Binding of monomeric organic compounds to marcomolecular dissolved organic matter in seawater

Several monomeric organic compounds, including amino acids, sugars, and fatty acids, were found to bind abiologically to dissolved macromolecular materials in particle-free seawater at natural substrate concentrations. The binding primarily occurred in ocean surface waters, at rates slower than in situ biological utilization rates of most of the compounds. Seasonal patterns of binding in Gulf of Maine waters may have been related to seasonal variations in macroalgal exudation of polyphenolic materials. Enhanced reactivity of relatively hydrophobic monomers implicated hydrophobic effects as potentially important in marine organic condensations. The resultant condensates showed high particle reactivity, consistent with low concentrations of dissolved condensed materials in seawater.     

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.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

Metaproteomic characterization of dissolved organic matter in coastal seawater

We performed a comprehensive metaproteomic analysis of the dissolved organic matter (DOM) in Japanese coastal waters using liquid chromatography–tandem mass spectrometry and demonstrated that these proteomes were characterized by proteins with various functions, including metabolic enzymes, membranes, and photosynthetic proteins. The protein sources included cyanobacteria, heterotrophic bacteria, and eukaryotic phytoplankton. Most of the components were similar among samples and also similar to pelagic components. We also observed differences in the compositions of the microbial communities of origin among the different dissolved protein samples and differences in the relative abundance of specific dissolved protein types (e.g., cytoskeletal proteins), possibly indicating potential dynamics in the coastal DOM pool.     

Sampling of dissolved organic material from seawater with reversed-phase techniques

Trichloro-n-octadecyl silanized porous glass is used to sample compounds of low polarity from natural seawater. Recoveries of some spike compounds were found to be semiquantitative. However, silanized porous glass is easy to keep free of contamination, has a comparatively high adsorption capacity, and permits the fractionated desorption of sampled compounds.     

Automatic determination of dissolved organic carbon in seawater in the sub-ppm range

The improvement of a dissolved organic carbon (DOC) analysis technique is described. This continuous flow system, based on both persulfate and UV oxidations, allows the automatic determination of DOC in sea and estuarine waters. The use of FID detection gives a very high sensitivity, permitting the detection of small variations in carbon content. The efficiency of the method and its sensitivity are tested, together with the influence of initial pH and duration of nitrogen bubbling. The system can also be used to determine total or inorganic carbon.     

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.     

Sources and sinks of low molecular weight organic carbonyl compounds in seawater

Results from laboratory studies indicated that low molecular weight (LMW) carbonyl compounds, especially formaldehyde, acetaldehyde, acetone and glyoxal, can be formed in seawater by photochemical processes. Once formed, these compounds appear to be readily consumed by biota. These results suggest that concentrations of LMW carbonyl compounds should undergo diurnal variations in the illuminated layer of the sea. In support of this, diurnal fluctuations of LMW carbonyl concentrations were observed in humic-rich surface waters off the west coast of Florida over a three day sampling period using a shipboard HPLC system. Fluctuations in acetaldehyde were particularly strong and reproducible, with steady night-time concentrations of 2–3 nM and day-time concentrations reaching a maximum of 20–30 nM in the early afternoon. In contrast, diurnal fluctuations in formaldehyde were less distinct, ranging from 15 to 50 nM.The laboratory and field results are discussed in terms of biotic/abiotic sources and sinks of LMW carbonyl compounds in surface seawater. It is speculated that photooxidative cleavage of biologically refractory dissolved organic matter (DOM) in seawater to yield LMW organic fragments, such as carbonyl compounds, may be important in the breakdown and geochemical cycling of DOM in the ocean.     

Analysis of the basic classes of organic compounds dissolved in seawater and their behaviour in the estuaries of rivers and coastal zone of the sea

On the basis of the available literature data, we analyze basic classes of organic compounds dissolved in seawater and study the transformations of proteins, carbohydrates, and lipids produced in the process of photosynthesis in seawater and their behaviour in river water and estuaries of the Black Sea. We also discuss the causes and distinctive features of the processes of production and destruction in the Black Sea. Translated by Peter V. Malyshev and Dmitry V. Malyshev     

Fluctuation of dissolved organic carbon in seawater of Sagami Bay during 1971–1972

