Carbon dioxide and carbon monoxide photoproduction quantum yields in the Delaware Estuary

Photochemical mineralization of dissolved organic matter (DOM) plays an important role in the cycling of carbon in estuarine systems. A key to modeling this process is knowledge of apparent quantum yields (AQYs) for the photochemical products. Here we determined spectral AQYs for carbon dioxide (CO₂) and carbon monoxide (CO), the main products of DOM photomineralization, along the main axis of the Delaware Estuary. Apparent quantum yields for CO₂ photoproduction were determined shipboard using a multi-spectral irradiation system. Carbon monoxide AQYs were determined in stored samples by employing a narrow band spectral irradiation system. A single AQY spectrum described carbon dioxide photochemical production within the estuary whereas CO AQY spectra varied with salinity, suggesting different precursors and mechanisms for the production of these two species. CO₂ AQYs were used along with shipboard measurements of DOM absorbance and solar irradiance to calculate photoproduction rates. Calculated CO₂ photoproduction rates agreed with directly measured rates (2 to 4 μM CO₂ d^? 1) within experimental error, supporting the further development and use of AQYs to calculate regional-scale photochemical fluxes.     

Stocks and dynamics of dissolved and particulate organic matter in the southern Ross Sea, Antarctica

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 μM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 μM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO₃ concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DIC_equiv). The fraction of DIC_equiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DIC_equiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as “semi-labile” DOM. The “semi-labile” pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.     

Marine dissolved organic matter: can its C : N ratio explain carbon overconsumption?

Carbon overconsumption, i.e. the consumption of inorganic carbon relative to inorganic nitrogen in excess of the Redfield ratio at the sea surface, was examined in relation to the dynamics of dissolved organic carbon and nitrogen (DOC and DON) in the northeast Atlantic. We observed the presence of N-poor dissolved organic matter (DOM) in surface water during summer, requiring the consumption of inorganic carbon and nitrogen in a ratio exceeding the Redfield ratio. The C : N ratio of bulk DOM is not only different from the Redfield ratio but also variable, i.e. no fixed conversion factor of C and N exists where DOM is important in C and N transformations. The existence of N-poor DOM is recognized as a feature typical of oligotrophic systems. At the same time, the C : N ratios of particles conform to Redfield stoichiometry as does deep-ocean chemistry. The implications of this finding are discussed, the conclusion being that, while DOM buildup contributes to CO₂ drawdown seasonally, its impact on long-term carbon and nitrogen balance of the ocean is small.     

Biogeochemical ocean-atmosphere transfers in the Arabian Sea

Transfers of some important biogenic atmospheric constituents, carbon dioxide (CO₂), methane (CH₄), molecular nitrogen (N₂), nitrous oxide (N₂O), nitrate , ammonia (NH₃), methylamines (MAs) and dimethylsulphide (DMS), across the air–sea interface are investigated using published data generated mostly during the Arabian Sea Process Study (1992–1997) of the Joint Global Ocean Flux Study (JGOFS). The most important contribution of the region to biogeochemical fluxes is through the production of N₂ and N₂O facilitated by an acute, mid-water deficiency of dissolved oxygen (O₂); emissions of these gases to the atmosphere from the Arabian Sea are globally significant. For the other constituents, especially CO₂, even though the surface concentrations and atmospheric fluxes exhibit extremely large variations both in space and time, arising from the unique physical forcing and associated biogeochemical environment, the overall significance in terms of their global fluxes is not much because of the relatively small area of the Arabian Sea. Distribution and air–sea exchanges of some of these constituents are likely to be greatly influenced by alterations of the subsurface O₂ field forced by human-induced eutrophication and/or modifications to the regional hydrography.     

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.     

The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

The ‘International Intercomparison Exercise of fCO₂ Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO₂) systems, one discrete fCO₂ system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO₂ measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO₂, temperature measurements) and a common procedure for calculation of final fCO₂ were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO₂ in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO₂ measurements can be made in good agreement (±3 μatm) with underway fCO₂ data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO₂ system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO₂ results. Calculation of fCO₂ from high-quality total dissolved inorganic carbon (C_T) and total alkalinity (A_T) measurements does not yield results comparable in accuracy and precision to fCO₂ measurements.     

