Studies on the determination of inorganic iodine in seawater

Existing methods for the determination of the various forms of iodine present in seawater are laborious or unwieldy in use. This paper describes modified forms of the iodate and total iodine methods described by Barkley and Thompson (1960), a spectrophotometric procedure for iodate determination derived from Johannesson's (1958) work, and an automatic method for total iodine determination. Procedures for iodate and total-iodine determination which are suitable for use aboard ship, are recommended. Both procedures for iodate determination returned a standard deviation close to 0.5 μg/l when several replicate samples of a seawater containing approximately 30 μg/l of iodate-iodine were analysed. The automatic method for total iodine determination yielded a standard deviation of 0.8 μg/l by the repeated analysis of a seawater containing a total of approximately 50 μg/l of iodine. Suitable methods for the filtration and storage of seawater are also described.     

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...     

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。     

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.     

Sequential injection spectrophotometric determination of nanomolar nitrite in seawater by on-line preconcentration with HLB cartridge

The unstable state of nitrite results in its very low concentration in seawater,which is below the limit of detection(LOD) of conventional techniques of analysis. Some sensitivity-enhanced methods have been proposed for the determination of nitrite at nanomolar level to illustrate the role of nitrite in the marine nitrogen cycle. However,most of previous reports are not widely accepted,because of their complexity and cost equipment or intensive labor requirement. In this study,a simple automatic system for the determination of nanomolar level nitrite using on-line preconcentration with spectrophotometric detection was described. An Oasis HLB cartridge was adopted to quantitatively enrich the pink-colored azo compound,formed from nitrite via Griess reaction. The cartridge was rinsed with water and ethanol(volume fraction is 55%,the same below) ,in turn,then eluted by an eluent containing 50% ethanol and 0.25 M(mol/dm 3 ) H 2 SO 4,and determined at 543 nm with a 2 cm path-length flow cell. Under the optimized experimental conditions,the calibration curve showed a good linearity in the range of 1.4-85.7 nM,and the LOD(3σ) was estimated to be 0.5 nM. The relative standard deviations of 7 measurements were 4.0% and 1.0% for the samples spiked at 7.1 and 28.6 nM,respectively. The recoveries for the different natural water samples were between 92.2%-108.4%. Each HLB cartridge could be reused for at least 50 times. As compared with other SPE methods,the advantages of this method included the free of interference from salinity variation and less sample consuming. The results of the application of the proposed method to natural water showed good agreement with liquid waveguide capillary cell detection method.     

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.     

Recovery of ammonium nitrogen by solvent extraction for the determination of relative 15N abundance in regeneration experiments

A new sample preparation method for ¹⁵N tracer measurement of ammonium regeneration in seawater is described. Ammonium nitrogen is incorporated into indophenol, extracted into dichloromethane and concentrated by evaporation. The isotopic ratio of the indophenol nitrogen is determined by emission spectroscopy. A small amount (0.2 μmol) of unlabeled nitrogen is introduced by reagents used during sample preparation. For samples of equal nitrogen content, the coefficient of variation is constant and the precision of the isotopic ratio determination is inversely related to the relative ¹⁵N abundance. Differences of 0.19 atom% ¹⁵N can be measured in 5.0 μM NH₄⁺ samples of 5.0 atom% ¹⁵N (SD = 0.07, n = 3, p = 0.05). Interface from forms of dissolved organic nitrogen prevalent in marine environments are negligible.     

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 chemiluminescent technique for the determination of nanomolar concentrations of nitrate and nitrite in seawater

A chemiluminescent analysis technique for the determination of nanomolar quantities of nitrate, nitrate plus nitrite or nitrite alone in seawater is described. The method depends on the selective reduction of these species to nitric oxide which is then determined by its chemiluminescent reaction with ozone, using a commercial nitrogen oxides analyzer. The necessary equipment is compact and sufficiently sturdy to allow shipboard use. A precision of ±2 nM is claimed with analytical rates of 10–12 samples h^?1, and modifications are discussed to allow doubling the analytical rate.     

Nitrogen cycle in the earth climatic system and its modeling

Investigations into the nitrogen cycle in the climatic system of the earth are reviewed with special emphasis on the biospheric nitrogen cycle. Approaches to modeling the biogeochemical nitrogen turnover are described. Excluding the nitrogen cycle from consideration when probable consequences of climate change are analyzed can lead to inaccurate estimates of the ecosystem response, in particular, for regions where mineral compounds of soil nitrogen are a limiting factor for the development of vegetation cover. Numerical experiments with climatic models point to a substantial influence of the nitrogen turnover on the feedback between climatic characteristics and the carbon cycle. Models of the combined dynamics of carbon and nitrogen make it possible to obtain realistic estimates of present-day resources and fluxes of these elements in ecosystems, as well as to estimate their changes during possible climatic changes.     

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.     

Determination of experimentally enriched15N in nitrate nitrogen based on an improved method of azo dye formation

A method has been developed for determination of¹⁵N isotope ratio in nitrate nitrogen, which is a major analytical step in tracer experiments for studies of nitrate metabolism in the marine environment. The method is based on diazotization of nitrite with sulfanilic acid following reduction of nitrate to nitrite by a cadmium-copper column. The diazonium compound is then subject to the azo coupling reaction with 2-naphthol, and the azo dye formed is extracted by a solid phase extraction column. The dye eluted from the column is collected, and total nitrogen and¹⁵N content of the dye are determined by mass spectrometry. Sulfanilic acid can also remove preexisting nitrite by heating the sample under acidic conditions before passing through the cadmium-copper reduction column. The average recovery of nitrate nitrogen was 86%. A procedure for reducing the background nitrogen that derives from the analytical operations has been developed; background nitrogen was limited to about 0.25 μg-atomN. The variation in the background nitrogen levels reflects the range of error in¹⁵N determination of nitrate nitrogen by this method. Application of the present method to a¹⁵NO₃ ⁻ isotope dilution experiment for determination of nitrification rate in sea water is demonstrated.     

