ICP-OES标准加入法准确测定海水中的硼

硼作为海水中的重要组分,其准确测定对海洋环境生物地球化学过程研究具有重要意义。海水中硼的常用测定方法具有前处理步骤繁琐、耗时长、样品易被污染、灵敏度低等缺点,不适于大批量海水样品的准确测定。为剔除海水高盐基体效应及干扰,本文运用电感耦合等离子体发射光谱法(ICP-OES),将海水样品进行稀释,采用标准加入法建立工作曲线,对海水中硼含量进行准确测定。正交实验显示,ICP-OES最佳工作条件为射频功率1400 W,雾化气流量0.7 L/min,观测高度14 mm,进样泵速1.5 m L/min。标准加入法标准曲线相关系数大于0.999,相对标准偏差为0.76%~1.27%,加标回收率为94.6%~101.8%,方法检出限为1.073μg/L。实际的海水样品分析表明,该方法可消除海水基体干扰,减少测定误差,并且前处理操作简单快速,化学试剂用量少,回收率高,精密度好,灵敏度高,可用于海水及其它高盐样品中硼含量的准确测定。     

标准海水研究现状及其应用

标准海水作为海水盐度量值的标准物质,广泛用于检定和校准海水盐度测量仪器和装置.主要介绍两种标准物质-中国-级标准海水和中国系列标准海水,系统介绍我国现阶段标准海水的制备,封装工艺,保存方法,并阐述其在使用过程中的注意事项.     

标准海水制备系统的设计与工艺

标准海水应用于海洋盐度测量、盐度计的检定/校准等工作,在我国海水盐度量值传递体系中起着承上启下的作用。本文阐述标准海水制备系统的组成及其改造的设计方案,就海水的浓缩、杀菌、海水瓶的选择、灌装等关键问题做出详细分析;从天然海水的采集、水质处理、海水瓶的清洗与烘干、海水的灌装与定值等部分介绍了标准海水的现有制备工艺,通过对样品海水的盐度数据进行分析,举例验证该制备系统的可操作性和准确性。     

Comprehensive polynomial simulation and prediction for Langmuir volume and Langmuir pressure of shale gas adsorption using multiple factors

In this study, 32 experimental measurements on the isothermal adsorption of methane for 18 shale samples from China's three largest continental oil basins—Songliao, Bohai Bay, and Ordos basins—were used to construct comprehensive polynomial simulation and prediction models for Langmuir volume and Langmuir pressure. The models were based on shale properties (total organic carbon (TOC) content, amount of residual hydrocarbon S₁, and mineral composition of rocks) and adsorption condition (temperature) using a weighted sum of multiple variables. The influences of various factors were quantitatively characterized, and the prediction accuracy was verified. Langmuir volume is mainly affected by temperature, shale TOC content, amount of residual hydrocarbon, and clay mineral content; Langmuir pressure is mainly affected by clay, carbonate, feldspar and illite content (because shale pore size can be affected by shale mineral composition). Based on the resource potential and the producibility of shale gas, the area suitable for shale gas exploration and development should have high abundance of organic matter (TOC and residual hydrocarbon S₁), low clay mineral content and feldspar content, high conversion rate of montmorillonite to illite (strong diagenesis), and high carbonate content. The comprehensive polynomial prediction model can effectively simulate and predict Langmuir volume and Langmuir pressure, thereby reducing the amount of work necessary for evaluation of shale gas resource potential and economic feasibility.     

低盐度海水中重金属标准物质研制

本文介绍了低盐度海水中5种重金属元素混合溶液标准物质的研究和制备过程。以稀释的大洋海水为基体,用容量法以加标方式制备了低盐度海水中重金属标准物质。各元素统计结果表明样品的均匀性和稳定性良好。经9家具有中国计量认定(CMA)资质的实验室分别采用原子吸收分光光度法、电感耦合等离子体质谱法和阳极溶出伏安法对标准溶液进行分析定值,并用国家标准物质作量值溯源,以分析结果的总平均值作为标准值,标准值及不确定度的结果分别为铜15.2±0.7 μg/L、铅15.3±0.7 μg/L、锌98.9±4.7 μg/L、镉2.02±0.10 μg/L以及铬15.3±0.6 μg/L。该标准物质可用于近岸、河口区低盐度海水重金属分析过程的量值传递和质量控制。     

Review on current and seawater volume transport through the Taiwan Strait

Patterns and features of currents and seawater volume transports in the Taiwan Strait have been reviewed by examining the results from more than 150 research papers in recent decades. It is noted that there are diverse or even conflicting viewpoints on these subjects. Here both common and different opinions are summarized. This review paper covers the studies involving in situ measurements and numerical modeling of current velocity, analyses of hydrographic data, and classification of water masses. Generally speaking, there are three currents in the Taiwan Strait: the China Coastal Current along the Fujian coast in the western Taiwan Strait, the extension of the South China Sea Warm Current in the western and central Taiwan Strait, and the Kuroshio’s branch or loop current intruding through the eastern Taiwan Strait. The current pattern in winter is quite different from that in summer, and the currents also exhibit differences between the upper and lower layers. The seawater volume transport through the Taiwan Strait is about 2.3 Sv northward in summer but about 0.8 Sv northward in winter. Both the current pattern and the seawater transport vary with local winds in the Taiwan Strait. This is particularly true in winter when the currents and the transport in the upper layer are significantly affected by strong northeasterly winds.     

