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.     

Helium Isotopes in Pacific Waters from Adjacent Region of Honshu, Japan

We have measured helium isotopic ratios of thirty-seven Pacific water samples from various depths collected in adjacent regions of Honshu, Japan. The ³He/⁴He ratios vary significantly from 0.989 R _atm to 1.208 R _atm where R _atm is the atmospheric ratio of 1.39 × 10⁻⁶. The mid-depth (750–1500 m) profile of ³He/⁴He ratios at ST-1 located Northwestern Pacific Ocean east of Japan (Off Joban; 37°00′ N, 142°40′ E) is significantly different from that at ST-2 of the Northern Philippine Sea south of Japan (Nankai Trough; 33°07′ N, 139°59′ E), suggesting that these waters were separated by a topographic barrier, the Izu-Ogasawara Ridge. Taking ³He/⁴He data of the Geosecs expeditions in the western North Pacific, an extensive plume of 15% excess ³He relative to the air may be traced at ST-1 over 12,000 kilometers to the northwest of the East Pacific Rise where the mantle helium may originate. The 20% excess found at ST-2 may be attributable to the additional source of the subduction-type mantle helium in the Okinawa Trough. A 15% excess of ³He has also been discovered at a depth of about 1000∼1500 m at ST-3 adjacent to Miyakejima Island (33°57′ N, 139°22′ E) and ST-4 of Sagami Bay (35°00′ N, 139°22′ E). It is confirmed that mid-depth all over the western North Pacific water is affected by the mantle helium with a high ³He/⁴He ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dissolved inorganic carbon (DIC) and its carbon isotopic composition in sediment pore waters from the Shenhu area,northern South China Sea

The Shenhu area is one of the most favorable places for the occurrence of gas hydrates in the northern continental slope of the South China Sea. Pore water samples were collected in two piston cores (SH-A and SH-B) from this area, and the concentrations of sulfate and dissolved inorganic carbon (DIC) and its carbon isotopic composition were measured. The data revealed large DIC variations and very negative δ ¹³C-DIC values. Two reaction zones, 0–3 mbsf and below 3 mbsf, are identified in the sediment system. At site SH-A, the upper zone (0–3 mbsf) shows relatively constant sulfate and DIC concentrations and δ ¹³C-DIC values, possibly due to bioturbation and fluid advection. The lower zone (below 3 mbsf) displays good linear gradients for sulfate and DIC concentrations, and δ ¹³C-DIC values. At site SH-B, both zones show linear gradients, but the decreasing gradients for δ ¹³C-DIC and SO₄ ²⁻ in the lower zone below 3 mbsf are greater than those from the upper zone, 0–3 mbsf. The calculated sulfate-methane interface (SMI) depths of the two cores are 10.0 m and 11.1 m, respectively. The depth profiles of both DIC and δ ¹³C-DIC showed similar characteristics as those in other gas hydrate locations in the world oceans, such as the Blake Ridge. Overall, our results indicate an anaerobic methane oxidation (AMO) process in the sediments with large methane flux from depth in the studied area, which might be linked to the formation of gas hydrates in this area.     

Nitrogen and oxygen isotopic composition of N2O from suboxic waters of the eastern tropical North Pacific and the Arabian Sea—measurement by continuous-flow isotope-ratio monitoring

Nitrous oxide (N₂O) is a trace gas that is increasing in the atmosphere. It contributes to the greenhouse effect and influences the global ozone distribution. Recent reports suggest that regions such as the Arabian Sea may be significant sources of atmospheric N₂O.In the ocean, N₂O is formed as a by-product of nitrification and as an intermediary of denitrification. In the latter process, N₂O can be further reduced to N₂. These processes, which operate on different source pools and have different magnitudes of isotopic fractionation, make separate contributions to the ¹⁵N and¹⁸O isotopic composition of N₂O. In the case of nitrification in oxic waters, the isotopic composition of N₂O appears to depend mainly on the ¹⁵N/¹⁴N ratio of NH⁺₄ and the ¹⁸O/¹⁶O ratio of O₂ and H₂O. In suboxic waters, denitrification causes progressive ¹⁵N and ¹⁸O enrichment of N₂O as a function of degree of depletion of nitrate and dissolved oxygen. Thus the isotopic signature of N₂O should be a useful tool for studying the sources and sinks for N₂O in the ocean and its impact on the atmosphere.We have made observations of N₂O concentrations and of the dual stable isotopic composition of N₂O in the eastern tropical North Pacific (ETNP) and the Arabian Sea. The stable isotopic composition of N₂O was determined by a new method that required only 80–100 nmol of N₂O per sample analysis. Our observations include determinations across the oxic/suboxic boundaries that occur in the water columns of the ETNP and Arabian Sea. In these suboxic waters, the values of δ¹⁵N and δ¹⁸O increased linearly with one another and with decreasing N₂O concentrations, presumably reflecting the effects of denitrification. Our results suggest that the ocean could be an important source of isotopically enriched N₂O to the atmosphere.     

<Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium and particulate organic carbon export in the northern South China Sea

We utilized ²³⁴Th, a naturally occurring radionuclide, to quantify the particulate organic carbon (POC) export rates in the northern South China Sea (SCS) based on data collected in July 2000 (summer), May 2001 (spring) and November 2002 (autumn). Th-234 deficit was enhanced with depth in the euphotic zone, reaching a subsurface maximum at the Chl-a maximum in most cases, as commonly observed in many oceanic regimes. Th-234 was in general in equilibrium with ²³⁸U at a depth of ∼100 m, the bottom of the euphotic zone. In this study the ²³⁴Th deficit appeared to be less significant in November than in July and May. A surface excess of ²³⁴Th relative to ²³⁸U was found in the summer over the shelf of the northern SCS, most likely due to the accumulation of suspended particles entrapped by a salinity front. Comparison of the ²³⁴Th fluxes from the upper 10 m water column between 2-D and traditional 1-D models revealed agreement within the errors of estimation, suggesting the applicability of the 1-D model to this particular shelf region. 1-D model-based ²³⁴Th fluxes were converted to POC export rates using the ratios of bottle POC to ²³⁴Th. The values ranged from 5.3 to 26.6 mmol C m⁻²d⁻¹ and were slightly higher than those in the southern SCS and other oligotrophic areas. POC export overall showed larger values in spring and summer than in autumn, the seasonality of which was, however, not significant. The highest POC export rate (26.6 mmol C m⁻²d⁻¹) appeared at the shelf break in spring (May), when Chl-a increased and the community structure changed from pico-phytoplankton (<2 μm) dominated to nano-phytoplankton (2–20 μm) and micro-phytoplankton (20–200 μm) dominated.     

氧掺杂碳气体扩散电极用于电催化产活性氧抗菌防污研究

过氧化氢(H₂O₂)等活性氧(ROS)物质因具有绿色高效的特点,在废水处理、杀菌消毒等领域受到研究者广泛关注。利用电催化生成H₂O₂是一种实时提供活性氧物质的有用方法。然而,目前报道的大多数高性能催化材料都是粉体形式,不便于在实际场景中的应用。因此,制备可直接应用的电极材料显得尤为重要。本研究利用喷涂-热解的制备方法,制备了高活性氧催化活性的氧化炭黑(O−CB)/多孔碳毡电极,通过聚四氟乙烯(PTFE)的修饰优化电极表面的氧气传质,成功制备氧掺杂碳气体扩散电极。研究结果表明,O−CB/PTFE-5 wt%电极具有最高的催化性能,其合成H₂O₂的速率达27.19 mg·L^-1(mg catalyst)^-1·cm^-1·h^-1。海洋典型污损微生物假单胞菌(Pseudomonas sp.)的抗菌实验表明,该电极电催化作用60 min产生的活性氧对Pseudomonas sp.的杀菌率可达到97.69%,作用120 min的杀菌率可达到99.99%。     