Seasonal variations in dissolved organic carbon concentrations and characteristics in a shallow coastal bay

Dissolved organic matter (DOM) composition and dynamics in temperate shallow coastal bays are not well described although these bays may be important as local sources of organic carbon to ocean waters and are often sites of economically-important fisheries and aquaculture. In this study surface water samples were collected on a monthly to bi-monthly basis over two years from a mid-Atlantic coastal bay (Chincoteague Bay, Virginia and Maryland, USA). Dissolved organic carbon (DOC) concentrations and light absorbance characteristics were measured on sterile-filtered water, and high-molecular weight (> 1 kDa) dissolved OM (DOM) was isolated to determine stable isotope composition and molecular-level characteristics. Our time series encompassed both a drought year (2002) and a year of above-average rainfall (2003). During the dry year, one of our sites developed a very intense bloom of the brown tide organism Aureococcus anophagefferens while during the wet year there were brown tide bloom events at both of our sampling sites. During early spring of the wet year, there were higher concentrations of > 1 kDa DOC; this fraction represented a larger proportion of overall DOC and appeared considerably more allochthonous. Based upon colored dissolved organic matter (CDOM) and high-molecular weight DOM analyses, the development of extensive phytoplankton blooms during our sampling period significantly altered the quality of the DOM. Throughout both years Chincoteague Bay had high DOC concentrations relative to values reported for the coastal ocean. This observation, in conjunction with the observed effects of phytoplankton blooms on DOM composition, indicates that Chincoteague Bay may be a significant local source of “recently-fixed” organic carbon to shelf waters. Estimating inputs of DOC from Chincoteague Bay to the Mid-Atlantic Bight suggests that shallow productive bays should be considered in studies of organic carbon on continental shelves.     

Coulometric total carbon dioxide analysis for marine studies: maximizing the performance of an automated gas extraction system and coulometric detector

A global survey of the distribution of dissolved CO₂ taking advantage of sampling opportunities provided by the World Ocean Circulation Experiment: World Hydrographic Program (WOCE-WHP) is being carried out through 1995. Goals include the measurement of oceanic inorganic carbon transport and the development of a data base from which future fossil-fuel CO₂ build-up can be monitored. The analytical method selected for total carbon dioxide (C_T) is gas extraction of acidified seawater with coulometric titration of the acid formed by the resultant carbon dioxide and monoethanolamine. To combine high accuracy and precision (± 1.5 μmol/kg for C_T ≥ 2000 μmol/kg) with a high rate of analysis, we have modified an automated single-parameter system. Following prototype development between 1987 and 1990, an instrument emerged with the acronym Somma standing for single-operator multiparameter metabolic analyzer. Improved functional and operating procedures have integrated electronic calibration, CO₂ gas calibration, and sample analysis with automated pressure, temperature, and conductivity (salinity) sensing into a single convenient transportable package.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

High-accuracy measurements of total dissolved inorganic carbon in the ocean: comparison of alternate detection methods

High-accuracy measurements of total dissolved inorganic carbon in the ocean are currently performed using an automated coulometric system based on that described by Johnson et al. (1987). These measurements require highly-trained technicians and the manipulation of expensive and hazardous chemicals. We tested an alternate detection method based on non-dispersive infra-red analysis. All of the dissolved carbonate species from a seawater sample were extracted as CO₂ gas by acidification and nitrogen stripping. The CO₂ gas was then quantitatively detected with either a coulometric system or an infra-red analyzer. The reproducibility of the two detection methods is similar. Although the infra-red system requires further testing, it holds promise as an alternative to coulometry. The detection of the CO₂ gas by infra-red analysis presents several advantages over coulometric detection: it simplifies and reduces the cost of the measurements, shortens the analysis time, reduces the sample size requirement by at least a factor of five, and allows us to consider complete automation of the system for underway surface seawater measurements.     

On the CO2O2 system in the Northeastern Pacific

The TCO₂, O₂, TA and δ¹³C data of the 1969 Geosecs Intercalibration Cruise was analyzed and found to be consistent with a vertical mixing model which assumes that each point along a vertical profile is a mixture of the upper and lower boundaries. Calculated regression coefficients are in agreement with the model of Redfield et al. (1963) and with the assumption that TA variation is due to carbonate reaction. Oxygen consumption and TCO₂ production decrease exponentially with depth and approximately 80% of ΔCO₂ can be accounted for, on average, by O₂ consumption. The remaining 20% are probably due to carbonate solution which seems to take place at depths below 2,500 m. The present study suggests that the isotopic composition (δ¹³C) of the carbon source, required to account for most of the oxygen consumed, may be heavier than the value of −23%. assigned to dissolved organic carbon and particulate organic carbon.     

