Fluxes of dissolved inorganic carbon in three estuarine systems of the Cantabrian Sea (north of Spain)

The diffusive and in situ fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA) have been measured and an estimation has been made of the water–atmosphere fluxes of CO₂ in three estuarine systems of the Cantabrian Sea during the spring of 1998. Each of these systems undergoes a different anthropogenic influence. The diffusive fluxes of dissolved inorganic carbon and total alkalinity obtained present values ranging between 0.54–2.65 and 0.0–2.4 mmol m⁻² day⁻¹, respectively. These ranges are in agreement with those of other coastal systems. The in situ fluxes are high and extremely variable (35–284 mmol TA m⁻² day⁻¹, 43–554 mmol DIC m⁻² day⁻¹ and 22–261 mmol dissolved oxygen (DO) m⁻² day⁻¹), because the systems studied are very heterogeneous. The values of the ratio of the in situ fluxes of TA and DIC show on average that the rate of dissolution of CaCO₃ is 0.37 times that of organic carbon oxidation. Equally, the interval of variation of the relationship between the benthic fluxes of inorganic carbon and oxygen (F_DIC/F_DO) is very wide (0.3–13.9), which demonstrates the different contributions made by the processes of aerobic and anaerobic degradation of the organic matter, as well as by the dissolution–precipitation of CaCO₃. The water–atmosphere fluxes of CO₂ present a clear dependence on the salinity. The brackish water of these systems (salinity<20), where maximum fluxes of 989 mmol m⁻² day⁻¹ have been estimated, act as a source of CO₂ to the atmosphere. The more saline zones of the estuary (salinity>30) act as a sink of CO₂, with fluxes between −5 and −10 mmol m⁻² day⁻¹.     

A box model approach for a long-term assessment of estuarine eutrophication, Szczecin Lagoon, southern Baltic

We develop a layered “box model” to evaluate the major effects of estuarine eutrophication of the Szczecin lagoon which can be compared with integrating measures (chlorophyll a (Chl a), sediment burial, sediment oxygen consumption (SOC), input and output of total nutrient loads) and use it to hindcast the period 1950–1996 (the years when major increase in nutrient discharges by the Oder River took place). The following state variables are used to describe the cycling of the limiting nutrients (nitrogen and phosphorus): phytoplankton (Phy), labile and refractory detritus (D_N, D_Nref, D_P, D_Pref), dissolved inorganic nitrogen (DIN), dissolved inorganic phosphorus (DIP), and oxygen (O₂). The three layers of the model include two water layers and one sediment layer. Decrease of the carrying capacity with respect to the increased supply of organic matter of the system with advancing eutrophication over the period studied is parameterized by an exponential decrease of the sediment nitrogen fluxes with increasing burial, simulating changing properties from moderate to high accumulating sediments. The seasonal variation as well as the order of magnitude of nutrient concentrations and phytoplankton stocks in the water column remains in agreement with recent observations. Calculated annual mean values of nutrient burial of 193 mmol N m⁻² a⁻¹ and 23 mmol P m⁻² a⁻¹ are supported by observed values from geological sediment records. Estimated DIN remineralization in the sediments between 100 and 550 mmol N m⁻² a⁻¹ corresponds to SOC measurements. Simulated DIP release up to 60 mmol P m⁻² a⁻¹ corresponds to recent measurements. The conceptual framework presented here can be used for a sequential box model approach connecting small estuaries like the Szczecin lagoon and the open sea, and might also be connected with river box models.     

Inter-annual variability of hypoxic conditions in a shallow estuary

Water quality data from two monitoring programs in the Pamlico River Estuary (PRE) were analyzed for dissolved oxygen (DO), salinity, temperature, and nutrient concentrations. Data were collected bi-weekly at 8 stations from 1997 to 2003 by East Carolina University and continuously at three stations from 1999 to 2003 by the U.S. Geological Survey. Hypoxic conditions were observed mostly in the upper to middle estuary, but the frequency of hypoxic events varied between years. During June to October in 1997–1999 (referred to as the oxic summers) bottom water hypoxia (DO < 2 mg l^− 1) was found in 8.7% of the observations. By contrast, during June to October in 2001–2003 (referred to as the hypoxic summers), 37.9% of the total measurements had DO concentrations less than 2 mg l^− 1. The more frequent and/or prolonged hypoxic conditions during the hypoxic summers were closely associated with stronger salinity stratification and greater loadings of nutrient and particulate matter.Salinity stratification appeared to be governed by patterns of freshwater discharge, and frequency of wind mixing events. The “oxic” summers were characterized by continuous low freshwater inflow (except one extremely high flow event due to hurricanes), stronger northeastward wind, and more frequent wind mixing events. In contrast, the hypoxic summers were characterized by frequent moderate freshwater inflow events, and fewer wind mixing events.The greater loadings of nutrient (nitrate, ammonium, and phosphate) and particulate matter during the hypoxic summers were primarily due to higher river discharges. At the head of the PRE, no significant differences were found in concentrations of nutrient and particulate nitrogen between the oxic and the hypoxic summers. In addition, chlorophyll a concentrations were averaged above 30 μg l^− 1 (maximum 167 μg l^− 1) during the hypoxic summers, significantly higher than those during the oxic summers (averaged around 15 μg l^− 1).     

