Calcium-alkalinity-nitrate relationship in the north pacific and the Japan Sea

When biogenic particles of calcium carbonate and organic matter are formed or decomposed in sea water, calcium concentration, alkalinity and nitrate concentration are changed according to the following equation: ΔCa=0.5 ΔTA+0.63 ΔNO ₃, where ΔCa, ΔTA and ΔNO ₃ are the differences in calcium, alkalinity and nitrate concentration, respectively, between two waters. This relationship was pointed out in a previous paper of ours, and it holds well for data obtained from the North Pacific and the Japan Sea. Furthermore, in sea water containing little or no nutrients, the variations in calcium concentration and alkalinity are consistent with the variations expected from the formation and dissolution of calcium carbonate alone.     

Influence of variable rates of neritic carbonate deposition on atmospheric carbon dioxide and pelagic sediments

Short-term imbalances in the global cycle of shallow water calcium carbonate deposition and dissolution may be responsible for much of the observed Pleistocene change in atmospheric carbon dioxide content. However, any proposed changes in the alkalinity balance of the ocean must be reconciled with the sedimentary record of deep-sea carbonates. The possible magnitude of the effect of shallow water carbonate deposition on the dissolution of pelagic carbonate can be tested using numerical simulations of the global carbon cycle. Boundary conditions can be defined by using extant shallow water carbonate accumulation data and pelagic carbonate deposition/dissolution data. On timescales of thousands of years carbonate deposition versus dissolution is rarely out of equilibrium by more than 1.5 x 10(13) mole yr-1. Results indicate that the carbonate chemistry of the ocean is rarely at equilibrium on timescales less than 10 ka. This disequilibrium is probably due to sea level-induced changes in shallow water calcium carbonate deposition/dissolution, an interpretation that does not conflict with pelagic sedimentary data from the central Pacific.     

Errors in the retrieval of oceanic concentrations of optically active materials from multispectral sensor signals by observations through atmospheric layer

This paper presents an algorithm for retrieving the oceanic concentrations of optically active materials (OAMs)—phytoplankton, particulate matter, and dissolved organics—from signals of a multispectral sensor placed at an arbitrary height above the sea surface. The algorithm takes into account sensor noises (both photon (shot) and dark current). The joint distribution of the upwelling radiance and OAM spectra required for the algorithm is constructed using optical models of water and the oceanic atmosphere. A method based on correlations between inherent optical properties is proposed to improve the retrieval accuracy. The calculations showed that this method significantly increases the accuracy of OAM retrieval.     

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.     

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.     

Geochemical study on the formation of carbonate sediment

It is indeed my great honor to receive the Oceanographical Society of Japan Prize (1986) for my geochemical study on the formation of carbonate sediment. The present article reviews my work on crystal form and minor element distribution in marine biogenic carbonates, which is an important part of my study on the above title. The contents of this article are: (1) outline of my research work, (2) aim of geochemical study on carbonate sediment, (3) basic knowledge for crystal form and minor element distribution in carbonates, (4) influence of chemical constituents dissolved in a parent solution on the polymorphic crystallization of calcium carbonate, (5) crystal form and type of marine biogenic carbonates, (6) synthesis of magnegian calcite in aqueous solution, (7) distribution of minor elements between solution and calcium carbonate precipitate, (8) amount of biogenic carbonate deposition annually in the ocean and (9) role of biogenic carbonate accumulating on the sea floor in the geochemical balance of chemical elements.     

