福建寿宁高山红茶矿质元素和稀土元素特征分析

徐梦婷; 邵淑贤; 魏明秀; 陈强; 陈静; 陈晓岚; 林馨颖; 罗钦; 叶乃兴

doi:10.19303/j.issn.1008-0384.2023.09.009

福建寿宁高山红茶矿质元素和稀土元素特征分析

doi: 10.19303/j.issn.1008-0384.2023.09.009

徐梦婷^1,,
邵淑贤¹,
魏明秀²,
陈强²,
陈静³,
陈晓岚²,
林馨颖³,
罗钦^4, ,,
叶乃兴^1, ,

1.
福建农林大学园艺学院，福建　福州　350002
2.
寿宁县茶产业发展中心，福建　寿宁　355500
3.
宁德职业技术学院茶学院，福建　福安　355000
4.
福建省农业科学院农业质量标准与检测技术研究所/福建省农产品质量安全重点实验室，福建　福州　350003

基金项目: 福建省科技计划公益类专项（2022R1022004）；福建农林大学寿宁乡村振兴研究院高山茶产业技术服务项目（2023-02）；福建农林大学横向课题（KH210103A）；福建张天福茶叶发展基金会科技创新基金项目（FJZTF01）

详细信息

作者简介:
徐梦婷（1999 —），女，硕士研究生，主要从事茶树栽培育种与茶叶品质化学研究，E-mail：925670892@qq.com

通讯作者:
罗钦（1979 —），男，副研究员，主要从事农产品质量安全过程控制研究，E-mail：33044390@qq.com

叶乃兴（1963 —），男，教授，硕士研究生导师，主要从事茶树栽培育种和品质化学研究，E-mail：ynxtea@126.com

中图分类号: TS272
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出版历程
- 收稿日期: 2023-06-21
- 修回日期: 2023-07-29
- 网络出版日期: 2023-09-21
- 刊出日期: 2023-09-28

Minerals and Rare-earth Elements in Alpine Black Tea from Shouning, Fujian

1.
College of Horticulture, Fujian Agriculture and Forestry University, Fuzhou, Fujian　350002, China
2.
Shouning County Tea Industry Development Center, Shouning, Fujian　355500, China
3.
Tea College, Ningde Vocational and Technical College, Fu'an, Fujian　355000, China
4.
Institute of Agricultural Quality Standards and Testing Technology Research/Fujian Key Laboratory of Agro-products Quality & Safety, Fuzhou, Fujian　350003, China

摘要

摘要: 目的探明福建寿宁高山红茶的矿质元素和稀土元素的含量特征及变化规律，为福建高山红茶的品质特征研究及高山红茶良种的推广应用提供参考依据。方法以60份不同等级寿宁高山金牡丹红茶为研究对象，分别进行感官审评、矿质元素和稀土元素含量测定，并结合化学计量学方法分析其化学元素差异特征，构建高山红茶等级判别模型。结果 15种矿质元素含量由高到依次为钾（K）＞钙（Ca）＞镁（Mg）＞锰（Mn）＞铝（Al）＞铁（Fe）＞钠（Na）＞锌（Zn）＞铜（Cu）＞铅（Pb）＞锡（Sn）＞硒（Se）＞砷（As）＞镉（Cd）＞汞（Hg），其中，K、Ca、Mg、Mn在寿宁高山红茶样品中含量丰富，占矿质元素总量的96.78%；15种稀土元素含量由高到依次为铈（Ce）＞镧（La）＞钇（Y）＞钕（Nd）＞钆（Gd）＞镨（Pr）＞镝（Dy）＞铒（Er）＞镱（Yb）＞钐（Sm）＞铕（Eu）＞钬（Ho）＞镥（Lu）＞铽（Tb）＞铥（Tm），其中，寿宁高山红茶Ce、La、Y、Nd含量较高，占稀土总量的82.44%。单因素方差分析结合受试者工作特征曲线共筛选出Cu、Al、Sn、Ce、Tm、Lu、Se、Mn、Dy、Ho、Gd、Tb、Er和Yb等14种特征元素（P＜0.05，AUC＞0.7）。基于此14种元素含量构建多层感知神经网络判别模型，训练组和检验组判别率分别为90.48%和94.44%。结论寿宁高山金牡丹红茶K、Ca、Mg、Mn等矿质元素含量丰富，基于化学元素含量构建多元统计分类模型可以有效地区分红茶样品等级。
- 红茶 /
- 金牡丹 /
- 矿质元素 /
- 稀土元素 /
- 电感耦合等离子体质谱法 /
- 寿宁
Abstract: Objective Contents of minerals and rare-earth elements in the alpine black teas from Shouning, Fujian were analyzed for grade classification. Methods On 60 Jinmudan alpine black tea of various grades, sensory evaluation and chemical analysis were performed. A chemometric method was applied on the data to construct a grade discrimination model for the tea. Results Based on the analytical data, 15 minerals detected in the specimens were ranked by their contents as K＞Ca＞Mg＞Mn＞Al＞Fe＞Na＞Zn＞Cu＞Pb＞Sn＞Se＞As＞Cd＞Hg. Among them, K, Ca, Mg, and Mn were more abundant and accounted for 96.78% of the total. The rank on the 15 rare-earth elements was Ce＞La＞Y＞Nd＞Gd＞Pr＞Dy＞Er＞Yb＞Sm＞Eu＞Ho＞Lu＞Tb＞Tm, with Ce, La, Y, and Nd being the dominant at contribution rate of 82.44%. For constructing a grading model, 14 characteristic elements, including Cu, Al, Sn, Ce, Tm, Lu, Se, Mn, Dy, Ho, Gd, Tb, Er, and Yb, were selected by the analysis of variance (ANOVA) combined with receiver operating characteristic curve (ROC curve) (P＜0.05, AUC＞0.7). A discriminant model of multi-layer perceptual neural network with a discriminant rate of 90.48% on the training group and 94.44% on the test group was established. Conclusion K, Ca, Mg, Mn, and other minerals were richly found in the Shouning Jinmudan alpine black teas. The constructed multivariate statistical model based on the chemical composition could be used to classify the grades of the teas.
- Black tea /
- Jinmudan /
- minerals /
- rare-earth elements /
- ICP-MS /
- Shouning

