Variability of organic δC and C/N in the Mersey Estuary, U.K. and its implications for sea-level reconstruction studies

Microfossil analysis (e.g. diatoms, foraminifera and pollen) represents the cornerstone of Holocene relative sea-level (RSL) reconstruction because their distribution in the contemporary inter-tidal zone is principally controlled by ground elevation within the tidal frame. A combination of poor microfossil preservation and a limited range in the sediment record may severely restrict the accuracy of resulting RSL reconstructions. Organic δ¹³C and C/N analysis of inter-tidal sediments have shown some potential as coastal palaeoenvironmental proxies. Here we assess their viability for reconstructing RSL change by examining patterns of organic δ¹³C and C/N values in a modern estuarine environment. δ¹³C and C/N analysis of bulk organic inter-tidal sediments and vegetation, as well as suspended and bedload organic sediments of the Mersey Estuary, U.K., demonstrate that the two main sources of organic carbon to surface saltmarsh sediments (terrestrial vegetation and tidal-derived particulate organic matter) have distinctive δ¹³C and C/N signatures. The resulting relationship between ground elevation within the tidal frame and surface sediment δ¹³C and C/N is unaffected by decompositional changes. The potential of this technique for RSL reconstruction is demonstrated by the analysis of part of an early Holocene sediment core from the Mersey Estuary. Organic δ¹³C and C/N analysis is less time consuming than microfossil analysis and is likely to provide continuous records of RSL change.     

The blooms of a cyanobacterium, Microcystis cf. aeruginosa in a severely polluted estuary, the Golden Horn, Turkey

The distribution of toxic cyanobacterium Microcystis cf. aeruginosa in the severely polluted Golden Horn Estuary was studied from 1998 to 2000. Microcystis persisted at the upper estuary where the water circulation was poor and values ranged between 2.9 × 10⁴ and 2.7 × 10⁶ cells ml⁻¹ throughout the study. Simultaneously measured physical (salinity, temperature, rainfall and secchi disc) and chemical parameters (nutrients and dissolved oxygen) were evaluated together with Microcystis data. Although the Microcystis blooms generally occur in summer due to the increase in temperature, the blooms were recorded in winter in the present study. The abundance of Microcystis depended on the variations in salinity and both blooms were recorded below S = 2. A moderate partial correlation between Microcystis abundance and salinity was detected in the presence of temperature, dissolved oxygen and precipitation data (r = −0.561, p = 0.002). The M. cf. aeruginosa abundance was low in the summer when the salinity was higher than winter. A remarkable increase in the eukaryotic phytoplankton abundance following the improvements in the water quality of the estuary occurred, whilst the Microcystis abundance remained below bloom level.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

The distribution and δC of dissolved organic carbon and its humic fraction in estuaries of southeastern USA

In this study, we examine the distribution and carbon stable isotope signature of dissolved organic carbon (DOC) and humic substances (HS) along a salinity gradient in the Altamaha and Satilla River estuaries. The maximum DOC concentrations in the Altamaha and Satilla were 10 and 29 mg C l⁻¹, respectively, though concentrations were similar at the mouth of both estuaries. There was a decrease in HS content of DOC from 50 to 80% at the head of the estuaries to 10% at salinities higher than 30‰. The δ¹³C DOC varied between −25.5 and −19‰ and between −27 and −21‰ in the Altamaha and Satilla estuaries, respectively. The tendency towards more depleted δ¹³C DOC in the Satilla, especially in the lower salinity portion of this estuary, suggests greater terrestrial inputs in the Satilla than in the Altamaha. Seasonal fluctuations were observed in the form of increased (two to three times) range in DOC concentration, heavier δ¹³C DOC and increased proportion of estuarine–marine-derived DOC (average enrichment of δ¹³C DOC from +1 to +2) during low river flow (July–October). The δ¹³C HS in both rivers showed a similar trend, but was consistently more depleted than DOC, with an average range from −28 to −24.5‰. This suggests that HS have larger proportions of terrestrial components (a maximum of >60% at the mouth of the estuary) than DOC. The less depleted δ¹³C values of DOC in comparison with HS indicate a different source for the non-humic (non-HS) component of DOC (range in δ¹³C non-HS, −22 to −16‰). That source could either be the decomposition of detrital material derived from saltmarsh environments or microalgal-derived DOC of estuarine or marine origins.     