Nitrogenous discharges to the eastern Gulf of Finland, the Baltic Sea: Elemental flows, stable isotope signatures, and their estuarine modification

We studied the nutrient input to the Gulf of Finland via River Neva, the largest river discharging freshwater to the Baltic Sea, and characterised the isotopic signatures (¹⁵N, ¹⁸O, ¹³C) in dissolved and particulate substances (NO₃⁻, PON, POC, DIC) in the River Neva over two seasonal cycles, as well as in samples from St. Petersburg wastewater treatment plants (NO₃⁻, NH₄⁺, PON, POC). These riverine and municipal discharges account for 40% of terrestrial inorganic N loading to the Gulf of Finland, representing annually 7% of the total nitrogen pool in the water mass of the whole Gulf. To describe and evaluate the modification of these isotopic signals along a Gulf of Finland transect towards the Baltic Proper, two cruises were arranged, one in late spring after the annual maximum in River Neva runoff, and one in autumn, in the late phase of the annual growth season.River Neva nitrate signatures of ¹⁵N and ¹⁸O indicated major agricultural fertilizer origin of nitrogen, and the isotopic composition was clearly lighter (δ¹⁵N-NO₃⁻ mean of 2.4‰ air) than previously measured from more southern rivers discharging into the Baltic Sea. Because of the light composition of the River Neva N source, close to the ¹⁵N signatures of the open Gulf, as well as of the efficient depletion of the inorganic load already in the innermost estuary, straightforward end-member tracer analysis of the transport of N in the basin is problematic. St. Petersburg wastewater ammonium showed, however, high δ¹⁵N values (ca. 13‰), which gives a first estimate of 5.8‰ for δ¹⁵N of the easternmost estuarine total inorganic N source. The available sediment data from the basin (δ¹⁵N 6 to 8‰) somewhat exceeds the average source signature. This emphasizes the significance of biological transformation processes, most importantly assimilation of inorganic nitrogen, food web interactions and denitrification, which all involve isotopic fractionation, for the mass balance models describing the dynamics of the sources and sinks of the N cycle of the basin.     

Changes in apparent oxygen removal in the Baltic proper deep water

By developing a steady state diagnostic model for a stratified deep-water mass, one is able to quantify both the mass flows and apparent oxygen removal in the Baltic proper deep water. The model is based on continuity of the assumed conservative observable volume, salinity and temperature. Second degree polynomials are fitted to observed vertical profiles of temperature as well as oxygen concentration to give a functional correspondence with the used spatial variable salinity. These relations are used in the model that calculate the water flows, oxygen flows and oxygen removal during four periods between 1959 and 1997. The model forms a boundary value problem, which is solved with a finite difference scheme. The model seems to give reasonable estimates of the flows. The oxygen removal is mainly balanced by inflow of oxygen with incoming water. The oxygen consumption is 4–8 μl O₂ l⁻¹ day⁻¹, which corresponds to a degradation of organic matter in the range 30–60 g C m⁻² year⁻¹.     

Monitoring trace elements (Al, As, Cr, Cu, Fe, Mn, Ni and Zn) in deep and surface waters of the estuary of the Nerbioi-Ibaizabal River (Bay of Biscay, Basque Country)

