Potentiometric determination of calcium and magnesium in seawater

Methods are described for the complexometric determination of calcium and magnesium in seawater, using an amalgamated silver electrode for end-point detection. In the presence of a small amount of mercury(II)-chelonate, the amalgamated silver electrode serves as a pM indicator during the complexometric titration, the Hg complex being stronger than Ca, Mg and Sr complexes. Calcium is determined by titration with EGTA, calcium+magnesium+strontium by titration with EDTA and magnesium is obtained by difference. Average values of 0.02120 (standard deviation 0.00004) for Ca:Cl‰ and 0.06671 (standard deviation 0.00014) for Mg:Cl‰ were obtained for samples from tropical North Atlantic Ocean.     

The steady-state calcium carbonate ion activity product of recent shallow water carbonate sediments in seawater: a comparison of field observations and laboratory experiments

Closed system equilibration experiments between natural seawater and shallow water calcium carbonate-rich sediments from the Bahamas yielded steady-state calcium carbonate ion activity products (CCIAP). Results obtained from initially supersaturated and undersaturated solutions were in good agreement. Experiments conducted with the addition of a biocide and/or the destruction of sediment organic matter gave results similar to those obtained in systems where these treatments were not used. Excellent agreement was also found between CCIAP values for 8 day and more than 50 day equilibration times. Our results, therefore, meet the major criteria for at least metastable equilibrium between the solution and carbonate sediment.Fine-grained samples produced a CCIAP close to the value predicted for aragonite, which is the major carbonate phase in all samples. Coarse-grained sediments produced larger CCIAP values of up to 2.8 times that predicted for aragonite equilibrium. The CCIAP for the coarse-grained sediments is probably produced by high-Mg calcite which is a significant component of these sediments. Oolite samples were among the coarse-grained sediment samples studied. They also produced results much greater than expected for aragonite equilibrium. This brings into question their use as material for measuring aragonite solubility as has been done in the past.The CCIAP measured in the laboratory experiments are in good agreement with field observations of pore-water CCIAP values from the fine-grained sediments. Coarse-grained sediments showed greater variability, with higher CCIAP values generally occurring in the pore waters than in the laboratory experiments. Since the overlying waters were always at a higher CCIAP than the pore waters, the major factor causing this difference is believed to be the short residence time of pore waters in the coarse-grained sediments, which is the result of the high-energy hydrodynamic environments in which they reside.     

海水电沉积作用碳酸钙结晶与珊瑚骨骼晶体的比较

电沉积促进珊瑚生长和岸礁修复技术是国际上常采用的生态修复方法,但电沉积技术中电流条件与沉积晶体之间的关系却鲜有研究,关于其形成的电沉积物的晶体结构的报道更是少有。本文探索了在不同电流密度的条件下海水形成碳酸钙晶体的特点,并与珊瑚骨骼晶体进行了对比。本实验设置了300、600、900和1200 m A/m2四组电流密度,在海水中进行5 d电沉积反应,实验后称量了阴极上形成的电沉积物质量,用扫描电子显微镜和X-射线衍射分析了电沉积物中晶体特点并与珊瑚骨骼进行了比较。结果发现,随着电流密度增大,电沉积物质量增加,电流密度为600 m A/m2条件下电沉积物形成的速率与南海的滨珊瑚的生长速率相当。在各个电流密度梯度条件下形成的晶体均与珊瑚骨骼的晶体结构相似。较低电流密度下电沉积物中碳酸钙比例较高。其中,在电流密度为600 m A/m2的条件下,形成的沉积物碳酸钙文石比例最高,和珊瑚骨骼晶体最为接近。本研究为促珊瑚生长的电沉积技术提供了基础数据和理论。     

模拟添加氮对海水溶解无机碳体系的影响

碳和氮作为主要的生源要素对维持海洋生态系的正常运转起着至关重要的作用,碳与氮的变化是相互耦合的且呈双向作用,为探讨海水无机碳与氮的相互作用规律,研究了室内模拟添加硝酸盐对海水无机碳体系pH、溶解无机碳(DIC)、HCO3-、二氧化碳分压(Pco2)的影响。结果表明,在室内培养的条件下,单纯添加硝酸盐(增加至原海水硝酸盐浓度的5-20倍)可引起培养体系浮游生物量的变化,但不能引起海水pH及DIC、HCO-3含量的明显变化,对DIC而言,其变化率仅仅在1%以内,但可导致海水Pco2的相对明显升高,其最终结果导致海水碳汇强度的减弱,碳源强度的增加。     

Phase stability and kinetics of methane hydrate formation in presence of calcium and magnesium carbonate