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

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

Possible Density Change of the Origin of North Pacific Intermediate Water Due to Double Diffusion in the Mixed Water Region

In this study we test Talley's hypothesis that Oyashio winter mixed-layer water (26.5–26.6σ _θ) increases its density to produce the North Pacific Intermediate Water (NPIW) salinity minimum (26.7– 26.8σ_θ) in the Mixed Water Region, assuming a combination of cabbeling and double diffusion. The possible density change of Oyashio winter mixed-layer water is discussed using an instantaneous ratio of the change of temperature and salinity along any particular intrusion (R _l ). We estimate the range of R _l ^DD required to convert Oyashio winter mixed-layer water to the NPIW salinity minimum due to double diffusion, and then assume double-diffusive intrusions as this conversion mechanism. A double-diffusive intrusion model is used to estimate R _l ^DD in a situation where salt fingering dominates vertical mixing, as well as to determine whether Oyashio winter mixed-layer water can become the NPIW salinity minimum. Possible density changes are estimated from the model R _l ^DD by assuming the amount of density change due to cabbeling. From these results, we conclude that Oyashio winter mixed-layer water contributes to a freshening of the lighter layer of the NPIW salinity minimum (around 26.70σ_θ) in the MWR.     

Stable carbon isotope ratios of plankton carbon and sinking organic matter from the Atlantic sector of the Southern Ocean

The stable carbon isotope composition of particulate organic carbon (POC) from plankton, sediment trap material and surface sediments from the Atlantic sector of the Southern Ocean were determined. Despite low and constant water temperatures, large variations in the δ¹³C values of plankton were measured. ¹³C enrichments of up to 10‰ coincided with a change in the diatom assemblage and a two-fold increase in primary production. Increased CO₂ consumption as a result of rapid carbon fixation may result in diffusion limitation reducing the magnitude of the isotope fractionation. The δ¹³C values of plankton from sea-ice cores display a relationship with the chlorophyll a content. High ‘ice-algae’ biomass, in combination with a limited exchange with the surrounding seawater, results in values of about − 18 to − 20‰. It is assumed that these values are related to a reduced CO₂ availability in the sea-ice system. In comparison with plankton, sinking krill faeces sampled by traps can be enriched by 2–5‰ in ¹³C (e.g. central Bransfield Strait). In contrast, the transport of particles in other faeces, diatom aggregates or chains results in minor isotope changes (e.g. Drake Passage, Powell Basin, NW Weddell Sea). A comparison between the δ¹³C values of sinking matter and those of surface sediments reveals that ¹³C enrichments of up to 3–4‰ may occur at the sediment-water boundary layer. These isotopic changes are attributed to high benthic respiration rates.     

Trophic position of Calanus finmarchicus (Copepoda, Calanoida) in the Trondheim Fjord

The trophic position of Calanus finmarchicus in the Trondheim Fjord in 2004 was determined through stable isotope analyses. Wild specimens were sampled monthly in the fjord and δ¹³C and δ¹⁵N signatures of the developmental stages from CIII to adults were measured. There were statistically significant differences in the δ¹³C and δ¹⁵N signatures of three identified groups: overwintered parental generation, developing new generation and new generation preparing for overwintering. C. finmarchicus individuals raised in a laboratory on a pure algal diet (Dunaliella tertiolecta and Isochrysis galbana) provided stable isotope signatures for purely herbivorous copepods. With these signatures as comparison, the trophic position of C. finmarchicus in the Trondheim Fjord in 2004 was determined as trophic level 2.4, thus indicating omnivory under natural conditions. Additionally, our data suggest that seasonal differences in the δ¹³C signatures of C. finmarchicus are due to the varying lipid content of the different developmental stages.     

On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.     

Controls on carbon cycling in two contrasting temperate zone estuaries: The Tyne and Tweed, UK

In order to evaluate the respiration–photosynthesis dynamics in two contrasting North Sea estuaries, pH, temperature, alkalinity, chlorophyll-a (chl-a), and isotopic ratios of dissolved inorganic carbon (δ¹³C_DIC) and dissolved oxygen (δ¹⁸O_DO) were measured in the Tyne (July 2003) and Tweed (July 2003 and December 2003) estuaries. Using a concentration-dependent isotope mixing line, δ¹³C_DIC values in the Tweed (July 2003) demonstrated mostly conservative behaviour across the estuary, reflecting mixing between riverine and marine sources, although some samples were slightly more ¹³C-enriched than predicted δ¹³C_DIC values. Low pCO₂ (less than 2 times atmospheric pressure) and ¹⁸O-depleted δ¹⁸O_DO signatures below equilibrium with the atmosphere provided further evidence for net autotrophy in the Tweed estuary in summer 2003. Conversely, in the Tyne during the summer and in the Tweed during the winter higher pCO₂ (up to 6.5 and 14.4 times atmospheric partial pressure in the Tweed and Tyne, respectively), slightly ¹³C-depleted δ¹³C_DIC and ¹⁸O-enriched δ¹⁸O_DO values indicated heterotrophy as the dominant process. The relatively large releases of CO₂ observed during these two estuarine surveys can be attributed to significant oxidation of terrigenous organic matter (OM). This study therefore demonstrates the usefulness of combined δ¹⁸O_DO and δ¹³C_DIC isotopes in examining the relationship between respiration–photosynthesis dynamics and the fate of terrestrially derived OM during estuarine mixing.     