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.     

Conductivity/salinity/temperature relationship of diluted and concentrated standard seawater

The conductivity ratio of diluted and concentrated standard seawater has been measured very accurately in a salinity range from 0 to42permiland at temperature from -1 to30degC. All the data have been fitted into polynomials which are compared with previous data. The specific conductance of seawater is deduced and a polynomial for the full range of salinity and temperature is proposed. Data presented in this paper have been used, with those of Dauphinee presented in this issue, to elaborate the new "Practical Salinity Scale 1978."     

海水为溶剂合成纳米粉煤灰沸石及其性能表征

以海水为溶剂,采用熔融法合成了纳米粉煤灰沸石。粉煤灰与NaOH的质量比为1:1.2,熔融温度550℃,熟料质量与海水固液的体积比为1:5(g/mL),晶化温度100℃,晶化时间6h。通过仪器分析和化学方法,对产物的结构、形貌、性能进行表征。同时,研究了产物的矿物组成、形貌、比表面积、阳离子交换量及化学组成。结果表明:产物为NaX型沸石和羟基方钠石的复合型沸石,海水晶化粉煤灰通过碱熔融法得到沸石质量优于传统水热法。合成沸石的性能和各项应用指标表明,所合成的沸石具有良好的实际应用价值。     

The latest batch-to-batch difference table of standard seawater and its application to the WOCE onetime sections

An updated batch-to-batch difference table of IAPSO standard seawater (SSW) up to P145 is proposed. The batch-to-batch difference table is based on several recent SSW comparison experiments, including the experiments conducted independently at the Japan Agency for Marine-Earth Science and Technology (JAMSTEC) and Woods Hole Institute of Oceanography (WHOI) at about the same time using the same procedure. Proposed batch-to-batch differences range from 1.2 × 10⁻³ to −1.9 × 10⁻³ with reference to the average of those from P91 to P102. Batch-to-batch differences from P29 to P145 with reference to the recent batches and this average over every 5 years since 1960 are also presented, together with standard deviation. This reveals that inconsistency among batches has improved since 1980s. In particular, the standard deviation was 0.3 × 10⁻³ in this decade, which is about one-half the value reported previously and almost equal to the modern measurement precision (0.2 × 10⁻³) and is within-batch difference (<0.3 × 10⁻³). Proposed batch-to-batch differences were applied to the observational results of the WOCE hydrographic onetime section (WHP onetime) in the Indian Ocean. Average absolute salinity differences at 14 crossover points in the Indian Ocean were slightly larger, from 1.2 × 10⁻³ to 1.5 × 10⁻³, when the batch-to-batch difference table was applied; however, when results from the Indian, Pacific, and Atlantic Oceans were combined, application of the batch-to-batch difference table yielded statistically acceptable salinity differences. The table was also applied to WHP sections P1 and P17 (revisited about 10 years after the original observations during the WOCE period) and sections I1, I7, and I8 (visited twice by different research vessels in the same year). In all cases, the table corrected unrealistically large salinity changes in space and time. The results suggest that the application of the batch-to-batch table to well-controlled salinity data such as WOCE datasets would be effective in making the datasets more consistent in space and time.     

海口湾的溶解氧及海水水质指标限制值问题

海水溶解氧对海洋生物的生存、生长和发育相当重要,与生物活动有着密切的联系,它的含量变化是反映生物生长状况的一个重要标志,同时也是污染监测的重要指标.海口湾是海南省的重点海域,1989年以来,陈春华等对海口湾的环境问题进行了大量的研究^[1~6],本论文就海口湾的溶解氧监测结果进行分析,并发现了溶解氧水质标准限制值存在的问题.每年在该湾布设10余个站点进行污染监测,有必要对海口湾近7年监测结果进行综合分析.     

An improved specific interaction model for seawater at 25°C and 1 atmosphere total pressure

Equations recently developed by Pitzer are applied to a seawater model on the assumption that only interactions between ions of opposite charge sign are significant. This model is shown to give good agreement with available experimental data for the osmotic coefficient and for the mean-ion activity coefficients of the major electrolyte components. The results are compared with the predictions of the ion-association model and with a number of models using the concept of specific ionic interaction. The relative merits of the various models are discussed. Pitzer's original equations are modified to enable the calculation of conventional single-ion activity coefficients. These values are compared with those obtained on the basis of alternative conventions and an encouraging measure of agreement is observed. It is concluded that the new model introduces a fluency into the specific interaction approach that should greatly facilitate the incorporation of trace components into future models.     

