Physico-chemical study of the dead sea waters. I. Activity coefficients of major ions in dead sea water

Conventional single-ion activity coefficients of major ions in Dead Sea brines, and their osmotic coefficients, have been estimated using Pitzer's thermodynamic treatment of mixed electrolyte solutions. For these calculations, higher-order terms have been taken into consideration. It has been shown that Pitzer's equations are applicable to such natural concentrated brines. The problem of gypsum solubility in the Dead Sea was examined. Dead Sea brines were shown to be oversaturated with respect to gypsum, and the degree of oversaturation increased very significantly during the last 20 years.     

Physico-chemical study of Dead Sea waters: II. Density measurements and equation of state of Dead Sea waters at 1 atm

The densities (p) of artificial solutions of Dead Sea waters have been measured at 20°, 25°, 30°, 35° and 40°C using a vibrating tube densimeter. The resulting relative densities (p — p_o, where p_o is the density of water) have been used to determine an equation of state for Dead Sea waters. The average deviation between experimental values and those calculated from the obtained equation was 0.000020 g ml^?1. A thermal expansion coefficient and the coefficients characterizing the influence of the changes in salt or ionic concentrations on the density of Dead Sea waters were calculated, and they were shown to be temperature and concentration dependent. The densities of Dead Sea waters were found to be very sensitive to any changes in ionic composition. The partial molal volumes of salt components were calculated and discussed.     

On dense water formation criteria and their application to the Mediterranean Sea

Recently proposed criteria to identify sites, periods and characteristics of dense water formation in the Mediterranean Sea are analyzed. These criteria were first obtained through tank experiments and numerical and theoretical analyses. They can be useful for discriminating between processes that reach the sea bottom and those involving only the less thick superficial layers. With these criteria, general characteristics of newly formed dense water can be inferred from a knowledge only of winter density stratification g′, of the buoyancy increase B due to the violent winter storms, and of the horizontal space scale R of the region of interest, a quantity usually identified by a decrease of 0.5–1°C of the SST. For the Mediterranean Sea, these criteria are applied here to the few known field observations and to more indirect “routine” information, namely climatological values of the stratification, numerical estimates of the buoyancy flux and remotely sensed SST from satellite imagery. In this way a stimulating picture of these dramatic phenomena is obtained, giving some insight into the possibility of forecasting and into other characteristics of dense water formation processes.     

Mercury speciation in surface and deep waters of the Mediterranean Sea

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.     

Viral abundance and distribution in mesopelagic and bathypelagic waters of the Mediterranean Sea

Despite the fact that marine viruses have been increasingly investigated in the last decade, knowledge on virus abundance, biomass and distribution in mesopelagic and bathypelagic waters is limited. We report here the results of a large-spatial-scale study (covering more than 3000 km) on the virioplankton distribution in epi-, meso- and bathypelagic waters in 19 areas of the Mediterranean Sea, from the Alboran Sea and Western Mediterranean, to the Tyrrhenian Sea, Sicily Channel and Ionian Sea. Integrated viral abundance in epipelagic waters was significantly higher than in deep-sea waters (on average, 2.4 vs. 0.5×10¹² viruses m⁻³). However, abundance of viruses in the deep-Mediterranean waters was the highest reported so far for deep seas worldwide (7.0 and 3.1×10¹¹ viruses m⁻³ in mesopelagic and bathypelagic waters, respectively) and their biomass accounted for 13–18% of total prokaryotic C biomass. The significant relationship between viral abundance and prokaryotic abundance and production in deep waters suggests that also deep-sea viruses are closely dependent on the abundance and metabolism of their hosts. Moreover, virus to prokaryote (and nucleoid-containing cell (NuCC)) abundance ratio increased with increasing depths suggesting that deep waters may represent optimal environments for viral survival or proliferation. Overall, our results indicate that deep waters may represent a significant reservoir of viruses and open new perspectives for future investigations of viral impact on the functioning of meso-bathypelagic ecosystems.     

Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

Stable isotope study of water, gypsum and carbonate samples from the Bannock and Tyro Basins, eastern Mediterranean

Seawater and brine samples collected along vertical profiles above the Bannock and Tyro Basins (eastern Mediterranean), and gypsum samples collected by dredging and coring the anoxic section of the Bannock Basin, have been studied for their δ¹⁸O values. The following conclusions may be drawn from these data: (1) The water of the deep brines is isotopically slightly different from modern Mediterranean bottom water and might be a ‘fossil water’ possibly formed during a recent, climatically cooler stage or when the evaporation was slightly higher than nowadays. (2) The similarity between the δ¹⁸O values of the brine samples from the Bannock and Tyro Basins supports the possibility that the ages of the two basins are very close to each other. (3) Gypsum crystals on the bottom of the Bannock Basin are probably being formed by the dissolution and reprecipitation of sub-bottom (or outcropping) Messinian evaporites. This hypothesis is supported by the oxygen isotopic values exhibited by the gypsum crystallization water and by the oxygen and sulphur isotopic composition of gypsum. (4) The shells of pelagic organisms included in gypsum are probably very recent, but not contemporary, and may be referred to cooler environmental conditions.     

Mercury methylation,demethylation and reduction rates in coastal and marine surface waters of the Mediterranean Sea

In situ experiments using isotopically labeled mercury species (¹⁹⁹Hg(II) and Me²⁰¹Hg) are used to investigate mercury transformation mechanisms, such as methylation, demethylation and reduction, in coastal and marine surface waters of the Mediterranean Sea. The aim of this work is to assess the relative contribution of photochemical versus biological processes to Hg transformation mechanisms. For this purpose, potential transformation rates measured under diurnal and dark incubation conditions are compared with major biogeochemical parameters (i.e. hydrological and biological data) in order to obtain the relative contribution of various biotic and abiotic mechanisms in both surface (high light) and bottom (low light) waters of the euphotic zone. The results demonstrate that coastal and marine euphotic zones are significant reactors for all Hg transformations investigated (i.e. methylation, demethylation, reduction). A major outcome demonstrates that Hg methylation is taking place in oxic surface seawater (0.3–6.3% day^− 1) and is mainly influenced by pelagic microorganism abundance and activities (phyto- and bacterioplankton). This evidences a new potential MeHg source in the marine water column, especially in oligotrophic deep-sea basins in which biogeochemistry is mostly governed by heterotrophic activity. For coastal and marine surface waters, although MeHg is mainly photochemically degraded (6.4–24.5% day^− 1), demethylation yields observed under dark condition may be attributed to microbial or chemical pathways (2.8–10.9% day^− 1). Photoreduction and photochemical reactions are the major mechanisms involved in DGM production for surface waters (3.2–16.9% day^− 1) but bacterial or phytoplanktonic reduction of Hg(II) cannot be excluded deeper in the euphotic zone (2.2–12.3% day^− 1). At the bottom of the euphotic zone, photochemical processes are thus avoided due to the attenuation of UV-visible sunlight radiation allowing biotic processes to be the most significant. These results suggest a new potential route for Hg species cycling in surface seawater and especially at the maximum biomass depth located at the bottom of the euphotic zone (i.e. maximum chlorophyll fluorescence). In this environment, DGM production and demethylation mechanisms are thus probably reduced whereas Hg methylation is enhanced by autotrophic and heterotrophic processes. Experimental results on mercury species uptake during these investigations further evidenced the strong affinity of MeHg for biogenic particles (i.e. microorganisms) that correspond to the first trophic level of the pelagic food web.     