Deep water samples (in contact with the sediment) were collected at eight different points of the estuary of the Nerbioi-Ibaizabal River (Bay of Biscay, Basque Country), both at low and high tides, during four sampling campaigns (May, September and December 2005 and March 2006). Superficial water was also sampled in March 2006. Temperature, pH, redox potential, dissolved oxygen and electrical conductivity corresponding to each sample were measured in situ at each sampling point using a multiparametric probe. The physico-chemical parameters found are typical of highly stratified estuaries, with an acceptable oxygenation level. After filtering and acidifying the samples, they were analysed by inductively coupled plasma/mass spectrometry (ICP/MS) to simultaneously determine the total concentration of Al, As, Cr, Cu, Fe, Mn, Ni and Zn. Concentrations in the μg kg^− 1 level were found in all cases (c_Cr and c_Ni, 1–10; c_Al, c_As and c_Zn, 10–50; c_Cu and c_Mn, 10–100 and c_Fe, 100–400 μg kg^− 1). A probable net input of Al, Cr, Mn and Zn via the main (Nerbioi-Ibaizabal) and some of the tributary rivers (Galindo, Asua and Gobela) was identified. Evidence of a common source of Al and Zn to the estuary was found. Correlation analysis of data revealed connections between variables (concentration of Cu, Fe and As with salinity, as well as c_Al with c_Zn, c_Cu with c_Fe, c_As with c_Fe, and c_As with c_Cu). Principal Component Analysis (PCA) of data allowed the samples to be grouped according to sampling campaign, with two principal components accounting for 62% of the total variance. In addition, plots of element concentration against salinity suggested a conservative behaviour for As, Cu and Fe and a non-conservative one for Cr. Not clear mixing behaviour was observed for the rest of elements.     

Biogeochemistry of sulfur in a sediment core from the west-central Baltic Sea: Evidence from stable isotopes and pyrite textures

The biogeochemistry of the sulfur cycle in a ca. 5-m-long sediment core from the eastern slope (221 m water depth) of the Landsort Deep in the west-central Baltic Sea was investigated by analyzing the solid phase records of sulfur isotopes and pyrite textures, besides selected main and minor elements. The sediments were deposited during post-glacial history of the Baltic Sea when the basin experienced alteration of brackish (Yoldia Sea, Littorina Sea) and freshwater (Baltic Ice Lake, Ancylus Lake) conditions. The stable isotopic composition of total sulfur was analyzed as a function of depth. In selected samples pyrite (FeS₂), greigite (Fe₃S₄), and barite (BaSO₄) fractions were separated for isotope analyses. Pyrite textures were analyzed by SEM and optical microscopy.Microbial reactions associated with the oxidation of organic matter resulted in assemblages of authigenic sulfide minerals which for the post-Ancylus Lake brackish water environment are dominated by pyrite and for freshwater environments by Fe-monosulfides. The sulfur isotopic composition of the brackish water Littorina Sea sediments (δ³⁴S between −40 and −27‰ vs. V-CDT) is believed to be determined by cellular sulfate reduction rates and reactions involving intermediate sulfur species. The availability of reactive iron and decomposable organic matter as well as sedimentation rate and the chemocline position are important variables upon the δ³⁴S values of sulfides in brackish water environment. The syn-depositional abundance of sulfur and organic matter, and transport of dissolved sulfur species vs. rates of microbial reactions determine δ³⁴S in the freshwater sediments. The upper part of the Ancylus Lake sediments is sulfidized by downward diffusing H₂S and/or sulfate from overlying brackish water sediments. Minor concretionary barite formation in the freshwater sediments is most likely due to the reaction of pore water sulfate diffusing downward from brackish water sediments with barium desorbed from freshwater sediments. The size distribution of pyrite framboids in the brackish sediments indicates that the formation mainly occurred from anoxic pore waters, although some pyrite formation in an anoxic water column cannot be excluded.     

Silicon dynamics in the Oder estuary, Baltic Sea

Studies on dissolved silicate (DSi) and biogenic silica (BSi) dynamics were carried out in the Oder estuary, Baltic Sea in 2000–2005. The Oder estuary proved to be an important component of the Oder River–Baltic Sea continuum where very intensive seasonal DSi uptake during spring and autumn, but also BSi regeneration during summer take place. Owing to the regeneration process annual DSi patterns in the river and the estuary distinctly differed; the annual patterns of DSi in the estuary showed two maxima and two minima in contrast to one maximum- and one minimum-pattern in the Oder River. DSi concentrations in the river and in the estuary were highest in winter (200–250 μmol dm^− 3) and lowest (often less than 1 μmol dm^− 3) in spring, concomitant with diatom growth; such low values are known to be limiting for new diatom growth. Secondary DSi summer peaks at the estuary exit exceeded 100 μmol dm^− 3, and these maxima were followed by autumn minima coinciding with the autumn diatom bloom. Seasonal peaks in BSi concentrations (ca. 100 μmol dm^− 3) occurred during the spring diatom bloom in the Oder River. Mass balance calculations of DSi and BSi showed that DSi + BSi import to the estuary over a two year period was 103.2 kt and that can be compared with the DSi export of 98.5 kt. The difference between these numbers gives room for ca. 2.5 kt BSi to be annually exported to the Baltic Sea. Sediment cores studies point to BSi annual accumulation on the level of 2.5 kt BSi. BSi import to the estuary is on the level of ca. 10.5 kt, thus ca. 5 kt of BSi is annually converted into the DSi, increasing the pool of DSi that leaves the system. BSi concentrations being ca. 2 times higher at the estuary entrance than at its exit remain in a good agreement with the DSi and BSi budgeting presented in the paper.     