Circulation of Intermediate and Deep Waters in the Philippine Sea

The circulation of intermediate and deep waters in the Philippine Sea west of the Izu-Ogasawara-Mariana-Yap Ridge is estimated with use of an inverse model applied to the World Ocean Circulation Experiment (WOCE) Hydrographic Program data set. Above 1500 m depth, the subtropical gyre is dominant, but the circulation is split in small cells below the thermocline, causing multiple zonal inflows of intermediate waters toward the western boundary. The inflows along 20°N and 26°N carry the North Pacific Intermediate Water (NPIW) of 11 × 10⁹ kg s⁻¹ in total, at the density range of 26.5σ_θ–36.7σ₂ (approximately 500–1500 m depths), 8 × 10⁹ kg s⁻¹ of the NPIW circulate within the subtropical gyre, whereas the rest is conveyed to the tropics and the South China Sea. The inflow south of 15°N carries the Tropical Salinity Minimum water of 35 × 10⁹ kg s⁻¹, nearly half of which return to the east through a narrow undercurrent at 15–17°N, and the rest is transported into the lower part of the North Equatorial Countercurrent. Below 1500 m depth, the deep circulation regime is anti-cyclonic. At the density range of 36.7σ₂, – 45.845σ₄ (approximately 1500–3500 m depths), deep waters of 17 × 10⁹ kg s⁻¹ flow northward, and three quarters of them return to the east at 16–24°N. The remainder flows further north of 24°N, then turns eastward out of the Philippine Sea, together with a small amount of subarctic-origin North Pacific Deep Water (NPDW) which enters the Philippine Sea through the gap between the Izu Ridge and Ogasawara Ridge. The full-depth structure and transportation of the Kuroshio in total and net are also examined. It is suggested that low potential vorticity of the Subtropical Mode Water is useful for distinguishing the net Kuroshio flow from recirculation flows. This revised version was published online in August 2006 with corrections to the Cover Date.     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的p H、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(PP)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(FCO₂),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chl a、DIC、HCO₃^–和PP显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和FCO₂显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量FCO₂平均值分别是(42.04±9.56)、(276...     

Carbonate chemistry and projected future changes in pH and CaCO3 saturation state of the South China Sea

To study the dissolved carbonate system in the South China Sea (SCS) and to understand the water mass exchange between the SCS and the West Philippine Sea (WPS), pH, total alkalinity and total CO₂ were measured aboard the R/V Ocean Researcher 1. Because of the sill that separates these two seas in the Luzon Strait with a maximum depth of 2200 m, the SCS Deep Water has characteristics similar to those of water at about 2200 m in the WPS. The minimum pH and the maxima of normalized alkalinity and total CO₂ commonly found in the open oceans at mid-depth also prevail in the WPS but are, however, very weak in the SCS. Rivers and inflows from Kuroshio Surface and Deep Waters through the Luzon Strait as well as those through the Mindoro Strait transport carbon to the SCS year-round. Meanwhile, the outflowing Taiwan Strait water as well as the SCS Surface and Intermediate Waters of the Luzon Strait transports carbon out of the SCS year-round. The Sunda Shelf is also a channel for carbon transport into the SCS in the wet season and out of the SCS in the dry season.fCO₂ data and mass balance calculations indicate that the SCS is a weak CO₂ source in the wet season but an even weaker CO₂ sink in the dry season. With these facts taken together, the SCS is likely a very weak CO₂ source. Anthropogenic CO₂ penetrates to about 1500 m in depth in the SCS, and the entire SCS contains 0.60 ± 0.15 × 10¹⁵ g of excess carbon. Typical profiles of pH as well as the degree of saturation of each of calcite and aragonite in 1850 and 1997 are presented, and those for 2050 AD are projected. The maximum decrease in pH is estimated to be 0.16 pH units in the surface layer when the amount of CO₂ is doubled. It is anticipated that aragonite in the upper continental slope will likely start to dissolve, thereby neutralizing excess CO₂ by around 2050 AD. This paper is unique in that it presents the results of the first attempt ever to estimate the past, present and future physico-chemical properties of the world's largest marginal sea.     

N2 fixation variability in the oligotrophic Sulu Sea, western equatorial Pacific region over the past 83 kyr