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图 1 不同等级寿宁高山红茶中各元素含量比较

A：矿质元素；B：稀土元素；*表示两组间差异显著（P＜0.05）；**表示两组间差异极显著（P＜0.01）。

Figure 1. Contents of various elements in Shouning alpine black tea of different grades

A: minerals; B: rare earth elements; * indicates significant difference at P＜0.05;** indicates very significant difference at P＜0.01.

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图 2 寿宁高山红茶中30种元素之间的相关性

Figure 2. Heat map on correlation between 30 elements in Shouning alpine black teas

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图 3 寿宁高山红茶差异元素的ROC曲线

Figure 3. ROC curve of various elements in Shouning alpine black tea of different grades

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表 1 寿宁高山红茶中矿质元素和稀土元素含量特征

Table 1. Contents of minerals and rare-earth elements in Shouning alpine black tea

	元素 Elements	所有样品 All samples/(mg·kg⁻¹)				特级 Super grade/(mg·kg⁻¹)			一级 First grade/(mg·kg⁻¹)
	元素 Elements	平均值 Average	最小值 Min.	最大值 Max.	变异系数 CV/%	平均值 Average	最小值 Min.	最大值 Max.	平均值 Average	最小值 Min.	最大值 Max.
矿质元素 Mineral elements	K	15400.00±2473.18	12400.00	21300.00	16.06	15683.33±2481.39	12700.00	21300.00	15116.67±2474.01	12400.00	20500.00
	Ca	4129.17±785.89	2740.00	7480.00	19.03	3999.33±909.32	2740.00	7480.00	4259.00±628.34	3310.00	6800.00
	Mg	1650.50±116.06	1390.00	1980.00	7.03	1689.67±114.76	1450.00	1980.00	1611.33±105.17	1390.00	1830.00
	Mn	643.98±187.34	299.00	1290.00	29.09	568.73±134.80	299.00	864.00	719.23±203.75	504.00	1290.00
	Al	591.90±238.98	213.00	1550.00	40.37	471.00±185.99	213.00	1100.00	712.80±226.62	418.00	1550.00
	Fe	54.37±28.44	15.80	156.00	52.31	52.26±29.15	15.80	150.00	56.48±28.05	26.90	156.00
	Na	37.71±27.06	6.47	123.00	71.74	42.48±29.08	10.40	110.00	32.94±24.43	6.47	123.00
	Zn	33.60±6.71	20.40	56.40	19.97	34.54±7.21	22.10	56.40	32.67±16.15	20.40	46.90
	Cu	9.17±2.59	5.51	24.20	28.30	10.41±2.95	7.81	24.20	7.92±1.32	5.51	10.90
	Pb	0.28±0.14	0.12	0.98	48.95	0.29±0.18	0.12	0.98	0.27±0.08	0.14	0.49
	Sn	0.08±0.07	0.02	0.53	82.45	0.11±0.09	0.05	0.53	0.06±0.02	0.02	0.12
	Se	0.06±0.02	0.02	0.12	35.39	0.05±0.02	0.02	0.10	0.06±0.02	0.04	0.12
	As	0.04±0.03	0.02	0.18	66.57	0.03±0.01	0.02	0.06	0.04±0.03	0.02	0.18
	Cd	0.011±0.005	0.003	0.024	40.37	0.012±0.004	0.005	0.024	0.011±0.005	0.003	0.018