Carbon and nitrogen isotope composition of particulate organic matter in relation to mucilage formation in the northern Adriatic Sea

Carbon and nitrogen stable isotope ratios of particulate organic matter (POM) were studied approximately weekly during spring and summer 2003 and 2004 in the Gulf of Trieste (northern Adriatic Sea) in order to track the temporal variations and differences between two years. In parallel, particulate organic carbon (POC) and particulate nitrogen (PN), phytoplankton biomass (chlorophyll a), and N and P nutrients were monitored. All studied parameters, especially N and P nutrients and chlorophyll a, showed higher concentrations and larger variability in spring 2004. As a consequence the macroaggregates were produced in late spring 2004. The C and N isotope composition of POM was not directly linked to phytoplankton biomass dynamics. The δ¹³C_POC values covaried with temperature. In 2004, δ¹³C_POC variations followed the δ¹⁵N_PN values as well as the δ¹³C_DIC values which were probably more dependent on the photosynthetic use of ¹²C. Variations in δ¹⁵N_POM values were most probably the consequence of variations in N nutrient sources used in phytoplankton assimilation. The significant correlation between δ¹⁵N_PN values and nitrate concentrations in 2004 implies intense nitrate assimilation in the presence of higher nitrate concentration. This suggests nitrate as the key nutrient in the »new primary production«, later producing macroaggregates with a mean δ¹³C and δ¹⁵N values of − 19‰ and 5‰, respectively. A low fractionation factor ε, < 1‰, lower than that reported in other marine and lacustrine systems, was found probably to be a consequence of distinct phytoplankton species, i.e. several classes of autotrophic nanoflagellates, and specific growth conditions present in the Gulf of Trieste. The tentative use of C isotope composition of POM revealed a higher contribution of allochthonous organic matter in 2004 compared to 2003 due to higher riverine inflow.     

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.     

Effect of native and invasive cordgrass on Macoma petalum density, growth, and isotopic signatures

Ecosystem engineers can influence community and ecosystem dynamics by controlling resources, modifying the flow of energy or biomass, or changing physical characteristics of the habitat. Invasive hybrid cordgrass (Spartina alterniflora × Spartina foliosa) is an ecosystem engineer in salt marshes in San Francisco Bay, California, U.S.A. that raises intertidal elevations and may be either increasing C₄ plant carbon input into food webs or tying up carbon in a form that is not usable by consumers. A manipulative experiment compared abundance, growth, and stable isotope (δ¹³C and δ¹⁵N) composition of the clam Macoma petalum (=M. balthica) among native marsh, hybrid Spartina, and mudflats in central San Francisco Bay. We found higher densities (individuals m⁻²) of M. petalum on mudflats compared to either native or hybrid Spartina (p < 0.001). Macoma petalum shell growth was significantly greater in mudflats than in either vegetation type in 2002 (p = 0.005) but not 2003. Differences in shell growth between native and hybrid Spartina were not significant. Stable isotope results showed differences between habitats in δ¹³C but not δ¹⁵N. Carbon signatures of M. petalum placed in Spartina were much more depleted than the isotopic signature of Spartina. Neither native nor hybrid Spartina appears to be a significant carbon source for M. petalum in San Francisco Bay, and we found no evidence that hybrid Spartina contributes carbon to M. petalum beyond what is provided by S. foliosa, despite the hybrid's much greater biomass. Our results show that loss of mudflat habitat, rather than increased input of C₄ carbon, is the greatest effect of the invasion of hybrid Spartina on M. petalum.     

δC and δN variations in Weddell Sea particulate organic matter

The δ¹³C and δ¹⁵N of particulate organic matter (POM) sampled from the Weddell Sea in 1986 and 1988 ranged from −30.4 to − 16.7%o and from −5.4 to +41.3%o, respectively. These large variations in POM δ¹³C and δ¹⁵N may reflect spatial/temporal changes in the concentrations and isotope abundances of CO₂(aq.) and NH₄⁺, respectively. Elevated isotope values were found exclusively in POM in or closely associated with sea ice, which may be the source of the ¹³C- and ¹⁵N-enriched sediments observed in this region.     

