Simultaneous vertical measurements of in situ pH and CO2 in the sea using spectrophotometric profilers

We have developed new systems capable of profiling to >1000 m for measuring in situ pH and fugacity of CO₂ (fCO₂) in the ocean using spectrophotometric analysis (pH and CO₂ profilers). The in situ pH is determined by detecting the color change of the pH indicator (m-cresol purple). It can withstand ambient pressure to 1000 m depth. The CO₂ profiler analyzed in situ fCO₂ by detecting the change of pH in an inner solution, equilibrated with the seawater through a gas permeable membrane. It can be operated to 2500 m depth. We used an amorphous fluoropolymer tubing form of AF-2400 for the gas permeable membrane due to its high gas permeability coefficients. The inner solution was a mixture of 2 μM bromocresol purple (BCP) and 5 μM sodium hydroxide. This system gave us a response time of 1 minute, which is twice as fast as previous systems. The precisions of pH and CO₂ profilers were within 0.002 and 2.5% respectively. We have used these profilers to study the North Pacific, obtaining good agreement with the difference between the data from profilers and a discrete bottle of 0.002 ± 0.005 pH (SE, n = 25) and −0.4 ± 3 μatm (SE, n = 31).     

Utility of an automatic water sampler to observe seasonal variability in nutrients and DIC in the Northwestern North Pacific

Concentrations of nutrients (NO₃, NO₂, Si(OH)₄, PO₄ and dissolved inorganic carbon (DIC) were measured in a series of seawater samples collected over approximately 15 months in 2005 and 2006 by an automatic water sampler (Remote Access Sampler, RAS) in the Northwestern North Pacific. Seasonal variability and concentrations of NO₃ + NO₂ (NO_x and Si(OH)₄ were comparable to previous shipboard observations, although there were small errors associated with measurements of PO₄ and DIC. Concentrations of these nutrients began to decrease in late April. After the end of June, NO_x and Si(OH)₄ decreased rapidly, with large fluctuations. After October, these nutrients increased again until late spring 2006. The ratio of the decrease of Si(OH)₄ to that of NO_x suggests that numbers of biogenic opal-producing creatures, such as diatoms, increased after the end of June. This conclusion was supported by a rapid increase in biogenic opal flux recorded in a sediment trap at 150 m. The relationship between NO_x concentrations at the RAS depth of 35 m and NO_x integrated over the upper 100 m was determined using previous shipboard hydrocast data. This relationship was used to estimate integrated mixed layer NO_x concentration from RAS data. Estimated new production based on seasonal drawdown of integrated NO_x averaged approximately 156 mg-C m⁻²day⁻¹ annually, which agrees with previous estimates. Thus, an automatic seawater sampler that documents annual maximum and minimum nutrient concentrations and episodic events such as storms and spring blooms, which might be missed by an ordinary research vessel, will contribute to time-series observations of nutrients and, by extension, biological pump activity.     

Diagnostic analysis of water circulations in Lake Biwa

A diagnostic model is developed for the study of steady water-circulations during summer in Lake Biwa. The most characteristic feature of the present model is to include the vertical friction terms in the basic equations, so that it is not necessary to assume a level of no-motion. Under no-wind condition, the velocity field is calculated from the density field obtained by successive observations of water temperature using a bathythermograph.The comparisons of the present calculation with a dynamical calculation and direct current measurements indicate that the present model surpasses a dynamical calculation in the respects that 1) vertical circulations can be estimated and 2) the flow pattern in the deep layers can be obtained more reliably. One of important results of the present calculation is that a large vertical circulation has been found accompanied by the large counterclockwise gyre in the north basin. Preliminary results of direct current measurements by cross-boad drogues also seem to suggest the existence of the circulation.     

Chlorofluorocarbons in the western North Pacific in 1993 and formation of North Pacific intermediate water

Chlorofluorocarbons (CFC-11 and CFC-12) in the intermediate water having between 26.4 and 27.2 were determined at 75 stations in the western North Pacific north of 20°N and west of 175.5°E in 1993. The intermediate water of 26.4–26.6 was almost saturated with respect to the present atmospheric CFC-11 in the zone between 35 and 45°N around the subarctic front. Furthermore, the ratios of CFC-11/CFC-12 of the water were also of those formed after 1975. These suggest that the upper intermediate water (26.4–26.6) was recently formed by cooling and sinking of the surface water not by mixing with old waters. The water below the isopycnal surface of 26.8 contained less CFCs and the area containing higher CFCs around the subarctic front was greatly reduced. However, the CFC age of the lower intermediate water (26.8–27.2) in the zone around the subarctic front was not old, suggesting that the water was formed by diapycnal mixing of the water ventilated with the atmosphere with old waters not containing appreciable CFCs, probably the Pacific Deep Water. The southward spreading rate decreased with depth and it was one sixth of its eastward spreading rate of the North Pacific Intermediate Water (NPIW).     

CFC Indicating Renewal of the Japan Sea Deep Water in Winter 2000–2001

The distributions of CFC (chlorofluorocarbon) in the water column was determined twice in 2000 and 2001 in the northwestern Japan Sea. In 2000 the CFC-11 concentration decreased almost exponentially with depth from 6 pmol/kg at a few hundred m deep to 0.3 pmol/kg or less at the bottom of about 3400 m depth at three stations (40–41°N, 132–133°E) about 300 km off Vladivostok. In 2001 the CFC-11 concentration increased sharply up to 2 pmol/kg in the bottom water, while it did not increase at a station (42.0°N, 136.5°E) about 450 km away to the northeast. This is due to the renewal of the bottom water which is replaced by the surface water flowing down along the continental slope, as suggested by Tsunogai et al. (1999), who proposed the continental shelf pump. Furthermore, an increase in the CFC-11 concentration was observed throughout the entire water column above 3000 m depth, although the proportion of the increase was about 20%, which was one order of magnitude smaller than that in the bottom water. The increase in inventory is almost four times larger than that in the bottom water below 3000 m depth which is equivalent to about 1/6 of the total inventory found in 2000. The increase also means that 3% of the deep water was replaced by the recent surface water, or, if the turnover occurs every year, that the turnover time of the deep water to be about 30 years. This revised version was published online in July 2006 with corrections to the Cover Date.     

