable in this environment, although still affected by particulate scavenging, while the other four halocarbon species shows signs of significant removal in the oxic/anoxic interface. The first-order removal coefficients were calculated to be 0.35, 0.19, 1.23 and 0.31 year⁻¹ for CFC-11, CFC-113, CCl₄ and CH₃CCl₃, respectively. Significant downward flux of halogenated tracers by sinking organic matter is suggested by the model; the tracers are subsequently released to the water column by the remineralisation of the particles. This process acts as a sink of halogenated tracers in the surface waters, whereas it is a source for the deep waters. Our results points to bioaccumulation factors (BF) for the CFC tracers in the order of 4.4–5.4 (log BF), which is 100–600 times those previously reported. This might be of significance to near-shore, semi-enclosed, basins with a high flux of organic matter, but would still have little importance in open ocean basins.     

Metal complex formation in sulphidic seawater

It is shown that the data of Kremling (1983) for iron concentrations in sulphidic basin water fit to a solubility curve assuming reasonable constants for FeS in equilibrium with Fe²⁺, Fe(HS)₂ and FeHS₂⁻. Explanations are offered for the fact that the iron and manganese concentrations are considerably lower in the Framvaren bottom water with high sulphide concentrations (6–8 mM) than in the Gotland Deep with lower sulphide concentrations (0.001–0.052 mM). For other trace metals (Co, Ni, Cu, Zn, Cd, Hg and Pb) equilibrium conditions do not seem to exist.     

Some chemical characteristics of the brines in Bannock and Tyro Basins: salinity, sulphur compounds, Ca, F, pH, At, PO4, SiO2, NH3

Results of the chemical investigation on the Bannock and Tyro Basins are reported.Both basins were found to be hypersaline ( 10 times higher than salinity of normal seawater) and anoxic. In all investigated basins a region of transition, a few meters thick, was identified at depths > 3327 dbar. It is characterized by a sharp gradient of salinity, and all concentrations of analysed species increase strongly except for dissolved oxygen and nitrate, which immediately drop to zero. This region appears as a sharp boundary that prevents mixing. As a result, in the presence of organic matter, an anoxic condition developed with the complete depletion of dissolved oxygen. At the same time, hydrogen sulphide and ammonium accumulated within the brine. Between the Bannock and the Tyro brines differences occur in the measured concentrations of H₂S, SO²⁻₄, Ca²⁺ and NH₃. There are some differences also within the Bannock area sub-basins.The Libeccio sub-basin, in the Bannock area, contains a double-layered brine: the upper layer is 140 dbar thick and the lower layer is 300 dbar thick. A second interface between upper and lower brines develops at a depth of 3500 dbar. Nearly all of the measured concentrations vs. depth show the double layer, with the exception of ammonium, the concentration of which remains nearly constant throughout the anoxic column. Profiles of the other species analyzed show remarkable differences on passing from the upper to the lower brine. Hydrogen sulphide, sulphate and fluoride concentrations appear constant and then increase at the second interface. The calcium concentration is also constant in the upper brine, but decreases at the second interface. Total alkalinity and phosphate concentrations show a maximum peak just below the first interface. However, after passing through the second interface all the chemical parameters exhibit an almost constant behaviour down to the bottom.Hypersaline conditions are attributed to the dissolution of Messinian evaporite, and anoxia is suggested to originate from the oxidation of organic matter present in sediments and from the absence of bottom water circulation in such a deep and enclosed environment.The chemical conditions can be summarized as follows: in the Libeccio Basin the values for the species analysed have the ranges: 39–321 psu for ‘salinity’, 8.2−6.5 for pH, 2.7–4.0 mM for total alkalinity, 0.2-0 mM for dissolved oxygen, 0–1669 μM for hydrogen sulphide, 0–198 μM for thiol, 31–99 mM for sulphate, 11–21 mM for calcium, 7–100 μM for fluoride, 0.2–3080 μM for ammonium, 5.8-0 μM for nitrite, 0.2–12 μM for phosphate and 8–130 μM for silicate.     

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high SO²⁻₄ reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. δ³⁴S values of pyrite are −33‰ to −50‰. Below the sapropels δ³⁴S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.     

Oceanographic controls on the carbon isotopic compositions of sinking particles from the Cariaco Basin

This study examined the relationship between carbon isotopic composition of sinking organic matter (OM) and the biological, physical and chemical properties of the surface ocean in the Cariaco Basin. The ¹³C/¹²C ratio of OM (δ¹³C_org) in sinking particles was determined on sediment trap samples from four depths collected from 1996 to 1999 as part of the CArbon Retention In A Colored Ocean time series. Water column properties, including temperature, productivity, chlorophyll and concentration of dissolved CO₂, were concurrently measured on monthly cruises. The δ¹³C_org varied from a high of –17.7‰ to a low of –22.6‰ during the study period. The variation of the δ¹³C_org throughout seasonal cycles was directly proportional to the strength of upwelling and was negatively correlated with temperature (r²=0.64). During the 1996–1997 upwelling event, the strongest during the study period, the δ¹³C_org increased by 4.4‰ whereas during the 1998–1999 upwelling event, the weakest during the study period, the δ¹³C_org only increased by 3.3‰. Contrary to most previous studies, we observed a negative relationship (r²=0.53) between [CO_2 aq] and the estimated isotopic fractionation factor (ε_p). However, there was no correlation between ε_p and the calculated growth rates indicating that there was non-diffusive uptake of carbon into phytoplankton cells. It thus appears that [CO_2 aq] does not control the δ¹³C_org in the water column of the study site. The best explanation for the isotopic enrichment observed is a carbon concentrating mechanism (CCM) in phytoplankton. The existence of a CCM in phytoplankton has major implications for the interpretation of the δ¹³C_org in the Cariaco Basin.     

