Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

A preliminary study of carbon system in the East China Sea

In the central part of the East China Sea, the activity of CO₂ in the surface water and total carbonate, pH and alkalinity in the water column were determined in winter and autumn of 1993. The activity of CO₂ in the continental shelf water was about 50 ppm lower than that of surface air. This decrease corresponds to the absorption of about 40 gC/m²/yr of atmospheric CO₂ in the coastal zone or 1 GtC/yr in the global continental shelf, if this rate is applicable to entire coastal seas. The normalized total carbonate contents were higher in the water near the coast and near the bottom. This increase toward the bottom may be due to the organic matter deposited on the bottom. This conclusion is supported by the distribution of pH. The normalized alkalinity distribution also showed higher values in the near-coast water, but in the surface water, indicating the supply of bicarbonate from river water. The residence time of the East China Sea water, including the Yellow Sea water, has been calculated to be about 0.8 yr from the excess alkalinity and the alkalinity input. Using this residence time and the excess carbonate, we can estimate that the amount of dissolved carbonate transported from the coastal zone to the oceanic basin is about 70 gC/m²/yr or 2 GtC/yr/area-of-global-continental-shelf. This also means that the rivers transport carbon to the oceans at a rate of 30 gC/m²/yr of the coastal sea or 0.8 GtC/yr/ area-of-global shelf, the carbon consisting of dissolved inorganic carbonate and terrestrial organic carbon decomposed on the continental shelf.     

红海及亚丁湾间之海水交换

分析表观耗氧量、滴定碱度及总二氧化碳量等资料来研判红海及亚丁湾间之海水交换。结果显示,红海深层水的方解石及霰石饱和度均比亚丁湾和阿拉伯海深层水的饱和度高。红海全水柱之方解石和霰石都处於过饱和状态,亚丁湾和阿拉伯海中各深度之方解石亦呈过饱和状态,但霰石的饱和探度则大约在500m左右。分析深层水之生物体无机碳与有机碳的分解比值,可以发现此地区深层水中,大约有25％的总二氧化碳增加量是由无机碳酸钙溶解而来。     

海盐粒子沉积下碳钢的大气腐蚀初期行为

利用体视显微镜和电化学极化技术原位考察了碳钢上NaCl盐粒的吸潮及其液滴的扩展行为。实验结果表明,NaCl液滴的吸潮水解过程主要受环境相对湿度的影响。相对湿度越高,水解越容易。在极化状态下,NaCl液滴的扩展随极化电流的增加而线性加速。NaCl液滴的扩展与碳钢大气腐蚀的电化学过程相互影响。一方面,NaCl液滴扩展的动力来自于大气腐蚀过程所形成的腐蚀电流,另一方面,NaCl液滴的扩展加大了大气腐蚀过程的阴极面积。进而加速了碳钢的腐蚀过程。     

Roles of Biogeochemical Processes in the Oceanic Carbon Cycle Described with a Simple Coupled Physical-Biogeochemical Model

To evaluate the contribution of biogeochemical processes to the oceanic carbon cycle and to calculate the ratio of calcium carbonate to organic carbon downward export, we have incorporated biological and alkalinity pumps in the yoked high-latitude exchange/interior diffusion-advection (YOLDA) model. The biogeochemical processes are represented by four parameters. The values of the parameters are tuned so that the model can reproduce the observed phosphate and alkalinity distributions in each oceanic region. The sensitivity of the model to the biogeochemical parameters shows that biological production rates in the euphotic zone and decomposition depths of particulate matters significantly influence horizontal and vertical distributions of biogeochemical substances. The modeled vertical fluxes of particulate organic phosphorus and calcium carbonate are converted to vertical carbon fluxes by the biological pump and the alkalinity pump, respectively. The downward carbon flux from the surface layer to the deep layer in the entire region is estimated to be 3.36 PgC/yr, which consists of 2.93 PgC/yr from the biological pump and 0.43 PgC/yr from the alkalinity pump, which is consistent with previous studies. The modeled rain ratio is higher with depth and higher in the Pacific and Indian Oceans than in the Atlantic Ocean. The global rain ratio at the surface layer is calculated to be 0.14 to 0.15. This value lies between the lower and higher ends of the previous estimates, which range widely from 0.05 to 0.25. This study indicates that the rain ratio is unlikely to be higher than 0.15, at least in the surface waters.     