	Hg	0.006±0.004	0.0004	0.017	69.23	0.005±0.003	0.0004	0.014	0.006±0.004	0.0004	0.017
	总量 Total	22550.87±2876.99	18701.63	29428.38	12.76	22552.26±2819.30	18781.54	28291.44	22549.49±2981.79	18701.63	29428.38
稀土元素 Rare earth elements	La	0.26±0.16	0.05	1.01	61.57	0.23±0.13	0.05	0.65	0.29±0.18	0.06	1.01
	Ce	0.49±0.22	0.11	1.08	43.45	0.41±0.17	0.16	1.08	0.58±0.23	0.11	0.92
	Pr	0.04±0.02	0.01	0.15	67.06	0.03±0.02	0.01	0.07	0.04±0.03	0.01	0.15
	Nd	0.12±0.08	0.03	0.53	68.35	0.10±0.05	0.03	0.24	0.15±0.10	0.04	0.53
	Sm	0.02±0.01	0.01	0.09	72.27	0.02±0.01	0.01	0.04	0.02±0.02	0.01	0.09
	Eu	0.010±0.006	0.002	0.038	59.97	0.008±0.004	0.002	0.016	0.012±0.008	0.005	0.038
	Gd	0.052±0.030	0.013	0.184	59.06	0.041±0.019	0.017	0.096	0.062±0.036	0.013	0.184
	Tb	0.003±0.002	0.001	0.014	66.59	0.002±0.001	0.001	0.006	0.004±0.002	0.002	0.014
	Dy	0.033±0.029	0.006	0.186	85.16	0.023±0.012	0.006	0.055	0.044±0.036	0.006	0.186
	Ho	0.007±0.006	0.001	0.042	84.32	0.005±0.003	0.001	0.013	0.009±0.008	0.002	0.042
	Er	0.022±0.020	0.003	0.141	92.42	0.015±0.008	0.003	0.038	0.028±0.026	0.005	0.141
	Tm	0.003±0.003	-	0.020	104.48	0.002±0.001	-	0.004	0.004±0.004	0.001	0.020
	Yb	0.021±0.023	0.002	0.156	113.10	0.013±0.008	0.002	0.037	0.029±0.031	0.004	0.156
	Lu	0.004±0.004	-	0.024	100.63	0.002±0.001	-	0.006	0.005±0.005	0.001	0.024
	Y	0.144±0.117	0.015	0.789	81.32	0.110±0.062	0.015	0.281	0.178±0.147	0.032	0.789
	轻稀土 Light rare earth	0.94±0.44	0.27	2.45	46.50	0.79±0.35	0.27	2.09	1.10±0.46	0.29	2.45
	重稀土 Heavy rare earth	0.29±0.23	0.05	1.56	79.99	0.21±0.11	0.05	0.52	0.36±0.29	0.07	1.56
	总量 Total	1.23±0.64	0.36	4.00	51.78	1.00±0.46	0.36	2.56	1.46±0.71	0.38	4.00
表中 “-”表示未检测到。 “-” indicates not detected.

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表 2 不同等级寿宁高山红茶多层感知神经网络判别结果

Table 2. Multilayer perceptron discriminants on Shouning alpine black tea of different grades

实测类别 Class category	训练组预测类别 Training sets prediction category		检验组预测类别 Test sets prediction category
实测类别 Class category	特级 Super grade	一级 First grade	特级 Super grade	一级 First grade
特级样品数 Number of super grade samples	21	3	8	1
一级样品数 Number of first grade samples	1	17	0	9
准确率 Accuracy/%	95.45	85.00	100.00	90.00

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