Seasonal and depth-related dynamics of prokaryotes and viruses in surface and deep waters of the northwestern Mediterranean Sea

The study site located in the northwestern Mediterranean Sea was visited nine times in 2005–2006 to collect water samples from the epi- (5 m), meso- (200, 600 m), and bathypelagic (1000, 2000 m) zone. Total abundance of prokaryotes and viruses was determined by flow cytometry (FCM). Prokaryotic abundance in the epi-, meso-, and bathypelagic varied between 0.9 and 15.9×10⁵, 0.6 and 2.1×10⁵, and 0.3 and 1.3×10⁵ ml⁻¹, respectively. Variation of viral abundance in the epi-, meso-, and bathypelagic was between 1.2 and 57.5×10⁶, 0.5 and 3.5×10⁶, and 0.4 and 1.3×10⁶ ml⁻¹, respectively. The fraction of low (LNA) and high (HNA) nucleic acid prokaryotes averaged 42.9% and 57.1% throughout the water column and did not differ between depth layers. Throughout the water column the fraction of low, medium, and high fluorescent viruses (Vir-LF, Vir-MF, Vir-HF) averaged 66.3%, 30.2%, and 3.5%. Vir-LF and Vir-MF did not differ between depth layers; however, Vir-HF showed a preference for surface waters. The fraction of LNA cells decreased in the epi- and increased in the bathypelagic with decreasing stratification. The fraction of Vir-LF viruses increased in the epipelagic and decreased in the bathypelagic with increasing prokaryotic abundance. Also, the relationship between viral abundance and the bacterial community was different in surface and deep waters. The data suggest that different mechanisms of interaction between viruses and their prokaryotic hosts prevail at the surface and in deep waters.     

南海表面浮力通量、水型变性及南海"暖水"的消长分析

利用英国南安普敦海洋中心(SOC)海-气界面的热量和淡水通量资料以及世界大洋图集(WOA01)的海面温度和盐度资料计算了南海表面各月的有效浮力通量及水型变性矢量场,分析了南海表层暖水形成和发展的季节性特征。研究结果表明,南海表层暖水的发展、维持以及消亡在很大程度上受到海洋表层浮力通量的影响;此外,南海上层水体密度的垂直结构和变化也深受表面浮力通量和表层水型变性的影响。在中、北部,南海的垂向结构季节性变化较为明显,其中冬季表层水体的下沉强度最大,深度最深,而夏季表层水体却无下沉趋势。     

Exchange fluxes of nutrients between sediment and sea water in the Bohai Sea

IrocrIowThere is a linkage in shallow marine systerns between sea-noor biOgaxhemical pmeessesand water column pnductivity (Bereson et al., l998). Benthic fluxes provide a significantsource of nutrients to the overlying water tO supPOrt primary pnduction and play a role in de-.creasing oxygen concentrations (van et al., l999; Cowan and Boynton, l996; Berelson etal., 1998; Friedl et al., l998; Zabel et al., l998). TherefOre, it is imPOrtant to define theediment di8genetic pathways for the …     

Size distribution of detrital mineral grains suspended in surface waters of the Yellow Sea and East China sea

Anisotropic detrital mineral grains were segregated microscopically from the suspended matter in surface waters of the Yellow Sea and East China Sea. Microscopic grain-size measurements of the anisotropic minerals were carried out for more than 80 slide specimens which are distributed homogeneously in the Yellow Sea and East China Sea. The distribution maps of mean grain size and sorting coefficients indicate that the mean size becomes coarser as one goes offshore, and the sorting coefficients are larger in the southern portion and smaller in the northern portion of this region. The clay-sized minerals in the suspended sediments carried out by the deltaic rivers of the continent were deposited in the nearshore area while coarser silt-sized minerals were suspended in offshore waters. The larger sorting coefficients (standard deviations) in the southern portion may imply that the silt-sized grains of offshore waters contain coarser sand-sized grains. The sand-sized grains may be supplied from offshore Taiwan and the Bashi Channel and transported by the main flow of the Kuroshio current.     

