Eddy Diffusion Coefficients of Suspended Particulate Matter: Effects of Wind Energy Transfer and Stratification

Gross sedimentation rates (GSR) have been measured using sediment traps placed at nine different levels above the bed (0·3, 0·5, 0·8, 1·0, 2·0, 4·0, 6·0, 8·0 and 10·0 m). The sediment traps were deployed for 1·25 years and recovered 28 times during the study period. Low average GSR values of 5·5 g m^-2 day^-1 were obtained at 10·0 m, and high average GSR values of 114·8 g m^-2 day^-1 were obtained at 0·3 m. An expression for the eddy diffusion coefficient of suspended particulate matter (K_s), based on the measured GSR is given. The expression has been used for modelling of K_s at the different trap levels above the bed. High values (≈42 cm² s^-1) of K_s were obtained at the upper traps, whereas low values (≈2 cm² s^-1) were obtained near the bed. Comparison between level of turbulent energy in terms of shear stress at the boundaries of the water column, i.e. from the wind and the bed flow, showed that wind energy exceeded that of the bed flow by a factor 16. At 5·0 m K_s was positively correlated (r=0·66) to the eddy diffusion coefficient of momentum (K_m) derived from the wind energy transfer to the water, giving an average β of 0·5 for K_s =βK_m. The density difference between surface and bottom waters has been designated a parameter of stratification, and is discussed in relation to variations of K_s and K_m .     

Settleable and Non-Settleable Suspended Sediments in the Ogeechee River Estuary, Georgia, U.S.A.

Suspended particle dynamics were investigated in the Ogeechee River Estuary during neap tide in July 1996. Samples were operationally separated into ‘ truly suspended ’ (settling velocity <0·006 cm s⁻¹) and ‘ settleable ’ (settling velocity >0·006 cm s⁻¹) fractions over the course of a tidal cycle to determine whether these two fractions were comprised of particles with differing biological and chemical characteristics. Total suspended sediment, organic carbon and nitrogen, chlorophyll a and phaeopigment concentrations were measured in each fraction, as well as rates of bacterial hydrolytic enzyme activity [β-1,4-glucosidase (βGase) and β-xylosidase (βXase)]. The majority of the suspended sediment (by weight) was in the truly suspended fraction; all measured parameters were largely associated with this fraction as well. When compared to the settleable material, the truly suspended material was significantly higher in % POC (5·7±0·6 vs. 3·9±1·8), % chlorophyll (0·07±0·02 vs. 0·03±0·01), % phaeopigment (0·030±0·006 vs. 0·018±0·012), and weight-specific maximal uptake rates (V_maxper mg suspended sediment) of both enzymes (1·8±0·4 vs. 0·7± 0·2 nmol mg⁻¹ h⁻¹βGase and 1·1±0·3vs . 0·3±0·2 nmol mg⁻¹ h⁻¹βXase), providing clear evidence for a qualitative distinction between the two fractions. These results are interpreted to mean that the more organic-rich, biologically active material associated with the suspended fraction is likely to have a different fate in this Estuary, as ‘ truly suspended ’ sediments will be readily transported whereas ‘ settleable ’ sediments will settle and be resuspended with each tide. These types of qualitative differences should be incorporated into models of particle dynamics in estuaries.     

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.     

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.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

Sediment–water interactions of natural oestrogens under estuarine conditions

The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol⁻¹ was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (K_p^true) and colloidal particles (K_c^true) have been calculated, and a K_p^true value of 141 and 102 ml g⁻¹ was obtained for oestrone and 17β-oestradiol, respectively. In addition, K_c^true values for oestrone (222×10² ml g⁻¹) and 17β-oestradiol (135×10² ml g⁻¹) were two orders of magnitude higher than their respective K_p^true values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.     