The importance of estuarine gravitational circulation in the early life of the Bohai Penaeid Prawn

Estuaries along the southern shore of the Bohai Sea are the major habitat of the Bohai Penaeid Prawn (Penaeus chinensis). Since the 80's, however, many of the rivers have been dammed. Field observations, as well as laterally integrated 2-D numerical experiments, were conducted to understand both the role of estuarine gravitational circulation and the impact of the damming of the rivers on the early life of the Bohai Penaeid Prawn.For a river with runoff, especially for small discharge, the gravitational circulation tends to transport the planktonic larvae in their metamorphosis phase near the river mouth where condition is favorable for survival. The gravitational circulation inside the estuary tends to transport the mysis phase larvae towards the upstream end of the estuary when the most part of the larvae suspended in the bottom layer, and it transports the post larvae to the low salinity near upstream side of the estuary when the larvae become benthic, if the larvae enter the estuary.Damming causes long periods of zero runoff in the river, resulting in the alteration of the estuarine circulation and in the change of the estuarine environment. In addition, excess evaporation may prematurely transport the planktonic larvae into the estuary. On the other hand, sudden release of a large volume of freshwater from behind the dam may exert undesirable stress on the larvae.     

Old woman creek,Ohio: The designation of a freshwater estuarine sanctuary

The Ohio Department of Natural Resources and the U.S. Office of Coastal Zone Management have proposed the Old Woman Creek estuary on Lake Erie as the nation's first freshwater estuarine sanctuary. Designation as an estuarine sanctuary will preserve 637 acres of marshland, sand bar, a barrier beach, and surrounding forested uplands for public education and research. The original January 1975 grant application required modification following local residents’ objections to purchases of highly productive farmland and land‐use controls on a watershed‐wide buffer zone. A federal grant award was made in July 1977, with full acquisition anticipated by the end of 1978.     

Bacterial production and microbial food web structure in a large arctic river and the coastal Arctic Ocean

Globally significant quantities of organic carbon are stored in northern permafrost soils, but little is known about how this carbon is processed by microbial communities once it enters rivers and is transported to the coastal Arctic Ocean. As part of the Arctic River-Delta Experiment (ARDEX), we measured environmental and microbiological variables along a 300 km transect in the Mackenzie River and coastal Beaufort Sea, in July–August 2004. Surface bacterial concentrations averaged 6.7 × 10⁵ cells mL^− 1 with no significant differences between sampling zones. Picocyanobacteria were abundant in the river, and mostly observed as cell colonies. Their concentrations in the surface waters decreased across the salinity gradient, dropping from 51,000 (river) to 30 (sea) cells mL^− 1. There were accompanying shifts in protist community structure, from diatoms, cryptophytes, heterotrophic protists and chrysophytes in the river, to dinoflagellates, prymnesiophytes, chrysophytes, prasinophytes, diatoms and heterotrophic protists in the Beaufort Sea.Size-fractionated bacterial production, as measured by ³H–leucine uptake, varied from 76 to 416 ng C L^− 1 h^− 1. The contribution of particle-attached bacteria (> 3 µm fraction) to total bacterial production decreased from > 90% at the Mackenzie River stations to < 20% at an offshore marine site, and the relative importance of this particle-based fraction was inversely correlated with salinity and positively correlated with particulate organic carbon concentrations. Glucose enrichment experiments indicated that bacterial metabolism was carbon limited in the Mackenzie River but not in the coastal ocean. Prior exposure of water samples to full sunlight increased the biolability of dissolved organic carbon (DOC) in the Mackenzie River but decreased it in the Beaufort Sea.Estimated depth-integrated bacterial respiration rates in the Mackenzie River were higher than depth-integrated primary production rates, while at the marine stations bacterial respiration rates were near or below the integrated primary production rates. Consistent with these results, P_CO2 measurements showed surface water supersaturation in the river (mean of 146% of air equilibrium values) and subsaturation or near-saturation in the coastal sea. These results show a well-developed microbial food web in the Mackenzie River system that will likely convert tundra carbon to atmospheric CO₂ at increasing rates as the arctic climate continues to warm.     