Sedimentary records of multidecadal-scale variability of diatom productivity in the Bungo Channel, Japan, associated with the Pacific Decadal Oscillation

In order to examine the responses of primary productivity in the southern coastal sea of Japan to the Pacific Decadal Oscillation (PDO) in the 20th century, sedimentary records of diatom productivity (diatom valve fluxes) were reconstructed using core samples from the Bungo Channel (BC) in southwest Japan. The record of the Thalassionema spp. flux—the best index of fall primary productivity in the BC—indicated a multidecadal-scale duration with a low flux (1943–1982) and those with a high flux (1913–1943 and 1982–2001); apparent shifts were recognized in 1943 and 1982. The shift in 1982 was also recognized in the flux records of other early summer to fall predominant genera in the BC and, previously, in the biogenic silica records from a broad region of the southeast BC. This indicates that in our records, this shift reflects a general trend in the primary production in the southeast BC. A comparison among the Thalassionema spp. flux records, meteorological data from an observatory adjacent to the core site, and the PDO index showed that the flux records were more similar to the PDO index than the other meteorological records, which suggests that the multidecadal-scale variability of the BC primary productivity may be associated with some marine-derived forcing. The bottom intrusions of nutrient-rich water that upwelled from the shelf slope into the BC, the axis movement or the transport of the Kuroshio Current off the BC, and a basin-scale wind stress in the North Pacific might play an important role in this forcing and mediate between the BC primary productivity and the PDO.     

Intraannual and long-term variations of the carbonate system of the aerobic zone in the black sea

We provide an expert quality assessment of the data for 1932–1993 and used these data to perform the numerical analysis of the carbonate system of the aerobic zone in the Black Sea. The intraannual and long-term variations of the carbonate system are studied in the abyssal part of the sea for 1960–1993. We propose explanations of the intraannual variations of the analyzed system for various layers of the aerobic zone and reveal long-term variations of the pH values, total alkalinity, and the ratios of the components of the carbonate system. We discover and explain the observed increase in the concentrations of TCO₂ and CO₂ and the partial pressure of carbon dioxide pCO₂, as well as a decrease in pH values and the concentration of CO₃²⁻ in waters of the aerobic zone of the Black Sea.     

Distribution of alkalinity and dissolved calcium in the Sea of Okhotsk

During the summer seasons of 2002 and 2004, the total alkalinity (TA) and dissolved calcium (Ca) were studied at 41 stations in different areas of the Sea of Okhotsk: the Kuril depression, Deryugin Basin, the slopes of the Kamchatka Peninsula and Sakhalin Island, and in Sakhalin Bay. It was shown that the distributions of the TA and Ca in the water mass of deep sea areas are determined by the processes of CaCO₃ formation and dissolution according to the relation Δ Ca = 0.5 Δ TA (1). The variations of the TA and Ca values observed in the upper 10-m layer and in the near-bottom layers of local depressions in the Deryugin Basin do not satisfy relationship (1). Probable reasons for this discrepancy are considered: organic matter mineralization, mixing of water masses with different preform TA and Ca values, sea ice melting, runoff from land, and sea bottom effects. It is shown that the enrichment in the alkalinity and calcium is caused by the Amur River runoff in the desalinated sea surface layer and by the high geochemical activity in the Deryugin Basin in the near-bottom 200-m layer of local depressions.     

Rare earth element geochemistry in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reduction as dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE (∑REE) concentrations is evident immediately below the sediment–water interface, which can be related to early diagenetic release of REEs into pore water resulting from the re-mineralization of particulate organic matter. The highest pore water ∑REE concentrations were measured close to the sediment–water interface at ~2 cm depth. Distinct shale-normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shale-normalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in ∑REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.     

海洋二号微波散射计极地海冰识别算法研究

An Antarctic sea ice identification algorithm on the HY-2A scatterometer(HSCAT) employs backscattering coefficient(σ0) and active polarization ratio(APR) for a preliminary sea ice identification.Then standard deviation(STD) filtering and space filtering are carried out.Finally,it is used to identify sea ice.A process uses a σ0,STD threshold and an APR as sea ice indicators.The sea ice identification results are verified using the sea ice distribution data of the ASMR2 released by the National Snow and Ice Data Center as a reference.The results show very good consistence of sea ice development trends,seasonal changes,area distribution,and sea ice edge distribution of the sea ice identification results obtained by this algorithm relative to the ASMR2 sea ice results.The accuracy of a sea ice coverage is 90.8% versus the ASMR2 sea ice results.This indicates that this algorithm is reliable.     