Radium isotopes in coastal and open ocean surface waters of the Western North Pacific

Using manganese-impregnated fiber extraction and high-efficiency gamma counting techniques, we measured the distribution of ²²⁸Ra and ²²⁶Ra in surface waters near the coast of Japan and in the western North Pacific. There is no evidence in our data that any significant amount of ²²⁸Ra is added to open ocean surface waters from the coastal waters around Tokyo Bay. High ²²⁸Ra concentrations (> 10 dpm/10³ kg), were observed along the Kuroshio Current as compared to < 2.5 dpm/10³ kg between 10° and 30°N of the central gyre, and hence the major source of ²²⁸Ra in the surface water is likely to be the East Asian continental shelf zones. A simple one-dimensional eddy diffusion and advection model is used to explain the observed decrease of ²²⁸Ra from coast to the open ocean. The model results indicate two mixing regimes across the Kuroshio Current System with apparent eddy diffusion coefficients of K_y = 4 × 10⁵ cm² s⁻¹ at distance y < 200 km from the coast, and K_y = 4 × 10⁷ cm² s⁻¹ at y > 200 km. Along 40°N where an eastward flow of the ‘Kuroshio Extension’ prevails, an advective flow of > 0.1 knot is consistent with the observation of nearly constant ²²⁸Ra along the track.The geographical distribution pattern of ²²⁸Ra is clearly different from that of atmospherically derived ²¹⁰Pb. Thus the ²²⁸Ra in surface water serves as a useful tracer that accompanies fluvially and coastally derived elements during their subsequent lateral transport toward the central gyre.     

The Significance of Diagenesis versus Riverine Input in Contributing to the Sediment Geochemical Matrix of Iron and Manganese in an Intertidal Region

Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (r_s), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (r_s=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (r_s=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.     

Sublethal effects of hydrogen sulfide in sediments on the Urchin Lytechinus pictus

Laboratory exposures of the urchin Lytechinus pictus to sediment dosed with varying concentrations of hydrogen sulfide (H₂S), but without elevated organic material, were conducted. Changes in mortality, behavior, growth and gonad production were measured during 49 days' flow through exposures. Hydrogen sulfide concentrations of 165·8 μ liter⁻¹ in pore water caused significant changes in all parameters measured. Concentrations as low as 32·9 μ liter⁻¹ caused significant decreases in wet weight and male gonad production. A concentration of 91·8 μ liter⁻¹ caused the mortality rate to increase 100-fold over control exposures (0·63 μ liter⁻¹). Sublethal effects on growth and gonad production could have been caused by either direct biochemical inhibition by H₂S or secondarily through behavioral modifications. Hydrogen sulfide concentrations above 165·8 μ liter⁻¹ are common near sewage outfalls and could contribute to changes in species composition and sediment toxicity that occur there.     

Submarine hydrothermal brine seeps off Milos, Greece. Observations and geochemistry

A shallow hydrothermal brine seep located off the Greek island of Milos in the Aegean Sea was studied. The brine fluid outcropped as a pool of water in a seabed depression and was detected in the surrounding pore-waters of sediments colonised by the sulphur bacterium Achromatium volutans. The seep fluid was highly saline and sulphidic, depleted in Mg²⁺ and SO₄²⁻, but enriched over seawater in Na⁺, Ca²⁺, K⁺, Cl⁻, SiO₂, reduced species and dissolved gases. The high concentrations of Na⁺, Ca²⁺ and K⁺ were consistent with the Milos tectonic setting. Na-K and Na-K-Ca geothermometers predicted a reservoir temperature of 300–325 °C for the most concentrated seep samples. The deep geothermal reservoir within the metamorphic basement of Milos island has already been located and studied and may represent the source of the seep fluid. Faunal diversity was lowest in seep-influenced sediments, but a sulphide-intolerant species was found in areas of the bacterial mat where salinity and temperature were much lower. Pressure-induced variations in the vertical depth of the brine interface may be occurring in the sediment.     

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.     

Benthic microalgal biomass in sediments of Onslow Bay, North Carolina

Sediment samples were collected at stations along cross-shelf transects in Onslow Bay, North Carolina, during two cruises in 1984 and 1985. Station depths ranged from 11 to 285 m. Sediment chlorophyll a concentrations ranged from 0·06 to 1·87 μg g⁻¹ sediment (mean, 0·55), or 2·6–62·0 mg m². Areal sediment chlorophyll a exceeded water column chlorophyll a a at 16 of 17 stations, especially at inshore and mid-shelf stations. Sediment ATP concentrations ranged from 0 to 0·67 μg g⁻¹ sediment (mean, 0·28). Values for both biomass indicators were lowest in the depth range including the shelf break (50–99 m). Organic carbon contents of the sediments were uniformly low across the shelf, averaging 0·159% by weight. Photography of the sediments revealed extensive patches of microalgae on the sediment surface.Our data suggest that viable benthic microalgae occur across the North Carolina continental shelf. The distribution of benthic macroflora on the North Carolina shelf indicates that sufficient light and nutrients are available to support primary production out to the shelf break. Frequent storm-induced perturbations do not favour settling of phytoplankton, an alternative explanation for the presence of microalgal pigments in the sediments. Therefore, we propose that a distinct, productive benthic microflora exists across the North Carolina continental shelf.     