Seasonal study of dissolved CH4, CO2 and N2O in a shallow tidal system of the bay of Cádiz (SW Spain)

During 2004, 10 samplings were performed in order to measure dissolved methane (CH₄), carbon dioxide (CO₂) and nitrous oxide (N₂O) in the surface waters of Río San Pedro, a tidal creek in the salt marsh area of the Bay of Cádiz (SW Spain). The inner partvs of the creek is affected by the inputs coming from an intensive fish farm and the drainage of an extensive salt marsh area.Dissolved CH₄, CO₂ and N₂O concentrations ranged from 11 to 88 nM, 36 to 108 μM and 14 to 50 nM, respectively. Surface waters were in all cases oversaturated with respect to the atmosphere, reaching values of up to 5000% for CH₄, 1240% for CO₂ and 840% for N₂O. Dissolved CH₄, CO₂ and N₂O showed a significant tidal and seasonal variability. Over a tidal cycle, concentrations were always highest during low tide, which points to the influence of the inputs from the fish farm effluent and the drainage of the adjacent salt marsh area, as well as in situ production within the system. Dissolved CH₄, CO₂ and N₂O seasonal patterns were similar and showed maximum concentrations in summer conditions. Using four different parameterizations to calculate the gas transfer coefficients [Liss, P.S. and Merlivat, L., 1986. Air-sea exchange rates: introduction and synthesis. In P. Buat-Ménard (Ed.), The Role of Air-Sea Exchanges in Geochemical Cycling. Reidel, Dordrecht, The Netherlands, p. 113–127.; Clark, J.F., Schlosser, P., Simpson, H.J., Stute, M., Wanninkhof, R., and Ho, D.T., 1995. Relationship between gas transfer velocities and wind speeds in the tidal Hudson River determined by the dual tracer technique. In: B. Jähne and E. Monahan (Eds.), Air-Water Gas Transfer: AEON Verlag and Studio, Hanau, Germany, pp. 785–800.; Carini, S., Weston, N., Hopkinson, G., Tucker, J., Giblin, A. and Vallino, J., 1996. Gas exchanges rates in the Parker River estuary, Massachusetts. Biol. Bull., 191: 333–334.; Kremer, J.N., Reischauer, A. and D'Avanzo, C., 2003. Estuary-specific variation in the air-water gas exchange coefficient for oxygen. Estuaries, 26: 829–836.], the averaged air–water fluxes of CH₄, CO₂ and N₂O from the creek to the atmosphere ranged between 34 and 150 μmol CH₄ m^− 2 day^− 1, 73 and 177 mmol CO₂ m^− 2 day^− 1 and 24 and 62 μmol N₂O m⁻² day⁻¹, respectively.     

Seasonal variability in sea surface oceanographic conditions in the Aegean Sea (Eastern Mediterranean): an overview

Seasonal variability and the spatial distribution of sea surface temperatures (SST) and salinities (SSS) are reviewed, in relation to the prevailing climatological conditions, heat fluxes, water budget and general water circulation patterns. Within this context, consideration is given to: sea surface temperatures; air temperatures; precipitation; evaporation; wind speeds and directions; freshwater (mainly riverine) discharges throughout the Aegean; and the exchange of water masses with the Black Sea and eastern Mediterranean Sea. The investigation of satellite images, covering a 6-yr period (1988–1994), has enabled a synthesis of the monthly sea surface thermal distribution to be established.The climate of the Aegean Sea is characterised by annual air temperatures of 16–19.5°C, precipitation of about 500 mm yr⁻¹ and evaporation of some 4 mm d⁻¹. The Aegean has a negative heat budget (approximately −25 W m⁻²) and positive water balance (+ 1.0 m yr⁻¹), when inflow from the Black Sea is considered. During the summer, the (northerly) Etesians are the dominant winds over the Sea.Mean monthly sea surface temperatures (SST) vary from 8°C in the north during winter, up to 26°C in the south during summer. SST depends mainly upon air temperature; there is a month's delay between the former and latter maxima. The sea surface salinity (SSS) varies also spatially and seasonally, ranging from less than 31 psu, in the north, to more than 39 psu, in the southeast; lower values (< 25 psu) occur adjacent to the river mouths. SSSs present their maximum differences during summer, whilst during winter and autumn the distribution of SSS is more uniform. The overall spatial SST and SSS distribution pattern is controlled by: distribution of the (colder) Black Sea Waters; advection of the (warmer) Levantine Waters, from the southeastern part of the Aegean; upwelling and downwelling; and, to a lesser extent, but locally important, freshwater riverine inflows.     