Flow analysis for determination of inorganic arsenic and antimony in seawater with on-line liquid nitrogen trap and hydride generation

An automatic flow analysis system with on-line liquid nitrogen trap, hydride generation and flame-less atomic absorption spectrophotometry was presented for the determination of inorganic arsenic and antimony in seawater. The experimental conditions such as acidity of reduction reaction, the amount of sodium borohydride , the flow rate of carry gas (high purity of nitrogen) were tested and selected optimally. The limit detection of the method presented was 0. 15 ug/L for arsenic and 0. 24 μ/L for antimony . During the determination of seawater samples with levels microgram arsenic and antimony pa litre th?variation coefficient would be ±4% for arsenic and ±10% for antimony. The volume needed for one measurement was 9 mL for arsenic and 12 mL for antimony. The frequency of sample determination reached 20 times per hour for arsenic and 15 times per hour for antimony.     

Chemical forms of zinc in sea water

Recent experimental evidence concerning the chemical forms of zinc occurring in sea water is reviewed in order to aid in the systematic understanding of zinc geochemistry in the marine environment. The review indicates the necessity of systematizing the results obtained by different methods for the determination of zinc in sea water with respect to the chemical nature of the zinc fractions measured. Analytical procedures for the zinc determinations in sea water by spectrophotometry with dithizone extraction and anodic stripping voltammetry with composite mercury graphite electrodes are described. By using these methods, various pre-treatment tests were carried out to relate the results of different modes of measurements to the chemical forms of zinc involved. The comparisons of the results of these tests lead to an estimation of the occurrence of the following categories of chemical forms of zinc in sea water: (1) ionic plus labile form, (2) inorganic complexes and colloids as well as weak organic complexes and (3) occuled fraction in large organic molecules and/or organic colloids. Capabilities of different analytical procedures for differentiating one category from another are discussed.     

海洋浮游植物初级生产力及碳生物量的检测技术研究进展

浮游植物是海洋生态系统中的主要初级生产者，构建海洋食物网、生物泵和元素循环（包括碳循环、氮循环和硅循环等）的基石。因此，海洋生态系统中的元素循环和能量流动均与浮游植物的生长和代谢息息相关。海洋碳循环是全球碳循环的关键环节，也是全球生态系统中生物地化循环的重要组成部分。尽管浮游植物在海洋碳循环中起着至关重要的作用，但是直接测定浮游植物的初级生产力和碳生物量依旧受到传统技术和方法的限制。本文详细介绍了有关浮游植物初级生产力和碳生物量检测的各种技术和方法，列举了其各自的优缺点。目前，测定海洋浮游植物初级生产力的主要方法有黑白瓶法、遥感估算法、碳同位素测定、快速重复率荧光法；测定海洋浮游植物碳生物量的主要方法有细胞体积转换法、流式细胞术、电子探针X射线显微分析、分位数回归模型估算法。通过对比分析发现碳同位素与快速重复率荧光法相结合可以更高效测定出初级生产力，而最具优势与应用前景的碳生物量检测方法是基于分位数回归模型估算法。其中，基于分位数回归模型估算法具有拟合异常值、测定结果准确等优势，能够实现现场浮游植物群落以及各个功能群碳生物量的估算，并能够与卫星遥感技术手段相结合，可以应用于大尺度和长时间序列的海洋浮游植物碳生物量估算。通过本文的综述，一方面为海洋浮游植物初级生产力和碳含量的研究提供一个基本和系统的认识，另一方面为深入研究浮游植物在海洋碳循环以及全球碳循环中的作用提供参考。     

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.     

Optimization of the indophenol blue method for the automated determination of ammonia in estuarine waters

Existing automated methods for the determination of ammonia in natural waters suffer from serious ‘salt error’ in estuaries because of changes in pH, ionic strength and optical properties with salinity. A modified automated indophenol blue method is described which minimizes the ‘salt error’ to less than 8% over the entire salinity of estuaries.     

A comparison of sample handling and analytical methods for determination of acid volatile sulfides in sediment

Proper sample storage and analytical techniques are required when analyzing anoxic sediment for acid volatile sulfide (AVS), because a change in redox state may alter sediment parameters. The goal of this study was to determine the optimum sample handling, storage, and analytical techniques to adopt when determining AVS concentrations in sediment. To determine the correct handling and storage protocols for use with anoxic sediment, samples of three different AVS levels were manipulated under a combination of the following handling and storage plans: handled on benchtop or under nitrogen atmosphere; preserved with zinc acetate (ZnAc) or not preserved, and stored at 4 °C or frozen (< − 20 °C). The data indicate that sulfide levels are best maintained when samples are handled under a nitrogen atmosphere, stored at 4 °C or frozen, and analyzed within 2 weeks of collection. To determine the best analytical procedure for the determination of AVS in sediment, the following methods were compared: colorimetric, gravimetric, ion-selective electrode, and photoionization detection. The colorimetric method was preferred.     

水中总氮的紫外分光光度分析法

本文采取K_2 S_2O_8氧化法,研究了氧化条件、紫外分光光度法测定总氮的最佳条件以及可能产生的干扰及消除方法。利用本法测定天然水中总氮回收率100±2％,检出限为0.010mg·dm~(-3)。方法快速准确,与Kjedahl法相比可提高工效27倍。