Dissolved inorganic carbon dynamics in the waters surrounding forested mangroves of the Ca Mau Province (Vietnam)

Dissolved inorganic carbon (DIC) and ancillary data were obtained during the dry and rainy seasons in the waters surrounding two 10-year-old forested mangrove sites (Tam Giang and Kiên Vàng) located in the Ca Mau Province (South-West Vietnam). During both seasons, the spatial variations of partial pressure of CO₂ (pCO₂) were marked, with values ranging from 704 ppm to 11481 ppm during the dry season, and from 1209 ppm to 8136 ppm during the rainy season. During both seasons, DIC, pCO₂, total alkalinity (TAlk) and oxygen saturation levels (%O₂) were correlated with salinity in the mangrove creeks suggesting that a combination of lower water volume and longer residence time (leading to an increase in salinity due to evaporation) enhanced the enrichment in DIC, pCO₂ and TAlk, and an impoverishment in O₂. The low O₂ and high DIC and pCO₂ values suggest that heterotrophic processes in the water column and sediments controlled these variables. The latter processes were meaningful since the high DIC and TAlk values in the creek waters were related to some extent to the influx of pore waters, consistent with previous observations. This was confirmed by the stochiometric relationship between TAlk and DIC that shows that anaerobic processes control these variables, although this approach did not allow identifying unambiguously the dominant diagenetic carbon degradation pathway. During the rainy season, dilution led to significant decreases of salinity, TAlk and DIC in both mangrove creeks and adjacent main channels. In the Kiên Vàng mangrove creeks a distinct increase of pCO₂ and decrease of %O₂ were observed. The increase of TSM suggested enhanced inputs of organic matter probably from land surrounding the mangrove creeks, that could have led to higher benthic and water column heterotrophy. However, the flushing of water enriched in dissolved CO₂ originating from soil respiration and impoverished in O₂ could also have explained to some extent the patterns observed during the rainy season. Seasonal variations of pCO₂ were more pronounced in the Kiên Vàng mangrove creeks than in the Tam Giang mangrove creeks. The air–water CO₂ fluxes were 5 times higher during the rainy season than during the dry season in the Kiên Vàng mangrove creeks. In the Tam Giang mangrove creeks, the air–water CO₂ fluxes were similar during both seasons. The air–water CO₂ fluxes ranged from 27.1 mmol C m⁻² d⁻¹ to 141.5 mmol C m⁻² d⁻¹ during the dry season, and from 81.3 mmol m⁻² d⁻¹ to 154.7 mmol m⁻² d⁻¹ during the rainy season. These values are within the range of values previously reported in other mangrove creeks and confirm that the emission of CO₂ from waters surrounding mangrove forests are meaningful for the carbon budgets of mangrove forests.     

海水中溶解有机碳的测定方法

海水中溶解有机碳(DOC)的测定方法主要有过硫酸盐氧化法;紫外光氧化法和高温氧化法。近年来,随着仪器分析的进步,国外已出现能自动连续测定DOC的商售设备。 Menzel等发展的过硫酸钾氧化法,由于设备简单,容易实施,至今仍为很多人采用。     

Impacts of elevated CO2 on particulate and dissolved organic matter production: microcosm experiments using iron-deficient plankton communities in open subarctic waters

Response of phytoplankton to increasing CO₂ in seawater in terms of physiology and ecology is key to predicting changes in marine ecosystems. However, responses of natural plankton communities especially in the open ocean to higher CO₂ levels have not been fully examined. We conducted CO₂ manipulation experiments in the Bering Sea and the central subarctic Pacific, known as high nutrient and low chlorophyll regions, in summer 2007 to investigate the response of organic matter production in iron-deficient plankton communities to CO₂ increases. During the 14-day incubations of surface waters with natural plankton assemblages in microcosms under multiple pCO₂ levels, the dynamics of particulate organic carbon (POC) and nitrogen (PN), and dissolved organic carbon (DOC) and phosphorus (DOP) were examined with the plankton community compositions. In the Bering site, net production of POC, PN, and DOP relative to net chlorophyll-a production decreased with increasing pCO₂. While net produced POC:PN did not show any CO₂-related variations, net produced DOC:DOP increased with increasing pCO₂. On the other hand, no apparent trends for these parameters were observed in the Pacific site. The contrasting results observed were probably due to the different plankton community compositions between the two sites, with plankton biomass dominated by large-sized diatoms in the Bering Sea versus ultra-eukaryotes in the Pacific Ocean. We conclude that the quantity and quality of the production of particulate and dissolved organic matter may be altered under future elevated CO₂ environments in some iron-deficient ecosystems, while the impacts may be negligible in some systems.     