Indication of thiols in black sea deep water

Potentiometric titrations of deep Black Sea water give reasonably precise values of sulphide in the concentration range 30–300 μmol l⁻¹ and a strong indication of thiols in the concentration range 10–30 μmol l⁻¹. Organic analysis of Black Sea water should therefore include the search for compounds containing SH groups. A simple stoichiometric model indicates that sulphur-containing proteins might be the main source of thiols after hydrolysis and deamination. The alkalinity and total sulphide are simply related by A_t = 3287 ± 30 + (3.84 ± 0.10) [H₂ S]_t μmol kg⁻¹. The slope of 3.84 instead of the stoichiometric slope of 2.31 indicates a lack of reduced sulphate in the form of hydrogen sulphide.     

Changes in sediment processes across the western Irish Sea front

Sediment characteristics, sediment respiration (oxygen uptake and sulphate reduction) and sediment–water nutrient exchange, in conjunction with water column structure and phytoplankton biomass were measured at five stations across the western Irish Sea front in August 2000. The transition from thermally stratified (surface to bottom temperature difference of 2.3 °C) to isothermal water (14.3 °C) occurred over a distance of 13 km. The influence of the front on phytoplankton biomass was limited to a small region of elevated near surface chlorophyll (2.23 mg m⁻³; 50% > biomass in mixed waters). The front clearly marked the boundary between depositional sediments (silt/clays) with elevated sediment pigment levels (≈60 mg m⁻²) on the western side, to pigment impoverished (<5 mg m⁻²) sand, through to coarse sand and shell fragments on the eastern side. Maximal rates of sedimentary respiration on the western stratified side of the front e.g. oxygen uptake S2 (852 μmol O₂ m⁻² h⁻¹) and sulphate reduction at S1 (149 μmol SO₄²⁻ m⁻² h⁻¹), coupled to significant efflux of nitrate and silicate at the western stations indicate closer benthic–pelagic coupling in the western Irish Sea. Whether this simply reflects the input of phytodetritus from the overlying water column or entrapment and settlement of pelagic production from other regions of the Irish Sea cannot yet be resolved.     

Interactions between sediment chemistry and frenulate pogonophores (Annelida) in the north-east Atlantic

The small frenulate pogonophores (Annelida: Pogonophora a.k.a. Siboglinidae) typically inhabit muddy sediments on the continental slope, although a few species occur near hydrothermal vents and cold seeps. We present data on the distribution and habitat characteristics of several species on the European continental shelf and slope from 48°N to 75°N and show how the animals interact with the chemistry of the sediments. The environments inhabited include: shallow (30 m), organic-rich, fjord sediments; slope sediments (1000–2200 m) and methane seeps at 330 m depth. All the species studied obtain nutrition from endosymbiotic bacteria. They take up reduced sulphur species, or in one case, methane, through the posterior parts of their tubes buried in the anoxic sediment. We conclude that most species undertake sulphide ‘mining’, a mechanism previously demonstrated in the bivalves Lucinoma borealis and Thyasira sarsi. These pogonophores participate in the sulphur cycle and effectively lower the sulphide content of the sediments. Our results show that the abundance of frenulate pogonophores increases with increasing sedimentation and with decreasing abundance of other benthos, particularly bioturbating organisms. The maximum sustainable carrying capacity of non-seep sediments for frenulate pogonophores is limited by the rate of sulphate reduction.     

Radiocarbon-derived sedimentation rates in the Gulf of Mexico

Sedimentation rates were determined for the northern Gulf of Mexico margin sediments at water depths ranging from 770 to 3560 m, using radiocarbon determinations of organic matter. Resulting sedimentation rates ranged from 3 to 15 cm/kyr, decreasing with increasing water depth. These rates agree with long-term sedimentation rates estimated previously using stratigraphic methods, and with estimates of sediment delivery rates by the Mississippi River to the northern Gulf of Mexico, but are generally higher by 1–2 orders of magnitude than those estimated by ²¹⁰Pb_xs methods. Near-surface slope sediments from 2737 m water depth in the Mississippi River fan were much older than the rest. They had minimum ¹⁴C ages of 16–27 kyr and δ¹³C values ranging from −24‰ to −26.5‰, indicating a terrestrial origin of organic matter. The sediments from this site were thus likely deposited by episodic mass wasting of slope sediment through the canyon, delineating the previously suggested main pathway of sediment and clay movement to abyssal Gulf sediments.     

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.     