Fluctuation of dissolved organic carbon (DOC) was studied during 1971–1972 at monthly intervals in surface layers of Sagami Bay. Concentration of DOC varied from 0.8 to 1.7 mgC/l in surface water (0 m). Maximum concentration of 1.7 mgC/l was observed in July 1971 and after then DOC decreased gradually to a minimum of 0.8 mgC/l in May 1972. The fluctuation of DOC during the observation periods seems to have close relations with those of water temperature and salinity. High DOC concentration found in summer months may be associated with bloom of phytoplankton or intrusion of seawater from Tokyo Bay and/or inland water containing high DOC.     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

Chromophoric dissolved organic matter (CDOM) is the light absorbing fraction of dissolved organic carbon (DOC). The optical properties of CDOM potentially permit remote sensing of DOC and CDOM, and correction for CDOM absorption is essential for remote sensing of chlorophyll a (chl a) in coastal and estuarine waters. To provide data for this purpose, we report the distributions of CDOM, DOC, and chl a from seven cruises in Chesapeake Bay in 1994–1997. We observed non-conservative distributions of chl a and DOC in half of the cruises, indicating net accumulations within the estuary; however, there were no net accumulations or losses of CDOM, measured as absorption at 355 nm or as fluorescence. Freshwater end member CDOM absorption varied from 2.2 to 4.1 m⁻¹. Coastal end member CDOM absorption was considerably lower, ranging over 0.4–1.1 m⁻¹. The fluorescence/absorption ratio was similar to those reported elsewhere for estuarine and coastal waters; however, in the lower salinity/high CDOM region of the Bay, the relationship was not constant, suggestive of the mixing of two or more CDOM sources. Chl a was not correlated with the absorption for most of the cruises nor for the data set as a whole; however, CDOM and DOC were significantly correlated, with two groups evident in the data. The first group had high CDOM concentrations per unit DOC and corresponded to the conservative DOC values observed in the transects. The second group had lower CDOM concentrations per unit DOC and corresponded to the non-conservative DOC values associated with net DOC accumulation near the chl a maximum on the salinity gradient. This indicates the production of non-chromophoric DOC in the region of the chl a maximum of Chesapeake Bay. In terms of remote sensing, these data show that (1) the retrieval of the absorption coefficient of CDOM from fluorescence measurements in the Bay must consider the variability of the fluorescence/absorption relationship, and (2) estimates of DOC acquired from CDOM absorption will underestimate DOC in regions with recent, net accumulations of DOC.     

长江口外海水中有色溶解有机物（CDOM）的光吸收特性

基于2008年5、11月2次调查数据,研究了长江口邻近海域水体有色溶解有机物（CDOM）的光吸收特性及其时空分布特征,探讨了CDOM含量、光谱斜率Sg值及其与特征波长下吸收系数a（440）的关系.结果表明,春季该海域有色溶解有机物的吸收系数a（440）的范围为2.232~8.671 m-1,平均值为4.523 m-1;秋季其吸收系数a（440）的变化范围为0.390~6.135 m-1,平均值为2.209 m-1.该水体CDOM吸收曲线基本呈指数衰减趋势.在400~440 nm波段内,春季其光谱斜率Sg值范围为0.002 0~0.014 2 nm-1,平均值为0.008 7 nm-1秋季的介于0.020 8~0.052 6 nm-1之间.平均值为0.037 5 nm-1.同时有色溶解有机物吸收系数a（440）与Sg值存在着较显著的负相关关系.     

Molecular weight distribution of dissolved organic materials in seawater determined by ultrafiltration: a re-examination

Most of the dissolved organic materials (DOM) in coastal Maine, Gulf of Maine, and North Atlantic seawaters had molecular weights (MW), determined by ultrafiltration, less than 1000. Only 34% of the DOM had MW greater than 1000, only 6% had MW greater than 30 000, and only 1% was of MW greater than 100 000. The majority of ultrafilter-derived MW data are consistent with patterns shown here; earlier reports of high-MW DOM in seawater were apparently exaggerated due to procedural and ultrafilter artifacts. It is also shown that most ultrafiltration data do not clearly indicate loss of high-MW DOM during estuarine mixing, and that apparent removal could result from decreased retention as ionic strength increases.     

