Relationship between Cd and PO4 in the Subtropical Sea near the Ryukyu Islands

The relationship between dissolved cadmium (Cd) and phosphate (PO₄) was examined at three stations in the subtropical area near the Ryukyu Islands in May 1999. Preformed PO₄ was obtained using the Redfield ratio in order to separate the surface water and the other layers in this study area. Almost 0 μM (−0.043 μM to 0.094 μM) was estimated in the layers above 300 m and 250 m at Sts. 1 and 3 and at St. 2, respectively. Up to these depths, water was considered to be uniform, and these layers were defined as the surface water in this study area. In the surface water, the slopes of the regression lines of the Cd-PO₄ plot were 0.162, 0.156, and 0.226 (nM/μM) at Sts. 1, 2, and 3, respectively, and these values were much closer to the estimated regenerated ratio of Cd to PO₄ from the Apparent Oxygen Utilization (AOU)-Cd/PO₄ plots, which was 0.197 (nM/μM) in this study area. Below surface layers, the slopes of the Cd-PO₄ plot changed to 0.371, 0.352, and 0.362 (nM//μM) at Sts. 1, 2, and 3, respectively. In the relationships between Cd and PO₄, clear deviations or kinks were observed at three stations at a PO₄ concentration of approximately 0.2 μM in the plot, which was attributable to the discontinuity of surface water and the other layers across the North Pacific subtropical mode water. In studies of the interaction between surface water and biogenic particles concerning the Cd/PO₄ ratio, separate analyses of seawater (surface water and the other layers) should be carried out to obtain the individual surface water ratio because the Cd/PO₄ ratio in the surface water is expected to differ from that of the underlying water. Furthermore, the biological fractionation of these constituents is based on the surface water ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

南海“耗氧”及“贫氧”水体中消耗氧与硝酸盐和磷酸盐再生比值估算

通过对南海深海区硝酸氮、活性磷酸盐垂直分布的研究,分析了南海垂向耗氧和贫氧水体中硝酸氮、活性磷酸盐和表观耗氧量之间的关系.结果表明垂向上次表层、中层和深层水团中氧的消耗与营养盐再生比值均小于理论值,由此推断水体的混合为有机物再矿化提供氧的补充,但水团混合对水柱中硝酸氮、活性磷酸盐的影响不大,在次表层和中层水团中造成营养盐浓度变化主要是由于有机物再矿化的结果;在深层水团中有机物再矿化对水柱中营养盐梯度变化已不占主导地位.     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Tracing dissolved organic matter cycling in the eastern boundary of the temperate North Atlantic using absorption and fluorescence spectroscopy

Apparent oxygen utilization (AOU), dissolved organic carbon (DOC), coloured dissolved organic matter (CDOM) absorption spectra, and CDOM fluorescence characteristic of aromatic amino acids (excitation/emission 280 nm/320 nm; F(280/320)) and marine-humic like substances (320 nm/410 nm; F(320/410)) were measured in full depth during a cruise in the temperate Eastern North Atlantic (ENA). An optimum multi-parameter (OMP) inverse method was run to calculate water mass proportion-weighted average (archetypal) concentrations of these chemical parameters for all water masses and samples. Archetypal concentrations retain the variability due to water mass mixing and basin scale mineralization from the water mass formation sites to the study area. Conversely, the difference between measured and archetypal concentrations, retain the variability due to dissimilarities in mineralization processes within the study area. Our analysis indicates that DOC supported 26±3% of the AOU in the dark temperate ENA and that basin scale processes occurring at and from the formation area of the water masses explained 63% of the total DOC variability. Our data also suggests that DOC remineralized at the basin scale was of lower molecular weight, and with a lower proportion of fluorescent aromatic amino acids than found within the study area. The relationship between the absorption coefficient at 254 nm (a_CDOM(254)) and AOU indicates that a_CDOM(254) was consumed during organic matter remineralization in the dark ocean, with 55% of the variability being explained by basin scale processes. The relationships of F(320/410) with AOU and DOC confirmed that marine humic-like substances are produced by microbial degradation processes, at a rate of 6.1±0.9×10⁻³ mg equivalents of QS mol AOU⁻¹. Our results also indicate that basin-scale remineralization processes account for 85% of the total variability of F(320/410), emphasizing that large scale processes control the formation of humic-like substance in the dark ENA.     

