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。     

The reliability of the thermodynamic constants for the dissociation of carbonic acid in seawater

Laboratory measurements of all four CO₂ parameters [f_CO2 ( = fugacity of CO₂), pH, TCO₂ ( = total dissolved inorganic carbon), and TA ( = total alkalinity)] were made on the same sample of Gulf Stream seawater (S = 35) as a function of temperature (5–35 °C) and the ratio of TA/TCO₂ (X) (1.0–1.2). Overall the measurements were consistent to ±8 μ atm in f_CO2, ± 0.004 in pH, ± 3 μ mol kg⁻¹ in TCO₂, and ± 3 μ mol kg⁻¹ in TA with the thermodynamic constants of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). Deviations between the measured pH, TCO₂, TA and those calculated from various input combinations increase with increasing X when the same constants are used. This trend in the deviations indicates that the uncertainties in pK₂ become important with increasing X (surface waters), but are negligible for samples with the lower X (deep waters). This trend is < 5 μ mol kg⁻¹ when the pK₂ values of Lee and Millero (1995) are used.The overall probable error of the calculated f_CO2 due to uncertainties in the accuracy of the parameters (pH, TCO₂, TA, pK₀, pk₁, and pK₂) is ± 1.2%, which is similar to the differences between the measured values and those calculated using the thermodynamic constants of Millero (1995).The calculated values of pK₁, (from f_CO2-TCO₂-TA) agree to within ± 0.004 compared to the results of Dickson and Millero (1987), Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995) over the same experimental conditions. The calculated values of pK₂ (from pH-TCO₂-TA) are in good agreement (± 0.004) with the results of Lee and Millero (1995) and also in reasonable agreement (± 0.008) with the results of Goyet and Poisson (1989), Roy et al. (1993), and Millero (1995). The salinity dependence of our derived values of pK₁ and pK₂, (S = 35) can be estimated using the equations determined by Millero (1995).     

EGTA滴定法测定海水Ca2+浓度精度评估及其在近海海域实测的必要性

海水Ca²⁺浓度是计算碳酸钙饱和度的重要参数之一,通常由海水钙盐比值计算得出,但该方法在受多种因素影响的近海海域可能不适用。本研究开展了EGTA自动电位滴定法对不同盐度海水Ca²⁺浓度测定精度和准确度的研究,探究“盐效应”对Ca²⁺浓度测定可能存在的影响,并比较了近海养殖区海水实测Ca²⁺浓度与通过钙盐比估算值的差异。研究表明：(1)EGTA自动电位滴定法测定不同盐度海水Ca²⁺浓度精度较高,在各个盐度条件下,5次平行测定的标准偏差为0.001～0.006 mmol/kg,精度均优于0.1%;(2)在盐度20.00～34.62范围内,Ca²⁺的实测值与通过钙盐比值计算所得的相对误差为-0.043%～0.023%,准确度在±0.05%内;(3)不同盐度海水样品Ca²⁺浓度的实测值与理论值基本吻合,电位滴定法测定Ca²⁺浓度不存在“盐效应”问题;(4)受陆源输入过程的影响,近海(烟台牟平养殖区)表层及底层海水Ca     

Mineral carbon MinC(%) from Rock-Eval analysis as a reliable and cost-effective measurement of carbonate contents in shale source and reservoir rocks

The abundance of carbonate minerals in rocks is an important element for petroleum geochemists, geologists and engineers to consider during hydrocarbon exploration and production. Carbonate minerals can be related to the depositional environments of the source rocks and hence the type of organic matter that can be subsequently modified through diagenetic processes. The total carbonate content in shales can also be used to deduce their fracability as reservoir rock for shale gas/oil extraction. At present, mineralogical analysis by X-ray diffraction (XRD) is the most widely used technique in the oil and gas-related petrophysical and geochemical laboratories for identifying and quantifying carbonate minerals in rock samples. In contrast, the use of the total mineral carbon content parameter MinC (%) from Rock-Eval analysis has been limited despite (1) the parameter's effectiveness as demonstrated through instrument and methodology development; and (2) the presence of a large volume of Rock-Eval results due to its widespread use in the oil and gas industry.In this study, we acquired XRD and Rock-Eval analytical results on over nine hundred rock samples ranging from Ordovician to Cretaceous age from four petroleum sedimentary basins in Canada. Least-squares regression analyses produce empirical equations with R² values greater than 0.92 for the correlations between XRD total carbonate contents and the Rock-Eval MinC (%) values of six different suites of samples. This indicates that the MinC (%) values generated by Rock-Eval 6 and other instruments of similar capability can be used with confidence for estimating the amounts of total carbonates in sedimentary rock samples. While the correlation between the two types of carbonate content measurements is geology-specific, a global linear regression model (R² of 0.97) based on the large combined data set has been proposed for approximating the total carbonate abundances based on Rock-Eval MinC (%) values.