Characterization and seasonal variations of surface active substances in the natural sea surface micro-layers of the coastal Middle Adriatic stations

Surface micro-layer (ML) samples were collected in different seasons over a long time period in the coastal area of the Middle Adriatic Sea including the seawater Rogoznica lake location and the semi-enclosed estuarine Martinska station. Natural surface micro-layers were studied as original samples and as ex-situ reconstructed films after previous extraction by organic solvents of different polarities (n-hexane and dichloromethane). Using alternating current (AC) voltammetry (out-of-phase mode) the concentration of surface active substances (SAS) in original ML of both locations was determined, and the enrichment factor (EF) in the ML was related to the underlayer water (ULW) samples collected at 0.5 m depth. Seasonal variability of SAS concentrations of the ML was observed at both locations. The ex-situ films were studied using a modified AC voltammetry method (out-of-phase mode) transferring an organic extract of natural micro-layers spread onto electrolyte from the air-water interface to the mercury electrode surface. The comparison of adsorption characteristics for model lipids of different polarities and those of transferred ex-situ reconstructed films has revealed that different types of lipid material were present in each ex-situ film of the same micro-layer. Additional characterization of the surface active material of natural MLs was carried out by AC voltammetry (in-phase mode) using cathodic reduction of cadmium ions as an indicator of permeability of different films adsorbed at the mercury electrode. The SAS of ML of both investigated locations induced an inhibition effect to the reduction of cadmium ions. Seasonal variations of inhibition have also been noticed. The electrochemical study contributed to the physicochemical characterization of the surface active matter of the surface micro-layer with the emphasis to the role of lipids which, although they represent a minor fraction of the total micro-layer organic material, contribute considerably to the micro-layer formation and stabilization at the air–water interface.     

天然水体中微量过氧化氢的测定方法

天然环境中的H2O2与水体中的光化学反应、氧化还原反应有密切关系,是影响化学物质（金属离子、腐殖质等）在水环境中的迁移、转化、归宿及生态效应的重要因素,也是酸雨形成的主要原因之一。地表天然水中的H2O2主要来自表层水中可溶解有机物（DOM）的光化学反应,     

The surface chemistry of calcium carbonate minerals in natural waters: An overview

The behavior of carbonates in natural waters is strongly influenced by surface chemistry. Such major aspects of carbonate behavior as the retention of supersaturation in the surface ocean, persistence of metastable phases, and carbonate accumulation in sediments overlain by undersaturated waters have been attributed to processes occurring on carbonate mineral surfaces. Adsorption on carbonate minerals is often strongly influenced by epitaxial considerations and dominated by strong chemical interactions which lead to irreversible behavior. It has been demonstrated for several inorganic ions that their adsorption onto carbonate mineral surfaces can lead to new surface phases, such as apatite and rhodochrosite. A variety of organic compounds have been found to strongly adsorb on carbonate mineral surfaces. However, our understanding of the role of organic matter in natural systems is significantly complicated by the biogenic nature of most marine carbonates.     

A simple fractionation method for determination of phosphorus components in phytoplankton: Application to natural populations of phytoplankton in summer surface waters of Tokyo Bay

A simple procedure for fractionation of phosphorus components in natural populations of phytoplankton has been developed. By a combination of a trichloroacetic acid (TCA) extraction, a hot dilute acid treatment, a charcoal treatment and an organic solvent extraction, cellular phosphorus was divided into orthophosphate, nucleotide phosphorus, sugar phosphates, acid-soluble polyphosphates, lipid phosphorus, nucleic acid phosphorus, acid-insoluble polyphosphates, and residual phosphorus. The recovery of phosphorus was 94±5%. This technique was applied to natural populations of phytoplankton in summer surface waters of Tokyo Bay. Nucleic acid phosphorus and orthophosphate were most abundant, and accounted for 30 to 50% of total phytoplankton phosphorus. The nucleic acid phosphorus was proportional to the biomass of phytoplankton, irrespective of ambient nutrient concentrations. The orthophosphate showed the largest change in association with the change in cellular phosphorus content as well as in ambient phosphate. The orthophosphate serves as a phosphorus reserve in the natural populations of phytoplankton in summer surface waters of Tokyo Bay whereSkeletonema costatum was dominant. Acid-insoluble polyphosphates tended to increase when ambient concentration of phosphate was high, but their amounts were almost one order of magnitude lower than that of orthophosphate.     