动态式抽取、气相色谱法测定海水中的甲烷

本文报道了用动态（ｄｙｎａｍｉｃ）技术，经抽取、气相色谱法测定海水中溶存甲烷浓度的方法．详细论述了溶存甲烷经起泡、收集（吸附）、解吸和检测四步完成，并逐步讨论了起泡时间、起泡气体流速以及收集温度等有关因子对测定的影响。结果表明：该方法分析速度快、精密度好、灵敏度高，可广泛应用于海上现场测定海水中溶存的甲烷。     

Experimental determination of the silica solubility and of the H4SiO 4 0 activity ratio in standard and desalinated seawater

The solubility of amorphous silica was studied in mixtures of riverine and marine waters simulating the water composition at the river-sea geochemical barrier. The value of the thermodynamical equilibrium constant was determined for the reaction of silicon solubility as K _r ⁰ = (1.71 ± 0.01) × 10^?3 at 22°C. A near-linear dependence was found for the activity ratio of the H₄SiO ₄ ⁰ and the salinity with the increase of this ratio from 1.00 in the riverine to 1.15 in the standard seawater.     

The electrical conductivity of weight diluted and concentrated standard seawater as a function of salinity and temperature

The ratiosR_{s,t,o}of electrical conductivity of seawater samples of precisely known salinity to standard seawater at the same temperature have been measured over a wide range of salinities from 0 to42permilS and over the full range of oceanic temperatures from -2 to35degC. The samples withS<35permilwere prepared by accurate weight dilution of standard seawater with distilled water. High salinity samples were prepared by fast evaporation of standard seawater and subsequent weight dilution into the already determined <35permilrange. An equation was derived which expresses the S versusR_{s,t,o}relationship very precisely from1-42permiland at all temperatures, i.e.,S = f_{1}(R_{s,t,o}) + f_{2}(R_{s, t,o},t) =Sigma_{n=0}^{5} a_{n}R^{n/2}+ frac{Delta t}{1+kDelta t} Sigma_{n=0}^{5} b_{n}R^{n/2}whereDelta t = t-15degC,R = R_{s, t.o}; only the first termf_{1}is required at15degC. The effeet of temperature on the electrical conductivity of standard seawater was also measured. The ratior_{t}of the conductivity at temperaturetto the conductivity at15degC (C_{35,t, o}/C_{35,15,o}) is very aeenrately expressed by a fourth degree equation int. i.e,r_{t}=Sigma_{n=0}^{4} c_{n}t^{n}These two equations are sufficient for all salinity determinations at normal atmospheric pressure.     

The quantification of amino acids in seawater using thin-layer chromatography and fluorimetry

Through the use of dansyl chloride, thin-layer chromatography, and fluorimetry, the dissolved free amino acid composition of estuarine water samples has been quantified. The fluorescent agent, dansyl chloride, is sensitive to both amino and imino acids, and a complex mixture of the dansyl compounds can be separated by using two-dimensional thin layer chromatography. At low concentrations, the fluorescence: concentration ratio is strictly a Beer-Lambert relation, while at higher concentrations it appears to fit an exponential curve. Compounds which contain the simple amino group as well as additional reactive groups have slope relations of more than one, relative to glycine.     

Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy

High-resolution fluorescence spectroscopy was used to characterize dissolved organic matter (DOM) in concentrated and unconcentrated water samples from a wide variety of freshwater, coastal and marine environments. Several types of fluorescent signals were observed, including humic-like, tyrosine-like, and tryptophan-like. Humic-like fluorescence consisted of two peaks, one stimulated by UV excitation (peak A) and one by visible excitation (peak C). For all samples, the positions of both excitation and emission maxima for peak C were dependent upon wavelength of observation, with a shift towards longer wavelength emission maximum at longer excitation wavelength and longer wavelength excitation maximum at longer emission wavelength. A trend was observed in the position of wavelength-independent maximum fluorescence () for peak C, with maximum at shorter excitation and emission wavelengths for marine samples than for freshwater samples. Mean positions of these maxima were: rivers = nm; coastal water = nm; marine shallow transitional = nm; marine shallow eutrophic = nm; and marine deep = nm. Differences suggest that the humic material in marine surface waters is chemically different from humic material in the other environments sampled. These results explain previous conflicting reports regarding fluorescence properties of DOM from natural waters and also provide a means of distinguishing between water mass sources in the ocean.     

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。     

Theoretical model for the formation of ion-pairs in seawater

Predictions of association constants for ion-pair formation in seawater were compared to measured constants as a test for the existence of ion-pairs. A fair agreement was obtained in most cases, although the theoretical electrostatic calculations indicate that significant chloride ion-pairing should occur which has not been observed in most experimental investigations.     

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...