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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

浒苔绿潮暴发期间海水溶解有机碳的生物可利用性及其碳汇作用

自2007年以来,浒苔绿潮已经连续15年在南黄海暴发。浒苔(Ulva prolifera)作为主要肇事藻种,在暴发过程中向海水释放大量的溶解有机碳(DOC)。然而,这些藻源DOC能否长期保存在海洋中,主要取决于它们的生物可利用性,目前关于此方面的研究甚少。本研究在浒苔绿潮大规模暴发时期(2019年6月),分别在浒苔暴发海区和无浒苔海区各选择3个站位富集表层海水,在实验室进行长期(300 d)的DOC降解实验。结果发现,在60 d内,不同站位富集海水中的DOC浓度随着微生物的利用快速下降,微生物丰度也在第60天达到峰值,表明这些被消耗的DOC是生物可利用性高的活性DOC(LDOC)。60 d后,剩余的DOC可抵抗微生物的降解,在60～300 d内保持稳定,表明这些DOC是具有强稳定性的惰性DOC(RDOC)。最终发现,浒苔暴发海水的RDOC占富集DOC的46%,明显高于无浒苔海水的(36%)。并且,荧光溶解有机物(FDOM)中活性的类蛋白组分随着微生物的利用被快速消耗,惰性的类腐殖质组分逐渐积累,暗示了在降解过程中LDOC逐渐向RDOC转化。可见,浒苔绿潮暴发除了在短时间内增加海水中的D...     

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 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.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

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.     

燃烧氧化-非分散红外吸收总有机碳分析仪测定海水DOC 的不确定度分析

采用实验测定和误差分析的方法, 对燃烧氧化-非分散红外吸收总有机碳分析仪vario TOC cube测定海水DOC 含量的不确定度进行了分析, 对导致测定结果不确定度的各分量进行了量化估算。结果表明, 其测定结果的不确定度主要来源于四个方面, 即样品重复性测量、标准曲线拟合、标准溶液配制(包括称量、定容、移液产生的不确定度, 标准物质纯度和相对原子质量产生的不确定度)及测量仪器本身, 相对标准不确定度分量分别为0.016、0.018、0.0086、0.0079。标准曲线拟合与样品重复性测量是影响海水DOC 测定不确定度的主要因素, 但标准溶液配制和测量仪器所引起的不确定度亦不可忽略。对实际海水DOC 浓度为1.20 mg/L 的样品分析,合成以上四种不确定度分量得到DOC 测定结果的标准不确定度为0.21 mg/L。按照正态分布,取扩展因子k=2, 则扩展不确定度为0.07 mg/L, 此海水样品中DOC 含量的测定结果应为(1.20±0.07) mg/L(k= 2)。     

A new dry combustion method for the simultaneous determination of total organic carbon and nitrogen in seawater

A new dry combustion method for the simultaneous determination of total organic carbon and nitrogen in seawater is presented. Concentrations of total organic carbon obtained using this method average about 2.0 mg/l in surface water and 1.5 mg/l in deep water in the Northwest Atlantic. These concentrations are significantly greater than those reported using wet oxidation and wet combustion methods, but are comparable to concentrations reported by Russian workers using a similar dry combustion method. Organic nitrogen concentrations average 0.44 mg/l in surface water and 0.12 mg/l in deep water, yielding CN ratios for total organic matter of 5 and 12 respectively.     

TOC-IRMS联用在线高温氧化测定溶解有机碳稳定同位素组成的方法研究

本研究利用总有机碳分析仪联用稳定同位素质谱仪(TOC-IRMS)技术,探讨了高温氧化法测试水体中溶解有机碳(Dissolved Organic Carbon, DOC)含量及稳定碳同位素组成。根据溶解有机碳的组成特征,从氧化难易程度、分子结构等方面选取5种可溶于水的化合物：咖啡因、葡萄糖、邻苯二甲酸、乙酸钾和腐殖酸钠,配置成DOC溶液。通过改变溶液碳含量、氧化温度、通氧量大小,载气流速等参数,研究不同实验条件对DOC碳转化率及δ¹³C值的影响。TOC-IRMS在氧化温度850℃,通氧时长20 s(流速10 cm³/min),载气流速80 cm³/min的条件下,测得5种化合物不同浓度DOC溶液的平均碳转化率为95.69%～103.57%;δ¹³C值与标定参考值基本一致,差值范围为-0.82‰～0.55‰。在上述实验条件下,测得不同类型水样的DOC含量相对标准偏差小于3.7%,δ¹³C值的标准偏差小于0.2‰,结果表明TOC-IRMS联用在线高温氧化法测定不同类型水样的DOC含量...     

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.