A precise and rapid analytical procedure for alkalinity determination

A potentiometric analytical method is proposed for the determination of the alkalinity of seawater. The precision is 0.1% and each determination takes 3 min. The technique is very easy to use, even on board ship since it is carried out in open flasks. A polynomial equation is also proposed which greatly simplifies the theoretical expression.     

A simple indirect method for the determination of organic-carbon in marine particles

A simple indirect method for the determination of organic carbon in marine particulate matter is proposed. The recommended procedure is as follows: The dried sample is ashed at 450°C for about 24 hr. The ashed sample is put into a Teflon vessel followed by a mixed solution of nitric acid, perchloric acid and hydrofluoric acid. The vessel is sealed and allowed to stand at 150°C for 5 hr. The concentrations of Si and Al in the digested solution are determined. The organic carbon content (Cal-C, %) is calculated by the following equation: Cal-C=0.52 ([CF]–0.10 [Opal]–0.03 [A-Si]), where [CF] is the combustible fraction (%), [Opal] is the biogenic-SiO₂(%), and [A-Si] is the content of aluminosilicate mineral (%).     

Silicate determination in sea water: Toward a reagentless electrochemical method

Silicate has been determined in sea water by four different electrochemical methods based on the detection of the silicomolybdic complex formed in acidic media by the reaction between silicate and molybdenum salts. The first two methods are based on the addition of molybdate and protons in a seawater sample in an electrochemical cell. Cyclic voltammetry presents two reduction and two oxidation peaks giving four values of the concentration and therefore increasing the precision. Then chronoamperometry is performed on an electrode held at a constant potential. A semi-autonomous method has been developed based on the electrochemical anodic oxidation of molybdenum, the complexation of the oxidation product with silicate and the detection of the complex by cyclic voltammetry. This method is tested and compared with the classical colorimetric one during ANT XXIII/3 cruise across Drake Passage (January–February 2006). The detection limit is 1 μM and the deviation between both methods is less than 3% for concentrations higher than 10 μM. Finally a complete reagentless method with a precision of 2.6% is described based on the simultaneous formation of the molybdenum salt and protons in a divided electrochemical cell. This latter method should be very useful for developing a reagentless sensor suitable for long term in situ deployments on oceanic biogeochemical observatories.     

A simple analytical model for surface water waves on a depth-varying current

A perturbation analysis is presented in which a series of small amplitude regular waves co-exist with an arbitrarily sheared current, U(z). Assuming that the current velocity is weak, i.e. U(z)/c=O(ε), the solution is extended to O(ε²), where c is the phase velocity and ε=ak the wave steepness. This provides a first approximation to the non-linear wave-current interaction, and allows simple explicit solutions for both the modified dispersion relation and the water-particle kinematics to be derived. These solutions differ from the existing irrotational models commonly used in design and, in particular, highlight the importance of the near-surface vorticity distribution. These results are shown to be in good agreement with laboratory data provided by Swan et. al. [J. Fluid Mech (2001, in press)]. Perhaps more surprisingly, good agreement is also achieved in a number of strongly non-linear wave-current combinations, where the results of the present analytical solution are compared with a fully non-linear numerical wave-current model.     

海水中铁的测定方法

铁在地壳中的丰度为5.6% [1],但是在海水中的浓度却很低 ,特别是大洋中只有0.05～2nmol/L [2]。在整个海水体系的生物地球化学过程中 ,铁是一种举足轻重的元素。特别是对浮游植物 ,铁的重要性远远超过了其它微量元素 ,在植物的光合作用、电子呼吸链、氮的还原、叶绿素合成等方面有重要作用[3]。在类似南大洋[2]和赤道太平洋[4]的海域 ,同其中的主要营养盐 (氮、磷、硅 )的高浓度相比 ,其浮游植物的生物量却很低。近年来的研究表明这些区域的生物量是由铁限制的[5]。赤道太平洋海域(IronEX)[4]和极地南大洋(SORIREE)[6]的表层海水施铁实…     

Progress in the determination of Ac in sea water

²²⁷Ac is a naturally occurring radioisotope with a unique combination of properties that make it suitable for the determination of deep ocean mixing and upwelling rates. Here, we present a method for the determination of ²²⁷Ac in sea water on sample sizes of 20–80 L. The measurement is based on co-precipitation of ²²⁷ Ac with MnO₂, followed by chemical isolation of actinium in the presence of an artificial Ac isotope. Actinium is then electrodeposited onto silver discs. In two alpha-spectrometric counting periods, first the artificial ²²⁵Ac isotope is counted, then after > 100 days five daughters of ²²⁷Ac. The first counting period gives a total yield for the procedure, integrating chemical recovery and detector efficiency. The total yield was found here to be on average 15 ± 5%, the chemical yield on average about 50%. The counting of five decay products of ²²⁷Ac in the second period makes the method particularly sensitive. Using appropriate decay corrections, the initial ²²⁷Ac activity can be determined to better than 10% relative error for concentrations < 10,000 atoms/L. We compare data acquired by the new method to a data set from in-situ pumps, from a parallel sampling campaign in the Eastern Weddell Gyre, and we can show excellent agreement. Repeated determinations of ²²⁷Ac in a uranium reference material (UREM-11) demonstrate the accuracy of the method.     

