The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

A sensor package for the simultaneous determination of nanomolar concentrations of nitrite, nitrate, and ammonia in seawater by fluorescence detection

A fluorescence-based chemistry has been developed for the detection of nitrite and nitrate (as excess nitrite following reduction of nitrate to nitrite). Detection limits are 4.6 and 6.9 nM, respectively. The technique capitalizes on the triple bond between the two nitrogen atoms within the diazonium ion formed via the well-known reaction between an acidified nitrite sample and an aromatic primary amine. Fluorescence of π-electrons within this bond allows this reaction to be probed with standard fluorescence spectroscopy. Reverse Flow Injection Analysis (rFIA) is used to correct for background fluorescence from leachates and naturally occurring dissolved organic matter (DOM). Comparisons of samples analyzed for nitrite with this technique and with a highly-sensitive chemiluminescent method [Braman, R.S., Hendrix, S.A., 1989. Nanogram nitrite and nitrate determination in environmental and biological materials by vanadium (III) reduction with chemiluminescence detection. Analytical Chemistry, 61 (24) 2716–2718] showed excellent agreement between the two methods (slope=0.9996 and r²=0.9956). These fluorescent nitrite and nitrate + nitrite chemistries were coupled in a sensor package with a modified version of a fluorescent ammonia chemistry [Jones, R.D., 1991. An improved fluorescence method for the determination of nanomolar concentrations of ammonia in natural waters, Limnology and Oceanography. 36(4) 814–819], which also has a nanomolar detection limit. The throughput rate of the fully automated three-channel instrumentation is 18 samples per hour. A field experiment demonstrated the capability of the nutrient sensor package to determine horizontal gradients in nitrate, nitrite, and ammonia in oligotrophic surface waters.     

The effect of seawater magnesium on natural fluorescence during estuarine mixing,and implications for tracer applications

Natural fluorescence, which is thought to result from low molecular weight humic and fulvic compounds, can be used as a tracer to distinguish between individual river waters. Natural fluorescence exhibits conservative mixing with seawater, except for a slight fluorescence increase which is sometimes observed in the low salinity range (0–5‰). This increase is not due to the inner filter effect (internal quenching). Laboratory experiments can reproduce this low-salinity natural fluorescence increase. Of the major seawater ions, only magnesium can cause a similar natural fluorescence increase. Variation in sample pH, ionic strength, or particle content cannot explain the natural fluorescence increase, nor does it appear to be related to the estuarine flocculation of humic material. Addition of seawater magnesium to the fluorescent material with subsequent loss of hydrogen ions could enhance fluorescence by adding crosslinking to the structure. Replacement of a fluorescence-depressing metal like copper or iron by magnesium could also enhance fluorescence, essentially by removing the quenching effect of the metal. Experimental data in this study are consistent with both of these possible mechanisms. Calcium also enhances fluorescence, however the effect of seawater calcium during estuarine mixing is not as apparent as the magnesium effect. The implications of this low-salinity natural fluorescence increase with respect to estuarine and coastal tracer applications depend on whether individual rivers mix in the high or low salinity region of an estuary or coastal area.     

In situ vane system for seafloor strength investigations

The In Situ Vane (ISV) system has been developed to determine the strength profile within the upper 1.5 m of deep sea clays. The system is designed to operate in 6000-m water depth after one-year dormancy on the bottom and consists of four integrated packages; controller and data acquisition system, mechanical system, volume compensator, and power supply. This paper describes development of a prototype which was used under a pressure of 550 bars after a 30-day dormancy and of the full system which was successfully used in a deep water (5800 m) test. In the first full application of the system the ISV will be used to measure changes in sediment strength caused by high temperature (300degC) as part of the U.S. Subseabed Disposal Program.     

