黑莓果实不同发育期8种矿质元素含量的ICP-MS测定及不确定度评定

ICP-MS determination and uncertainty assessment of eight mineral elements in blackberry fruits at different developmental stages

摘要

【目的】探究不确定度分量对黑莓成熟过程中8种矿质元素（钠、钾、钙、镁、铜、铁、锌、锰）含量动态变化的影响，为不确定度评定试验方法提供数据支持。【方法】采用电感耦合等离子体质谱法（inductively coupled plasma-mass spectrometry，ICP-MS），通过动态碰撞池模式，对比压力罐消解法（sealed digestion，SD）与微波消解法（microwave digestion，MD），研究黑莓成熟过程中钠、钾、钙、镁、铜、铁、锌、锰8种元素含量的动态变化，并引入13个不确定度分量以评价试验方法对结果的影响。【结果】8种元素标准曲线相关系数均大于0.999，加标回收率为93.33%~104.50%，方法灵敏度高、精密度高；在黑莓成熟过程中，8种元素含量整体呈明显下降趋势，青果期至转色期降幅最大，其中钠、钾、锰在果实成熟过程中下降幅度最明显；称量、定容、样品制备、标准溶液配制、样品基质是主要的不确定度来源，其中加标回收率 u₁（Sm）、移液管 u₂（std）、内标 u₂（Sm）、母液 u₁（std）4个分量对试验结果影响最大，8种元素合成不确定度为0.011 271~0.022 888，扩展不确定度变异系数为钠（2.76%）、钾（2.54%）、钙（2.25%）、镁（2.49%）、铜（2.66%）、铁（2.89%）、锌（4.58%）、锰（3.12%）。【结论】采用电感耦合等离子体质谱法测定黑莓中钠、钾、钙、镁、铜、铁、锌、锰元素含量，方法准确可行，且在果实成熟过程中8种元素含量均明显下降。

Abstract

【Objective】To clarify changes in the mineral composition of blackberry fruits, this study used organically grown blackberries at different maturity stages as raw materials. It compared wet digestion and microwave digestion methods, incorporated uncertainty analysis, and comprehensively evaluated the reliability of the experimental approach. This research would provide technical support for assessing dynamic changes in mineral elements during blackberry ripening. 【Methods】Using inductively coupled plasma-mass spectrometry (ICP-MS) with dynamic collision cell mode, this study compared the sealed digestion (SD) and microwave digestion (MD) methods to investigate the dynamic changes in sodium, potassium, calcium, magnesium, copper, iron, zinc, and manganese during blackberry ripening. The following parameters were included: Spiked recovery u ₁(Sm), pipette u ₂(std), internal standard u ₂(Sm), mother liquor u ₁(std), sample repeatability u ₂(Cp), volumetric flask temperature u ₂(V), fitting u ₃(std), blank solution repeatability u ₁(Cp), volumetric flask calibration u ₁(V), volumetric flask repeatability u ₃(V), balance repeatability u ₂(m), balance calibration u ₁(m), and instrument u ₃(Sm). 【Results】The correlation coefficients for the standard curves of all 8 elements exceeded 0.999, with spiked recovery rates ranging from 93.33% to 104.50%. This method demonstrated high sensitivity and precision. During blackberry development, as the fruits expanded and ripened, the contents of the 8 minerals showed a significant overall downward trend: an initial decline followed by stabilization. From the green fruit stage to the color change stage, the concentrations of all 8 minerals decreased substantially, with the most pronounced changes observed in sodium, potassium, and zinc. During color change stage Ⅱ, the concentrations of sodium, iron, magnesium, calcium, zinc, and manganese increased, while those of potassium and copper decreased. During color change stage Ⅲ, potassium and manganese increased, while the remaining six elements decreased. At maturity, sodium, potassium and manganese decreased, while the other five elements increased to varying degrees. This indicates that all eight elements show a significant downward trend during blackberry fruit coloration, suggesting that substantial physiological changes accompany this process and significantly impact mineral absorption and metabolism. The contents of sodium, potassium, and manganese show the most pronounced decline during fruit ripening, which would provide theoretical support for water and fertilizer management in blackberry cultivation. The uncertainty values for each component during the testing process, sorted from largest to smallest, are as follows: Spiked recovery u ₁(Sm) ＞ Pipette u ₂(std) ＞ Internal standard u ₂(Sm) ＞ Stock solution u ₁(std) ＞ Sample repeatability u ₂(Cp) ＞ Volumetric flask temperature u ₂(V) ＞ Fitting u ₃(std) ＞ Blank solution repeatability u ₁(Cp) ＞ Volumetric flask calibration u ₁(V) ＞ Instrument u ₃(Sm). Among the five uncertainty sources, volumetric flask repeatability u ₃(Sm) has the highest uncertainty, (V) ＞ volumetric flask repeatability u ₃(V) ＞ balance repeatability u ₂(m) ＞ balance calibration u ₁(m) ＞ instrument u ₃(Sm). For the other five uncertainty sources, the uncertainty contribution ranks as follows: sample matrix U _rel(Sm) ＞ standard curve preparation U _rel(std) ＞ sample preparation U _rel(Cp) ＞ volume adjustment U _rel(V) ＞ weighing U _rel(m). This indicates that standard curve preparation and the sample matrix are the dominant contributors to uncertainty in the determination of eight elements in blackberries by inductively coupled plasma mass spectrometry. Among these factors, spiked recovery, pipette usage, internal standards, and standard stock solutions exerted the greatest influence on the test results in this study. The expanded uncertainty coefficients for all 8 elements were below 5%, and in descending order, they are: Calcium ＜ magnesium ＜ potassium ＜ copper ＜ sodium ＜ iron ＜ manganese ＜ zinc. Component analysis revealed that the spiked recovery of manganese and zinc introduced relatively higher uncertainties. The combined uncertainty for the eight elements ranged from 0.011 271 to 0.022 888, with expanded uncertainty percentages as follows: sodium (2.76%), potassium (2.54%), calcium (2.25%), magnesium (2.49%), copper (2.66%), iron (2.89%), zinc (4.58%), and manganese (3.12%). 【Conclusion】This study established a microwave digestion-inductively coupled plasma mass spectrometry (ICP-MS) method to determine the contents of eight minerals in blackberries. After validating the method's linearity, detection capability, precision, accuracy, robustness, and measurement uncertainty, this research clarified the variation trends of these eight mineral contents during the fruit development of blackberries. The findings would provide data support and a theoretical basis for further relevant research.

关键词

黑莓 / 矿质元素 / 电感耦合等离子体质谱法 / 不确定度

Key words

Blackberry / Mineral elements / Inductively coupled plasma mass spectrometry / Uncertainty

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基金资助

北京市教委科研计划资助项目(KM202310858002)

国家重点研发计划项目(2024YFC3308500)