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.     

A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters

Total dissolved nitrogen(TDN) is an important parameter for assessing the nutrient cycling and status of natural waters.The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water.The TDN in various systems has been largely documented,and the concentrations of TDN are usually obtained using high-temperature catalytic(HTC) or persulfate oxidation(PO).However,the accuracy of these methods and their suitabil...     

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。     

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...     

Total organic carbon in seawater — comparison of measurements using persulfate oxidation and high temperature combustion

A method is described for the determination of organic carbon in liquid seawater samples by combustion at a high temperature. Although the method is not easy to perform, it has been successfully employed for a direct comparison to the standard method of persulfate oxidation. With seawater from the central western North Atlantic Ocean, the standard method measured an average of 78% as much carbon as the high temperature method. This indicates organic matter in seawater that is resistant to oxidation by persulfate; some of it appears to be of a colloidal nature. The persulfate resistant organic matter is most noticeable in a region below the surface 100 m and seems to decrease slowly with depth, indicating deep ocean biological utilization of organic matter. Due to a possible procedural error in the standard persulfate oxidation method, the differences indicated here may actually be conservative and the content of total organic carbon in the sea may be as much as twice as high as has been indicated by previous estimates.     

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.     

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.     

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.     

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.     

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 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.     

Measurements of dissolved organic carbon (DOC) in sea water by high temperature combustion method

Dissolved organic carbon (DOC) is the largest organic carbon reservoir in sea water and plays an imporrant role in the marine carbon cycle and other biogeochemical processes in the ocean. Accurate and precise determinalion of the bOC concentration in sea water is thus a prerequisite for any interpretation of DOC biogeochemistry. A key factor in analytical quality control is an accurate determination of the blank. The assessment and distinction of DOC blanks are essential for the precise measurements of oceanic DOC. The total DOC blank includes instrument and water blanks in the high temperature catalytic oxidation (HTCO) method. DOC can be measured accurately using the HTCO method only when the instrument blank is correctly distinguished from the total DOC blank and corrected in the sample measurements. Low DOC blanks can be achieved by extensive conditioning of new catalysts and the whole instrument system, whereas instrument blanks can be quantified by subtracting the water blank from the total DOC blank. We have been able to produce low carbon nanopure water [≤2μmol/dm³(C)] and have a low instrumental blank [< 5-6 μmol/dm³(C)] when using the HTCO method. Results of concentrations and distributions of DOC in the Gulf of Mexico and the North Atlantic are oceanographically consistent. Results from DOC measurements on samples from the international DOC methods comparison program further confirmed our low values of both nenopure water and the instrument blank.     

Optimisation of a catalytic procedure for the determination of total iodine in seawater

A precise method for the determination of total iodine in seawater, which uses a Technicon Auto-Analyser II system and is based on Truesdale and Spencer's (1974) and Truesdale and Smith's (1975) earlier works with a catalytic procedure, is described. The procedure operates over a range of 30–80 μg1^?1 of iodine. As requested by Mark (1973), the way in which the procedure can be varied to suit other applications, and therefore ranges, is explained in detail. The standard deviation at the 50 μg1^?1 level was found to be 0.12 μ1^?1 showing that the method's precision exceeds most, if not all, previously published procedures for this variable. This high degree of resolution makes the procedure suitable for oceanic investigations. The effects of varying the reaction time, the temperature at which the reaction proceeds and the salinity of samples and standards are described. The advantages of using a Technicon Auto-Analyser II system rather than an Auto-Analyser I system are discussed. With slight modification the procedure can also be used in the measurement of river flow where sodium iodide is used as tracer in the dilution method.     

厦门海域秋、冬季溶解有机氮时空分布及总溶解态氮的组成

根据2015年10月(秋季)和2016年1月(冬季)对厦门海域开展的2次水质调查,研究了该海域中溶解有机氮(DON)的时空分布特征及总溶解态氮(TDN)的组成,并探讨了DON与环境要素的相关性及其来源.结果表明:厦门海域DON浓度平均值冬季大于秋季,表层高于底层,整体呈内湾、河口区较高,湾口区低的分布格局.秋季DON浓度的空间分布为同安湾西海域九龙江口邻近海域东南海域大嶝海域,冬季为西海域同安湾九龙江口邻近海域东南海域大嶝海域.该海域秋、冬季DON浓度占比(CDON/CTDN)分别为56%和53%,DON浓度占比整体呈湾口区大、河口区及内湾小的分布特征.相关性分析表明,该海域秋、冬季表、底层DON浓度与盐度均呈极显著负相关,与磷酸盐、硅酸盐含量为极显著正相关,与叶绿素a、溶解氧、p H值存在一定相关性.厦门海域DON的来源主要有九龙江河流、城市生活污水、工农业废水等陆源输入和浮游植物活动等海源生成.     