N₂ fixation is an important biological process that adds new nitrogen to oceans and plays a key role in modulating the oceanic nitrate inventory. However, it is not known how, when, and where N₂ fixation rates have varied in response to past climate changes. This study presents a new record of nitrogen isotopic composition (δ¹⁵N) over the last 83 kyr from a sediment core (KH02-4 SUP8) taken in the Sulu Sea in the western equatorial Pacific region; data allow the N₂ fixation variability in the sea to be reconstructed. Sediments, sinking, and suspended particulate organic matter (POM) all have lighter isotopic values compared to the δ¹⁵N values of substrate nitrate (av. 5.8‰) in North Pacific Intermediate Water. These lighter δ¹⁵N values are regarded as reflecting N₂ fixation in the Sulu Sea surface water. A δ¹⁵N mass balance model shows that N₂ fixation rates were significantly enhanced during 54–34 kyr in MIS-3 and MIS-2. It has been speculated that higher interglacial denitrification rates in the Arabian Sea and the eastern tropical Pacific would have markedly decreased the global oceanic N inventory and contributed to the increase in N₂ fixation in oligotrophic regions, but such a model was not revealed by our study. It is possible that changes in N₂ fixation rates in the Sulu Sea were regional response, and accumulation of phosphate in the surface waters due to enhanced monsoon-driven mixing is thought to have stimulated enhancements of N₂ fixation during MIS-3 and MIS-2.     

Nearshore scavenging phenomenon elucidated by <Superscript>234</Superscript>th/<Superscript>238</Superscript>u disequilibrium in the coastal waters off Western Taiwan

Dissolved and particulate ²³⁴Th activities in surface seawater were determined at 27 stations along the coastline of western Taiwan during 19–23 November 2004. Contrasting scavenging settings were observed between the northern and southern regimes of the nearshore water off western Taiwan, separated by the Cho-Shui River. The northern regime is characterized by a large quantity of suspended load contributed by northward transport of a suspension plume from the Cho-Shui River, while the southern regime, low in suspended load and high in chlorophyll concentration, is a system controlled by biological activity. A scavenging model that takes account of the physical transport was used to estimate the ²³⁴Th budget in order to estimate the scavenging and removal rates from the nearshore water. The scavenging and removal rates ranged from 21 to 127 dpm m⁻³d⁻¹ and from 36 to 525 dpm m⁻³d⁻¹, for dissolved and particulate ²³⁴Th, respectively. The removal fluxes of particulate organic carbon (POC) and particulate organic nitrogen (PON) were estimated by multiplying the particulate ²³⁴Th removal flux to the organic carbon/²³⁴Th and nitrogen/²³⁴Th ratios in suspended particles, which ranged from 4.5 to 275.2 mmol-C m⁻²d⁻¹ and from 1.3 to 50.1 mmol-N m⁻²d⁻¹, respectively. These fluxes resulted in residence times of 1∼20 days for the POC in the surface water of nearshore water off western Taiwan.     

The spatial distribution of surface <Emphasis Type="Italic">f</Emphasis>CO<Subscript>2</Subscript> in the Southwestern East Sea/Japan sea during summer 2005

Fugacity of CO₂ (fCO₂), temperature, salinity, nutrients, and chlorophyll-a were measured in the surface waters of southwestern East Sea/Japan Sea in July 2005. Surface waters were divided into three waters based on hydrographic characteristics: the water with moderate sea surface temperature (SST) and high sea surface salinity (SSS) located east of the front (East water); the water with high SST and moderate SSS located west of the front (West water); and the water with low SST and SSS located in the middle part of the study area (Middle water). High fCO₂ larger than 420 μatm were found in the West water. In the Middle water, CO₂ was undersaturated with respect to the atmosphere, with values between 246 and 380 μatm. Moderate fCO₂ values ranging from 370 to 420 μatm were observed in the East water. For the East and West waters, estimates of temperature dependency of fCO₂ (12.6 and 15.1 μatm °C⁻¹, respectively) were rather similar to a theoretical value, indicating that SST is likely to be a major factor controlling the surface fCO₂ distribution in these two regions. In the Middle water, however, the estimated temperature dependence was somewhat lower than the theoretical value, and relatively high concentrations of surface chlorophyll-a coincided with the low surface fCO₂, implying that biological uptake may considerably affect the fCO₂ distribution. The net sea-to-air CO₂ flux of the study area was estimated to be 0.30±4.81 mmol m⁻² day⁻¹ in summer, 2005.     