The huge amount of methane hydrate deposits identified in deep marine sediments is considered as the new resource for future energy. Since carbonates are one of the major components of marine sediments, in the present study, an investigation has been made to study methane hydrate stability and kinetics in the presence of CaCO₃ and MgCO₃. Effect of the presence of carbonates on the solubility of methane in the system has also been examined as it directly affects the hydrate formation process. It has been observed that in presence of CaCO₃ and MgCO₃, the hydrate formation is inhibited. Comparative studies have also been done in the presence of artificial seawater to consider the effect of presence of different salts. Mole consumption of methane gas during hydrate formation in different carbonate samples was measured using real gas equation and found to be minimum in CaCO₃ in seawater sample due to the combined effect of the presence of CaCO₃ and different salts of seawater. An increase in nucleation and induction time was also observed demonstrating the inhibition of hydrate formation in the presence of these components. Further, the decrease in hydrate formation rate also confirmed the inhibition effect of CaCO₃ and MgCO₃ on hydrate formation.     

A community-wide intercomparison exercise for the determination of dissolved iron in seawater

The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously “blind” comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the “IRONAGES” sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (< 7%), although there was a decrease in iron concentration in the bottles over time (0.8–0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage.     

About the physicochemical state of dissolved beryllium in seawater

The solubility of Be₂(OH)₂CO₃ in seawater has been experimentally determined at a temperature of 25°C and salinity of 35‰. The [Be²⁺]-pH correlation curve gradually flattens within the pH range of 7.2 to 8.2, but the flattening of the curve stops at pH∼8 due to the increased contribution of carbonate, hydroxide, or (and) hydroxide-carbonate complexes.     

A catalytic oxidation method for the determination of total nitrogen dissolved in seawater

A detailed examination of a high-temperature catalytic oxidation method for liquid samples in the analysis of total nitrogen dissolved in seawater is reported. The nitrogenous compounds in liquid samples are oxidized on a platinum catalyzer at 680°C under oxygen atmosphere and the generated NO₂ is absorbed into a chromogenic reagent, followed by a spectrophotometric determination. The results of this method are much higher than those of wet oxidation methods. Molecular size dependency of the results clearly indicates that the above discrepancy is caused by the low oxidation capacity of the wet oxidation method against high-polymer organic matter dissolved in seawater. The results revealed that the concentration of total nitrogen in seawater is nearly constant from surface to bottom, ranging from 30 to 40 μM 1^?1, which organic nitrogen concentration higher in the surface layer, and a rapid decrease with depth. An examination of molecular size distribution indicates that the concentration of high-polymer organic nitrogen decreases rapidly from surface to deeper layers, with molecular sizes ranging from 5 × 10³ to 3 × 10⁴. Because of the well-defined principle of the oxidation process, its reliability, ease of sample handling and of analytical procedure on board or in the land laboratory, the present method is much more suitable for the marine analytical chemistry of total and organic nitrogen than the other previous methods.     

Decomposition and alteration of organic compounds dissolved in seawater

The dissolved organic matter in seawater is grouped into two fractions which are defined as having greatly differing reactivities with respect to both chemical and biological decomposition. One fraction, which constitutes the bulk of the material, is extremely stable and inert and is only slowly degraded by either chemical or biological processes. The other fraction, which is composed of trace organic compounds derived from living organisms, contains components such as free amino acids which are rapidly degraded, probably by marine organisms which use these compounds as a food source. Conclusions about the cycle of organic compounds in seawater based on total organic carbon concentrations could thus be misleading, since pathways involving labile trace organic constituents would be completely obscured. Investigations of the distribution, concentration, and possible diagenetic reactions of specific organic compounds are necessary in order to elucidate the cycle of these compounds in the oceans.     

海水溶解色氨酸的荧光分析

本文初步建立了直接测定海水中溶解色氨酸的方法,并进行各种条件影响实验.在0～0.070mg/dm3浓度范围内色氨酸荧光强度与浓度之间线性关系良好.在最佳实验条件下,方法检测限为7.6×10-4mg/dm3,精密度小于3.1%,回收率86%～120%.     

A sensitive and rapid method for analysis of dissolved mono- and polysaccharides in seawater

A spectrophotometric method is described for the determination of dissolved mono- and polysaccharides in seawater. It is based upon the well known alkaline ferricyanide reaction, but uses the reagent 2,4,6-tripyridyl-s-triazine (TPTZ) to give a strongly colored complex with the reduced iron. The method has been tested on model carbohydrates and other compounds, and also on natural samples of coastal and oceanic waters. Total carbohydrate content of the natural samples ranged from 5.2 to 25.1 μmol glucose-Cl⁻¹. The coefficient of variation was typically below 6% for values near 17 μmol Cl⁻¹ and approximately 10% for values near 3.5 μmol Cl⁻¹.     