On the distribution of dissolved lead in the Loire estuary and the North Biscay continental shelf, France

The dissolved lead was studied in the whole salinity gradient of the system composed of the Loire estuary and the North Biscay continental shelf. About 130 samples were collected in winter 2001 and spring 2002 during Nutrigas and Gasprod campaigns (Programme PNEC-Golfe de Gascogne, RV Thalassa) and metal measurements were conducted on board by Potentiometric Stripping Analysis. In the Loire estuary, levels of dissolved lead ranged from 0.15 to 0.24 nM and from 0.04 to 0.26 nM in winter and spring, respectively. Compared to the concentrations reported in 1987 and 1990 (0.4–1.7 nM; Boutier, B., Chiffoleau, J.F., Auger, D., Truquet, I., 1993. Influence of the Loire river on dissolved lead and cadmium concentrations in coastal waters of Brittany. Estuar. Coast. Shelf S., 36:133–143, Estuarine, Coastal and Shelf Science 36, 133–143) our study indicated much lower values. The fall in concentration in the estuary could be attributed to the stopping of activity of Octel, a big manufacturer of tetra alkyl lead. Discharge in dissolved metal to the continental shelf by the Loire river was assessed as 7.5 and 1.9 kg day^− 1 for winter and spring, respectively. On the continental shelf, levels of dissolved lead varied within 0.06 and 0.27 nM in winter (0.15 ± 0.06 nM, sd = 1.96, n = 49), whereas concentrations measured in spring were in the range 0.06–0.17 nM (0.09 ± 0.03 nM, sd = 1.96, n = 60). This difference in metal concentration was related to the amounts of rainfall that have fallen over the continental shelf: estimations of inputs by this way (74 and 32 kg day^− 1 in winter and spring, respectively) appeared to be significantly higher than inputs from the Loire river (7.5 and 1.9 kg day^− 1 in winter and spring, respectively). The distributions of dissolved metal in the surface waters highlighted the role of suspended particular matter (SPM) for a rapid “trapping” of lead near the mouth of the estuary. The vertical distributions showed, in the stratified area, a biological transfer of lead between winter and spring from surface waters to the halocline.     

Geochemical controls on distributions and speciation of As and Hg in sediments along the Gaoping (Kaoping) Estuary–Canyon system off southwestern Taiwan

Surface and box-cored sediments were collected along the Gaoping (formerly spelled Kaoping) Estuary–Canyon system and analyzed for As and Hg contents and speciation, ²¹⁰Pb-based sedimentation rates and various geochemical parameters to elucidate the mechanisms that control natural and anthropogenic inputs of As and Hg from the Gaoping (Kaoping) River (KPR). The contents of As and Hg in surface sediments ranged from 1.84 to 20.7 mg kg^− 1 and from 0.07 to 2.15 mg kg^− 1, respectively, in the estuary and canyon. The concentrations generally decreased from the lower river toward the mixing boundary and then increased toward the estuarine mouth, followed by a slight variation in the canyon. Both As and Hg concentrations correlated strongly with clay, total organic carbon (TOC), Al, Fe and Mn contents in estuarine sediments but not necessary the same cases for canyon surface sediments. The factor analysis of surface sediments shows that the first two factors, which account for 75.6% of the variance, may represent major roles of carriers (clay, Al and Fe–Mn oxides) and TOC in controlling As and Hg distributions, respectively. Accordingly, the spatial patterns of the enrichments of As (1.9–16.2) and Hg (1.8–30.8) with reference to the crust levels follow the individual element's distribution patterns, likely because of deposition variability following inputs from the river. The contents of mobile As and Hg correlated substantially with the contents of both metals that were extracted with 0.1 M HCl. In addition to the major pool in the residual fraction (65–87%), As was relatively abundant in Fe–Mn oxides/hydroxides, whereas Hg was abundant in the organic/sulfide fraction. The deposition and accumulation rates of As and Hg in the canyon clearly decreased as the depth of water increased. The depth distributions of both metals are likely controlled primarily by TOC and Fe–Mn oxides associated factors followed by a contribution from anthropogenic pollution. The metal pollution appears to have increased substantially around 1970, following the economic boom in Taiwan, suggesting that modern sediments in the Gaoping (Kaoping) Canyon were derived from the Gaoping (Kaoping) River (KPR).     