Distribution of 210Po and export of organic carbon from the euphotic zone in the southwestern East Sea (Sea of Japan)

The distribution of the natural radionuclide ²¹⁰Po in the water column along a horizontal transect of the continental shelf, slope and deep basin regions of the East Sea (Sea of Japan), a marginal sea of the Northwest Pacific Ocean, was investigated, and its behavior is described here. The settling fluxes of particulate ²¹⁰Po in the deep basin along with ²¹⁰Pb, ²³⁴Th and biogenic matter were also determined. ²¹⁰Po inventories in the water column were observed to decrease from winter to summer in all stations, probably due to increased influx of ²¹⁰Po-poor Kuroshio Water of the Northwest Pacific Ocean during summer. Vertical profiles of dissolved and particulate ²¹⁰Po along with the settling fluxes of particulate ²¹⁰Po in the deep basin station have enabled us to evaluate temporal variations and residence times of ²¹⁰Po. In the slope and basin, activities of dissolved ²¹⁰Po generally decreased from the surface to the bottom water, with maximum activity just below the subsurface chlorophyll a maximum at 50–75 m depth in spring and summer. These subsurface peaks of dissolved ²¹⁰Po activity were attributed to the release of ²¹⁰Po from the decomposition of ²¹⁰Po-laden biogenic particulate organic matter. In the deep basin, despite the decrease in total mass flux, the sinking flux of particulate ²¹⁰Po was higher in the deeper trap (2000 m) than in the shallower one (1000 m), probably due to scavenging of dissolved ²¹⁰Po from the water column during particle descent and/or break-down of ²¹⁰Po-depleted particulate matter between 1,000 m and 2,000 m depths. In general, the ratios of the particulate phase to the dissolved phase of ²¹⁰Po (K_d) increased with depth in the slope and basin stations. ²¹⁰Po removal from the water column appears to depend on the primary productivity in the upper waters. There is an inverse relationship between K_d and suspended particulate matter (SPM) concentration in the water column. From the ²¹⁰Po activity/chlorophyll a concentration ratios, it appears that sinking particles arriving at 1000 m depth were similar to those in the surface waters.     

Roles of Continental Shelves and Marginal Seas in the Biogeochemical Cycles of the North Pacific Ocean

Most marginal seas in the North Pacific are fed by nutrients supported mainly by upwelling and many are undersaturated with respect to atmospheric CO₂ in the surface water mainly as a result of the biological pump and winter cooling. These seas absorb CO₂ at an average rate of 1.1 ± 0.3 mol C m⁻²yr⁻¹ but release N₂/N₂O at an average rate of 0.07 ± 0.03 mol N m⁻²yr⁻¹. Most of primary production, however, is regenerated on the shelves, and only less than 15% is transported to the open oceans as dissolved and particulate organic carbon (POC) with a small amount of POC deposited in the sediments. It is estimated that seawater in the marginal seas in the North Pacific alone may have taken up 1.6 ± 0.3 Gt (10¹⁵ g) of excess carbon, including 0.21 ± 0.05 Gt for the Bering Sea, 0.18 ± 0.08 Gt for the Okhotsk Sea; 0.31 ± 0.05 Gt for the Japan/East Sea; 0.07 ± 0.02 Gt for the East China and Yellow Seas; 0.80 ± 0.15 Gt for the South China Sea; and 0.015 ± 0.005 Gt for the Gulf of California. More importantly, high latitude marginal seas such as the Bering and Okhotsk Seas may act as conveyer belts in exporting 0.1 ± 0.08 Gt C anthropogenic, excess CO₂ into the North Pacific Intermediate Water per year. The upward migration of calcite and aragonite saturation horizons due to the penetration of excess CO₂ may also make the shelf deposits on the Bering and Okhotsk Seas more susceptible to dissolution, which would then neutralize excess CO₂ in the near future. Further, because most nutrients come from upwelling, increased water consumption on land and damming of major rivers may reduce freshwater output and the buoyancy effect on the shelves. As a result, upwelling, nutrient input and biological productivity may all be reduced in the future. As a final note, the Japan/East Sea has started to show responses to global warming. Warmer surface layer has reduced upwelling of nutrient-rich subsurface water, resulting in a decline of spring phytoplankton biomass. Less bottom water formation because of less winter cooling may lead to the disappearance of the bottom water as early as 2040. Or else, an anoxic condition may form as early as 2200 AD. This revised version was published online in July 2006 with corrections to the Cover Date.     

