Characteristics of heavy metals and their influential factors between sediments and water of the Zhujiang River Estuary in summer
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摘要: 珠江口受复杂径−潮动力耦合作用的影响，河口重金属迁移转化机制复杂多变。本文基于2018年夏季珠江口及其邻近海域海水和沉积物的调查资料，研究了珠江口多动力因子驱动下7种重金属元素汞、砷、锌、镉、铅、铜和铬的沉积、迁移和积累机制。结果表明：相比于溶解态重金属（水体中）的赋存状况，吸附态重金属（沉积物中）更稳定，污染也更严重；采用皮尔逊相关分析和主成分分析计算出重金属元素与环境因子之间的响应关系，溶解态重金属主要以稀释混合过程为主，吸附态重金属受有机碳和氧化还原作用的影响较大；沉积物−水界面重金属的分配系数显示出铅和铬易被吸附在颗粒物上，而镉和汞易溶解在水体中，揭示了河口复杂动力影响下元素在不同介质的形态转换特征；除了镉−铬、镉−铜和铬−砷这3组元素间不显著相关，其他元素间的显著相关性表明了重金属元素具有相似的来源，并采用主成分分析探讨了重金属元素的潜在来源，主要来源为工业废水，农业和大气沉降次之。研究结果可为有效控制重金属的排放和河口污染治理提供重要支撑。Abstract: Characteristics of heavy metals in the Zhujiang River Estuary are mainly influenced by the interacting river-tide dynamics. Water and sediment samples were collected in the Zhujiang River Estuary and its adjacent zones in the summer of 2018. The present study aimed to investigate the estuarine behaviors (i.e., sedimentary, transportation, accumulation) of seven metals Hg, As, Zn, Cd, Pb, Cu, and Cr, which were co-influenced by the physicochemical properties in the estuary. The levels of heavy metals in sediments were higher than those dissolved in water. The heavy metals in sediments were more stable and the pollution was thus more serious. The results of Pearson correlation and principal component analysis showed that dissolved metals were more easily diluted and mixed, and the sediment metals were significantly influenced by the total organic carbon and redox. The metal partitioning between sediments and water was discussed as well in this study under the influence of estuarine dynamics, which indicated the phase exchange between multimedia in the estuary; Pb and Cr were more easily absorbed in the particulate particles, while Cd and Hg were intended to dissolve in water. The significant correlations between metals (e.g., Hg, Pb, and Zn) indicated the similar sources, and the principal component analysis was used to probe into the source contributions of heavy metals in sediments of the Zhujiang River Estuary, contributed mainly by industrial pollution, followed by agricultural pollution and atmospheric deposition. These findings will provide important information for the effective controls of heavy metal inputs and estuary management.
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图 2 珠江口海域水体和沉积物中的环境因子
Fig. 2 Environmental factors in sea waters and sediments in the Zhujiang River Estuary
图 3 珠江口表层海水重金属元素的空间分布
Fig. 3 Spatial distribution of heavy metals in surface water of the Zhujiang River Estuary
图 4 珠江口表层沉积物中重金属元素的空间分布
Fig. 4 Spatial distribution of heavy metals in surface sediments of the Zhujiang River Estuary
图 5 珠江口水体中溶解态重金属和环境因子的主成分分析（前4个主成分）
Fig. 5 PCA qualification of dissolved heary metals and environmental factors in the Zhujiang River Estuary seawater (the four most important principal components)
图 6 珠江口表层沉积物中重金属元素与环境因子的皮尔逊相关分析
*代表相关性在0.05水平上显著
Fig. 6 Pearson correlation analysis of heavy metals and environmental factors in surface sediments of the Zhujiang River Estuary
* Represent correlation is significant at the 0.05 level
图 7 珠江口重金属元素在水体和沉积物界面的分配系数
Fig. 7 Heavy metal partition coefficient between water and sediments of the Zhujiang River Estuary
图 8 珠江口表层沉积物中7种重金属元素主成分分析结果
Fig. 8 PCA results of seven heary metals in surface sediments of the Zhujiang River Estuary
表 1 不同重金属风险熵水平中站位比例
Tab. 1 The ratio of stations in different heavy metal risk quotient levels
风险熵 汞 砷 锌 镉 铅 铜 铬 表层水体风险熵 RQ<0.1 100% 100% 62% 100% 100% 0.1≤RQ <1 38% 100% 100% RQ≥1.0 底层水体风险熵 RQ<0.1 100% 100% 88% 100% 100% 0.1≤RQ<1 13% 100% 94% RQ≥1.0 6% 注：RQ<0.1为低生态风险；0.1≤RQ<1.0为中度生态风险；RQ≥1.0为高生态风险。 
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表 2 重金属分配系数与环境因子的皮尔逊相关系数
Tab. 2 Pearson correlation coefficient of heavy metal distribution coefficient and environmental factors
分配系数 S T DO含量 COD Chl a含量 SPM含量 DIN含量 SRP含量 Sulfide含量 Eh TOC含量 Hg −0.51* 0.54* −0.24 0.52* 0.16 −0.21 0.38 0.10 0.40 0.59* 0.69* Cd −0.33 0.54* −0.51* 0.43 0.01 −0.29 0.34 0.25 0.67* 0.51* 0.71* Pb −0.29 0.18 −0.23 0.27 0.01 0.14 0.42 0.54* 0.53 0.16 0.33 Cr −0.28 0.38 −0.09 0.34 −0.14 −0.20 0.32 0.23 0.44 0.28 0.55* As −0.54* 0.65* −0.41 0.66* 0.36 −0.30 0.44 0.05 0.55 0.57* 0.85* Zn −0.52* 0.52* −0.29 0.49* 0.07 −0.35 0.43 0.21 0.57 0.44 0.70* Cu −0.51* 0.32 0.02 0.65* 0.68* −0.08 0.22 −0.33 −0.03 0.32 0.65* 注：*代表相关性在0.05水平上显著。
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