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.     

N2O Production, Nitrification and Denitrification in an Estuarine Sediment

The mechanisms regulating N₂O production in an estuarine sediment (Tama Estuary, Japan) were studied by comparing the change in N₂O production with those in nitrification and denitrification using an experimental continuous-flow sediment–water system with¹⁵N tracer (¹⁵N-NO−3 addition). From Feburary to May, both nitrification and denitrification in the sediment increased (246 to 716 μmol N m⁻² h⁻¹and 214 to 1260 μmol N m⁻² h⁻¹, respectively), while benthic N₂O evolution decreased slightly (1560 to 1250 nmol N m⁻² h⁻¹). Apparent diffusion coefficients of inorganic nitrogen compounds and O₂at the sediment–water interface, calculated from the respective concentration gradients and benthic fluxes, were close to the molecular diffusion coefficients (0·68–2·0 times) in February. However, they increased to 8·8–52 times in May except for that of NO−2, suggesting that the enhanced NO−3 and O₂supply from the overlying water by benthic irrigation likely stimulated nitrification and denitrification. Since the progress of anoxic condition by the rise of temperature from February to May (9 to 16 °C) presumably accelerated N₂O production through nitrification, the observed decrease in sedimentary N₂O production seems to be attributed to the decrease in N₂O production/occurrence of its consumption by denitrification. In addition to the activities of both nitrification and denitrification, the change in N₂O metabolism during denitrification by the balance between total demand of the electron acceptor and supply of NO−3+NO−2 can be an important factor regulating N₂O production in nearshore sediments.     

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.     

Flux of Reduced Sulfur Gases Along a Salinity Gradient in Louisiana Coastal Marshes

Seasonal and diurnal reduced sulfur gas emissions were measured along a salinity gradient in Louisiana Gulf Coast salt, brackish and freshwater marshes. Reduced sulfur gas emission was strongly associated with habitat and salinity gradient. The dominant emission component was dimethyl sulfide (average: 57·3 μg S m⁻² h⁻¹) in saltmarsh with considerable seasonal (max: 144·03 μg S m⁻² h⁻¹; min: 1·47 μg S m⁻² h⁻¹) and diurnal (max: 83·58 μg S m⁻² h⁻¹; min: 69·59 μg S m⁻² h⁻¹) changes in flux rates. Hydrogen sulfide was dominant (average: 21·2 μg S m⁻² h⁻¹, max: 79·2 μg S m⁻² h⁻¹; min: 5·29 μg S m⁻² h⁻¹) form in brackishmarsh and carbonyl sulfide (average: 1·09 μg S m⁻² h⁻¹; max: 3·42 μg S m⁻² h⁻¹; min: 0·32 μg S m⁻² h⁻¹) was dominant form in freshwater marsh. A greater amount of H₂S was evolved from brackishmarsh (21·22 μg S m⁻² h⁻¹) as compared to the saltmarsh (2·46 μg S m⁻² h⁻¹) and freshwater marsh (0·30 μg S m⁻² h⁻¹). Emission of total reduced sulfur gases decreased with decrease in salinity and distance inland from the coast. Emission of total reduced sulfur gases over the study averaged 73·3 μg S m⁻² h⁻¹ for the saltmarsh, 32·1 μg S m⁻² h⁻¹ for brackishmarsh and 2·76 μg S m⁻² h⁻¹ for the freshwater marsh.     

Evidence for microbiological manganese oxidation in the river Tamar Estuary, South West England

Water samples from the Tamar Estuary oxidized manganese when supplemented with Mn²⁺ (2 mgl⁻¹). The rates of oxidation were depressed in the presence of various metabolic inhibitors. The effect of Mn²⁺ and temperature on the rate of manganese oxidation suggested that a biological process was largely responsible for converting Mn²⁺ to Mn⁴⁺. Rates of manganese oxidation were much higher in freshwater (3·32 μgl⁻¹ h⁻¹ in water containing 30 mgl⁻¹ of suspended matter) than in saline water (0·7 μgl⁻¹ h⁻¹ in water of salinity 32‰) containing the same amount of particulate matter. The rate of manganese oxidation was proportional to the particulate load (up to 100 mgl⁻¹ particulates).     

Total oxyradical scavenging capacity and cell membrane stability of haemocytes of the Arctic scallop, Chlamys islandicus, following benzo(a)pyrene exposure

Industrial activities, notably oil and gas industries, are expanding in the Arctic. Most of the biomarkers were developed using temperate organisms living at temperatures above 10 °C. Little is known about the biomarker responses of organisms living between −1.88 and 5 °C. Therefore, assessment of the toxicity of chemicals to cold-water adapted species is required. In this study, the Arctic scallop, Chlamys islandicus, was selected as a key species for bio-monitoring because of wide distribution in Arctic waters and its commercial value. Test animals, stored in seawater at 2 °C, were injected with benzo(a)pyrene (diluted in cod liver oil 5 mg ml⁻¹) in the adductor muscle every 24 h for four days giving a final dose of 0, 74 and 90.6 mg kg⁻¹ wet weight for control, low and high dose, respectively. The biomarkers used were total oxyradical scavenging capacity (TOSC) in the digestive gland and cell membrane stability of haemocytes. TOSC values were significantly reduced (ca. 30%) in exposed groups (P<0.05), indicating a depletion in oxyradical molecular scavengers. The antioxidant defences appeared to be overwhelmed by the reactive oxygen species as the plasma membranes of haemocytes were destabilised (P<0.05) probably due to lipid peroxidation. These data indicate that reactive oxygen species (ROS) were produced by Arctic scallops via the metabolisation of benzo(a)pyrene at 2 °C.     

