偏硼酸锂和四硼酸锂碱熔-电感耦合等离子体发射光谱法测定海域砂矿中的锆和钛

张逸君; 张宇航; 陈艳; 邓焱; 王佳翰

doi:10.15898/j.ykcs.202409110188

偏硼酸锂和四硼酸锂碱熔-电感耦合等离子体发射光谱法测定海域砂矿中的锆和钛

1.
海口市海洋污染物监测创新与应用重点实验室，中国地质调查局海口海洋地质调查中心，海南海口 571127

基金项目: 中国地质调查局地质调查项目“金矿等战略性矿产实验测试技术支撑与服务”(DD20242769)

详细信息

作者简介: 张逸君，硕士，工程师，主要从事地质样品检测工作。E-mail：buaachenyiwei@sina.com

通讯作者: 王佳翰，硕士，高级工程师，主要从事地质样品检测工作。E-mail：wangjiahanhao@163.com。

中图分类号: O657.63

收稿日期: 2024-09-11

修回日期: 2024-10-26

录用日期: 2024-11-01

网络出版日期: 2024-11-30

刊出日期: 2024-12-31

Determination of Zirconium and Titanium in Marine Placer Deposits by ICP-OES with Alkali Fusion of Lithium Metaborate-Lithium Tetraborate Composite Flux

1.
Haikou Key Laboratory of Marine Contaminants Monitoring Innovation and Application; Haikou Marine Geological Survey Center, China Geological Survey, Haikou 571127, China

More Information

Corresponding author: WANG Jiahan, wangjiahanhao@163.com

Received Date: 11 September 2024

Revised Date: 26 October 2024

Accepted Date: 01 November 2024

Available Online: 30 November 2024

Publish Date: 31 December 2024

摘要

摘要:
海南岛的海域砂矿蕴藏着丰富的锆钛资源，具有巨大的开发潜力。本文建立了一种基于偏硼酸锂-四硼酸锂复合熔剂(33∶67，m/m)的碱熔-电感耦合等离子体发射光谱法，用于测定海域砂矿中锆和钛的含量。样品采用0.8g复合熔剂混合，在1000℃下熔融15min，冷却后将熔融物倒入稀酸中，在恒温振荡仪中进行振荡溶解。通过简化操作流程、改进溶解熔融物的技术，本方法Zr的检出限为0.40µg/g，TiO₂的检出限为0.0025%。通过国家标准物质验证，Zr和TiO₂测定值的相对标准偏差(RSD)分别为 1.0%～3.5%、0.7%～3.3%，精密度和准确度均符合地质矿产实验室测试质量管理规范，适用于海域砂矿中锆和钛的快速连续分析。
- 海域砂矿 /
- 碱熔 /
- 偏硼酸锂-四硼酸锂熔剂 /
- 电感耦合等离子体发射光谱法 /
- 锆 /
- 钛
Abstract:
The marine placer deposits of Hainan Island contain abundant zirconium (Zr) and titanium (Ti) resources, which hold significant development potential. An alkali fusion-inductively coupled plasma-optical emission spectrometry method based on a composite flux of lithium metaborate and lithium tetraborate (m∶m=33∶67) was developed for determining Zr and Ti in marine placers. In this method, the sample was fused with 0.8g flux at 1000℃ for 15min. After cooling, the molten substance was poured into a dilute acid and dissolved by oscillation in a constant temperature oscillator. This approach simplifies the operation process by avoiding the complexity associated with high-temperature procedures while enhancing melt dissolution techniques. The detection limit for Zr in this method is 0.40μg/g while that for TiO₂ is 0.0025%. Based on standard materials, the relative standard deviation (RSD) of Zr ranges between 1.0%−3.5%; RSD of TiO₂ ranges between 0.7%−3.3%. These precision values align with quality management standards set forth by geological and mineral laboratory testing. The method is suitable for rapid continuous analysis of Zr and Ti in marine placer deposits.
- marine placer deposits /
- alkali fusion /
- lithium metaborate-tetraborate composite flux /
- inductively coupled plasma-optical emission spectrometry /
- zirconium /
- titanium

HTML全文

图 1 不同熔剂加入量对GBW07314测定结果的影响

Figure 1.

