Liu Man, Han Guilin
Institute of Earth Sciences, China University of Geosciences (Beijing), Beijing, China, China.
PeerJ. 2021 Oct 29;9:e12414. doi: 10.7717/peerj.12414. eCollection 2021.
In the river system, the geochemistry of rare earth elements (REEs, a series of elements from La to Lu) in suspended particulate matter (SPM) is generally controlled by rock weathering processes and hydrochemical characteristics, as well as being affected by anthropogenic activities. However, the variations of geochemical characteristics and behaviors of REEs in SPM with a salinity gradient from the inland river to the estuary have been short of a systematic understanding.
The REE concentrations, Post Archean Australia Shale (PAAS)-normalized REE, La/Yb, La/Sm, and Sm/Yb ratios of SPM were investigated in the Jiulongjiang River, which is a coastal river mainly flowing through granite rocks in Southeast China. The correlation relationships between physicochemical parameters (including water pH, total dissolved solids (TDS), HCO concentrations, and the concentrations of major elements of SPM) and PAAS-normalized REE ratios of SPM were analyzed to determine the factors that affect the REE concentration and fractionation of SPM in the different regions of Jiulongjiang River, including the main stream and tributary of Beixi River, Xixi River, Nanxi River, and estuary. Additionally, the Ce, Eu, and Gd anomalies of SPM were estimated.
The average ∑REE concentration of SPM (352 mg/kg) in the granite rock basin was twice higher than the mean value (175 mg/kg) of the world's rivers. The PAAS-normalized REE ratios of SPM in the main rivers including Beixi River (main stream), Xixi River, and Nanxi River were near due to the same lithologic distribution. In the tributary of Beixi River, the input of low-weathered carbonate minerals which contain very few REE caused the lower REE concentrations of SPM. The PAAS-normalized REE ratios of SPM in the estuary were significantly lower than those in the main rivers, which was mainly attributed to the significant REE removal with the increment of salinity. The enrichment of LREE relative to HREE in SPM increased with decreasing water pH in the main rivers. In the estuary, the preferential removal of dissolved LREE occurred compared to HREE with the increment of salinity. The negative Ce and Eu anomalies of SPM occurred in both the main rivers and estuary region and rare Gd pollution was present in the basin. Additionally, human activities caused the increment of REE concentrations and more negative Ce anomaly at some specific sites, such as dam effect and agricultural pollution.
The REE concentrations and fractionations of SPM in river water mainly depend on lithologic distribution and riverine pH, while they are affected by salinity in the estuary.
在河流系统中,悬浮颗粒物(SPM)中稀土元素(REEs,从镧到镥的一系列元素)的地球化学通常受岩石风化过程和水化学特征控制,同时也受到人为活动的影响。然而,从内陆河到河口,随着盐度梯度变化,SPM中REEs地球化学特征和行为的变化尚缺乏系统认识。
对中国东南部一条主要流经花岗岩地区的沿海河流——九龙江中的SPM的REE浓度、后太古宙澳大利亚页岩(PAAS)标准化的REE、La/Yb、La/Sm和Sm/Yb比值进行了研究。分析了物理化学参数(包括水的pH值、总溶解固体(TDS)、HCO₃⁻浓度以及SPM中主要元素的浓度)与SPM的PAAS标准化REE比值之间的相关关系,以确定影响九龙江不同区域(包括北溪主流和支流、西溪、南溪以及河口)SPM中REE浓度和分馏的因素。此外,还估算了SPM的Ce、Eu和Gd异常。
花岗岩岩盆中SPM的平均∑REE浓度(352mg/kg)是世界河流平均值(175mg/kg)的两倍。北溪(主流)、西溪和南溪等主要河流中SPM的PAAS标准化REE比值相近,这是由于岩性分布相同。在北溪支流中,低风化碳酸盐矿物的输入导致SPM中REE浓度较低,因为这些矿物含REE极少。河口处SPM的PAAS标准化REE比值明显低于主要河流,这主要归因于随着盐度增加REE显著去除。在主要河流中,随着水的pH值降低,SPM中轻稀土相对于重稀土的富集增加。在河口,随着盐度增加,溶解态轻稀土比重稀土优先被去除。在主要河流和河口区域,SPM均出现负Ce和Eu异常,且流域内存在罕见的Gd污染。此外,人类活动导致某些特定地点(如大坝效应和农业污染)的REE浓度增加以及Ce异常更负。
河水中SPM的REE浓度和分馏主要取决于岩性分布和河水pH值,而在河口则受盐度影响。