On-line determination of silver in natural waters by inductively-coupled plasma mass spectrometry: Influence of organic matter

We investigated interference effects on the analysis of silver in estuarine and oceanic waters using on-line high resolution inductively coupled plasma mass spectrometry (ICP-MS). A mini-column packed with a strong anion exchange resin (Dowex 1-X8) was used in a flow-injection system to separate and concentrate silver from the saline samples prior to on-line determination by ICP-MS. A series of analyses showed the concentrations of silver measured in San Francisco Bay estuary and the North Pacific that had been acidified (pH < 2) and stored for periods of 1–2 years were 10–70% lower than those measured in aliquots of those samples after ultraviolet (UV) irradiation. Additional silver released after UV irradiation of the estuarine waters, but not the ocean waters, was positively correlated (r = 0.77, simple linear correlation) with chlorophyll-a concentrations, but not with dissolved organic carbon (DOC) concentrations. Spatial distributions of chlorophyll-a and UV-released silver also exhibited similar patterns along a salinity gradient in the San Francisco Bay estuary, suggesting an in situ biogenic source of the interferent for the silver measurements.     

Colorimetric determination of nanomolar concentrations of silicate in natural waters after liquid-liquid extraction using methyl isobutyl ketone

A sensitive solvent extraction method for the determination of nonamolar concentrations of silicate in natural waters is developed. According to the traditional aqueous silicate method, silicomolybdenum blue formed by the reaction between silicate and ammoni- um molydate and reduced by metol-sulfite reagent is extracted by methyl isobutyl ketone. The absorbance can be enhanced substantially up to 10-folds. The detection limit of silicate is 8 nmol/dm^3 , which is one tenth smaller than the traditional method, with the precision of 4.0% at a silicate level of 50 nmol/dm^3 and 3.2% at a silicate level of 6 μmol/dm^3. Comparing the calibration curves in the distilled water and seawater, it can be seen that the salt effect also exists in the extraction method. However, the salt effect is a linear function of the salinity and can be corrected by simple calibration. The proposed method is successfully applied to the determination of silicate in natural waters. Natural concentrations of arsenate, arsenite and phosphate cause negligible interference.     

天然水的主要离子与水合氧化铁表面相互作用的实验研究

本文应用微电泳法研究天然水体的Na~+、K~+、Cl~-、Mg~(2+)、Ca~(2+)和SO_4~(2-)等主要离子与水合氧化铁表面的相互作用,分析了各离子浓度对水合氧化铁电泳淌度的影响和体系pH值的变化。结果表明,Na~+、K~+和Cl~-离子几乎不与水合氧化铁表面相互作用;Mg~(2+)、Ca~(2+)和SO_4~(2-)离子与水合氧化铁表面发生吸附作用,在pH为7.5左右的介质中,吸附能力的次序为Mg~(2+)>Ca~(2+)>SO_4~(2-)。     