Vertical distribution of dissolved organic carbon (DOC) in the Western Mediterranean Sea in relation to the hydrological characteristics

Vertical profiles of dissolved organic carbon (DOC) from eight hydrological stations in the Tyrrhenian Sea, Sardinia Channel and Algerian Sea, are reported. DOC exhibits concentrations ranging from 58 to 88 μM in surface water, 43–57 μM in the intermediate layer and 49–63 μM in deep waters. The assessment of the hydrological characteristics allows different water masses in the study area to be identified; moreover, different hydrological processes are observed in the Tyrrhenian and Algerian basins. DOC exhibits different values in the different water masses. The lowest DOC concentrations (43–46 μM) were found in the Tyrrhenian Levantine Intermediate Water (LIW). Correlations between DOC and apparent oxygen utilization (AOU), investigated within each water mass, exhibit different behaviors in the intermediate and deep waters, suggesting the occurrence of different processes of oxygen consumption in the different water masses.     

Tidal-induced inorganic carbon dynamics in the Strait of Gibraltar

This study presents the distribution of dissolved inorganic carbon (DIC) along the Strait of Gibraltar, its tidal-induced variability, as well as the inorganic carbon exchange between the Atlantic Ocean and Mediterranean Sea. During November 2003, water column samples were collected at nine stations to measure total alkalinity (TA), pH, and dissolved oxygen (DO) for the spatial characterization of the carbonate system. At the same time, anchored samplings were carried out, above the Camarinal Sill and in the Eastern Section of the Strait, in order to assess the tidal mixing effects for oxygen and DIC distribution on the water column. Three distinct water masses can be discerned in this area: the Surface Atlantic Water (SAW), the Mediterranean Water (MW), and the less abundant North Atlantic Central Water (NACW). The observations show an increase in the DIC and a decrease in oxygen concentration with depth, related to the different physico-chemical features of each water mass. The results show the high time-dependence of the vertical distribution of DIC with the interface oscillation, affected by the intense mixing processes taking place in the Strait. Intense mixing episodes over the Camarinal Sill are responsible for an increase in the DIC concentrations in the upper layer of the Eastern Section of the Strait. Higher DIC concentrations in the Mediterranean than in the Atlantic waters are responsible for a net DIC transport of 1.47×10¹² mol C yr⁻¹ to the Atlantic Ocean. Nevertheless, the net exchange is highly sensitive to the interface definition, as well as to the estimate of water volume transport used.     

Processes influencing iron distribution in the coastal waters of the Tsugaru Strait,Japan

We report measurements of iron, nutrients, dissolved oxygen, humic-type fluorescence intensity and chlorophyll a concentrations in the coastal waters at the inflow (western) and outflow (eastern) ends of Tsugaru Strait (Japan) in June 2003 and 2004. Two different water masses (intensive eastward flow “subtropical Tsugaru Warm Current Water (TWCw)” and weak westward flow “subarctic Oyashio Water (OW)”) were observed at the eastern end of the strait. TWCw at the southern part of the eastern strait was vertically homogeneous with a uniform concentrations of iron (0.7–1.1 nM for labile dissolved Fe and 14–20 nM for total dissolvable Fe in 2003) as well as other chemical, biological and physical components throughout the water column of 200 m due to strong vertical mixing in the strait. The degree of mixing in the Tsugaru Warm Current (TWC) is predominantly affected by diurnal tidal current, which is strong during the period of tropical tides and weak during the period of equinoctial ones. The especially strong vertical water mixing in 2003 is caused by large dissipation energy input due to the bottom friction of passage-flow through the strait and tidal current. At the northern part of the eastern strait, the fresh surface layer overlying the OW and the deep-bottom waters in 2003 contained large concentrations of dissolved iron, resulting from iron supplied from river runoff and shelf sediments, respectively. These results suggest that the most important mechanism for transporting iron in the strait is the strong vertical water mixing due to the tidal current, and that the iron sources in the coastal waters are the organic-associated, iron-rich freshwater input into the surface water.     

