The density functional calculations on the structural and electronic properties of the endohedral fullerene dimer (N2@C60)2

The generalised gradient approximation based on density functional theory is used to study the structural and electronic properties of the endohedral fullerene dimer (N₂@C₆₀)₂. Four N atoms sit at the cage centres in the form of two N_2 molecules. The density of states and Mulliken charge analysis explore that the energy levels from -6 to -10 eV are mainly influenced by the N₂ molecules.     

Photosynthesis-irradiance relationship of phytoplankton and primary production in the vicinity of Kuroshio warm core ring in spring

The light-saturated maximum value (P ^B _max) and initial slope (α) of the photosynthesis-irradiance (P-E) curve were examined in a warm streamer, a cold streamer and a warm core ring off the Sanriku area in the subarctic western North Pacific Ocean during an ADEOS/OCTS Sanriku field campaign in early May 1997. BothP ^B _max and α were within the ranges of temperate populations. A regional difference was apparent inP ^B _max: populations in the warm streamer tended to show higher value ranging between 1.92 and 4.74 mgC (mgChla)⁻¹h⁻¹ than those in the cold streamer and the warm core ring (1.35–2.87 mgC (mgChla)⁻¹h⁻¹). A depth variation was also observed in α in both the warm streamer and the warm core ring: shallow populations tended to have lower α than deep populations. The depth variations in bothP ^B _max and α resulted in a lower light intensity of the light saturation in a deeper population than that of a shallower one. These depth-related variations in the P-E parameters were likely a manifestation of “shade-adaptation” of photosynthesis. Photoinhibition was not observed over in situ surface light intensity varying below ca 1600 μmol photon m⁻²s⁻¹. Water-column primary productivity was biooptically estimated to be 233 to 949 mgC m⁻²d⁻¹ using vertical distributions of the P-E parameters, chlorophylla, phytoplankton light absorption and underwater irradiance. Applicability of surface data sets for estimation of water-column productivity is discussed.     

Inorganic carbon in the central California upwelling system during the 1997–1999 El Niño–La Niña event

Sea surface pCO₂ was monitored during 49 cruises from February 1997 to December 1999 along a section perpendicular to the central California Coast. Continuous measurements of the ocean–atmosphere difference of pCO₂ were made on a mooring in the same region from July 1997 to December 1999. The El Niño/La Niña cycle of 1997–1999 had a significant influence on local ocean–atmosphere CO₂ transfer. During the warm anomaly associated with El Niño, upwelling was suppressed and average sea surface pCO₂ was below atmospheric level. High rainfall and river runoff in the late winter and early spring of 1998 produced areas where pCO₂ was depressed by as much as 100 μatm. A flux ranging from 0.3 to 0.7 mol C m⁻² y⁻¹ from the atmosphere into the ocean was estimated for the El Niño period from wind and ΔpCO₂ data. Temperatures and upwelling returned to near normal in the summer of 1998, but a cold anomaly developed during autumn of that year. Temperature and pCO₂ data indicate that upwelling continued throughout much of the 1998–1999 winter and intensified significantly in the spring of 1999. During strong upwelling events, the estimate of ocean to atmosphere flux approached rates of 50 mol C m⁻² y⁻¹. The estimate for the average CO₂ flux from July 1998 to July 1999 was 1.5–2.2 mol C m⁻² y⁻¹ from the ocean to the atmosphere. While the flux estimate for the El Niño time period may be applicable to a larger area, the high ocean to atmosphere fluxes during La Niña might be the result of sampling near a zone of intense upwelling.     

