天然海水硝酸盐氮同位素组成的蒸馏法测定

建立了测定天然海水中硝酸盐氮同位素组成的蒸馏法,该方法主要是在碱性条件下利用戴氏合金将海水中的硝酸盐还原为氨,后利用稀盐酸吸收生产的氨,将得到的氨吸收液浓缩后干燥结晶,利用同位素比值质谱仪测定所得晶体的氮同位素组成。研究中开展了戴氏合金添加量及氨吸收溶液在不同条件下干燥结晶对氮同位素测值的影响研究。结果表明,戴氏合金添加量为3.0 g及60 ℃下直接干燥结晶为最佳的实验条件。所建立的氨蒸馏法氮空白值仅为(0.90±0.19) μmol,低于此前文献报道的氮空白值;氮同位素组成(δ15N)空白值为(-14.7±4.1)×10-3。运用所建立的氨蒸馏法实测得到的硝酸盐δ15N值与氨扩散法、硝酸盐直接测定法得到的数值非常吻合,进一步证明所建立氨蒸馏法的可靠性。改进后的氨蒸馏法适用于硝酸盐浓度在2~50 μmol/dm3内的天然海水硝酸盐氮同位素组成的测定,方法的标准偏差为±0.3×10-3。     

Practical considerations for the segmented-flow analysis of nitrate and ammonium in seawater and the avoidance of matrix effects

In this study we describe measures taken in our laboratory to improve the long-term precision of nitrate and ammonia analysis in seawater using a microflow segmented-flow analyzer. To improve the nitrate reduction efficiency using a flow-through open tube cadmium reactor (OTCR), we compared alternative buffer formulations and regeneration procedures for an OTCR. We improved long-term stability for nitrate with a modified flow scheme and color reagent formulation and for ammonia by isolating samples from the ambient air and purifying the air used for bubble segmentation. We demonstrate the importance of taking into consideration the residual nutrient content of the artificial seawater used for the preparation of calibration standards. We describe how an operating procedure to eliminate errors from that source as well as from the refractive index of the matrix itself can be modified to include the minimization of dynamic refractive index effects resulting from differences between the matrix of the samples, the calibrants, and the wash solution. We compare the data for long-term measurements of certified reference material under two different conditions, using ultrapure water (UPW) and artificial seawater (ASW) for the sampler wash.     

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.     

海水中低浓度亚硝酸盐和硝酸盐测定方法综述

海水中低浓度的亚硝酸盐和硝酸盐的测定方法主要有4种,即分光光度法(富集分光光度法和液芯波导分光光度法)、高效液相色谱法、荧光法和化学发光法。这些测定方法比传统的分光光度测定法有更高的灵敏度和更低的检测限,可以对海水中纳摩尔级低浓度的亚硝酸盐和硝酸盐进行测定。化学发光法和液芯波导分光光度法的自动化程度高,测定时对样品的需求量少,后者还实现了多个参数的实时现场测定,因而成为目前海水中低浓度亚硝酸盐和硝酸盐测定的主流方法,具有广阔的应用前景。     

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.     

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.     

Dissolved carbohydrates in seawater. II,A spectrophotometric procedure for total carbohydrate analysis and polysaccharide estimation

A procedure is described which adds a hydrolysis step to the Johnson and Sieburth 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) assay for total dissolved monosaccharides. The advantages of the monosaccharide test are retained in the total carbohydrate test, giving nearly equivalent responses for a variety of combined carbohydrates. A total sample of 50 ml is adequate for both total carbohydrate and monosaccharide assays which permit the estimation of polysaccharide by difference. Values for Narragansett Bay and adjacent waters ranged from 452 to 2023 μg l^?1 for total dissolved carbohydrate, 272 to 1353 μg l^?1 for polysaccharide, and 153 to 814 μg l^?1 for monosaccharide, which accounted for 6–18%, 4–13%, and 2–5% of the total dissolved carbon, respectively. We suggest that this is a sensitive and precise procedure which will be useful for investigating the distribution of dissolved carbohydrates in seawater and factors which affect its production, distribution and utilization.     

国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用

使用多种改性方法对几种国产天然沸石进行改性处理,提高其铵氮吸附率,制备符合海水硝酸盐氮同位素预处理要求的沸石。发现重力筛选可提高沸石铵氮吸附率16%以上,钠改性及酸改性后钠改性可提高沸石铵氮吸附率80%以上,微波改性和超声波改性均可进一步提高沸石铵氮吸附率。改性处理后,几种沸石在酸性条件下对低浓度铵氮吸附率达90%以上,其氮同位素分馏较美国UOP沸石分馏系数更小,且更稳定。改性后的国产沸石更适于海水硝酸盐氮同位素预处理。应用改性后沸石对长江口海域硝酸盐水样进行了分析,结果表明,改性后沸石可以应用于海水中溶解态硝酸盐的氮同位素分析,为海水中溶解态氮的来源问题及循环机理研究等提供了有效信息。     

Simplified procedure for laterally loaded drilled shafts in spatially random clays

Abstract

In this article, a simplified approach for the reliability-based design of laterally loaded drilled shafts considering the spatial variability of soil property is presented. This simplified approach utilizes a conventional reliability method implemented using the variance reduction technique. An algorithm for back-calculating the reduction factor and characteristic length for various shaft slenderness ratios is proposed. This simplified approach can yield responses for drilled shafts that are equivalent to those obtained using random field modeling (RFM), which is a far more complex process. The simplified approach does not require the knowledge of random field theory and can be an efficient design tool in geotechnical engineering practice.     

