Li Haitao, Tong Rui, Guo Wei, Xu Quanhui, Tao Danyang, Lai Yang, Jin Lanlan, Hu Shenghong
State Key Laboratory of Biogeology and Environmental Geology, School of Earth Sciences, China University of Geosciences Wuhan 430074 China
Guangzhou Prin-Cen Scientific Ltd Guangzhou 510730 China.
RSC Adv. 2022 Aug 24;12(37):24003-24013. doi: 10.1039/d2ra02833f. eCollection 2022 Aug 22.
Rare earth elements (REEs) are useful geological indicators of marine geochemistry. However, extremely low concentrations (sub-ng L) and high-salt matrices result in inefficient measurements. A fully automatic separation system (ELSPE-2 Precon) is used in the online determination of ultra-trace REEs in seawater using inductively coupled plasma mass spectrometry. This system mainly comprises three sections: (i) an auto-sampler (eas-2A) with 120 positions; (ii) a poly(styrene-divinylbenzene) resin column (Prin-Cen Col007) with iminodiacetic and ethylenediaminetriacetic acid functional groups to eliminate the high-salt matrix (, Na, Ca, K, Mg, Al, Ba, Fe, Sr, P, and S) and preserve the target REEs; and (iii) a Trp002 cleanup column for the reduction of the reagent and procedural blank values. The detection limits (3) were in the range 0.002 (Dy)-0.097 ng L (La), and the long-term reproducibility (8 h) was between 80% and 120% for all REEs in a 3.5% NaCl matrix solution. The accuracy of this method was verified using a seawater reference material (NASS-6), and the measured REE concentrations were consistent with those previously reported. The proposed online system was used to investigate coastal water samples with varying salinities from the Pearl River Estuary (Guangdong, China). Variations in the REE distribution patterns of different layers of seawater were observed, which could be due to the mixing of potentially light rare earth element-enriched bottom seawater. Moreover, a positive Gd anomaly in river water and seawater might be attributed to anthropogenic pollution from hospitals and the pharmaceutical industry.
稀土元素(REEs)是海洋地球化学中有用的地质指标。然而,极低的浓度(亚纳克/升)和高盐基质导致测量效率低下。一种全自动分离系统(ELSPE - 2预浓缩器)用于在线测定海水中的超痕量稀土元素,采用电感耦合等离子体质谱法。该系统主要由三个部分组成:(i)一个有120个位置的自动进样器(eas - 2A);(ii)一个带有亚氨基二乙酸和乙二胺三乙酸官能团的聚苯乙烯 - 二乙烯基苯树脂柱(Prin - Cen Col007),用于消除高盐基质(钠、钙、钾、镁、铝、钡、铁、锶、磷和硫)并保留目标稀土元素;(iii)一个Trp002净化柱,用于降低试剂和程序空白值。检测限(3σ)在0.002(镝) - 0.097纳克/升(镧)范围内,在3.5%氯化钠基质溶液中,所有稀土元素的长期重现性(8小时)在80%至120%之间。使用海水标准物质(NASS - 6)验证了该方法的准确性,测得的稀土元素浓度与先前报道的一致。所提出的在线系统用于研究来自中国广东珠江口不同盐度的沿海水样。观察到不同海水层稀土元素分布模式的变化,这可能是由于潜在富含轻稀土元素的底层海水混合所致。此外,河水和海水中的正钆异常可能归因于医院和制药行业的人为污染。