海水基质活性磷酸盐标准物质研制

张川, 于涛, 于小焱, 朱勇, 王丽芳, 张晓慧

海洋学研究 ›› 2023, Vol. 41 ›› Issue (3) : 92-100.

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海洋学研究 ›› 2023, Vol. 41 ›› Issue (3) : 92-100. DOI: 10.3969/j.issn.1001-909X.2023.03.009
研究论文

海水基质活性磷酸盐标准物质研制

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Preparation of standard reference material for reactive phosphorus with seawater matrix

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文章历史 +

摘要

本研究以西太平洋表层海水为基质,制备了浓度为0.5~4.0 μmol/L的海水活性磷酸盐系列标准物质。通过对所研制的4批次样品进行均匀性、稳定性评估,确定样品性能良好。对基于磷钼蓝分光光度法的气泡间隔连续流动分析系统的反应和操作条件进行优化,优化后的方法检出限低至0.03 μmol/L。不同浓度样品的相对标准偏差为0.37%~2.45%(n=9);通过与国际已有有证标准物质比对,本研究方法测量误差小于0.05 μmol/L。经6家具有中国计量认证资质且具备海水磷酸盐检测能力的实验室联合定值,确定了该系列标准物质的标准值,并对定值结果的不确定度进行了分析评价,相对扩展不确定度为2%~10%。

Abstract

Based on Western Pacific surface seawater as matrix, a series of reactive phosphorus reference materials with the concentration of 0.5-4.0 μmol/L were prepared. By investigating the uniformity and stability of the 4 batches of samples, it was confirmed that the performance met the needs of requirements. For the determination of reactive phosphorus in aqueous sample, segmented continuous flow analysis system with UV detector was used. The experimental conditions were optimized, the limit of detection(LOD) of the method was 0.03 μmol/L, and the relative standard deviation (RSD) of 4 different concentration batches was 0.37%-2.45%. The reliability of the method was verified by testing a CRM. The error was not more than 0.05 μmol/L. The concentration standard value of the series of reference substances was determined by 6 laboratories, and the relative expended uncertainty of characterization was evaluated, which was 2%-10%.

关键词

海水基质 / 活性磷酸盐 / 标准物质

Key words

seawater matrix / reactive phosphorus / reference material

引用本文

导出引用
张川, 于涛, 于小焱, . 海水基质活性磷酸盐标准物质研制[J]. 海洋学研究. 2023, 41(3): 92-100 https://doi.org/10.3969/j.issn.1001-909X.2023.03.009
ZHANG Chuan, YU Tao, YU Xiaoyan, et al. Preparation of standard reference material for reactive phosphorus with seawater matrix[J]. Journal of Marine Sciences. 2023, 41(3): 92-100 https://doi.org/10.3969/j.issn.1001-909X.2023.03.009
中图分类号: P734.44   