Wet-oxidation and automated colorimetry for simultaneous determination of organic carbon, nitrogen and phosphorus dissolved in seawater

We developed a simple and reliable method which allows simultaneous determination of organic forms of carbon (DOC), nitrogen (DON) and phosphorus (DOP) dissolved in seawater. Conversion of dissolved organic matter (DOM) to inorganic products (carbon dioxide, nitrate+nitrite and soluble reactive phosphate) is performed by a persulfate wet-oxidation in low alkaline condition. After oxidation, the concentration of the inorganic products dissolved in the sample was measured automatically by colorimetry using a 3-channel Technicon AutoAnalyzer system. A number of pure organic compounds were tested in the concentration range encountered in coastal and open ocean, indicating a high efficiency of the digestion procedure. The recovery range is similar to that obtained by other wet-oxidation procedures and by high-temperature catalytic oxidation techniques. Direct comparisons with usual methods used for separate determination of DOC, DON and DOP indicated a high efficiency of the procedure. Reproducibility tests demonstrated a very good precision (around 5%) for lagoonal and coastal waters, while precision was sometimes around 10–25% in oligotrophic oceanic waters, especially for DOP where values approached limits of detection for measuring phosphate. This method is highly suitable for routine analysis and especially appropriate for shipboard work.     

Chemical studies of dissolved carbohydrates in seawater

Charcoal column chromatography and a dialysis system using a Visking tube were used for the concentration and separation of dissolved carbohydrates in seawater. Recoveries of mono-, oligo-, and polysaccharides were 46–74, 61–89 and 70%, respectively, relative to the total amount of sugars initially submitted to analysis. The combined charcoal column chromatography and dialysis system was used to separate dissolved carbohydrates in seawater samples from Mikawa Bay into mono-, oligo- and polysaccharide fractions. The polysaccharides are separated into two fractions with molecular weights of <4,000 and >4,000 using Sephadex G-25 column chromatography. Monosaccharides, oligosaccharides, polysaccharides with M.W.<4,000 and polysaccharides with M.W. >4,000 accounted for 7–9, 15–26, 7–13 and 20–33% of total dissolved carbohydrates, respectively. However, 32–38% of dissolved carbohydrates were lost during the analytical procedures. Glucose, galactose, mannose, xylose, arabinose, ribose, fucose, and rhamnose were found upon acid hydrolysis of the oligo- and polysaccharide fractions, while fucose and rhamnose were not present in the monosaccharide fraction. Possible sources of the carbohydrates in these fractions are discussed with reference to the monosaccharide composition of cellular carbohydrate in marine algae.     

海水中总溶解氮测定的高温燃烧法和湿化学氧化法的比较

对测量海水中总溶解氮(TDN)的两种常用方法——高温燃烧法和过硫酸钾氧化法进行了比较。结果表明,两种方法在空白、精密度和准确度实验中不存在显著差异。对不同化合物的回收率均在92%～107%之间,加标回收实验回归曲线的斜率分别为0.93和0.92。对于现场海水样品的测定结果,两个断面拟合的斜率分别为0.92和0.97。HTC法比PO法对实际海水样品的氧化效率略高,在操作上也更方便、快捷。因此,高温燃烧法更适合海水中总溶解氮(TDN)的测定。     

Comparison of three oxidation methods used for the analysis of the dissolved organic carbon in seawater

Three methods for the determination of dissolved organic carbon in seawater were compared. Samples were analysed using persulphate oxidation, high-temperature combustion, and ultraviolet photo-oxidation. The dissolved organic carbon content of the seawater samples ranged from 0.6 to 1.6 mg C/I. This study shows that results of high-temperature oxidation and photo-oxidation procedures differ by less than 5%, whereas results with persulphate oxidation are about 15% less than those obtained with the high-temperature oxidation. The relative merits of each of the oxidation techniques for the determination of organic matter in seawater are discussed.     

Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements

Appropriate conditions have been achieved for the accurate, rapid, and highly precise shipboard simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation. A nitrogen-specific Antek 705D chemiluminescence detector and a CO₂-specific LiCor Li6252 IRGA have been coupled in-series with a Shimadzu TOC-5000 organic carbon analyser. Precision of both simultaneous measurements is ≤1.5%, i.e. ±1 μmol C l⁻¹ and ±0.3 μmol N l⁻¹, respectively. Quality of analysis is not compromised by vibrations associated with ocean going research vessels.     

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%.