Chemical speciation of copper and zinc in surface waters of the western Black Sea

The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate ²³⁴Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (C_L1=3–12 nM, log K₁′=13.1–13.9) and (C_L2=20–70 nM, log K₂′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (C_L1=8–23 nM, log K₁′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r²=0.64), which improved when the dissolved ligands alone were considered (r²=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Radiation balance and heat budget at the ocean/atmosphere interface in the western North Pacific

The downward short- and long-wave radiation fluxes at the sea surface (S, L) were measured aboard the R/VHakuho Maru, University of Tokyo, for the period of 117 days on six cruises from 1981 to 1985 in the western North Pacific near Japan. The upward fluxes of short- and long-wave radiation (S, L) were calculated by Payne's (1972) table and the Stefan-Boltzmann's law, respectively. The sensible and laten heat fluxes (Q _h ,Q _e ) were also estimated from an aerodynamic bulk method.From April to August, the daily mean value ofS varied with the amplitude of 100200 Wm^–2. The value ofS was estimated approximately 6% ofS in all seasons. The difference betweenL andL was so small that the net radiation flux (Q _n ) was dominated byS. In addition, the net heat flux at the sea surface was also dominated byS due to small values ofQ _h andQ _e , and then the ocean was warmed at the rate of 111 Wm^–2 in April and 63 Wm^–2 in August in the Oyashio Area, and 132 Wm^–2 in May and 164 Wm^–2 in June in the Kuroshio Area, respectively.From September to March, a remarkable negative correlation between the day to day variation ofS and that ofL was observed except when an intense cold air outbreak occurred. It was found that the correlation was caused by the cloud climatological feature of the western North Pacific in this period.S was not a dominant factor in the net heat flux. The value ofQ _h +Q _e in the Kuroshio Area ranged from 260 Wm^–2 to 630 Wm^–2, much larger thanQ _n which ranged from –8 Wm^–2 to 92 Wm^–2 in the leg mean values (each leg period was about 10 days). Then the ocean was cooled at the rate of –160–620 Wm^–2 during this period. The net heat flux in the Kuroshio Area averaged over five legs from late November to February was –473 Wm^–2. This value is 50100% larger than the climatological values reported so far.The temporal and spatial variability of radiation fluxes and heat fluxes during each leg was also discussed.     

Optimization of an ocean thermal energy conversion system

The optimum performance of a simple Rankine cycle ocean thermal energy conversion plant is investigated analytically. It is shown that the ratio of maximum net power output to heat exchanger surface area varies as H(Δt − t₀)² where H describes the overall heat transfer properties of the evaporator and condenser, Δt is the temperature difference between the warm and cold sea water supplies, and t₀ is a parameter depending primarily upon the pressure drops across the warm and cold sea water pumping systems. The model is relatively insensitive to the choice of working fluid, although ammonia is used as the illustrative example.     

On the importance of resolving the western boundary layer in wind-driven ocean general circulation models

The western boundary layer (WBL) plays a fundamental role in basin-scale wind-driven ocean circulations. In idealized ocean models with flat bottom topography, this layer is required not only to balance the interior Sverdrup transport to close the gyre circulation, but also to dissipate the vorticity imposed by the wind-stress curl. The width of the WBL in Munk-type models is estimated to be δ_M(A_H/β)^1/3, where A_H and β are horizontal eddy viscosity and the meridional derivative of the Coriolis parameter respectively. For commonly used values of A_H, the boundary-layer width δ_M ranges from 30 to less than 200 km in the mid-latitude ocean. This scale is often poorly resolved in large-scale climate models.This paper intends to demonstrate some consequences when the western boundary layer is not adequately resolved. It is found that coarse resolution models reach equilibrium states by distorting some important dynamics in order to dissipate wind-imposed vorticity. In three-dimensional models, for instance, very strong spurious upwelling and downwelling can occur along the WBL. In models of two-dimensional flow, however, spurious recirculations may develop near the boundary. These false features can be removed when the boundary layer is better resolved. We propose a method in which a spatially varying A_H is used to broaden the WBL without affecting mixing in the interior. The method improves the model results considerably.     