Siliceous plankton dominate primary and new productivity during the onset of El Niño conditions in the Santa Barbara Basin, California

The potential for carbon export and the role of siliceous plankton in the cycling of C and N was assessed in natural plankton assemblages in the Santa Barbara Basin, California, by examining uptake rates of inorganic carbon, nitrate and silicic acid. In April–August 1997, the concentrations of chlorophyll a, particulate organic carbon, particulate organic nitrogen and biogenic silica were measured twice monthly, and results revealed the occurrence of at least three blooms, the largest in June. Particulate elemental ratios of C, N and Si were similar to ratios of nutrient-replete diatoms, suggesting that they dominated this bloom. Mean integrated rates of carbon, nitrate and silicon uptake during the 4-month study period are similar to other productive coastal and upwelling regions (103, 8.3 and 13 mmol m⁻² day⁻¹, respectively). New production rates were twice as high as previously reported in this region and indicate that high rates of new production along eastern boundary currents are not confined to the major coastal upwelling regions. C/NO₃⁻, Si/NO₃⁻ and Si/C uptake ratios varied widely, and mean integrated ratios were 14±5.4, 1.6±1.0 and 0.12±0.07 (S.D.), respectively. That mean C/NO₃⁻ uptake ratio corresponds to an f-ratio of about 0.5 indicating a large potential for particulate export. Based on the average Si/NO₃⁻ and Si/C uptake ratios, diatoms could perform all of the primary production and nitrate uptake that occurred during the study; these rates also suggest that export is controlled by diatoms in this system. The mean Si/C biomass ratio was lower than the mean Si/C uptake ratio, consistent with the preferential export of Si relative to C observed in sediment traps in the basin. The study took place during a period of surface-water warming, with nitrate and silicic acid concentrations decreasing throughout the onset of the 1997–1998 El Niño conditions. Although diatoms contributed less to particulate biomass during the low nutrient conditions, high f-ratios (0.33–0.66) were maintained.     

Determination of anthropogenic CO2 in the North Atlantic Ocean using water mass ages and CO2 equilibrium chemistry

A new method to calculate the anthropogenic CO₂ (ΔDIC_ant) within the water column of the North Atlantic Ocean is presented. The method exploits the equilibrium chemistry of the carbonate system with reference to temperature, salinity and the partial pressure of atmospheric CO₂ (pCO_2,atm). ΔDIC_ant is calculated with reference to the ventilation ages of water masses derived from tracer data and to the time history of pCO_2,atm. The method is applied to data recorded during the WOCE program on the WHP A1/E transect in the North Atlantic Ocean, where we characterise six key water masses by their relationships of dissolved inorganic carbon (DIC) and apparent oxygen utilisation (AOU). The error in determining ΔDIC_ant is reduced significantly by minimising the number of values referred to, especially by avoiding any use of remineralisation ratios of particulate organic matter. The distribution of ΔDIC_ant shows highest values of up to 45 μmol kg⁻¹ in the surface waters falling to 28–33 μmol kg⁻¹ in the Irminger Sea west of the Mid-Atlantic Ridge. The eastern basin is imprinted by older water masses revealing decreasing values down to 10 μmol kg⁻¹ ΔDIC_ant in the Antarctic Bottom Water. These findings indicate the penetration of the whole water column of the North Atlantic Ocean by anthropogenic CO₂.     

Dynamics of inorganic nutrient species in the Bohai seawaters

Within the frame of a Sino-German Joint Research Program, two cruises of “R/V Dong Fang Hong 2” were carried out in September–October 1998 and April–May 1999, respectively, to understand the dynamics of nutrients in the Bohai. Nutrient species (NO₃⁻, NO₂⁻, NH₄⁺, PO₄³⁻ and SiO₃²⁻) are determined colorimetrically on board for five anchor and 30 grid stations. In situ incubation experiments are performed to determine planktonic nutrient uptake and benthic exchange flux. Nutrient concentrations display short-term variability and seasonal change in the Bohai, with higher levels in shallow coastal waters than in the Central Bohai. The influence of riverine discharge on nutrient levels can be seen from salinity isopleths, nutrient distribution and species ratios. Near-bottom (nb) waters have similar nutrient concentrations as to the surface waters in the Central Bohai, whereas stratification takes place in the Bohai Strait and North Yellow Sea. In situ incubation experiments provide evidence that the uptake ratio (i.e. N, P) by phytoplankton is proportional to the ratios among nutrient species in ambient waters. Based on the data of this study and previously publications, a preliminary estimate of nutrient budgets via riverine input and atmospheric deposition is established. The results indicate that atmospheric deposition gains importance over rivers in delivering nutrients into the Bohai and sustain the new production, following recent decrease in riverine inflow caused by drought periods in North China and damming practices. A historical review of nutrient data indicates that concentrations of nitrogen increase and phosphorus and silica decrease in the Central Bohai over last 40 years. This potentially has an important influence on the health of ecosystem in Bohai (e.g. food web and community structure), though further study is needed to examine the scenario in more detail.     