冬季大风影响下的渤黄海水交换特征

利用 ROMS海洋数值模式对 2006年冬季渤黄海的海洋动力环境进行模拟,基于温度、盐度模拟结果,使用谱混合 模型进行水团分析,定义了渤海海峡地区的水交换区。并进一步讨论了冬季大风事件对水交换区的影响,给出了冬季大风影 响下的渤黄海水交换特征。研究得出,冬季的黄海水团以“舌”形分布于渤海海峡地区,水交换区则表现为沿" 舌" 形边缘 呈带状分布,具有西北--东南的走向趋势,并且在“舌”尖处的水交换面积最大。通过缩小研究范围,发现位于黄海最北部 的沿岸海域并不参与渤黄海之间的水体交换。最后研究发现,冬季大风事件对渤海水交换具有促进作用,具体表现为：大风 过程使黄海暖流对渤海的入侵更加深入,水交换区向渤海方向伸展,南部的水交换带变宽,河流径流进入渤海后与渤海水的 混合区加大,并发生北移。     

南中国海海水中多环芳烃的分布特征及源分析

利用气相色谱-质谱联用(GC-MS)技术,对2012年10月采自南中国34个站位的表层、500 m层、底层海水中的16种多环芳烃(16PAHs)进行了检测分析。结果显示:南中国海海水中16PAHs的含量相对于其他类似广阔水域较低,分布特征大致呈现500 m层表层底层。经特征PAHs组分分析判定南中国海海水中PAHs主要来源于石油及其产品。     

Time-series measurements of Th in water column and sediment trap samples from the northwestern Mediterranean Sea

Disequilibrium between ²³⁴Th and ²³⁸U in water column profiles has been used to estimate the settling flux of Th (and, by proxy, of particulate organic carbon); yet potentially major non-steady-state influences on ²³⁴Th profiles are often not able to be considered in estimations of flux. We have compared temporal series of ²³⁴Th distributions in the upper water column at both coastal and deep-water sites in the northwestern Mediterranean Sea to coeval sediment trap records at the same sites. We have used sediment trap records of ²³⁴Th fluxes to predict temporal changes in water column ²³⁴Th deficits and have compared the predicted deficits to those measured to determine whether the time-evolution of the two coincide. At the coastal site (327 m water depth), trends in the two estimates of water column ²³⁴Th deficits are in fairly close agreement over the 1-month deployment during the spring bloom in 1999. In contrast, the pattern of water column ²³⁴Th deficits is poorly predicted by sediment trap records at the deep-water site (DYFAMED, 2300 m water depth) in both 2003 and 2005. In particular, the transition from a mesotrophic to an oligotrophic system, clearly seen in trap fluxes, is not evident in water column ²³⁴Th profiles, which show high-frequency variability. Allowing trapping efficiencies to vary from 100% does not reconcile the differences between trap and water column deficit observations; we conclude that substantial lateral and vertical advective influences must be invoked to account for the differences.Advective influences are potentially greater on ²³⁴Th fluxes derived from water column deficits relative to those obtained from traps because the calculation of deficits in open-ocean settings is dominated by the magnitude of the “dissolved” ²³⁴Th fraction. For observed current velocities of 5–20 cm s⁻¹, in one radioactive mean-life of ²³⁴Th, the water column at the DYFAMED site can reflect ²³⁴Th scavenging produced tens to hundreds of kilometers away. In contrast, most of the ²³⁴Th flux collected in shallow sediment traps at the DFYFAMED site was in the fraction settling >200 m d⁻¹; in effect the sediment trap can integrate the ²³⁴Th flux over distances 40-fold less than water column ²³⁴Th distributions. In some sense, sediment trap and water column sampling for ²³⁴Th provide complementary pictures of ²³⁴Th export. However, because the two methods can be dominated by different processes and are subject to different biases, their comparison must be treated with caution.     

On the potentiality of using the fluorescence of humic substances for the determination of hydrological structures in coastal sea waters and in inland water basins

This paper describes the potentialities of the characteristics of the fluorescence of humic substances (HS), namely, their intensity normalized to the Raman band intensity of water and the shape of their fluorescence band, as indications of the hydrological structures of the surface water layer in marine coastal areas (using the example of the North Sea region near the East Frisian Islands and the estuary zone of the Weser River) and in inland water basins (using the example of the Rybinsk Reservoir). We demonstrate that the HS fluorescence band??s shape parameters allow stricter discrimination of the dominant water masses as compared to the admixtures?? concentration-related indicators (the salinity, electric conductivity, and HS fluorescence intensity).     