Size partitioning of microbial and meiobenthic biomass and respiration on Brown's Bank, south-west Nova Scotia

Biomass and respiration (oxygen consumption) of bacteria, microfauna, and meiofauna were measured in coarse sand sediment from Brown's Bank (172 m) off Nova Scotia, Canada. Community biomass, excluding macrofauna, had a median value of 35 mg C m⁻², dominated by bacteria (51%), microfauna (25%), and a minor meiofauna component (2·5%). Protozoan microfauna were mostly microflagellates (colourless cryptomonads). The experimental design allowed partitioning of benthic metabolism without using subtraction from whole community rates. Addition-removal experiments with fauna separated into size categories were used to construct a respiration-biomass regression for all taxa. Respiration rates for faunal groups were then calculated from their biomass in the natural sediment. Total microbial and meiofaunal community respiration had a median rate of 0·55 ml O₂ m⁻² h⁻¹ which was partitioned into median proportions of bacteria (50%) microflagellates (27%), and metazoan meiofauna (4%). Correlations among faunal biomass values from incubated vials of sediment suggested that bacteria were important prey for protozoans. With added biomass of meiofauna, protozoans also became a potentially important source of prey. The results demonstrated the significance of microflagellate protozoans in these sediments and their metabolic and trophic importance relative to meiofauna and even bacteria.     

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.     

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.     

Diffusion coefficients of major ions in seawater

Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na⁺, Ca²⁺, Cl⁻, SO₄², and HCO₃⁻, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na⁺ and Cl⁻ which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na⁺, Ca ²⁺, Cl⁻, SO₄²⁻ and HCO₃⁻, corresponding to different salinity gradients.     

Nondetrital and total metal distribution in core sediments from the U-Tapao Canal, Songkhla, Thailand

The U-Tapao Canal is the main source of freshwater draining into the outer part of Songkhla Lake, which is the most important estuarine lagoon in Thailand. Songkhla Lake is located in southern Thailand between latitudes 7°08' and 7°50' N and longitudes 100°07' and 100°37' E. Acetic acid (HOAc)-soluble Cu, Fe, Mn, Pb, and Zn and the total concentration of these metals along with Al concentration, organic carbon, carbonate, sand, silt, and clay contents were determined in 4 sediment cores obtained at selected intervals from the mouth of the canal to 12 km upstream. Readily oxidizable organic matter in the cores varies from 1.52% to 7.30% and is generally found to decrease seaward. Total concentrations of Al (61.7–99.0 g kg⁻¹; 2.29–3.67 mol kg⁻¹), Cu (12.4–28.2 mg kg⁻¹; 195–444 μmol kg⁻¹), Fe (25.2–42.0 g kg⁻¹; 451–752 mmol kg⁻¹), Mn (0.22–0.49 g kg⁻¹; 4.0–8.9 mmol kg⁻¹), Pb (16.7–43.1 mg kg⁻¹; 80.6–208 μmol kg⁻¹), and Zn (48.6–122.7 mg kg⁻¹; 0.74–1.88 mmol kg⁻¹) vary to a certain extent vertically and seaward in the U-Tapao Canal core sediments. These concentrations are at or near natural levels and show no indication of anthropogenic contamination.Overall, the data show that total metal concentrations in the surface and near surface core sediments are enriched in varying degrees relative to Al in the order of Zn>Mn>Pb>Fe>Cu. Chemical partitioning shows that the enrichment in the surface and near surface sediments is related to the relatively high proportion of the total metal concentrations (Mn>Zn>Fe>Cu>Pb) that occur in the acetic acid-soluble (nondetrital) fraction, and they generally decrease with depth. Nondetrital Cu, Pb, and Zn likely derive from those metals held in ion exchange positions, certain carbonates, and from easily soluble amorphous compounds of Mn and perhaps those of Fe. Diagenetic processes involving Mn and to a lesser extent, Fe compounds, as well as the vertical changes in the oxidizing/reducing boundaries, appear to be the most important factors controlling the behavior of the metals in these cores. Organic matter and the aluminosilicate minerals, however, appear to be less important carriers of the metals studied.     