人工海水中碳酸根—碳酸氢根离子对的研究

本工作测定了有效离子强度I_=0.5277mol/L和25℃下碳酸在若干人工海水介质中的表现离解常数,计算了碳酸根和碳酸氢根与钾、钠、镁、钙的缔合常数,讨论了包括氯离子缔合和未考虑氯离子缔合的海水化学模型,还通过试验证实了钾与碳酸根、碳酸氢根的缔合是不可忽视的,其缔合常数与钠的缔合常数相近,从而扩展了Pytkowic和Hawley(1974)的碳酸根-碳酸氢根离子对的海水化学模型。     

A literature review of the saturation state of seawater with respect to calcium carbonate and its possible significance for scale formation on OTEC heat exchangers

An investigation has been made of available data on the saturation state of seawater with respect to calcium carbonate and its possible significance for scale formation on Ocean Thermal Energy Conversion (OTEC) heat exchangers. Pertinent oceanographic data is lacking at or near potential OTEC sites for the calculation of the degree of saturation of seawater with respect to calcium carbonate. Consequently, only “extrapolated” saturation values can be used. These indicate that near surface seawater is probably supersaturated, with respect to the calcium carbonate phases calcite and aragonite, at all potential OTEC sites. The deep seawater that would be brought to the surface at the potential Atlantic Ocean sites is also likely to be supersaturated with respect to calcium carbonate. The deep seawater at the potential Pacific Ocean sites may be slightly undersaturated.The fact that OTEC heat exchangers will be operating in seawater, which is supersaturated with respect to calcium carbonate, means that if nucleation of calcite or aragonite occurs on the heat exchanger surfaces, significant growth rates of calcium carbonate scale may be expected. The potential for calcium carbonate nucleation is highest at cathodic metal surface locations, which are produced as the result of aluminum corrosion in seawater. Consequently, corrosion and scale formation may be closely related. What the possible effects of biofouling may be on this process are not known.     

A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.     

The oxidation state diagram: stability of dissolved sulphur species in seawater

Oxidation state diagrams have been constructed for different sulphur species. Sulphur oxyacids are stressed with respect to their key role in the cycling of inorganic sulphur species, besides sulphides and elemental sulphur. Following the stable sulphate species in seawater, metastable species are S₄O₆²⁻, S₂O₃²⁻ and S⁰. Stability of different species found from these diagrams were compared with the earlier literature. A case study, from Solar Lake (Sinai) is inconcurrent with the results of the present diagrams.     

Isolation and characterization of low molecular weight carbohydrates dissolved in seawater

Chemical characterization and quantitative determination of dissolved low molecular weight carbohydrates in Mikawa Bay near Nagoya, Japan were conducted. The water samples were collected during the period of algal bloom of the dinoflagellate Prorocentrum minimum on 31 May 1980.Low molecular weight carbohydrates in seawater samples from depths of 1 and 6 m were first retained on a charcoal column and then eluted with aqueous ethanol. The carbohydrates obtained were permethylated and then isolated into each of the components by thin layer chromatography. The sugars isolated were characterized by gas chromatography (GC), combined gas chromatography and mass spectrometry (GC-MS), proton nuclear magnetic resonance spectroscopy (¹H-NMR) and some chemical analyses. Laminaribiose, laminaritriose, sucrose, raffinose,

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were fully characterized and quantified with ranges from 2.3 to 27.7 μg l⁻¹ and from 0.5 to 17.8 μg l⁻¹.These low molecular weight carbohydrates were also identified, with some difference in their relative abundance, in particulate matter consisting mainly of dinoflagellate cells collected on the same occasion from this bay. These results indicate that low molecular weight carbohydrates dissolved in seawater are directly derived from those of phytoplankton through extracellular release or cell lysis.     

Release and uptake of dissolved silica in seawater by marine sediments

Natural marine sediments can release dissolved silica to silica-poor seawater and can remove silica from seawater enriched with dissolved silica. These are fast reactions, with sufficient reaction occurring within the first 48 hours to indicate clearly the direction of the reaction. The relative importance of these two processes varies with the ratio of clays to biogenic silica in the sediment. Both the release and the uptake reactions approach the interstitial water concentration of dissolved silica as an end point, which suggests that these reactions may influence this concentration. No change in sediment reactivity with respect to silica uptake or release reactions was observed with increasing depth in core for the three sediment cores investigated; this indicates that uptake sites are not saturated, and silica is available for dissolution for a long time after deposition.     

Variations of particulate proteins and dissolved amino acids in coastal seawater

The relationships existing between the protein-containing fraction of particulate matter and amino acids dissolved in seawater were studied in the Gulf of Marseille at different periods of the year. The concentration of particulate proteins was almost zero in February and attained maximum values during April and May, the average concentrations of dissolved amino acids (total) varied between 900 and 1200 nmole l^?1 but larger variations were encountered at the surface and in the vicinity of the sediment. The influence of meteorological conditions and the effect of the sediment on the distribution of nitrogenous substances were taken into account. Combined dissolved amino acids were more abundant than free dissolved amino acids in 90% of the cases. The concentrations of dissolved amino acids observed in a zone bordering the North Mediterranean are comparable to those found in other regions of the world.