Heat budget in the Japan Sea

The long-term mean (31-year mean) surface heat fluxes over the Japan Sea are estimated by the bulk method using the most of the available vessel data with the resolution of 1^o×1^o. The long-term annual mean net heat flux is about –53 W m^–2 (negative sign means upward heat flux) with the annual range from 133 W m^–2 in May to –296 W m^–2 in December. The small gain of heat in the area near Vladivostok seems to indicate the existence of cold water flowing from the north. In that area in winter, the mean loss of heat attains about 200 W m^–2, and the Bowen's ratio is over the unity. The largest insolation occurs in May in the Japan Sea, and the upward latent heat flux becomes the largest in November in this area. The heat flux of Haney type is also calculated, and the result, shows that the constantQ ₁ has the remarkable seasonal and spatial variation, while the coefficientQ ₂ has relatively small variation throughout all seasons. Under the assumption of constant volume transport of 1.35×10⁶ m³s^–1 through the Tsugaru Strait, the long-term averages of the volume transport through the Tsushima and Soya Straits are estimated to be about 2.20 and 0.85×10⁶ m³s^–1 from the result of the mean surface heat flux, respectively.     

Volume and heat transports and material fluxes in the East China Sea during April 1994

INTRODUCTIONTherehavebeenmanystudiesandcomputationsonVToftheKuroshiointheEastChinaThisprojectwassupportedbytheNationalNaturalScienceFoundationofChinaundercontractNo.49476278.Asanditsvacation.Forexample,(1)basedonhydrographicobservationsatactionG(PN)f...     

Silicate correction in the colorimetric determination of phosphate in seawater

An improved Strickland and Parsons' method, in which silicate correction is made, is described for the colorimetric determination of phosphate in seawater. Silicate correction is made by subtracting the value of 0.025 (C/100)², whereC is silicate concentration (µg atoms 1^?1), from the observed phosphate concentration. The relative standard deviations are 2 % at the 1 µg atom PO ₄ ^3? ?Pl^?1 level and less than 1 % at the 3 µg atoms PO ₄ ^3? ?Pl^?1 level in seawater.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

Oceanographic controls on the carbon isotopic compositions of sinking particles from the Cariaco Basin

This study examined the relationship between carbon isotopic composition of sinking organic matter (OM) and the biological, physical and chemical properties of the surface ocean in the Cariaco Basin. The ¹³C/¹²C ratio of OM (δ¹³C_org) in sinking particles was determined on sediment trap samples from four depths collected from 1996 to 1999 as part of the CArbon Retention In A Colored Ocean time series. Water column properties, including temperature, productivity, chlorophyll and concentration of dissolved CO₂, were concurrently measured on monthly cruises. The δ¹³C_org varied from a high of –17.7‰ to a low of –22.6‰ during the study period. The variation of the δ¹³C_org throughout seasonal cycles was directly proportional to the strength of upwelling and was negatively correlated with temperature (r²=0.64). During the 1996–1997 upwelling event, the strongest during the study period, the δ¹³C_org increased by 4.4‰ whereas during the 1998–1999 upwelling event, the weakest during the study period, the δ¹³C_org only increased by 3.3‰. Contrary to most previous studies, we observed a negative relationship (r²=0.53) between [CO_2 aq] and the estimated isotopic fractionation factor (ε_p). However, there was no correlation between ε_p and the calculated growth rates indicating that there was non-diffusive uptake of carbon into phytoplankton cells. It thus appears that [CO_2 aq] does not control the δ¹³C_org in the water column of the study site. The best explanation for the isotopic enrichment observed is a carbon concentrating mechanism (CCM) in phytoplankton. The existence of a CCM in phytoplankton has major implications for the interpretation of the δ¹³C_org in the Cariaco Basin.     

Primary productivity in a cold water mass and the neighborhood area occurring off Enshu-nada in the late summer of 1989

Primary productivity off Enshu-nada was measured by the¹³C method in September 1989. Primary productivity was estimated in a cold water mass developed off Enshu-nada for the first time. The obtained value was 469 mgC·m^–2·d^–1 and higher than those in the pelagic area of Kuroshio, but equivalent to those in the neritic and the Oyashio areas. It was indicated that cold water mass is the place where organic matter is produced actively. Extremely high chlorophylla of more than 5g·l^–1 were found in the cold water mass. The high productivity was due to high standing crop of phyoplankton. Furthermore, calculated light efficiency and quantum yield showed consistent increase with depth and showed a maximum at 10% light level. Both were larger on the coastal side than those on the oceanic side of the Kuroshio current.     