适用于快速远程检测海水中氰化物的方法研究

建立了一种适用于海洋远程快速检测氰化物的检测方法,设计了一体化检测装置,未来可搭载到无人艇上实现自动快速检测。针对最佳检测条件进行了一系列优化,得到最佳检测条件:对于100 mL的待测样品,加入酒石酸固体1.5 g;用1～2滴浓度为150 g/L的碳酸钠溶液浸润苦味酸试纸;加热温度80℃,加热时间10min。在最佳检测条件下,检测检出限达0.3mg/L。该方法实现了适用于海水氰化钠的远程检测,大大提高了检测效率,无需人员进入污染现场,安全性高。可广泛用于海洋危化品泄漏、湖泊污染、现场应急筛选等场合的水体样品快速检测。     

标准海水制备系统的设计与工艺

标准海水应用于海洋盐度测量、盐度计的检定/校准等工作,在我国海水盐度量值传递体系中起着承上启下的作用。本文阐述标准海水制备系统的组成及其改造的设计方案,就海水的浓缩、杀菌、海水瓶的选择、灌装等关键问题做出详细分析;从天然海水的采集、水质处理、海水瓶的清洗与烘干、海水的灌装与定值等部分介绍了标准海水的现有制备工艺,通过对样品海水的盐度数据进行分析,举例验证该制备系统的可操作性和准确性。     

Determination of dissolved nucleic acids in seawater by the fluorescence dye, ethidium bromide

A new method for the determination of dissolved double-stranded deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) in seawater was developed, evaluated and used to study the fates of these nucleic acids in marine ecosystems. These nucleic acids, which were pre-concentrated on a hydroxyapatite column, were determined fluorometrically by the use of ethidium bromide dye, which binds specifically to the double-stranded polynucleotide. No dissolved organic matter coexisting in the pre-concentrated sample solution interfered in the analysis of DNA and RNA. Column recoveries of DNA and RNA in a sample volume of up to 11 were 93% and 97%, respectively, and 90% of both at 51. The detection limits of DNA and RNA concentrated from a 51 sample by this fluorometric method were 0.6 and 1.1 μg l⁻¹, respectively. The concentration of dissolved nucleic acids in the waters from Tokyo Bay and Sagami Bay showed great variation in space and time. DNA ranged from 1 to 32 μg l⁻¹, and RNA from below the detection limit to 34 μg l⁻¹. The total amount of phosphorus in nucleic acids was an important fraction (12.9 ± 8.2%) of the dissolved organic phosphorus (DOP) and showed a good correlation with DOP.     

A sample changer for automated seawater nutrient analysis systems

An automatic sample changer based upon a commercially available 20-port rotary valve has been developed for use in automated seawater nutrient analyses. All parts exposed to seawater are of stainless steel, Teflon®, or Kel-F®. The sampler has proven to be rugged and efficient in both shore and shipboard laboratories.     

X-Ray fluorescence analysis of the principal elements of the seawater salt composition in the tropical Atlantic

This paper reports on the results of determining the chlorine, potassium, calcium and sulphur concentrations obtained by X-ray fluorescence (XRF) during the 37th cruise of the R/VAkademik Vernadsky in the tropical Atlantic. The determination accuracies for the ratios of K/Cl, Ca/Cl, and S/Cl were 0.45, 0.58, and 2.5%, respectively. As follows from the data obtained, the variations of these ratios exceed the accuracy of the measurements at all stations, and they are connected with the structural features of the hydrochemical fields.Translated by Mikhail M. Trufanov.     

A Gibbs–Pitzer function for high-salinity seawater thermodynamics

A high-salinity Gibbs function for seawater is derived from Pitzer equations of the sea salt components, in conjunction with the 2003 Gibbs function of seawater for low salinities. Various properties, computed from both formulations by thermodynamic rules, are compared with each other, and with high-salinity measurements. The new Gibbs–Pitzer function presented in this paper is valid in the range 0–110 g kg⁻¹ in absolute salinity, −7 to +25 °C in temperature, and 0–100 MPa in applied pressure. The formulation is expressed in the International Temperature Scale 1990 (ITS-90), and is consistent with the International Standard for Fluid Water (IAPWS-95), and with the 2005/2006 equations of state of ice Ih.     

A simple model for seawater crystallization in the temperature spectrum

A model of sea ice growth as an expanded region of a phase transition (mushy zone) with a linear temperature profile is developed. The linear temperature distribution agrees with the mushy zone by introducing an equivalent porosity determined by its thermodynamical condition. This approach does not require any a priori information about the dependence of the porosity on the temperature and salinity; it rather allows us to obtain this relation from a solution of the mathematical problem. The model makes it possible to calculate the thickness of the growing ice and to estimate its main characteristics as well as the heat capacity of the underice layer under the conditions of undisturbed growth at any moment of the autumn-winter season up to its maximal thickness with account for the snow accumulation, basin depth, varying regime of cooling, and water salinity.     