Significance of pteropods in deciphering the late Quaternary sea-level history along the southwestern Indian shelf

The paper evaluates the usefulness of pteropods in palaeobathymetric synthesis along the southwestern continental shelf of India. Core samples collected from the shelf off north Kerala (SW coast of India) were studied for faunal assemblages (pteropods and foraminifers), calcium carbonate contents and lithological characteristics. A fundamental precept for considering any organism as a bathometer is that it should be highly sensitive to changing water depths. To ascertain this, the bathymetric distribution patterns of modern pteropods as well as planktonic and benthic foraminifers were recorded in core-top samples. The results reveal that certain pteropod species (Limacina inflata, Creseis acicula, Creseis virgula, and Creseis chierchiae) are highly depth sensitive. The response of these species to depth changes was assessed in terms of the L. inflata and Creseis spp. abundance ratio. A model for the relationship between water depths and the L. inflata/Creseis spp. ratio is proposed for the southwestern shelf of India. Variations of benthic/planktonic foraminifers (BF/PF) and pteropods/planktonic foraminifers (Pt/PF) in the modern sediments were also found to be depth controlled. Two sediment cores, representing the last 36,000 and 23,000 years, were collected to investigate past sea-level changes. These cores comprised two distinct lithological units, the upper unit corresponding to the Holocene, and the lower unit to the last glacial period. The L. inflata/Creseis spp. model was successfully applied to the fossil record for reconstructing the palaeobathymetry of the shelf study locations. Down-core variations in the BF/PF and Pt/PF ratios support these inferred sea-level changes. Major periods of sea-level oscillations were also found to have a strong influence on the calcium carbonate distribution. For both core sites, the palaeobathymetric curves reflect consistency in terms of changing sea level. The results suggest that the sea level stood around 100 m below the present mean sea level during the last glacial maximum. A rapid rise in sea level was documented between 15 and 10 ka B.P. The sea-level rise has been slower since 7 ka B.P.     

An estimate of the vertical diffusivity of the deep water

A simple advection-diffusion model is applied to the deep water of the North Pacific Ocean. The physical mixing parameter, i.e., the ratio of vertical advection velocity (W) to vertical eddy diffusivity (D), is obtained from the vertical distribution of a conservative property such as salinity. The rate of decomposition of organic matter is estimated from the oxygen consumption rate which is obtained from dissolved oxygen content. The calcium carbonate flux in the deep water is obtained from alkalinity. Using these values and the vertical distribution of a radioisotope,¹⁴C or²²⁶Ra, the vertical eddy diffusivity and the upwelling velocity are found to be 1.2 cm²/sec and 1.4 ×10^–5 cm/sec, respectively, at the Geosecs 1969 station. The oxygen consumption rate at 3 km depth of the station is found to be 1.4×10^–3ml/l/yr.     

热带东印度洋SST对气候变暖和变冷的响应

The response of the eastern tropical Indian Ocean(ETIO) to heat fluxes of equal amplitude but opposite sign is investigated using the Community Earth System Model(CESM). A significant positive asymmetry in sea surface temperature(SST) is found over the ETIO—the warming responses to the positive forcing exceeds the cooling to the negative forcing. A mixed layer heat budget analysis is carried out to identify the mechanisms responsible for the SST asymmetry. Results show that it is mainly ascribed to the ocean dynamical processes, including vertical advections and diffusion. The net surface heat flux, on the contrary, works to reduce the asymmetry through its shortwave radiation and latent heat flux components. The former is due to the nonlinear relationship between SST and cloud, while the latter is resulted mainly from Newtonian damping and air-sea stability effects. Changes in the SST skewness are also evaluated, with more enhanced negative SST skewness over the ETIO found for the cooling than heating scenarios due to the asymmetric thermocline-SST feedback.     