Copper in the resurrection fjord, Alaska

Copper concentrations have been measured in more than 200 samples collected from an Alaskan fjord and continental shelf and slope regions in the northwestern Gulf of Alaska. Concentrations were lowest (2·1 nmol kg⁻¹) at depths of 400–1000 m in the continental slope waters of the Gulf of Alaska. Copper increased systematically with decreasing salinities shoreward to concentrations >30 nmol kg⁻¹ in fjord surface waters during summer months of high freshwater runoff. Copper concentrations increased with depth at an inner fjord station where deep basin waters have restricted circulation, and these data together with surface (<5 cm) pore water copper concentrations (mean=122 nmol kg⁻¹) about an order of magnitude higher than bottom water copper concentrations are indicative of a flux of copper across the sediment-seawater interface. This latter was estimated at 32±12 nmol cm⁻² annually, and represented less than 20% of the annual input to fjord surface water (228–411 nmol cm⁻²) added during summer months. Mass balances in bottom waters indicate a vigorous recycling of copper with a residence time estimated at 21±11 days. Most copper that is remobilized in surface sediments is returned to bottom waters and little (3%) is removed by subsequent diagenetic reaction in the buried sediments. However, an estimate of copper accumulating in anoxic fjord sediments was comparable with copper added to fjord surface waters suggesting that input-removal reactions rather than internal cycling controls copper geochemistry in this estuary.     

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (δ¹³C) compositions and n-alkane (nC_16–38) concentrations were measured for Spartina alterniflora, a C₄ marsh grass, Typha latifolia, a C₃ marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. δ¹³C values of organic matter preserved in the upper fresh water site sediment were more negative (−23.0±0.3‰) as affected by the C₃ plants than the values of organic matter preserved in the sediments of middle (−18.9±0.8‰) and mud flat sites (−19.4±0.1‰) as influenced mainly by the C₄ marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC₂₁ to nC₃₃ long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC₂₉ was the most abundant homologue in all samples measured. Both δ¹³C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters.     

Impact of macroalgal dredging on dystrophic crises and phototrophic bacterial blooms (red waters) in a brackish coastal lagoon

The Prévost lagoon (Mediterranean coast, France), was subject to annual dystrophic crises caused by the biodegradation of opportunistic macroalgae (Ulva lactuca) in the past. These crises result in anoxic waters with subsequent blooms of Purple Sulphur Bacteria (red waters) which, by oxidizing sulphide, contribute to the reestablishment of oxic conditions in the water column. Mechanical dredging of the macroalgal biomass has been carried out in the lagoon since 1991 with the aim of preventing the ecological and economic disturbances caused by such crises. Dredging began just before the phototrophic bloom when the water was already hypoxic (O₂ = 0.7 mg·L⁻¹) and contained sulphilde (H₂S = 7.3 mg·L⁻¹) and purple patches of phototrophic bacteria (Thiocapsa sp.) that were beginning to develop on decaying macroalgae at the sediment surface. The dredging prevented red water formation and drastically modified both phototrophic community structure and activity and biogeochemical sulphur cycling. The dredging permitted the reestablishment of oxic conditions for a short period only (1–13 August). Resuspension of the superficial sediment layers disturbed the phototrophic bacterial community, whose numbers decreased by one order of magnitude (from 2 × 10⁶ to 3.9 × 10⁵ CFU.mL⁻¹). The phototrophic community was no longer effective in reoxidizing the reduced sulphur compounds remaining in the sediments, as shown by a drastic sulphate depletion in the superficial sediment layers. Moreover, the increase in the specific bacteriochlorophyll a concentration of the phototrophic purple bacteria and the rapid development of Green Sulphur Bacteria (Prosthecochloris-like microorganisms) indicated that the phototrophic community was growing under severe light-limiting conditions due to the resuspension of sediment particles in the water. These conditions did not allow the phototrophic bacterial community to efficiently reoxidize the reduced sulphur compounds originating from the sediments. In consequence, hypoxic conditions (O₂ = 4.7 to 4.8 mg·L⁻¹) and low sulphide concentrations (H₂S = 0.4 to 0.7 mg·L⁻¹) were detected in the water column until September. The ecological balance in the lagoon was reestablished only in October, whereas, in previous years it had been restored in August.     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

Total particulate and organic fluxes in anoxic Framvaren waters

Cylindrical sediment traps were deployed at various depths in the anoxic water of Framvaren for two periods of one year (1981–1982 and 1983–1984). The traps were emptied three times during 1981–1982 and five times during 1983–1984. The vertical fluxes of total suspended material, organic carbon and nitrogen were calculated on a daily and annual basis. The average annual sediment flux 20 m above the bottom was approximately 60 g m⁻² y⁻¹ and the flux of organic carbon was 20 g m⁻² y⁻¹. On the basis of an average C/N ratio of 8 and a constant carbon flux below a depth of 20 m, it is concluded that little mineralization of the organic matter takes place in the anoxic water column. Assuming a primary production of the order to 50–100 g m⁻² y⁻¹, 22–24% of that reaches the anoxic water masses. Further breakdown of organic matter takes place in the surface sediments.