The monosaccharide spectra of natural waters

Monosaccharides were determined in waters and sediment pore waters from a wide variety of environments and locations. Desalting was performed by electrodialysis and concentrated extracts were analyzed by two forms of liquid chromatography. At least 12 sugars were identified. Glucose and fructose were the dominant monosaccharides in nearly all samples examined. Analyses of over 150 seawater and sediment pore water samples showed that fructose is highly significantly correlated (>0.99) with glucose concentrations. Laboratory kinetic experiments on the epimerization reaction, glucose ? fructose, in sterilized natural seawater in the dark, yielded a forward rate constant, k₁, of 1.2 × 10^?5 h^?1 at 25°C and 1.6 × 10^?7 h^?1 at 2°C. The approximate time required to attain equilibrium at 25°C was 1.1 y and at 2°C, 15.4 y; the measured equilibrium constant was in the range 0.3–0.4. The actual ratio of fructose to glucose in natural water samples was usually in the range 1.0–1.4/l, independent of the total monosaccharide concentrations, which varied in the samples by a factor of ～100. Several possible explanations for the apparent discrepancy in the determined and found ratios are discussed: the presence of universal, as yet, undiscovered major biological sources for fructose in marine environments; preferential utilization of glucose; preferential incorporation of fructose into or onto inorganic colloids; and preferential formation of fructose-transition metal ion associations.     

Sources and sinks of methylgermanium in natural waters

New data have extended our understanding of the distribution and behavior of methylgermanium in the environment. Laboratory attempts to induce aerobic methylation with known biological and abiotic methylating agents were unsuccessful; this confirmed previous field observations of methylgermanium's unreactive behavior. However, biomethylation of inorganic germanium was observed in the anaerobic digestor of a sewage treatment plant, which suggested a terrestrial methanogenic source. Attempts to locate such a source in methanogenic swamps and their drainages reveal very low methylgermanium concentrations typical of other remote, pristine rivers. Polluted rivers have monomethylgermanium (MMGe) and dimethylgermanium (DMGe) concentrations 3–100 times higher than those of pristine rivers, which suggests an anthropogenic source of methylgermanium as a result of the synergistic effects of sewage treatment and coal-ash derived inorganic germanium contamination. A new high-precision profile of MMGe and DMGe in the Sargasso Sea shows conservative behavior with no vertical gradients. However, marine anoxic basins have both inorganic germanium enrichment and methylgermanium depletion, which suggests that of marine anaerobic processes are responsible for demethylating marine organogermanium. These results all suggest that methylgermanium is produced on the continents, is unreactive in the open ocean, and is destroyed in marine anoxic environments. The residence time of organogermanium in the sea, based on a continental source (pristine rivers), is at least 1 Ma, consistent with its unreactive nature, its observed distribution in the ocean, and rates of destruction in anoxic basins.     

Investigations on dissolved copper—organic substances in Baltic waters

A technique for the pH-controlled isolation and separation of dissolved copper—organic substances from large amounts of seawater is described. The method has been applied in two cruises in the Bothnian and Gotland Seas of the Baltic. In both areas the correlation between the amount of isolated dissolved organic material (DOM) and the concentration of organic copper in seawater has been found to be highly significant. Under the conditions established in our experiments, organic copper fractions detected in Baltic waters were in the range of about 5% of total copper. HPLC chromatograms and UV irradiation experiments from DOM extracts strongly indicate the existence of dissolved organic-copper compounds in Baltic waters.     

Voltammetric methods of sulfate ion analysis in natural waters

Sulfate anion can be measured in waters of widely varying salinity by polarography and amperometry. Polarography is the preferred method because it allows for measurement of sulfate in the 50-ppm range. The polarographic method is rapid, precise, and can be adapted for smaller sample volumes by simple modification of the sample preparation. We report a precision of 0.17% on I.A.P.S.O. standard seawater and 0.90% on 50-ppm samples. Amperometry requires more time overall for analyses because it is a titrimetric method, but it also is a precise technique (0.28% on I.A.P.S.O. standard seawater). Both techniques do not require any unusual sample preparation and are easily performed in most laboratories.     

A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters

Total dissolved nitrogen(TDN) is an important parameter for assessing the nutrient cycling and status of natural waters.The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water.The TDN in various systems has been largely documented,and the concentrations of TDN are usually obtained using high-temperature catalytic(HTC) or persulfate oxidation(PO).However,the accuracy of these methods and their suitabil...     