Sediment community biomass and respiration in the Northeast water polynya, Greenland: a numerical simulation of benthic lander and spade core data

Sediment community metabolism (oxygen demand) was measured in the Northeast Water (NEW) polynya off Greenland employing two methods: in situ benthic chambers deployed with a benthic (GOMEX) lander and shipboard laboratory Batch Micro-Incubation Chambers (BMICs) utilizing ‘cores’ recovered from USNEL box cores. The mean benthic respiration rate measured with the lander was 0.057 mM O₂ m⁻² h⁻¹ (n = 5); whereas the mean measured with the BMICs was 0.11 mM O₂ m⁻² h⁻¹ (n = 21; p < 0.01 that the means were the same). In terms of carbon fluxes (14 and 27 mg C m⁻² d⁻¹), these respiration rates represent ca. 5–15% of the average net primary production measured in the euphotic zone in 1992. The biomass of the bacteria, meiofauna and macrofauna were measured at each location to quantify the relationship between total community respiration and total community biomass (mean 1.42 g C m⁻²). Average carbon residence time in the biota, calculated by dividing the biomass by the respiration, was on the order of 50–100 days, which is comparable to relatively oligotrophic continental margins at temperate latitudes.The biomass and respiration data for the aerobic heterotrophic bacteria, the infaunal invertebrates (meiofauna and macrofauna), and the epifaunal megabenthos (two species of brittle stars) are summarized in a ‘steady-state’ solution of a sediment food chain model, in terms of carbon. This carbon budget illustrates the relative importance of the sediment-dwelling invertebrates in the benthic subsystem, compared to the bacteria and the epibenthos, during the summer open-water period in mud-lined troughs at depths of about 300 m. The input needed to drive heterotrophic respiratory processes was within the range of the input of organic matter recorded in moored, time-sequencing sediment traps.A time-dependent numerical simulation of the model was run to investigate the potential responses of the three size groups of benthos to abrupt seasonal pulses of particulate organic matter. The model suggests that there is a time lag in the increase in bottom community biomass and respiration following the POC pulse, and provides hypothetical estimates for the potential carbon storage in the summer (open water), followed by catabolic losses during each ensuing winter (ice covered).This sequence of storage and respiration may contribute to the process of seasonal CO₂ ‘rectification’ (sensu Yager et al., 1995) in some Arctic ecosystems.     

Large-scale physical controls on phytoplankton growth in the Irminger Sea, Part II: Model study of the physical and meteorological preconditioning

The upper water column in the Irminger Sea is characterized by cold fresh arctic and subarctic waters and warm saline North Atlantic waters. In this study the local physical and meteorological preconditioning of the phytoplankton development over an annual cycle in the upper water column in four physical zones of the Irminger Sea is investigated. Data from four cruises of the UK's Marine Productivity programme are combined with results from a coupled biological–physical nitrogen–phytoplankton–zooplankton–detritus model run using realistic forcing. The observations and model predictions are compared and analyzed to identify the key parameters and processes which determine the observed heterogeneity in biological production in the Irminger Sea. The simulations show differences in the onset of the bloom, in the time of the occurrence of the maximum phytoplankton biomass and in the length of the bloom between the zones. The longest phytoplankton bloom of 90 days duration was predicted for the East Greenland Current of Atlantic origin zone. In contrast, for the Central Irminger Sea zone a phytoplankton bloom with a start at the beginning of May and the shortest duration of only 70 days was simulated. The latest onset of the phytoplankton bloom in mid May and the latest occurrence of the maximum biomass (end of July) were predicted for the Northern Irminger Current zone. Here the bloom lasted for 80 days. In contrast the phytoplankton bloom in the Southern Irminger Current zone started at the same time as in Central Irminger Sea, but peaked end of June and lasted for 80 days. For all four zones relatively low daily (0.3–0.5 g C m^− 2d^− 1) and annual primary production was simulated, ranging between 35.6 g C m^− 2y^− 1 in the East Greenland Current of Atlantic origin zone and 45.6 g C m^− 2y^− 1 in the Northern Irminger Current zone. The model successfully simulated the observed regional and spatial differences in terms of the maximum depth of winter mixing, the onset of stratification and the development of the seasonal thermocline, and the differences in biological characteristics between the zones. The initial properties of the water column and the seasonal cycle of physical and meteorological forcing in each of the zones are responsible for the observed differences during the Marine Productivity cruises. The timing of the transition from mixing to stratification regime, and the different prevailing light levels in each zone are identified as the crucial processes/parameters for the understanding of the dynamics of the pelagic ecosystem in the Irminger Sea.