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表 1 测定元素分析谱线

Table 1. Analytical spectral lines for determination of elements

元素	谱线 (nm)	浓度为5.0mg/L时的平均响应
Zr	339.198	21890
	343.823	127200
	349.621	8603
Ti	334.941	327000
Ti	336.124	172100

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表 2 复溶介质的选择

Table 2. Selection of resolution medium

复溶介质	TiO₂含量		Zr含量
复溶介质	测定值 (%)	标准值 (%)	测定值 (µg/g)	参考值 (µg/g)
4%硝酸	0.780	0.825±0.030	222	229
8%硝酸	0.781		223
12% 硝酸	0.784		220
6% 盐酸	0.784		222
10% 盐酸	0.767		216
15% 盐酸	0.765		219
8% 王水	0.763		218
12% 王水	0.767		221
8% 逆王水	0.769		221
12% 逆王水	0.761		221

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表 3 海洋沉积物标准物质的准确性和精密度实验结果

Table 3. Analytical results of the accuracy and precision tests of marine sediment reference materials (n=6)

测试指标	参数	GBW07314	GBW07333	GBW07335	GBW07336
TiO₂	测定值(%)	0.777　　0.768　　0.779 0.778　　0.771　　0.792	0.710　　0.705　　0.705 0.709　　0.722　　0.716	0.660　　0.663　　0.652 0.662 　　0.654　　0.653	0.576　　0.566　　0.557 0.564　　0.599　　0.603
	平均值(%)	0.778	0.711	0.657	0.578
	标准值(%)	0.825±0.030	0.775±0.020	0.720±0.03	0.610±0.03
	相对误差(%)	5.8	8.2	8.7	5.3
	RSD(%)	1.1	0.9	0.7	3.3
Zr	测定值(µg/g)	215　　217　　217 212　　211　　217	131　　130　　134 133　　132　　133	183　　167　　184 179　　178　　183	122　　129　　127 121　　126　　128
	平均值(µg/g)	215	132	179	125
	标准值(µg/g)	229	144±13	184±24	134±12
	相对误差(%)	6.1	8.2	2.6	6.4
	RSD(%)	1.3	1.0	3.5	2.5

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表 4 本文方法与封闭酸溶方法的测定结果比对

Table 4. Comparison of the analytical results obtained by this method and sealed acid dissolution method

实际样品编号	TiO₂含量(%)		RSD (%)	Zr含量(µg/g)		RSD (%)
实际样品编号	本文方法（碱熔法）	封闭酸溶法	RSD (%)	本文方法	封闭酸溶法	RSD (%)
y1	0.360	0.366	1.2	364	359	1.0
y2	0.950	0.993	3.1	758	741	1.6
y3	0.765	0.760	0.5	362	362	0.0
y4	0.301	0.305	0.9	379	372	1.3
y5	0.275	0.274	0.3	329	322	1.5
y6	0.302	0.303	0.2	432	436	0.7
y7	0.576	0.604	3.4	701	726	2.5
y8	0.364	0.372	1.5	415	420	0.8
y9	0.504	0.541	5.0	374	374	0.0
y10	0.674	0.702	2.9	518	499	2.6
y11	2.19	2.41	4.9	4553	4563	0.2
y12	0.730	0.750	1.9	706	710	0.4
y13	1.56	1.66	4.5	2090	2203	3.7
y14	1.30	1.39	4.9	2002	2098	3.3
y15	0.894	0.949	4.2	1999	2102	3.6
y16	1.29	1.36	3.8	1728	1811	3.3
y17	0.625	0.644	2.1	1720	1827	4.3
y18	0.755	0.751	0.4	1555	1601	2.1
y19	0.995	0.998	0.2	1377	1402	1.3
y20	0.561	0.593	4.0	1212	1279	3.8
y21	0.830	0.886	4.6	1202	1244	2.4
y22	1.03	1.10	4.4	1054	1125	4.6
y23	0.833	0.844	0.9	872	884	1.0
y24	0.773	0.798	2.3	746	759	1.3
y25	0.533	0.558	3.3	664	689	2.6

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