参考文献

[1]
HOWARTH R W. Nutrient limitation of net primary production in marine ecosystems[J]. Annual Review of Ecology and Systematics, 1988, 19: 89-110.
[2]
LE MOAL M, GASCUEL-ODOUX C, MÉNESGUEN A, et al. Eutrophication: A new wine in an old bottle[J]. Science of the Total Environment, 2019, 651: 1-11.
[3]
BENNETT E M, CARPENTER S R, CARACO N F. Human impact on erodable phosphorus and eutrophication: A global perspective[J]. BioScience, 2001, 51(3): 227.
[4]
MAHER W, WOO L. Procedures for the storage and digestion of natural waters for the determination of filterable reactive phosphorus, total filterable phosphorus and total phosphorus[J]. Analytica Chimica Acta, 1998, 375(1/2): 5-47.
[5]
ROBARDS K, MCKELVIE I D, BENSON R L, et al. Determination of carbon, phosphorus, nitrogen and silicon species in waters[J]. Analytica Chimica Acta, 1994, 287(3): 147-190.
[6]
JARVIE H P, WITHERS J A, NEAL C. Review of robust measurement of phosphorus in river water: Sampling, storage, fractionation and sensitivity[J]. Hydrology and Earth System Sciences, 2002, 6(1): 113-131.
. This paper reviews current knowledge on sampling, storage and analysis of phosphorus (P) in river waters. Potential sensitivity of rivers with different physical, chemical and biological characteristics (trophic status, turbidity, flow regime, matrix chemistry) is examined in terms of errors associated with sampling, sample preparation, storage, contamination, interference and analytical errors. Key issues identified include: The need to tailor analytical reagents and concentrations to take into account the characteristics of the sample matrix. The effects of matrix interference on the colorimetric analysis. The influence of variable rates of phospho-molybdenum blue colour formation. The differing responses of river waters to physical and chemical conditions of storage. The higher sensitivities of samples with low P concentrations to storage and analytical errors. Given high variability of river water characteristics in space and time, no single standardised methodology for sampling, storage and analysis of P in rivers can be offered. ‘Good Practice’ guidelines are suggested, which recommend that protocols for sampling, storage and analysis of river water for P is based on thorough site-specific method testing and assessment of P stability on storage. For wider sampling programmes at the regional/national scale where intensive site-specific method and stability testing are not feasible, ‘Precautionary Practice’ guidelines are suggested. The study highlights key areas requiring further investigation for improving methodological rigour. Keywords: phosphorus, orthophosphate, soluble reactive, particulate, colorimetry, stability, sensitivity, analytical error, storage, sampling, filtration, preservative, fractionation, digestion\n
[7]
国家质量监督检验检疫总局, 国家标准化管理委员会. 海洋调查规范第4部分:海水化学要素调查:GB/T 12763.4—2007[S]. 北京: 中国标准出版社, 2007.
General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization administration. Specifications for oceanographic survey—Part 4: Survey of chemical parameters in sea water: GB/T 12763.4—2007[S]. Beijing: Standards Press of China, 2007.
[8]
国家质量监督检验检疫总局, 国家标准化管理委员会. 海洋监测规范第4部分:海水分析: GB 17378.4—2007[S]. 中国标准出版社, 2008.
General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization administration. The specification for marine monitoring—Part 4: Seawater analysis: GB 17378.4—2007[S]. Beijing: Standards Press of China, 2008.
[9]
王丽芳, 黄韬, 杜川军, 等. 不同海水营养盐现场连续观测系统的比较研究[J]. 热带海洋学报, 2021, 40(3):103-113.
摘要
海水营养盐自动观测技术是海洋观测技术的核心之一, 也是世界各国海洋观测技术发展的重点。本文概述了海水营养盐自动观测技术在海洋环境监测中的研究进展, 并基于航次的现场实践, 比较了海水营养盐自动观测设备的应用情况, 归纳了不同设备的优缺点。基于紫外光谱法的硝酸盐传感器(in-situ ultraviolet spectroscopy, ISUS)具有不需化学试剂、响应速度快、适合连续长期观测、耐压深度深的优点, 可广泛应用于海水和淡水环境的走航观测、现场剖面观测和浮标定点观测; 其缺点是测定参数少、灵敏度低。基于湿化学法的营养盐剖面自动分析仪(Autonomous Profiling Nutreint Analyzer, APNA)与连续流动在线分析仪(型号为QuAAtro)具有测定精度和准确度高、多营养盐参数同步测定的优点, 可用于浅水剖面和短时间连续观测, 但存在操作复杂、工作时间短、试剂用量大的缺点, 不适合长期时间序列或深水观测; APNA能进行原位观测, QuAAtro基于船载, 需要加载样品采集过滤系统。本研究基于以上实践与经验, 进一步探讨了现有海水营养盐自动观测技术目前所面临的技术瓶颈及未来发展趋势, 旨在为海洋现场自动监测仪器的选用提供参考。