Reproductive ecology of the dominant dinoflagellate, <Emphasis Type="Italic">Ceratium fusus</Emphasis>, in coastal area of Sagami Bay,Japan

The seasonal abundance of the dominant dinoflagellate, Ceratium fusus, was investigated from January 2000 to December 2003 in a coastal region of Sagami Bay, Japan. The growth of this species was also examined under laboratory conditions. In Sagami Bay, C. fusus increased significantly from April to September, and decreased from November to February, though it was found at all times through out the observation period. C. fusus increased markedly in September 2001 and August 2003 after heavy rainfalls that produced pycnoclines. Rapid growth was observed over a salinity range of 24 to 30, with the highest specific rate of 0.59 d⁻¹ measured under the following conditions: salinity 27, temperature 24°C, photon irradiance 600 μmol m⁻²s⁻¹. The growth rate of C. fusus increased with increasing irradiance from 58 to 216 μmol m⁻²s⁻¹, plateauing between 216 and 796 μmol m⁻²s⁻¹ under all temperature and salinity treatments (except at a temperature of 12°C). Both field and laboratory experiments indicated that C. fusus has the ability to grow under wide ranges of water temperatures (14–28°C), salinities (20–34), and photon irradiance (50–800 μmol m⁻²s⁻¹); it is also able to grow at low nutrient concentrations. This physiological flexibility ensures that populations persist when bloom conditions come to an end.     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

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

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

Sub-recent nitrogen-isotope trends in sediments from Skagerrak (North Sea) and Kattegat: Changes in N-budgets and N-sources?

We determined ¹⁵N/¹⁴N ratios of total nitrogen in surface sediments and dated sediment cores to reconstruct the history of N-loading of the North Sea. The isotopic N composition in modern surface sediments is equivalent to and reflects the isotopic mixture of oceanic nitrate on the one hand (δ¹⁵N = 5‰) and the imprint of river-borne nitrogen input into the SE North Sea (δ¹⁵N up to 12‰ in estuaries of the SE North Sea) on the other hand. We compare the results with δ¹⁵N records from pre-industrial sediment intervals in cores from the Skagerrak and Kattegat areas, which both constitute significant depositional centres for N in the North Sea and the Baltic Sea/North Sea transition. As expected, isotopically enriched anthropogenic nitrogen was found in the two records from the Kattegat area, which is close to eutrophication sources on land. Enrichment of δ¹⁵N in cores from the Skagerrak – the largest sediment sink for nitrogen in the entire North Sea – was not significant and values were similar to those found in sediment layers representing pre-industrial conditions. We interpret this isotopic uniformity as an indication that most riverine reactive nitrogen with its characteristic isotopic signature is removed by denitrification in shallow shallow-water sediments before reaching the main sedimentary basin of the North Sea.     

fCO2 variability at the CARIACO tropical coastal upwelling time series station

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

Seasonal Changes in Oceanic pCO2 in the Oyashio Region from Winter to Spring

We observed the partial pressure of oceanic CO₂, pCO₂ ^sea, and related surface properties in the westernmost region of the subarctic North Pacific, seasonally from 1998 to 2001. The pCO₂ ^sea in the Oyashio region showed a large decrease from winter to spring. In winter, pCO₂ ^sea was higher than 400 μatm in the Oyashio region and this region was a source of atmospheric CO₂. In spring, pCO₂ ^sea decreased to extremely low values, less than 200 μatm (minimum, 139 μatm in 2001), around the Oyashio region with low surface salinity and this region turned out to be a strong sink. The spatial variations of pCO₂ ^sea were especially large in spring in this region. The typical Oyashio water with minimal mixing with subtropical warm water was extracted based on the criterion of potential alkalinity. The contribution of main oceanic processes to the changes in pCO₂ ^sea from winter to spring was estimated from the changes in the concentrations of dissolved inorganic carbon and nutrients, total alkalinity, temperature and salinity observed in surface waters in respective years. These quantifications indicated that photosynthesis made the largest contribution to the observed pCO₂ ^sea decreases in all years and its magnitude was variable year by year. These year-to-year differences in spring biological contribution could be linked to those in the development of the density stratification due to the decrease in surface salinity. Thus, the changes in the surface physical structure could induce those in pCO₂ ^sea in the Oyashio region in spring. Furthermore, it is suggested that the direction and magnitude of the air-sea CO₂ flux during this season could be controlled significantly by the onset time of the spring bloom. This revised version was published online in July 2006 with corrections to the Cover Date.