Microstructure measurements in natural waters: Methodology and applications

Modern approaches to microstructure data processing, including wavelet denoising, are discussed. The wavelet procedure is applied to small-scale shear signals before estimating the dissipation rate ε and to the temperature/density profiles used to calculate Thorpe scales. Microstructure data obtained on the Mediterranean shelf of Catalonia are used to illustrate various approaches to the Thorpe displacement calculations. It is suggested that the Weibull probability function is an appropriate model for the Thorpe scale distribution. Microstructure measurements from the upper layer of the Boadella reservoir (Catalonia, Spain) support this finding.A new analytical approximation for the 1D Panchev–Kesich spectrum is deduced and the results of ε computation are compared with spectral fitting by the widely used Nasmyth spectrum. Applying the Kraichnan spectral model to compute ε from temperature spectra in the convective-viscous sub-range is examined as an alternative to the Batchelor spectrum. Microstructure measurements taken in Lake Banyoles (Catalonia, Spain) and in the North Atlantic were used for spectral calculations.Statistical analysis of eddy K_b and thermal K_θ diffusivities measured on a shallow shelf of the Black Sea shows the importance of process-orientated domain averaging of the diffusivities in obtaining good correspondence between K_b and K_θ in active turbulent regions. In weakly turbulent, stratified interior layers, the averaged K_b and K_θ differ significantly, which may point to the inapplicability of isotropic formulae used for ε and temperature dissipation χ_θ estimates, as well as to a dependence of the mixing efficiency γ on the Richardson number or in some cases on regions of fossil turbulence.     

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).     

A sampler for concentrating radionuclides from natural waters

A sampler which permits concentration of both particulate and dissolved radionuclides from large volumes of ocean and freshwater has been developed and tested. The water sample passes through a filtration section for particle removal, then through a sorption section where the radionuclides of interest are removed on sorption or ion exchange beds. Components of the sampler which contact the water are of polyvinyl chloride construction, and flow rates of about 40 l./min are employed. This sampler has been successfully employed in concentrating some twenty radionuclides from ocean and fresh waters.     

低共熔溶剂提取海洋活性物质研究进展

海洋活性物质是指对生命活动有影响的海洋生物组分或代谢产物,在医药、化妆品、保健食品等领域具有广泛的应用。低共熔溶剂(deepeutecticsolvent,DES)是基于离子液体所发展而来的一种新型绿色溶剂,它具备可设计、可回收、生物相容性高、合成简易及成本低廉等多重优势,在天然活性物质的提取中具有巨大的应用前景,引起了国内外研究学者的广泛关注。本文综述了DES在海洋活性物质(包括海洋多糖、蛋白质、DNA、生物柴油、酚类和萜烯类化合物等)提取中的应用,以期为海洋活性物质的绿色提取和应用提供新的策略。     

Sampling and analysis for Pu and Am in natural waters

Measurement of the concentrations and physico-chemical states of transuranic elements in natural waters is difficult because of the low levels and the lack of stable elements present for comparison. A sorption technique for sampling transuranic radionuclides from up to 4000 l of water in 3 h is discussed here. Particulate, soluble, and, what is believed to be, colloidal fractions are collected and analyzed separately. The technique has been tested in fresh and salt water for Pu and Am both in the field and in the laboratory and the results are reported. It is a reliable method for measuring the concentrations of Pu and Am in natural waters and simplifies the collection, transport and measurement of large-volume water samples.     

极地微生物活性物质研究进展

极地具有独特的地理及气候特征,除短暂的夏季部分地区有冰雪融化外,其余均被常年的冰雪所覆盖。变化极大的光照辐射、季节性的光照时间、极低的温度造就了极地微生物特殊的生物学特征。自1908年Ekelof首次报导在南极分离出微生物后,各国的微生物学家相继在极地进行了大量的研究工作,证明了极