A colorimetric procedure for the determination of aldehydes in seawater and in cultures of methylotrophic bacteria

A spectrophotometric procedure for the determination of aldehydes was optimized for use in seawater, it involves the sequential reaction of aldehydes with 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) and FeCl₃ to produce a colored compound which is soluble in 50% acetone. The standard curve obeyed Beer's law to 90 μM formaldehyde in 0.7 m NaCl. The molar absorptivity of 21 800 absorbance units μM^?1 cm^?1 at 635 nm was not affected by changes in salinity. The limit of detection was 180 nM HCHO l^?1 when a pathlength of 1 cm was used, and 72 nM HCHO l^?1 when a pathlength of 5 cm was used.The MBTH procedure was used to compare formaldehyde production in cultures of the marine methanotroph, Methylomonas pelagica, growing on methane or methanol. The average rate of formaldehyde production, normalized to cell number, was almost 20 times greater in cultures grown on methanol than in cultures grown on methane.A depth profile of aldehyde concentrations from a station in the Peru upwelling region (10°S, 79°W) showed one peak in the oxygen gradient in the photic zone (80 m), two in the oxygen minimum (200 and 300 m), and one in the oxygen gradient below the minimum (800m). Aldehyde concentrations ranged from 0.6 to 8.8 μM formaldehyde equivalents l^?1. Except for the maxima where the aldehydes account for 13–15% of expected DOC concentrations, the background level of aldehydes was approximately 1% of DOC.     

基于镀铜镉柱海水中硝酸盐氮的检测技术的研究

镀铜镉柱还原——重氮偶氮染色法在检测海水领域具有重要的位置,算法的不断创新优化成为海水水质检测质量的的关键.本研究以硝酸钾作为标准溶液,海水作溶剂做相关实验,并且在实际海水检测应用中得到良好的效果.通过对实验原理的分析及实验过程的探究,确定了本研究的最佳还原与显色条件.并采用偏最小二乘法(partial least s...     

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.     

Determination of nitrate in seawater: Nitrate to nitrite reduction with copper-cadmium alloy

Determination of nitrate in seawater first requires its reduction to nitrite. Construction of a reductor column for use during continuous flow analysis at sea is described. Novel use is made of an alloy of cadmium and copper ($\text{50}\text{50}\text{w}\text{w}$) crushed to between 500 and 350 μm. Its performance is similar to that of the cadmium wire type of reductor but offers advantages of easier preparation and control of reductor volume.     

Preparation of the standard solutions of nitrate and their application to seawater and freshwater

Responding to the recommendation at the first Meeting of the International Coordination Group for the Cooperative Study of the Kuroshio and Adjacent Regions (CSK) 1965, a series of nitrate standard solutions consisting of eight different concentrations ranging from 0 to 50g-at NO₃-N/l in 30.5 sodium chloride solution with the highest purity was prepared for nitrate-N determination in seawater. The solutions have been proved to be stable at least 520 days after preparation.The best way of handling and conditioning the copper-cadmium column was studied for securing the perfect and reproducible conversion of nitrate to nitrite for the procedure as proposed byWood et al. (1967).It was also shown that the method can be applied to freshwater samples by the addition of sodium chloride and adjusting pH properly.     

模拟添加氮对海水溶解无机碳体系的影响

碳和氮作为主要的生源要素对维持海洋生态系的正常运转起着至关重要的作用,碳与氮的变化是相互耦合的且呈双向作用,为探讨海水无机碳与氮的相互作用规律,研究了室内模拟添加硝酸盐对海水无机碳体系pH、溶解无机碳(DIC)、HCO3-、二氧化碳分压(Pco2)的影响。结果表明,在室内培养的条件下,单纯添加硝酸盐(增加至原海水硝酸盐浓度的5-20倍)可引起培养体系浮游生物量的变化,但不能引起海水pH及DIC、HCO-3含量的明显变化,对DIC而言,其变化率仅仅在1%以内,但可导致海水Pco2的相对明显升高,其最终结果导致海水碳汇强度的减弱,碳源强度的增加。     

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.     

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.     

Study on analysis method of tritium in seawater

-The reclamation rate formula for concentrating tritium by the addition of "regular and quantitative aqueous sample" is advanced.Effects of different adding modes on reclamation rate and the reclamation rate reappearance are studied; and the analytic program of tritium in seawater is also proposed. By using Fe-Ni electrodes and the electrolysis temperature of 2± 0. 5℃, β value reaches 20. Reclamation rates reach 83% and 76% when 250 cm3 and 500 cm3 seawater is concentrated to 8 cm3.The relatively appropriate toluene/Trition ratio for counting aqueous sample under the normal temperature is proposed.The computer program of different addition electrolytic concentrations for measuring tritium is coded, and the tritium data base is established.     

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.