夏季黄海不同水团溶解有机物分布特征

依据2017年8—9月对黄海海域溶解有机物(DOM)的调查,探讨了夏季黄海海水中溶解有机碳(DOC)和有色溶解有机物(CDOM)的空间分布特征。在表层海水中,受陆源影响较大的近岸海域CDOM含量相对较高,北黄海冷水团区域由于水产养殖的饵料引起DOC浓度升高,且该部分DOC以无色为主。DOC浓度随深度逐渐降低,而CDOM逐渐升高,该特征在冷水团区域更为显著,因此DOC和CDOM在冷水团区域的表底差异远大于浅水区的非冷水团区域。陆源输入和初级生产是引起表层DOC升高的主要原因,而光漂白则引起CDOM降低,同时光漂白还导致表层水体中CDOM分子量和芳香性低于底层。底层溶解氧饱和度在冷水团为80%～93%,均表现为弱不饱和状态。层化不仅阻碍了O₂向底层水体输送,还抑制了DOC和CDOM的垂向混合,这是引起冷水团区域表底层DOC和CDOM差异较大的主要原因。     

Carbon dioxide stored and acidified low oxygen bottom waters in coastal seas,Japan

Recently carbon dioxide fluxes between sea water and air have been measured in many coastal seas to clarify whether the coastal seas are source or sink of CO₂. In this study behavior of CO₂ within the water column was studied in a semi-enclosed coastal sea: the Seto Inland Sea, Japan. It was found that seasonal formation of hypoxic water mass is highly related to CO₂ dynamics in coastal seas. Bacterial remineralization of organic matter consumes dissolved oxygen (DO) and releases dissolved CO₂ in the bottom water when summertime thermal stratification develops. The CO₂ accumulates within the low DO bottom water (hypoxic water) and causes increasing of carbonic acid content which results in low pH. Concentrations of dissolved CO₂ and pH are highly correlated with DO concentration. The summertime low DO and acidification (low pH) occur in the lower layer every year. The accumulated CO₂ during the summer season is dispersed to the atmosphere at the beginning of mixing season.     

Annual cycle of fCO2 under sea-ice and in open water in Prydz Bay, East Antarctica

The annual cycle of dissolved nutrients and the fugacity of CO₂ (fCO₂), calculated from the concentration of dissolved inorganic carbon (DIC) and pH, was studied over a 14-month long period (December 1993 to February 1995) at a site in Prydz Bay near Davis Station, Vestfold Hills, East Antarctica. Significant spring decreases in fCO₂ began under the sea-ice in mid-October, when both water column and sea-ice algal activity resulted in the removal of nutrients and DIC and increased pH. Minimum fCO₂ (<100 μatm) and lowest nutrient and DIC concentrations occurred in December and January. The low summer fCO₂ values were clearly the result of biological activity. The seasonal depletion of dissolved nitrate reached 85% in mid-summer when chlorophyll-a concentrations exceeded 15 mg m⁻³. Oceanic uptake of carbon dioxide from the atmosphere, calculated from the fugacity difference and daily wind speeds, averaged more than 30 mmol m⁻² day⁻¹ during the summer ice-free period. This exchange replaced approximately half of the DIC consumed by biological activity. Apparent nutrient utilisation ratios (C/N/P) were close to Redfield values. In autumn fCO₂ began to rise, continuing slowly well into winter, and reaching a maximum close to modern atmospheric values between July and September. This increase can be attributed to a combination of local remineralisation of organic carbon in the water column and the steady increase in the mixing depth of the water column. At first glance, this suggests that air–sea equilibration occurred in winter despite the sea-ice cover, perhaps by horizontal circulation from regions outside the pack ice, or through openings in the ice. However, the persistent 15 to 20% undersaturation of dissolved oxygen throughout the winter suggests an alternate explanation. The late winter fCO₂ level may represent a characteristic established by global circulation, so that as a result of increasing atmospheric CO₂ concentrations, these Antarctic waters are in transition from being a winter-time source of CO₂ to the atmosphere to becoming a sink. Our fCO₂ observations emphasize the need to address seasonal variations in assessing Antarctic contributions to the oceanic control of atmospheric CO₂.     