Occurrence of an exceptional carbonate dissolution episode during early glacial isotope stage 6 in the Southeastern Atlantic

Concentration and mass accumulation rate profiles from Southeastern Atlantic sediment cores located off Namibia show that an exceptional episode in benthic carbonate dissolution occurred during early glacial isotope stage 6 (substages 6.6 and 6.5) between about 186 000 and 170 000 yr BP. Although this episode is restricted to or is more pronounced in this region than in other areas of the Atlantic Ocean, its exceptional character with respect to older and younger climatic episodes at the same site cannot be fully explained by local factors alone, but requires a combination of local and global influences. The onset of the carbonate dissolution episode is related to a more efficient transfer of organic matter from surface eutrophic areas to the lower and is due to low sea level, while its termination relates to a change in either global ocean alkalinity or bottom water circulation. An evaluation of the magnitude of this local carbonate dissolution episode suggests that its contribution to a global alkalinity change may have been significant. Carbonate dissolution was probably amplified by stronger upwelling activity of the Benguela System linked to an exceptional northern excursion of the boreal summer ITCZ during early glacial isotope stage 6. This low latitude global linkage may explain how this carbonate dissolution event as well as other ‘anomalies’ observed for early stage 6, like an important Dole effect minimum or a ‘cold’ Mediterranean sapropel, are related.     

Influence of export rain ratio changes on atmospheric CO<Subscript>2</Subscript> and sedimentary calcite preservation

The responses of atmospheric pCO₂ and sediment calcite content to changes in the export rain ratio of calcium carbonate to organic carbon are examined using a diffusion-advection ocean biogeochemical model coupled to a one-dimensional sediment geochemistry model. Our model shows that a 25% reduction in rain ratio decreases atmospheric pCO₂ by 59 ppm. This is caused by alkalinity redistribution by a weakened carbonate pump and an alkalinity increase in the whole ocean via carbonate compensation with decreasing calcite burial. The steady state responses of sedimentary calcite content and calcite preservation efficiency are rather insensitive to the deepening of the saturation horizon of 1.9 km. This insensitivity is a result of the reduced deposition flux that decreases calcite burial, counteracting the saturation horizon deepening that increases calcite burial. However, in the first 10,000 years the effect of reduced calcite deposition on the burial change is more prominent; while after 10,000 years, the effect of saturation horizon deepening is more dominant. The lowering of sediment calcite content for the first 10,000 years is effectively decoupled from the 1.9 km downward shift of the saturation horizon. Our results are in part a consequence of the more dominant role that respiration CO₂ plays in sediment calcite dissolution over bottom water chemistry in our control run and support the decoupling of calcite lysocline depth and saturation horizon shifts, as suggested originally by Archer and Maier-Reimer (1994) and Archer et al. (2000).     

Imbalance in the carbonate budget of surficial sediments in the North Atlantic Ocean: variations over the last millenium?

Fluxes contributing to the particulate carbonate system in deep-sea sediments were investigated at the BENGAL site in the Porcupine Abyssal Plain (Northeast Atlantic). Deposition fluxes were estimated using sediment traps at a nominal depth of 3000 m and amounted to 0.37±0.1 mmol C m⁻² d⁻¹. Dissolution of carbonate was determined using flux of total alkalinity from in situ benthic chambers, is 0.4±0.1 mmol C m⁻² d⁻¹. Burial of carbonate was calculated from data on the carbonate content of the sediment and sedimentation rates from a model age based on ¹⁴C dating on foraminifera (0.66±0.1 mmol C m⁻² d⁻¹). Burial plus dissolution was three times larger than particle deposition flux which indicates that steady-state is not achieved in these sediments. Mass balances for other components (BSi, ²¹⁰Pb), and calculations of the focusing factor using ²³⁰Th, show that lateral inputs play only a minor role in this imbalance. Decadal variations of annual particle fluxes are also within the uncertainty of our average. Long-term change in dissolution may contribute to the imbalance, but can not be the main reason because burial alone is greater than the input flux. The observed imbalance is thus the consequence of a large change of carbonate input flux which has occured in the recent past. A box model is used to check the response time of the solid carbonate system in these sediments and the time to reach a new steady-state is in the order of 3 kyr. Thus it is likely that the system has been perturbed recently and that large dissolution and burial rates reflect the previously larger particulate carbonate deposition rates. We estimate that particulate carbonate fluxes have certainly decreased by a factor of at least 3 and that this change has occurred during the last few centuries.     