Dissolved organic matter cycling in the confluence of the Atlantic and Indian oceans south of Africa

The boundary between the Atlantic and Indian sectors of the Southern Ocean is a key spot of the thermohaline circulation, where the following water masses mix up: Indian Central water (ICW), South Atlantic Central Water (SACW), Antarctic Intermediate Water (AAIW), Circumpolar Deep Water (CDW), North Atlantic Deep Water (NADW), Weddell Sea Deep Water (WSDW) and Antarctic Winter Water (WW). An optimum multiparameter analysis based on the distributions of potential temperature, salinity, NO (=O₂+9.3×NO₃) and silicate during the GoodHope 2004 (GH04) cruise allowed us to (i) define the realms of these water masses; (ii) obtain the water mass proportion weighted-average (archetypal) apparent oxygen utilization (AOU) and dissolved organic carbon (DOC) concentrations of each water mass; and (iii) estimate the contribution of DOC to the oxygen demand of the study area. WW represented only 5.2% of the water volume sampled during GH04, followed by WSDW with 10.8%, NADW with 12.7%, SACW with 15.3%, AAIW with 23.1% and CDW with 32.8%. The distributions of DOC and AOU were mainly explained by the mixing of archetypal concentrations of these variables, 75±5% and 65±3% respectively, which retained the variability due to the basin-scale mineralization from the formation area to the barycentre of each water mass along the GH04 line. DOC accounted for 26±2% and 12±5% of the oxygen demand of the meso- and bathypelagic ocean, respectively. Conversely, local mineralization processes, retained by the residuals of the archetypal concentrations of DOC and AOU, did not contribute to improve significantly the mixing model of DOC.     

Does a general relationship exist between fluorescent dissolved organic matter and microbial respiration?—The case of the dark equatorial Atlantic Ocean

The distributions of humic-like fluorescent dissolved organic matter (at excitation/emission wavelengths of 340 nm/440 nm, F(340/440)) and apparent oxygen utilization (AOU) are determined from water samples taken at 27 stations along 7.5°N, in the equatorial Atlantic Ocean. The relationship between F(340/440) and AOU is evaluated. The influence of water mass mixing is removed through multiple regressions of both F(340/440) and AOU with salinity and temperature for the ocean interior. A general and significant relationship between the residuals of F(340/440) and AOU is found for the entire water column deeper than 200 m (R²=0.79, n=360, p-value <0.001), endorsing the idea that changes in fluorescence intensity are directly related to in situ oxidation of organic matter by microbial activity in the dark equatorial Atlantic Ocean. In addition, we analyse and discuss the relationships between the residuals of F(340/440) and AOU for all individual water masses.     

Increased Stratification and Decreased Lower Trophic Level Productivity in the Oyashio Region of the North Pacific: A 30-Year Retrospective Study

An analysis of the time series data sets collected from the 1960s to 1990s in the Oyashio Water revealed signs of alteration in the physical, chemical and biological properties of the water column in the western subarctic North Pacific. Wintertime salinity, phosphate concentration and apparent oxygen utilization (AOU) in the subsurface increased linearly over the 30 years. At the same time, salinity and phosphate in the surface mixed layer decreased. An increase in the density gradient in the surface and subsurface suggested that the water column stratification intensified, reducing the vertical exchange of water properties during the period. The Net Community Production (NCP), estimated from the phosphate consumption from February through August, also declined. Water column Chl a was approximately halved and diatoms decreased by one order of magnitude in spring, consistent with the multi-decadal decreasing trend of NCP. Zooplankton biomass was also nearly halved during the same period. In contrast, wintertime Chl a increased by 63% and diatom abundance doubled. Developmental timing became earlier in Neocalanus flemingeri, and spring occurrence of N. plumchrus increased after the 1980s. Reduced vertical water exchange might have limited nutrient supply to the level, decreasing winter-summer NCP for these three decades. It is speculated that, in the meantime, the earlier stabilization of the surface layer might have enhanced wintertime diatom production in the Oyashio's light-limited environment. This condition could allow zooplankton to effectively utilize diatoms from earlier timing, resulting in the apparent early developmental timing and abundance increase. This revised version was published online in July 2006 with corrections to the Cover Date.