光谱法测定海水中溶解态无机氮的研究进展

溶解态无机氮(dissolved inorganic nitrogen,DIN)主要由亚硝酸盐-氮(NO^-₂-N)、硝酸盐-氮(NO^-₃-N)和铵氮(NH⁺₄-N)组成,它们在海洋的生物地球化学循环过程中起重要作用。但人类活动向海洋输入了大量无机氮,导致一系列环境问题。为了更好地开展海洋氮循环研究和环境污染管理,需对海水中的DIN进行测定。在众多分析方法中,光谱法因其通用性好、适用范围广、所需设备简单,成为测定海水DIN的首选。本文总结了近10年来基于光谱法测定海水DIN的研究进展,包括紫外分光光度法测定NO^-₃-N、萘乙二胺分光光度法测定NO^-₂-N和NO^-₃-N、次溴酸盐氧化-分光光度法测定NH⁺₄-N、靛酚蓝分光光度法测定NH⁺₄-N...     

Vertical distributions of dissolved organic carbon and nitrogen in the Southern Ocean

Detailed vertical profiles of dissolved organic carbon (DOC), nitrogen (DON) and DOC/DON ratios in the Australian sector of the Southern Ocean (56°–65°S around 140°W transect) were obtained by a high-temperature catalytic oxidation method with a modified Shimadzu TOC-5000 unit. The simultaneous analyses of DOC and total dissolved nitrogen (TDN) gave high precision results (±0.7 μMC and ±0.3 μMN). In surface layers, DOC concentrations were lower (45–55 μM) than those generally obtained from other oceanic environments (60–90 μM). The surface concentrations of DON varied from 4 to 9 μM, but within the range generally reported for other ocean regions. Surface excesses of DOC and DON were calculated against nearly constant subsurface concentrations. A consistent contribution of low C/N ratio (2.7–5.0) was found in the mid-surface layer (30–75 m), suggesting more extensive degradation of carbon-enriched materials and/or enhanced supply of nitrogen-enriched ones.     

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.     

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.     

自动电位滴定仪高效高精度测定海水碱度值

为研究海洋碳循环和海洋碳酸盐系统,需要测定样品的碳酸盐碱度。利用电位滴定仪(万通~(?)798MPT Titrino)配合软件tiamol.1检测了海水总碱度。根据碳酸盐解离常数计算出了海水碳酸盐碱度,相时标准偏差低于0.1%(±2μmol/kg),单个样品用量约25 mL,检测时间约9 min。实验结果表明,用自动电位滴定仪测定海水总碱度速度快,精度高,方法可行。     

Resistance to UV and persulphate oxidation of dissolved organic carbon produced by selected marine phytoplankton

We describe an investigation into the reactivity of dissolved organic carbon (DOC), produced from marine algae, to conventional persulphate and ultraviolet (UV) oxidation methods. Marine algae were grown in batch culture in the presence of ¹⁴C bicarbonate and filtered samples of the phytoplankton dissolved organic carbon (PDOC) were oxidized with persulphate and UV techniques. The amount of fixed label found in solution after the oxidation procedures was compared with the initial amount of labelled DOC. Marine algae examined in this way included: the diatoms, Chaetoceros gracilis, Skeletonema costatum, Phaeodactylum tricornutum; the flagellate, Isochrysis galbana; and the cyanobacterium, Synechococcus strain DC2. It was found that 5–18% of the DOC produced by these phytoplankton resisted persulphate oxidation. Samples were also measured for their resistance to UV oxidation by an autoanalyzer method. It was found that 15–27% of these samples resisted UV oxidation. However, 95% of PDOC was oxidized after exposure for 6 h to high intensity UV irradiation using a variable exposure time system. P. tricornutum and Synechococcus PDOC samples were ultrafiltered into low molecular weight (< 10 000 Da) and colloidal (> 10 000 Da) size fractions. Both species produced mainly (> 68%) low molecular weight material. Slightly greater resistance to persulphate oxidation was generally found for the colloidal Synechococcus PDOC (15–22%) than for the low molecular weight material (14–17%). However, the opposite was found for the P. tricornutum PDOC which generally showed less resistance for the colloidal fraction (5–12%) than for the low molecular weight fraction (10–15%).Experiments were also conducted to determine the effects of short-term (days) and long-term (months) ageing of PDOC solutions in the presence of microbial populations from coastal seawater. Long-term ageing decreased the amount of PDOC that resisted oxidation in all cases. However, the fraction of PDOC resisting persulphate oxidation increased by small amounts over a short-term experiment. Increased resistance was attributed to preferential degradation of biologically and chemically labile components of PDOC by bacteria.The percentages of phytoplankton-produced (and microbially aged) DOC found in this study to resist UV or persulphate oxidation were low (5–27%), compared with those values (50–65%) reported for DOC in surface seawater on the basis of recent high temperature catalytic oxidation analyses.