Carbon and nitrogen primary productivity in three North Carolina estuaries

Uptake of inorganic carbon and ammonium by the plankton community of three North Carolina estuaries was measured using ¹⁴C and ¹⁵N isotope methods. At 0% light, C appeared to be lost via respiration, and at increasing light levels uptake of inorganic carbon increased linearly, saturated (mean I_k = 358±30 μEin m⁻² s⁻¹), and frequently showed inhibition at the highest light intensities. At 0% light NH₄⁺ uptake was significantly greater than zero and was frequently equivalent to uptake in the light (light independent); at increasing light levels NH₄⁺ uptake saturated (mean I_k = 172±44 μEin m⁻² s⁻¹) and frequently indicated strong inhibition. Light-saturated uptake rates of inorganic carbon and NH₄⁺ were a function of chlorophyll a (r² = 0·7−0·9); average assimilation numbers were 625 nmol CO₂ (μg chl. a)⁻¹ h⁻¹ and 12·9 nmol NH₄⁺ (μg chl. a)⁻¹ h⁻¹ and were positively correlated with temperature (r² = 0·3−0·7). The ratio of dark to light-saturated NH₄⁺ uptake tended to be near 1·0 for large algal populations at low NH₄⁺ concentrations, indicating near light independence of uptake; whereas the ratio was lower for the opposite conditions. These data are interpreted as indicative of nitrogen stress, and it is suggested that uptake of NH₄⁺ deep in the euphotic zone and at night are mechanisms for balancing the C:N of cellular pools. A 24-h study using summed short-term incubations confirmed this; the cumulative C:N of CO₂ and NH₄⁺ uptake during the daylight period was 10–20, whereas over the 24-h period the ratio was 6 due to dark NH₄⁺ uptake. Annual carbon and nitrogen primary productivity were respectively estimated as 24 and 4·0 mol m⁻² year⁻¹ for the South River estuary, 42 and 7·3 mol m⁻² year⁻¹ for the Neuse River estuary, and 9·6 and 1·6 mol m⁻² year⁻¹ for the Newport River estuary.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Ionization of water in seawater

The ion product of water in seawater and the total activity coefficients of hydroxide and hydrogen ions were determined over the temperature range 2° to 35°C, and the salinity range 20‰ to 44‰. At 25°C and 35‰ salinity, the measured values are pK_W^SW = 13.20, f_OH = 0.22, f_H = 0.71 on the molar concentration scale.     

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.     

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.     

N2, N2O and O2Profiles in a Tagus Estuary Salt Marsh

Vertical gas profiles of N₂, N₂O and O₂were obtained in intact sediment cores from a Tagus estuary salt marsh using membrane inlet mass spectrometry. This technique allows direct measurements of dissolved gas concentrations with minimal disturbance. O₂concentrations decreased sharply with depth, becoming undetectable below 14mm. Denitrification products (N₂and N₂O) occurred in the surface layer of the sediment where O₂was present. Diffusion of N₂and N₂O from the anaerobic zone, denitrification in anaerobic microsites and aerobic denitrification are possible explanations for this observation. N₂was the sole product of denitrification in control sediment cores probably because of the great demand for electron acceptors in this sediment. The addition of NO₃ ⁻ and CH₃CO₂ ⁻ increased the concentrations of N₂and N₂O in the sediment. Significantly higher concentrations in treated cores occurred between 1·5 and 2·0cm for N₂and between 0·5 and 1·5cm for N₂O. The peak in N₂concentration occurred in the anaerobic zone of the sediment, close to the aerobic–anaerobic interface while the peak in N₂O concentration occurred above this interface where concentrations of O₂were approximately 10μM. This is indicative that, in this sediment, production of N₂O is less sensitive to the presence of O₂than reduction of N₂O to N₂.