南海北部莺歌海岭头岬近岸烃类渗漏喷口分布及气体地球化学

Natural hydrocarbon seeps in a marine environment are one of the important contributors to greenhouse gases in the atmosphere,including methane,which is significant to the global carbon cycling and climate change.Four hydrocarbon seep areas,the Lingtou Promontory,the Yinggehai Rivulet mouth,the Yazhou Bay and the Nanshan Promontory,occurring in the Yinggehai Basin delineate a near-shore gas bubble zone.The gas composition and geochemistry of venting bubbles and the spatial distribution of hydrocarbon seeps are surveyed on the near-shore Lingtou Promontory.The gas composition of the venting bubbles is mainly composed of CO_2,CH_4,N_2 and O_2,with minor amounts of non-methane hydrocarbons.The difference in the bubbles' composition is a possible consequence of gas exchange during bubble ascent.The seepage gases from the seafloor are characterized by a high CO_2 content(67.35%) and relatively positive δ~(13)C_(V_PDB) values(-0.49×10~(-3)-0.86×10~(-3)),indicating that the CO_2 is of inorganic origin.The relatively low CH_4 content(23%) and their negative δ~(13)C_(V-PDB) values(-34.43×10~(-3)--37.53×10~(-3)) and high ratios of C_1 content to C_(1-5) one(0.98-0.99)as well point to thermogenic gases.The hydrocarbon seeps on the 3.5 Hz sub-bottom profile display a linear arrangement and are sub-parallel to the No.1 fault,suggesting that the hydrocarbon seeps may be associated with fracture activity or weak zones and that the seepage gases migrate laterally from the central depression of the Yinggehai Basin.     

Variation of dissolved organic matter and fluorescence characteristics before,during and after phytoplankton bloom

The variation of dissolved organic matter (DOM) and fluorescence characteristics during the phytoplankton bloom were investigated in Yashima Bay, at the eastern part of the Seto Inland Sea, Japan. We found significant accumulations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), chromophoric dissolved organic matter (CDOM) fluorescence, and UV₂₆₀ during the phytoplankton bloom period in 2005, although lower accumulations of DOC and DON and only increases of CDOM fluorescence were observed during the bloom period in 2006. Little or no correlation between DOM and phytoplankton abundance might be due to the composition of DOM, which is a complex mixture of organic materials. The 3D-EEM results revealed that the DOM produced around the phytoplankton bloom period contained tyrosine, tryptophan, and humic-like substances. Our results showed that the occurrence of phytoplankton bloom contributed to the production of DOM in coastal water but the DOM accumulation depended on the type of phytoplankton bloom, the phytoplankton species in particular. From our results, we concluded that phytoplankton have a great role in the dynamics of DOM as a producer in a coastal environment.     

Time-series of surface water CO2 and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): Seasonality of uptake and release

High resolution measurements of carbon dioxide and oxygen were made in surface waters of the central Arkona Sea (Baltic Sea) from May 2003 to September 2004. Sensors for CO₂ partial pressure (pCO₂^w) and oxygen (O₂) concentration were mounted in 7 m depth on a moored platform which is used for hydrographic and meteorological monitoring. The pCO₂^w data were obtained in half hour intervals and O₂ was measured each hour as an average of a 10 min measurement. To check the performance of the sensors, pCO₂^w and O₂ were determined by shipboard measurements on a research vessel which visited the site in 1–2 month intervals. In addition, pCO₂^w was measured on a “volunteer observing ship” (VOS) passing the platform each second day at a distance of about 25 km. Minima of 220 to 250 μatm of pCO₂^w were observed at the time of the spring bloom and a cyanobacteria bloom in mid-summer. During winter the pCO₂^w was mostly close to equilibrium with the atmosphere but maxima of 430 to 530 μatm were also observed. The seasonality of oxygen and pCO₂^w showed an opposing pattern. From a multiple regression analysis, we concluded that two processes primarily controlled pCO₂^w during our study: biological turnover and mixing. A parameterization, based on apparent oxygen utilisation (AOU) and salinity (S) only (pCO₂^w = 1.23 AOU + 43 S), reproduced the seasonality of pCO₂^w in surface water reasonably well. Based on our pCO₂, salinity, and temperature data set, we attempted to separate processes changing total inorganic carbon concentrations (C_T) by using an alkalinity–salinity relation for the area. The contribution of CO₂ gas exchange and mixing were calculated and from this the biological turnover was deduced to reveal the calculated C_T changes.The net annual uptake of CO₂ in the central Arkona Sea was estimated to be about 1.5 Tg (1.5·10¹² g) which was approximately balanced by a net oxygen release considering the uncertainties of the flux calculations. Near-coast CO₂ emission due to episodic upwelling partly compensated the uptake of the central part of the Arkona Sea reducing the overall magnitude of the CO₂ uptake.