Uptake of atmospheric carbon dioxide in Arctic shelf seas: evaluation of the relative importance of processes that influence pCO2 in water transported over the Bering–Chukchi Sea shelf

The uptake of atmospheric carbon dioxide in the water transported over the Bering–Chukchi shelves has been assessed from the change in carbon-related chemical constituents. The calculated uptake of atmospheric CO₂ from the time that the water enters the Bering Sea shelf until it reaches the northern Chukchi Sea shelf slope (1 year) was estimated to be 86±22 g C m⁻² in the upper 100 m. Combining the average uptake per m³ with a volume flow of 0.83×10⁶ m³ s⁻¹ through the Bering Strait yields a flux of 22×10¹² g C year⁻¹. We have also estimated the relative contribution from cooling, biology, freshening, CaCO₃ dissolution, and denitrification for the modification of the seawater pCO₂ over the shelf. The latter three had negligible impact on pCO₂ compared to biology and cooling. Biology was found to be almost twice as important as cooling for lowering the pCO₂ in the water on the Bering–Chukchi shelves. Those results were compared with earlier surveys made in the Barents Sea, where the uptake of atmospheric CO₂ was about half that estimated in the Bering–Chukchi Seas. Cooling and biology were of nearly equal significance in the Barents Sea in driving the flux of CO₂ into the ocean. The differences between the two regions are discussed. The loss of inorganic carbon due to primary production was estimated from the change in phosphate concentration in the water column. A larger loss of nitrate relative to phosphate compared to the classical ΔN/ΔP ratio of 16 was found. This excess loss was about 30% of the initial nitrate concentration and could possibly be explained by denitrification in the sediment of the Bering and Chukchi Seas.     

Variation of the partial pressure of CO2 in surface water from Kuroshio to Oyashio and the relation between environmental factors and the partial pressure at 144°E off Sanriku, northwestern North Pacific in May, 1997

Partial pressure of CO₂ in surface sea water (pCO₂) was measured continuously off Sanriku in May, 1997 by a new pCO₂ measurement system. We have examined the relation of pCO₂ to physical factors such as temperature, salinity and density, chemical and biological factors such as nutrients and carbonate system and chlorophylla. In the Kuroshio region pCO₂ was not correlated to physical, chemical and biological factors in the range of 260 to 290 μatom. In transition water (Tr1) between Kuroshio and the Oyashio second branch, pCO₂ was weakly correlated to physical factors and strongly correlated to nutrients. In transition water (Tr2) between the Oyashio first and second branches, pCO₂ was highly correlated to temperature (SD: 10.9 μatom) and salinity (SD: 8.6 μatom) and also to nutrients. In transition water (Tr1+Tr2), pCO₂ was highly multivariately correlated to temperature (T), salinity (S), chlorophylla (CH) (or nitrate+nitrite (N)) as follows, pCO₂(μatom)= 10.8×T(°C)+27.7×S+2.57CH(μg/1) −769, R²= 0.86, SD = 20.9, or pCO₂(μatom)= 3.9×T(°C)+25.5×S+16.0NO₃(μM) −686, R²= 0.99, SD = 6.4. Moreover, pCO₂ was predicted by only two factors, one physical (S) and the other chemical/biological (N) as follows: pCO₂ (μatom)=32.8×S+19.4N−908, R²=0.97, SD=8.4. The pH measured at 25°C was well correlated with normalized pCO₂ at a fixed temperature. In the Oyashio region pCO₂ was decreased to 160 μatom, probably because of spring bloom, but was not correlated linearly to chlorophylla. The results obtained showed the possibility of estimating pCO₂ of the Oyashio and transition regions in May by satellite remote sensing of SST, but the problem of estimation of pCO₂ in Kuroshio water remains to be solved.     

Carbonate-related parameters of subsurface waters in the West Philippine, South China and Sulu Seas