A note on the Japan Sea Proper Water

The water under the main thermocline in the Japan Sea is a single water mass referred to as the Japan Sea Proper Water. It can be defined as having temperature below 2.0°C, salinity above 34.00%, and dissolved oxygen below 7.0 ml 1⁻¹. In the north most of the water above the potential temperature 0.1°C depth (about 800–1000 m) is a mode water, with σ_θ of 27.32 to 27.34 kg m⁻³. North of 40°N it has high oxygen (more than 6.00 ml 1⁻¹) with a distinct discontinuity (oxygen-cline) at the bottom of the mode water. The most probable region for the formation of the water is the area north of 41°N between 132° and 134°E. The deeper water probably is formed in the norther area of 43°N, and directly fills the main part of the Japan Basin north of 41°N and east of 134°E.     

The effect of ionic interaction on the rates of oxidation in natural waters

The effect of ionic interactions on the kinetics of disproportionation of HO₂, and the oxidation of Fe(II) and Cu(I) has been examined. The interactions of O₂ with Mg²⁺ and Ca²⁺ ions in seawater increases the lifetime by 3–5 times compared to water. The effect of OH⁻ on the oxidation of Fe(II) in water and seawater shows a second degree dependence from 5 to 45°C. The effect of salinity on the oxidation of Fe(II) was found to be independent of temperature, while the effect of temperature was found to be independent of salinity. The energy of activation for the overall rate constant was found to be 7 ± 0.5 kcal mol⁻¹.The effect of pH, temperature, salinity and ionic composition on the oxidation of Cu(I) has also been examined. In NaCl solutions from 0.5 to 6 M, the log k for the oxidation was a linear function of pH (6–8) with a slope of 0.2 ± 0.05. The reaction was strongly dependent on the Cl⁻ concentration with variation of from 0.3 to 340 min from 0.5 to 6 M Cl⁻. The rates of oxidation of Cu⁺ and CuCl⁰ responsible for these effects are dependent upon ionic strength. The energy of activation for the reaction was 8.5–9.9 kcal mol⁻¹ from 0.5 to 6 M. Studies of the oxidation in various NaX salts (X = I⁻, Br⁻ and Cl⁻) give rates in the order Cl⁻ > Br⁻ > I⁻ as expected, due to complex formation of Cu⁺ with X⁻.     

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.     

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

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

Benthic fluxes of nitrogen in the tidal reaches of a turbid, high-nitrate sub-tropical river

Benthic fluxes of dissolved inorganic nitrogen (NO₃⁻ and NH₄⁺), dissolved organic nitrogen (DON), N₂ (denitrification), O₂ and TCO₂ were measured in the tidal reaches of the Bremer River, south east Queensland, Australia. Measurements were made at three sites during summer and winter. Fluxes of NO₃⁻ were generally directed into the sediments at rates of up to −225 μmol N m⁻² h⁻¹. NH₄⁺ was mostly taken up by the sediments at rates of up to −52 μmol N m⁻² h⁻¹, its ultimate fate probably being denitrification. DON fluxes were not significant during winter. During summer, fluxes of DON were observed both into (−105 μmol m⁻² h⁻¹) and out of (39 μmol m⁻² h⁻¹) the sediments. Average N₂ fluxes at all sampling sites were similar during summer (162 μmol N m⁻² h⁻¹) and winter (153 μmol N m⁻² h⁻¹). Denitrification was fed both by nitrification within the sediment and NO₃⁻ from the water column. Sediment respiration rates played an important role in the dynamics of nitrification and denitrification. NO₃⁻ fluxes were significantly related to TCO₂ fluxes (p<0.01), with a release of NO₃⁻ from the sediment only occurring at respiration rates below 1000 μmol C m⁻² h⁻¹. Rates of denitrification increased with respiration up to TCO₂ fluxes of 1000 μmol C m⁻² h⁻¹. At sediment respiration rates above 1000 μmol C m⁻² h⁻¹, denitrification rates increased less rapidly with respiration in winter and declined during summer. On a monthly basis denitrification removed about 9% of the total nitrogen and 16% of NO₃⁻ entering the Bremer River system from known point sources. This is a similar magnitude to that estimated in other tidal river systems and estuaries receiving similar nitrogen loads. During flood events the amount of NO₃⁻ denitrified dropped to about 6% of the total river NO₃⁻ load.     

Development and assessment of an analytical system for the accurate and continual measurement of total dissolved inorganic carbon

An automated coulometric titration system based on that described by Johnson, Sieburth, Williams and Brandstrom (1987, Mar. Chem., 21: 117–133) has been evolved for the accurate and continual measurement of total dissolved inorganic carbon (TCO₂). The instrument achieves an analytical precision (1 SD) of ±0.5–1.0 μmol kg⁻¹ (0.025–0.05%). The accuracy of the system has been examined by a limited comparison with other coulometric-based titrators and with a manometric-based system; agreement was to 1 μmol kg⁻¹. The capability for automatic continual analysis allows surface mapping of TCO₂; a sample rate of 10 analyses h⁻¹ gives a mapping resolution of 1–2 km. Provision for frequent standardization with a liquid substandard has been included in the development. The ability to achieve high-density analyses while maintaining interlaboratory consistency and standardization constitutes a vital contribution to surveys of ocean carbon chemistry (e.g. Joint Global Ocean Flux Study, World Ocean Circulation Experiment).