Deep ocean fluxes and their link to surface ocean processes and the biological pump

Intense studies of upper and deep ocean processes were carried out in the Northwestern Indian Ocean (Arabian Sea) within the framework of JGOFS and related projects in order to improve our understanding of the marine carbon cycle and the ocean’s role as a reservoir for atmospheric CO₂. The results show a pronounced monsoon-driven seasonality with enhanced organic carbon fluxes into the deep-sea during the SW Monsoon and during the early and late NE Monsoon north of 10°N. The productivity is mainly regulated by inputs of nutrients from subsurface waters into the euphotic zone via upwelling and mixed layer-deepening. Deep mixing introduces light limitation by carrying photoautotrophic organisms below the euphotic zone during the peak of the NE Monsoon. Nevertheless, deep mixing and strong upwelling during the SW Monsoon provide an ecological advantage for diatoms over other photoautotrophic organisms by increasing the silica concentrations in the euphotic zone. When silica concentrations fall below 2 μmol l⁻¹, diatoms lose their dominance in the plankton community. During diatom-dominated blooms, the biological pathway of uptake of CO₂ (the biological pump) appears to be more efficient than during blooms of other organisms, as indicated by organic carbon to carbonate carbon (rain) ratios. Due to the seasonal alternation of diatom and non-diatom dominated exports, spatial variations of the annual mean rain ratios are hardly discernible along the main JGOFS transect.Data-based estimates of the annual mean impact of the biological pump on the fCO₂ in the surface water suggest that the biological pump reduces the increase of fCO₂ in the surface water caused by intrusion of CO₂-enriched subsurface water by 50–70%. The remaining 30 to 50% are attributed to CO₂ emissions into the atmosphere. Rain ratios up to 60% higher in river-influenced areas off Pakistan and in the Bay of Bengal than in the open Arabian Sea imply that riverine silica inputs can further enhance the impact of the biological pump on the fCO₂ in the surface water by supporting diatom blooms. Consequently, it is assumed that reduced river discharges caused by the damming of major rivers increase CO₂ emission by lowering silica inputs to the Arabian Sea; this mechanism probably operates in other regions of the world ocean also.     

The dynamics of the carbon cycle in the surface water of the Norwegian Sea

Historical data of total dissolved inorganic carbon (C_T), together with nitrate and phosphate, have been used to model the evolution of these constituents over the year in the Atlantic water of the Norwegian Sea. Changes in nutrient concentration in the upper layer of the ocean are largely related to biological activity, but vertical mixing with the underlying water will also have an impact. A mixing factor is estimated and used to compute the entrainment of these constituents into the surface water from below. After taking the mixing contribution into account, the resulting nutrient concentration changes are attributed to biological production or decay. The results of the model show that the change in C_T by vertical mixing and by biological activity based on nutrient equivalents needs another sink to balance the carbon budget. It cannot be the atmosphere as the surface water is undersaturated with respect to carbon dioxide and is, thus, a source of C_T in this region. Inasmuch as the peak deficit of carbon is more than a month later than for the nutrients, the most plausible explanation is that other nitrogen and phosphate sources than the inorganic salts are used together with dissolved inorganic carbon during this period. As nitrate and phosphate show a similar trend, it is unlikely that the explanation is the use of ammonia or nitrogen fixation but rather dissolved organic nitrogen and phosphate, while dissolved organic carbon is accumulating in the water.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Seasonal DOC accumulation in the Black Sea: a regional explanation for a general mechanism

During three cruises in the Black Sea, organised in July 1995 and April–May 1997, biological and chemical parameters that can influence the carbon budget were measured in the water column on the NW shelf, particularly in the mixing zone with Danube River waters. We observed in early spring (end of April–May) conditions an important input of freshwater organisms that enhanced the microbial activity in the low salinity range. High bacterial activity regenerates nitrogen in the form of nitrates, but is also responsible for an important consumption of ammonium and phosphate, leading to a high N/P ratio and a strong deficit in phosphorus. The consequence is a limitation of phytoplankton development but also a production of carbohydrates that accumulate all along the salinity gradient. These mechanisms are responsible for a seasonal accumulation of dissolved organic carbon (DOC) that increases from 210 μM in winter to about 280 μM in summer. All this excess DOC disappears during winter, probably degraded by bacterial activity. The degradation of carbon-rich organic matter increases the phosphorus demand by bacteria bringing limitation to phytoplankton primary production.