热带印度洋降水、蒸发的时空特征及其对海表盐度的影响

本文利用降水、蒸发等资料分析热带印度洋年降水量、蒸发量、净淡水通量的分布特征,并选取4个典型海域来分析降水量、蒸发量、净淡水通量的季节变化和年际变化。结果表明:东印度洋的苏门答腊岛西部海域年降水量最大,季节变化较小,属全年降雨型;孟加拉湾的东北部和安达曼海的北部海域年降水量较大,其年际变化以4.2 mm/a的速率增长,强降水出现在5-9月;阿拉伯海的西部海域年降水量较小;南印度洋东部（20°~30°S,80°~110°E）海域年降水量较小,年蒸发量较大,年蒸发量在2000年之前以5.1 mm/a的速率增长,之后以4.5 mm/a的速率减小。本文还采用Argo盐度等资料探讨降水、蒸发对海表盐度的影响,研究结果表明:降水量远大于蒸发量的海域,海表盐度较低;降水量远小于蒸发量的海域,海表盐度较高。表层水平环流是导致高净淡水通量中心与低盐中心并不重合的主要原因,也是导致强蒸发中心与高盐中心并不重合的主要原因。选取的4个典型海域海表盐度的季节变化与净淡水通量关系不大,而是与表层水平环流有关。孟加拉湾强降水对表层盐度的影响显著,强降水发生后表层盐度降低0.2~0.8,其影响深度为30~50 m。     

北部湾东北部春、夏季表层海水CO2分压的24 h变化及其调控机制研究

周日观测对掌握近海碳酸盐体系变化和海-气CO₂交换过程是必要的,有助于降低碳源汇评估的不确定性。针对北部湾东北部的英罗湾-安铺港海域,于2018年4月和8月利用24 h定点逐时采样观测了该区域表层海水碳酸盐体系及相关要素,分析了春、夏季的表层海水CO₂分压(p CO₂)24 h逐时变化规律及其调控因子。观测结果表明,春、夏季p CO₂变化范围分别为530～628μatm和427～748μatm,平均海-气CO2通量分别为(1.7±0.8)mmol/(m²·d)和(1.2±0.8)mmol/(m²·d),均表现为大气CO₂的弱源。其中春季p CO₂ 24 h逐时变化受温度的影响相比夏季更显著,而夏季p CO₂对潮汐作用以及区域内沿岸河流、地下水等淡水汇入引起的生物生产和呼吸代谢过程增强的响应更明显。海水升温主导了春季区域表层高p CO₂的形成,夏季咸淡水的物理混合过程中增...     

Alkalinity of sea ice in the high-latitudinal arctic according to the surveys performed at north pole drifting station 34 and characterization of the role of the arctic ice in the CO<Subscript>2</Subscript> exchange

The variability of the total alkalinity in the sea ice of the high-latitudinal Arctic from November 2005 to May 2006 is considered. For the bulk of the one- and two-year sea ice, the alkalinity dependence on the salinity is described as TA = k × Sal, where k is the salinity: alkalinity ratio in the under-ice water. The given relationship is valid within a wide salinity range from 0.1 psu in the desalinated fraction of two-year ice to 36 psu in the snow on the young ice surface. Geochemically significant deviations from the relationship noted were observed exclusively in the snow and the upper layer of one-year ice. In the upper layer of one-year ice, an alkalinity deficiency is observed (ΔTA ～ ?0.07 mequiv/kg, or ?15%). In the snow on the surface of the one-year ice, an alkalinity excess is formed under the desalination (ΔTA is as high as 1.3 mequiv/kg, 380%). The deviations registered are caused by the possibility of carbonate precipitation in the form of CaCO₃ · 6H₂O under the seawater freezing. It is shown that the ice formation and the following melting might cause a loss of the atmospheric CO₂ of up to 3 × 10¹² g C/year.