WANG L F, HUANG T, DU C J, et al. Comparison of different continuous in situ observation systems in seawater[J]. Journal of Tropical Oceanography, 2021, 40(3):103-113.
[10]
CHOQUETTE S J, DUEWER D L, SHARPLESS K E. NIST reference materials: Utility and future[J]. Annual Review of Analytical Chemistry, 2020, 13: 453-474.
[11]
卢晓华, 薄梦, 吴雪, 等. 标准物质领域发展现状及趋势[J]. 化学试剂, 2022, 44(10):1403-1410.
LU X H, BO M, WU X, et al. Current situation and trends on the development of reference materials[J]. Chemical Reagents, 2022, 44(10): 1403-1410.
[12]
朱勇, 施晓来, 刘强, 等. 海水营养盐标准物质的研制和发展[J]. 海洋开发与管理, 2018, 35(6):30-33.
ZHU Y, SHI X L, LIU Q, et al. Current status and development of a certified reference material for nutrients in seawater[J]. Ocean Development and Management, 2018, 35(6): 30-33.
[13]
AOYAMA M, ABAD M, LUDWICHOWSKI K U, et al. IOCCP-JAMSTEC 2015 inter-laboratory calibration exercise of a certified reference material for nutrients in seawater[M]. Yokosuka: Japan Agency for Marine-Earth Science and Technology, 2016.
[14]
徐燕青, 高生泉, 陈建芳, 等. 氢氧化镁共沉淀法测定海水中纳摩尔级活性磷酸盐[J]. 分析化学, 2011, 39(1):133-136.
XU Y Q, GAO S Q, CHEN J F, et al. Determination of reactive phosphate in nanomolar level in sea water with Mg(OH)2 Co-precipitation[J]. Chinese Journal of Analytical Chemistry, 2011, 39(1): 133-136.
[15]
MURPHY J, RILEY J P. A modified single solution method for the determination of phosphate in natural waters[J]. Analytica Chimica Acta, 1962, 27: 31-36.
[16]
CHEN Y L L, CHEN H Y. Seasonal dynamics of primary and new production in the northern South China Sea: The significance of river discharge and nutrient advection[J]. Deep Sea Research Part I: Oceanographic Research Papers, 2006, 53(6): 971-986.
[17]
LIANG Y, YUAN D X, LI Q L, et al. Flow injection analysis of nanomolar level orthophosphate in seawater with solid phase enrichment and colorimetric detection[J]. Marine Chemistry, 2007, 103(1/2): 122-130.
[18]
MA J, YUAN D X, LIANG Y. Sequential injection analysis of nanomolar soluble reactive phosphorus in seawater with HLB solid phase extraction[J]. Marine Chemistry, 2008, 111(3/4): 151-159.
[19]
YUAN Y, WANG S, YUAN D X, et al. A simple and cost-effective manual solid phase extraction method for the determination of nanomolar dissolved reactive phosphorus in aqueous samples[J]. Limnology and Oceanography: Methods, 2016, 14(2): 79-86.
[20]
国家市场监督管理总局. 标准物质的定值及均匀性、稳定性评估: JJF 1343—2022[S]. 北京: 中国标准出版社, 2022.
State Administration for Market Regulation. Characterization, homogeneity and stability assessment of reference materials: JJF 1343—2022[S]. Beijing: Standards Press of China, 2022.
[21]
BECKER S, AOYAMA M, WOODWARD E M S, et al. GO-SHIP repeat hydrography nutrient manual: The precise and accurate determination of dissolved inorganic nutrients in seawater, using continuous flow analysis methods[J]. Frontiers in Marine Science, 2020, 7: 581790.
[22]
PAI S C, YANG C C, RILEY J P. Effects of acidity and molybdate concentration on the kinetics of the formation of the phosphoantimonylmolybdenum blue complex[J]. Analytica Chimica Acta, 1990, 229: 115-120.
[23]
ZHANG J Z, FISCHER C J, ORTNER P B. Continuous flow analysis of phosphate in natural waters using hydrazine as a reductant[J]. International Journal of Environmental Analytical Chemistry, 2001, 80(1): 61-73.
[24]
LEVINE H, ROWE J J, GRIMALDI F S. Molybdenum blue reaction and determination of phosphours in waters containing arsenic, silicon, and germanium[J]. Analytical Chemistry, 1955, 27(2): 258-262.
[25]
DRUMMOND L, MAHER W. Determination of phosphorus in aqueous solution via formation of the phosphoantimon-ylmolybdenum blue complex. Re-examination of optimum conditions for the analysis of phosphate[J]. Analytica Chimica Acta, 1995, 302(1): 69-74.

基金

自然资源部计量检测及质量监督资助项目(121154000000190010)

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