秋季南黄海水文特征及海水的混合与交换

根据1996年10月中韩合作调查获得的CTD资料,分析探讨了南黄海秋季跃层的分布特征及垂直混合状况,同时对黄海冷水团的垂向混合进行了初步探讨.还利用改进后的逐步聚类分析法划分了表、底层水团,确定了各水团的温度、盐度、溶解氧和PH值4要素的平均特征值,并根据各水团的特性和温度、盐度的平面分布特征,重点探讨了黄海水与沿岸水及东海水的混合和交换.     

Effects of sea ice formation and diapycnal mixing on the Okhotsk Sea intermediate water clarified with oxygen isotopes

Processes relating to the formation of dense shelf water and intermediate water in the Okhotsk Sea were studied by examining oxygen isotope ratios (δ¹⁸O), salinity, and temperature. The salinity and δ¹⁸O of the cold dense shelf water on the northern continental shelf showed peculiar relationship. The relationship indicates that 3% of the mixed-layer water, having salinity of 32.6, froze and the remaining 97% became dense shelf water of salinities of more than 33.2 (σ_θ>26.7) during the sea ice formation. The salinity–δ¹⁸O relationship also shows that 20% of the Okhotsk Sea Intermediate Water at the σ_θ=26.8 level was derived from the dense shelf water. The remaining 80% came from the Western Subarctic Pacific water modified by diapycnal mixing of water affected by the surface cooling and freshening within the Okhotsk Sea. The mixing with dense shelf water contributes to only 26% of the temperature difference or 8% of the salinity difference between the original Pacific water and the Okhotsk Sea Intermediate Water at σ_θ=26.8. This result suggests that the cold and less saline properties of the Okhotsk Sea Intermediate Water are produced mainly by diapycnal mixing, rather than by mixing of the Pacific water with the dense shelf water.     

Use of lipids and their degradation products as biomarkers for carbon cycling in the northwestern Mediterranean Sea

Changes in phytoplankton composition and degradation of particulate organic matter (POM) in the northwestern Mediterranean Sea were studied using time-series sediment trap samples collected during the spring of 2003 at the DYFAMED station. Lipid biomarkers (pigments, fatty acids, sterols, acyclic isoprenoids, alkenones and n-alkanols) were used to identify the main contributors to the POM produced during two phytoplankton blooms, while the effects of photooxidation, autoxidation and biodegradation were differentiated using characteristic lipid degradation products. Traps collected material corresponding to pre-bloom, bloom and post-bloom periods. Pigment analyses in the integrated (0-200 m) water column samples indicated that diatoms dominated the initial stages of the bloom event, with smaller amounts of haptophytes and pelagophytes. During the second part of bloom event there was a switch to haptophyte dominance with significant contributions from diatoms and pelagophytes, and an increased contribution from cryptophytes. Fatty acid distributions in the trap samples reflected contributions from marine bacteria, phytoplankton and zooplankton. Photooxidation and autoxidation products of monounsaturated oleic, cis-vaccenic and palmitoleic acids were detected along with photooxidation products from the chlorophyll side-chain. The relatively good correlation between the variation of U₃₇^K′ index and specific phytol autoxidation product percentage allowed us to attribute the alterations of U₃₇^K′ observed during the pre-bloom period and in the deeper traps to the involvement of selective autoxidative degradation processes. A variety of sterol oxidation products formed by biohydrogenation, autoxidation and photooxidation were detected. Sterol degradation products appeared to be less suited than oxidation products of monounsaturated fatty acids for the precise monitoring of the degradation state of POM, but their stable functionalized cyclic structure constitutes a useful tool to estimate the part played by biotic and abiotic processes. In these waters, biotic degradation generally predominates, but abiotic degradation is not negligible and, as expected, the extent of biotic degradation increases with depth. To obtain a more complete picture of POM degradation, the use of a pool of lipid degradation products (i.e. from unsaturated fatty acids, the phytyl side-chain and sterols) should be employed.