A modified analytical method for the shipboard determination of nanomolar concentrations of orthophosphate in seawater

A method for the determination of nanomolar concentrations of orthophosphate in oligotrophic seawater developed by Liang et al. (2007) has been modified to make it fully feasible for shipboard application and for faster sample throughput with minimized sample volume. The technique is based on the flow injection method with solid phase extraction on a Sep-Pak C18 cartridge and colorimetric detector. The Schlieren effect was minimized by rinsing the cartridge sequentially with 5 mL water and 2 mL 95% ethanol solution. With three micro pumps in parallel, savings of up to 80% in amount of reagents and 25% volume of seawater samples could be achieved in comparison to the previous method. Variation of stopped flow time and sample loading time gave 3 different standard curves, which corresponded to 3 linear ranges within 3.4 and 515 nM. The modified method permits the analysis of samples over a wide range of concentrations, and has been successfully applied to shipboard determination of trace orthophosphate in more than 200 seawater samples during a one-month cruise in the South China Sea. For seawater at concentrations of 20.6, 82.5, 206.2 nM orthophosphate, the relative standard deviations (RSD) (n = 6), determined daily for 6 days on board ship were 4.45%, 4.73% and 6.75%, respectively. Five seawater samples collected in the Station SEATS (South East Asia Time Series Station at 18°N, 116°E) were analyzed using the present method both on board and in a land-based laboratory, as well as with the magnesium hydroxide-induced coprecipitation (MAGIC) method, and showed no significant difference according to the statistical t-test.     

Computer-processed potentiometric titration for the determination of calcium and magnesium in sea water

An improved potentiometric titration method for the determination of calcium and magnesium in sea water has been newly devised. In this method, a mini-computer is used for the automation of titrations, and ion-selective electrodes are used as an end-point detector. Calcium is determined by titration with EGTA, and total alkaline earth metals (magnesium + calcium + strontium) by titration with EDTA. Magnesium can be determined by the difference, strontium having been determined by a suitable method. In the present method, calcium and magnesium in sea water can be determined with a precision of 0.1 %.     

A simplified automated chelometric method for the determination of sulfate in interstitial water and seawater

A method is described for the determination of sulfate in interstitial water and seawater. After BaSO₄ precipitation, the Ba²⁺ excess is titrated with EDTA using an amalgated silver electrode for end-point detection. An accuracy better than 0.5% is obtained using this method.     

A new fluorometric method of analysis of selenium in sea water

A new method of determination of selenium and separation of Se(IV) and Se(VI) in sea water is described. The selenium is determined by fluorometric method using Se-DAN complex in cyclohexane media. Prior to the fluorometric determination, Se(IV) is separated from sea water by means of Se(IV)-DDTC complex which is adsorbed on the macroreticular resin. As to the separation of the total selenium from sea water sample, the reduction and coprecipitation method is used. Se(VI) is determined with the same method as used for the total selenium after the separation of Se(IV). The average recoveries are 92.5±1.3% for Se(IV) and 97.4±0.9% for Se. The standard deviation of analytical results is below 10%.     

Sugars and uronic acids in sediment and water from the black sea and north sea with emphasis on analytical techniques

Sugars and uronic acids have been extracted from marine sediment and seawater by various hydrolysis techniques and analyzed by ion-exchange chromatography. All stages of the extraction methods were examined for sources of error arising from contamination, destruction and incomplete extraction. Tested were: (1) sample drying procedure; (2) acid hydrolysis, i.e., effect of different acids, variations in acid concentration and hydrolysis time, and effect of variations in organic and CaCO₃ contents of sediment on the quantity of released sugars and uronic acids; (3) deionization, i.e., neutralization of acid by precipitation or by ion-exchange resins, separation of sugars from uronic acids; and (4) volume reduction, i.e., rotary evaporation, freeze-drying, effect of added glycerin. It is shown that the hydrolysis efficiencies of the acids tested varied with the nature of the organic matter in sediment. Simultaneous hydrolyses with different acids may give insights into the sources of the organic input and the environment of deposition. For all sediment types examined pretreatment with 72 w/w% H₂SO₄ gave the highest yields and is, thus the optimal hydrolysis method for sediment.Sugar and uronic acid yields from seawater varied with the type of acid used for hydrolysis. The highest yield for North Sea surface water was obtained with p-toluene sulfonic acid.Since most previous investigators employed non-optimal techniques, it is recommended that intercalibration studies be performed.     