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.     

海水液压作业工具系统的研制

介绍了一种以海水液压驱动的水下作业工具,分析了该系统的组成、工作原理、研制难点及解决方案。该工具系统能工作于300m以浅的海域,完成水下钢缆切断、船体和水下结构物表面的清刷、打磨等工作。     

A tentative determination of methylmercury in seawater

A bioassay experiment using caged mussels has suggested a total concentration of methylmercury in the seawater of a polluted estuary of 0.06 ng dm^?3. The technique may provide a useful tool for the assessment of relative concentrations of methylmercury in seawater at different locations.     

A high accuracy method for determining nitrogen, argon and oxygen in seawater

An improved gas chromatographic system was constructed to analyze oceanic dissolved N₂, Ar and O₂ with a higher accuracy and shorter analytical time. To obtain a higher accuracy of N₂, Ar and O₂ measurements, the following was added to the system: (I) an air trapping system; (II) a N₂–CO₂ trapping system after the operation of the air trapping system; (III) an active carbon column system for separating N₂ and CO₂ completely and (IV) the introduction of automatic valves controlling most of the system. Compared to previous studies, the precision of the measurements of N₂, Ar and O₂ concentrations was higher at 0.04%, 0.05% and 0.02%, respectively, and our analytical time was shorter at 600 s. Using the improved analytical technique, concentrations of N₂ (C_N2, 561.69–611.81 μmol/kg) and Ar (C_Ar, 15.126–16.238 μmol/kg), saturation states of N₂ (ΔN₂, − 5.1–0.9%) and Ar (ΔAr, − 7.0 to − 1.1%) from 0 m to 3000 m depth in the western North Pacific were observed during March 2005. Based on these data, we propose a new concept for estimating the amount of bubble injection (B). The total error in calculating B was estimated to be about 20%. We estimated B from 12 to 43 μmol/kg in this region using the observational values of N₂ and Ar. As each water mass had a significantly different value of B even with an error of 20%, it is possible to use it as an index of sea surface state for when each water mass is produced in the sea surface mixed layer. Moreover, based on our values of B, we estimated preformed dissolved oxygen (DO) (C_preDO, 309–332 μmol/kg) and the saturation state of C_preDO (ΔpreDO, − 7.0 to − 1.2%) in this region. Thus, the difference between C_preDO and DO content in the ocean interior may be a more useful index for biogenic organic decomposition in the ocean field compared to Apparent Oxygen Utilization (AOU). Until now, the estimation of oceanic uptake of anthropogenic CO₂ has used AOU as a major parameter. Therefore, it may be necessary to re-evaluate the oceanic uptake of anthropogenic CO₂ based on our new concept of B.     

Analytical investigations on loop-manoeuvre of underwater towed cable-array system

The paper reports on analytical case studies on the loop manoeuvre of an underwater towed cable-array system to give an insight into the tactical aspects of their naval applications. The analytical formulation and the solution procedure adopted for this three dimensional dynamic problem is also described. The case studies have been carried out for different loop radii, tow lengths, tow speeds and truncated loops. The resulting X,Y,Z co-ordinates of the towed cable-array and tow-point tensions have been computed. Based on these results, the tow-length to loop radii ratio, leading to cable-array system looping, has been found. The values of speed reduction and turning radius, causing dangerous relaxation in tow-point tension have been worked out. After exit from the loop, the timing required for realignment of the cable-array system with the ship's heading can be obtained from plots of the results. These timings help to plan ship manoeuvres to optimise reestablishment of stable listening conditions during underwater surveillance.     

A dry oxidation method for the analysis of the TOC in seawater

A high-temperature oxidation method is described for the accurate and precise determination of the total organic carbon (TOC) in seawater. Problems of contamination in sample storage, preparation, and oxidation which are evident in previous dry oxidation methods have been controlled. The TOC results from different areas are determined and compared directly with the results obtained on duplicate samples with the persulfate oxidation method. Significantly higher TOC values (15–20%) are obtained with the dry oxidation procedure, but the relative difference in the methods is relatively constant over depth and geographic areas. A high correlation between the methods was obtained. For accurate results, the dry method is recommended but conclusions based on profiles of TOC determined by either method should be similar if the proper precautions in analysis are followed.     

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.