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.     

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.     

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 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.     

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 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.     

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.     

A simplified resorcinol method for direct spectrophotometric determination of nitrate in seawater

A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 10⁴ L mol^− 1 cm^− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.     

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.     

基于分光光度法的多量程海水营养盐原位传感器检测系统设计

针对传统海水营养盐检测方法不能满足海水营养盐长期原位监测需求的问题,研制了一种基于分光光度法的多量程海水营养盐原位传感器检测系统,通过对系统的高度集成及对多量程检测、低功耗技术、漏液保护技术的应用,实现了对海水5项营养盐参数快速、宽范围、高精度的原位测量。经过实验室和青岛中苑码头现场测试,表明本营养盐传感器检测系统具有低功耗、高可靠性能,可满足对5项营养盐参数的快速精确测量要求,实现了对海水营养盐参数的原位监测,为相关部门及时了解海洋生态环境和水体富营养化程度提供了数据支持,具有重大现实意义。     

A comparative study of three methods for the determination of iodate in seawater

A comparative study of three methods for the determination of iodate-iodine in seawater is described. In one method the iodate is determined polarographically while in the others the iodate is determined colorimetrically as iodonium ions. In one of the colorimetric methods each sample is pre-treated with excess iodine-water in an attempt to eliminate suspected interference from naturally occurring reducing agents. The tests were conducted on a selection of open-ocean and near-shore waters with iodate concentrations ranging from 0 to 60 μg 1^?1-I. The tests indicated that the polarographic method and the colorimetric method without iodine-water give the more reliable measurement of iodate concentration. Also, the method with iodine water was found to be in error especially at low iodate concentrations. Reducing agents, if present, were found not to interfere significantly.     

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.     

Mercos — A simple Teflon sampler for ultratrace metal analysis in seawater

This paper describes an uncomplicated sampling technique for ultratrace element analysis of coastal and surface seawaters (maximum depth 100 m). The sampler system is very easy to operate. To prevent contamination problems, interchangeable 500-ml Teflon bottles are used as both sampling and storage vessels. The seawater samples are stabilized in situ by preacidifying the sampling bottles. For the determination of mercury in seawater the desired system has been developed: sampling bottle = storage bottle = reaction vessel.     

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.