液体闪烁计数测定海水中氚的条件优化研究

本研究采用常压蒸馏法测量,利用Quantulas 1220超低本底液闪谱仪测量海水样品中氚活度的方法,对影响测量结果的测量时间、无氚水、闪烁液以及二者混合比例等进行研究.在优化了这几个参数后,使得方法检测限为1.07Bq/dm~3.为了检测方法的适用性,本研究课题组参与IAEA海水氚样品测量,测量结果为2.91±0.35 Bq/dm~3,与IAEA参考值(2.80±0.06 Bq/dm~3)相对偏差仅为3.9%,证明了该方法测量海水的可行性.此外,与文献值比较,本方法适用于核电厂运行后,邻近海域海水中氚的测量.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

On lipid surface films on the sea. I. A simple method for sampling and studies of composition

A method for collection of surface films on the sea has been developed and tested at various places along the Swedish West Coast. Considerable amounts of lipids on the sea surface were found even when no seaslicks were observed. Triglycerides, free fatty acids, and wax esters are the dominating constituents, and there are characteristic deviations in the fatty-acid patterns compared to the corresponding lipids dissolved in the sub-surface water. Organochlorine residues, phthalic acid esters and heavy metals also occur in considerable amounts.     

An automated photochemical method for the determination of dissolved organic carbon in sea and estuarine waters

An improved version of Ehrhardt's (1969) method for the analysis of dissolved organic carbon is described. The method, which is automated, determines the carbon dioxide with a non-dispersive infra-red analyser. The conditions of photo-oxidation have been examined in order to achieve maximum performance. It was found that careful attention needed to be paid to U-V source, “oxygen source”, pH and time or irradiation. The completeness of the method was examined by three independent procedures. We concluded that in all cases the extent of oxidation of organic material was in excess of 98%. Typical performance figures were: precision ±2.5% above 2.0 mg C l^?1, approaching 0.03 mg C l^?1 below 1.0 mg Cl^?1; blank, equivalent to 0.3 mg C l^?1; sampling frequency, 10 samples per hour. The lower limit of sensitivity is mainly governed by the blank. The upper limit of the method is greater than 40 mg C l^?1.A wholly continuous modification of the method has been devised which permits on line analyses. An attentuated version of the method has been used for the analysis of total carbonate.The present and other published methods for the analysis of dissolved organic carbon in natural waters are discussed in relation to one another.     

A new expression for the production rate of sea water droplets on the sea surface

A new set of empirical formulas for the production rate and the number concentration of sea-water droplets on the sea surface are proposed, synthesizing past observation data of sea-salt particles in the sea and water droplets in wind-wave tanks. A new levelz _c is introduced as the effective wind-sea surface where seawater droplets are produced. The new formulas are expressed in linear functions in logarithmic scales ofu*²/v _p , a parameter to describe overall conditions of airsea boundary processes, whereu _* is the friction velocity of air,v the kinematic viscosity of air and _p the peak angular frequency of wind-wave part of wave spectra. A model of coexistence of spray droplets and suspended particles near the sea surface is proposed. As for the independent parameter, a comparison between the uses ofu*²/v _p and ofu _* ³ which was the traditional way of parameterization excluding wave measure, shows that the advantage of usingu*²/v _p is statistically significant with a confidence limit 89% in F-test.     

海水中胶体有机碳的测定──高温燃烧法和紫外/过硫酸钾法的比较

利用切向超滤(cross-flow ultrafiltration)技术对海水中胶体有机碳(COC)和真溶解有机碳(UOC)进行了分离,并分别用高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳进行了测定。测定结果表明,切向超滤能定量分离海水中的胶体有机碳,高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳的测定结果没有明显的系统误差,表明这两种方法的氧化效率基本相同,胶体粒子的存在,对紫外/过硫酸钾法的氧化效率没有显着影响。     

海水中磷氮不同形态的同时测定

采用过硫酸钾-硼酸-氢氧化钠混合试剂作为氧化剂,同时测定海水中总磷、氮和总溶解态磷、氮,从而建立了海水中磷、氮不同形态的分析流程及步骤。总磷、总溶解态磷浓度为0.35～1.09μmol/dm3时,相对标准偏差小于6.6%;总氮、总溶解态氮浓度为11.8～54.8μmol/dm3时,相对标准偏差小于5.6%。总磷、总溶解态磷和总氮、总溶解态氮的回收率分别为95.0%～106.0%和94.0%～106.0%。本文的分析方法可用于对近岸海水及河口水中磷、氮不同形态的同时测定。