Methane in Izena Cauldron,Okinawa Trough

Methane in the deep water of Izena Cauldron (maximum depth: ca. 1650 m) at the east side of mid-Okinawa Trough was studied by casting a CTD system with 12 Niskin bottles for water sampling at 11 stations inside and outside the cauldron. The water contained much methane up to 706 nmoles/l. The depths of maximum concentration varied widely from station to station, indicating the existence of a considerable number of vents emitting methane and heat. The waters containing less methane formed a straight line in theT-S diagram, while those containing more methane were more largely deviated from the line. The temperature anomaly was virtually proportional to the methane concentration, suggesting that the oxidation rate of methane inside the cauldron is negligibly small and methane can be used as a tracer of the cauldron water. The relation and the estimated vertical diffusivity gave the following fluxes. The emissions of methane and heat out of the bottom below 1450 m turn out to be 1400 moles/day and 7×10¹⁰ cal/day, respectively. The total emission rates inside the cauldron are presumed to be about twice the above values. The turnover time of methane has been estimated to be 240 days, which is also that of heat generated from the bottom and probably that of the bottom water.     

Time-series observation of dissolved inorganic carbon and nutrients in the northwestern North Pacific

Time-series measurements of dissolved inorganic carbon (DIC) and nutrient concentrations were conducted in the northwestern North Pacific from October 2002 to August 2004. Assuming that data obtained in different years represented time-series seasonal data for a single year, vertical distributions of DIC and nutrients showed large seasonal variabilities in the surface layer (∼100 m). Seasonal variabilities in normalized DIC (nDIC) and nitrate concentrations at the sea surface were estimated to be 81–113 μmol kg⁻¹ and 12.7–15.7 μmol kg⁻¹, respectively, in the Western Subarctic Gyre. The variability in nutrients between May and July was generally at least double that in other seasons. In the Western Subarctic Gyre, estimations based on statistical analyses revealed that seasonal new production was 39–61 gC m⁻² and tended to be higher in the southwestern regions or coastal regions. The seasonal new productions in the northwestern North Pacific were two or more times higher than in the North Pacific subtropical gyre and the northeastern North Pacific. It is likely that this difference is due to spatial variations in the concentrations of trace metals and the species of phytoplankton present. In addition, from estimations of surface pCO₂ it was verified that the Western Subarctic Gyre is a source of atmospheric CO₂ between February and May and a sink for CO₂ between July and October.     

Biogeochemistry of Dimethylsulfoniopropionate (DMSP) in the Surface Microlayer and Subsurface Seawater of Funka Bay,Japan

Twenty-eight sea surface microlayer samples, along with subsurface bulk water samples were collected in Funka Bay, Japan during October 2000–March 2001 and analyzed for dimethylsulfoniopropionate, dissolved (DMSP_d) and particulate (DMSP_p), and chlorophyll a. The aim of the study was to examine the extent of enrichment of DMSP in the microlayer and its relationship to chlorophyll a, as well as the production rate of dimethylsulfide (DMS) from DMSP and the factors that influence this. The enrichment factor (EF) of DMSP_d in the surface microlayer ranged from 0.81 to 4.6 with a mean of 1.85. In contrast, EF of DMSP_p in the microlayer varied widely from 0.85–10.5 with an average of 3.21. Chlorophyll a also appeared to be enriched in the microlayer relative to the subsurface water. This may be seen as an important cause of the observed enrichment of DMSP in the microlayer. The concentrations of DMSP_p in the surface microlayer showed a strong temporal variation, basically following the change in chlorophyll a levels. Moreover, the microlayer concentrations of DMSP_p were, on average, 3-fold higher than the microlayer concentrations of DMSP_d and there was a significant correlation between them. Additionally, there was a great variability in the ratios of DMSP_p to chlorophyll a over the study period, reflecting seasonal variation in the proportion of DMSP producers in the total phytoplankton assemblage. It is interesting that the production rate of DMS was enhanced in the microlayer and this rate was closely correlated with the microlayer DMSP_d concentration. Microlayer enrichment of chlorophyll a and higher DMS production rate in the microlayer provide favorable evidence supporting the view that the sea surface microlayer has a greater biological activity than the underlying water.     

Evolution of oceanic crust on the Kolbeinsey Ridge, north of Iceland, over the past 22 Myr

The evolution of oceanic crust on the Kolbeinsey Ridge, north of Iceland, is discussed on the basis of a crustal transect obtained by seismic experiment from the Kolbeinsey Ridge to the Jan Mayen Basin. The crustal model indicates a relatively uniform structure; no significant lateral velocity variations are observed, especially in the lower crust. The uniform velocity structure suggests that the postulated extinct axis does not exist over the oceanic crust formed at the Kolbeinsey Ridge, but supports a model of continuous spreading along the ridge after oceanic spreading started west of the Jan Mayen Basin. The oceanic crust formed at Kolbeinsey Ridge is 1–2.5 km thicker than normal oceanic crust due to hotter-than-normal mantle from the Iceland Mantle Plume. The observed generally uniform thickness throughout the transect might also indicate that the temperatures of the astheno-spheric mantle ascending along the Kolbeinsey Ridge have not changed significantly since the age of magnetic anomaly 6B.