The mechanism of the development of wind-wave spectra

The mechanism of the development of wind-waves will be proposed on the basis of the observed wave spectra in the wind tunnels and at Lake Biwa (Imasato, 1976). It consists of two aspects: One is that the air flow over the wind-waves transfers momentum concentratively to the steepest component waves and the other is that the upper limit of the growth of a wave spectral density is given by the ultimate value in the slope spectral density. The first aspect means that the wave field has the momentum transfer filter on receiving the momentum from the air flow. Wind-waves in the stage of sea-waves receive the necessary amount of momentum by the form drag,e.g. according to the Miles' (1960) inviscid mechanism, through a very narrow frequency region around a dominant spectral peak. On the other hand, wind-waves in the stage of initial-wavelets receive it according to the Miles' (1962a) viscous model through a fairly broad frequency region around the peak. The upper limit ofS _max developing according to viscous mechanism is given byS _max =6.40×10^–4 k _max ^–2cm²s andS _max =2.03C(f _max )^–2cm²s(S _max is the power density of the wave spectral peak with the frequencyf _max ,k _max is the wave number corresponding to the frequencyf _max andC is the phase velocity).From the second aspect, the upper limit of the growth of wave spectral density is given by 33.3f ^–4cm²s in the frequency region of late stage of sea-waves. Therefore, the spectral peak, which has the largest value in the slope spectral density in the component waves of the wave spectrum, rises high over the line 4.15f ^–5cm²s. The energy is transported from the spectral peak to the high frequency part and to the forward face of a wave spectrum by nonlinear wave-wave interaction. This nonlinearity is confirmed by the bispectra calculated from the observed wind-wave data. In the stage of sea-waves, nonlinear rearrangement of the wave energy comes from a narrow momentum transfer filter, and, in the stage of initial-wavelets, it comes mainly from small corrugations and small steepness of the wave field.     

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pH、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(P_P)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(F_CO2),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Chla、DIC、HCO₃^–和P_P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F_CO2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F_CO2平均值分别是(42.04±9.56)、(276.14±52.55)、(–11.59±18.15)和(–13.02±6.71)mmol/(m²·d),冬季各站位F_CO2值离散度较大,其中位数是–10.73mmol/(m²·d)。在全年尺度,表层海水p(CO₂)及F_CO2与水温呈显著正相关,与盐度呈显著负相关。在非养殖区,浮游植物光合作用可能对影响表层海水p(CO₂)及F_CO2起主导作用。养殖牡蛎钙化、呼吸作用等生理因素释放的CO₂对表层海水p(CO₂)及F_CO2未产生显著影响。考洲洋养殖海域养殖旺季为CO₂的源,养殖淡季整体为CO₂的弱汇。     

Study on the chemical forms of radionuclides in seawater—I

The stability constants for sulfate, chloride and hydroxide ions with cerium (III) in the solution at ionic strength of 0.67 have been determined by cation exchange method, the values of ₁ and ₂ for sulfate complexes of cerium being 40±13 and 453±140, respectively and those for chloride complexes being 1.28±0.23 and 0.56±0.076, respectively. The values of ₁, ₂ and ₃ for hydroxide complexes of cerium were (4.5±0.9)×10⁷, (3.3±0.7)×10¹⁴ and (1.8±0.7)×10²³, respectively.Using the above constants the ratios of individual chemical species of¹⁴⁴Ce were calculated in a solution at ionic strength of 0.67 containing sulfate and chloride ions approximately the same as in seawater of 35 %. The result of calculation indicates that the dominant species of¹⁴⁴Ce in this solution is Ce(OH)₃ ⁰ at pH 8.