Like most other deep basins in Southeast Asia, the deep Sulu Sea (SS) basin is isolated from the neighboring seas by surrounding topography. While the near-surface circulation is mainly governed by the seasonally reversing monsoon winds, below the warm and fresh surface layer, the core of the incoming Subtropical Lower Water from the West Philippine Sea (WPS), by way of the South China Sea (SCS), can be seen, at a depth of around 200 m, to have a distinct salinity maximum. It lies well above the sill depth (420 m) in the Mindoro Strait and thus, its spreading is not hampered by topography. The deep circulation is forced by an inflow of upper North Pacific Intermediate Water (NPIW) from the SCS through the Mindoro Str. Below 1000 m, the physico-chemical properties are remarkably homogeneous. The higher temperature, but lower salinity, oxygen and nutrients, of the deep SS waters, compared to those of the SCS, is indicative of the intrusion of NPIW above the sill depth. The excess, anthropogenic CO₂ penetrates the entire water column, because of the over-spill of the excess CO₂-laden water from the SCS.It has been reported that the bottom of the SS is CaCO₃ rich, relative to the SCS. Previous investigators attribute this to the higher θ in the SS. Indeed, the aragonite does not become undersaturated in the SS until below 1400 m, compared to 600 m in both the WPS and SCS; and the calcite does not become undersaturated until below 3800 m in the SS, compared to 2500 m in the SCS and around 1600 m in the WPS. However, the temperature effect is relatively small. These large differences are, in fact, largely a result of higher CO₃²⁻ concentrations in the SS, relative to the WPS and SCS. The higher CO₃²⁻ concentration in the SS, in turn, is mainly caused by the smaller amounts of organic carbon decomposition.     

The effect of a tidal cycle on the dynamics of nutrients in a tidal estuary in the Seto Inland Sea, Japan

A 24 hour time series survey was carried out during a spring tide (tidal range ca.2 m) of May 1995 on a tidal estuary in the Seto Inland Sea, Japan, in the context of an integrated program planned to quantify the dynamics of biophilic elements (carbon, nitrogen and phosphorus) and the roles played by the macrobenthos on the processes. Three stations were set along a transect line of about 1.4 km, which linked the river to the rear to the innermost part of the subtidal zone. Every hour, at each station, measurements were made of surface water temperature, salinity and dissolved oxygen concentration, and surface water was collected for the determination of nutrients [NH₄ ⁺−N, (NO₃ ⁻+NO₂ ⁻)−N, PO₄ ³⁻−P and Si (OH)₄−Si]. During the ebb flow, riverine input of silicate and nitrate+nitrite significantly increased the concentrations of both the intertidal and the subtidal stations. Conversely, during the high tide, river nutrient concentrations were lowered by the mixing of fresh water with sea water. As a result, best (inverse) correlations were found at the river station for salinity against silicate (y=-2.9 Sal.+110.7,r ²=0.879) and nitrate+nitrite (y=-1.3 Sal.+48.4,r ²=0.796). In contrast, ammonium nitrogen concentrations were higher at intermediate salinities. Indeed, no significant correlation was found between salinity and ammonium. The effect of the macrobenthos, which is abundant on the intertidal flat, is discussed as a biological component that influences the processes of nutrient regeneration within the estuary. The effect of the tidal amplitude is an important one in determining the extent of the variations in nutrient concentrations at all three stations, which were stronger between the lower low tide and the higher high tide.     

Nitrogen, Oxygen and Argon Dissolved in the Northern North Pacific in Early Summer

Major gases dissolved in seawater were accurately determined with a shipboard gas chromatographic method. The standard deviations were 0.28, 0.34 and 0.36% for N₂, O₂ and Ar, respectively. The method was applied to water from the northwestern North Pacific Ocean collected in May to June 2000. We got 127 duplicate seawater samples from the surface 200 m layer at 11 stations. The O₂ concentrations obtained by this method agreed with those given by the Winkler method. All the seawater samples from the surface 200 m, especially those from the upper 30 m, were supersaturated with respect to atmospheric N₂ and Ar concentrations. In the topmost 30 m layer, the degrees of supersaturation in the inventory were 2.7–4.3% for N₂ (ΔN₂) and 1.7–2.6% for Ar (ΔAr), and their ratios, ΔN₂/ΔAr, ranged from 1.53 to 1.81. This supersaturation seems to be chiefly due to air bubbles injected into the water and dissolved due to the water pressure, because the N₂/Ar ratio of the air is around 2. The amounts of air bubbles dissolved in the upper 30 m water were relatively large, with mean value of 0.41 ml/kg or 18.4 μmol/kg. The ΔN₂, ΔAr and ΔN₂/ΔAr values were all positively well correlated with the wind velocities averaged for the last 24 hours prior to sampling, allowing the conclusion to be drawn that the weaker the wind velocity, the dissolved gas composition approaches in equilibrium with the air; while the stronger the wind velocity, it approaches in the air composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.