Heavy Metal Pollution of Sediments in Northern Jiaozhou Bay and the Influence of DOM on Their Environmental Behavior
-
摘要: 海岸带沉积物是污染物迁移转化的主要载体和归宿地. 溶解性有机质（DOM）作为重金属在环境中迁移的重要媒介，对沉积物中重金属的分布和迁移具有重要控制作用.运用因子指数和地累积指数法对胶州湾北部海岸带表层沉积物中Cr、Cu、Zn、As和Pb五种重金属的污染现状进行了评估，并结合三维荧光光谱分析沉积物中不同DOM组分的空间分异规律，探讨了胶州湾北部地区表层沉积物DOM组成与重金属迁移行为的关系.研究结果表明，海岸带沉积物重金属整体呈轻度污染水平；沉积物中的天然DOM组分包括陆地类富里酸（C1）、陆地类腐殖质（C2）、微生物源腐殖质（C3）和类色氨酸（C4）4种，整个地区类腐殖酸组分占比显著高于类蛋白组分，其来源同时受地面输入和生物代谢的影响；各重金属可能存在相似的污染来源，但迁移机制不同，造成其分布的差异；C1促进了Cr的自然迁移，DOM各组分通过不同的吸附络合机理影响着重金属在沉积物中的分布，且DOM各组分之间存在一定的相互转化过程.Abstract: Coastal zone sediments are the main carriers and destinations for the migration and transformation of pollutants. Dissolved organic matter (DOM), as an important medium for heavy metal migration in the environment, plays an important role in controlling the distribution and migration of heavy metals in sediments. The paper used the factor index and ground accumulation index methods to assess the current pollution status of five heavy metals, Cr, Cu, Zn, As and Pb, in the Surface sediment of the northern coastal zone of Jiaozhou Bay, and combined with three-dimensional fluorescence spectroscopy to analyze the spatial partitioning patterns of different DOM components in sediments, to explore the relationship between DOM composition and heavy metal migration behavior in the Surface sediment of the northern Jiaozhou Bay area. The results showed that the overall heavy metals in the coastal zone sediments were lightly contaminated; the natural DOM fractions in the sediments included four types of terrestrial fulvic acid (C1), terrestrial humic substances (C2), microbial-derived humic substances (C3) and tryptophan-like (C4), and the proportion of humic acid fractions was significantly higher than that of protein-like fractions in the whole area, and their sources were influenced by both terrestrial input and biological metabolism. Each heavy metal may have similar pollution sources, but different migration mechanisms cause differences in their distribution; C1 promotes the natural migration of Cr, each DOM fraction influences the distribution of heavy metals in sediments through different adsorption complexation mechanisms, and there are certain mutual transformation processes among DOM fractions.
-
Key words:
- Northern Jiaozhou Bay /
- heavy metals /
- risk assessment /
- DOM /
- fluorescence index /
- environmental geology
-
图 1 研究区范围及沉积物采样点分布图
Fig. 1. Distribution of the study area and sediment sampling points
图 2 研究区表层沉积物重金属元素含量分布图
a. 重金属总量；b. As含量；c. Cr；d. Cu；e. Pb；f. Zn
Fig. 2. Distribution of heavy metal elements in the surface sediments of the study area
图 3 重金属因子指数和地累积指数箱线图
Fig. 3. Box line of heavy metal factor index and ground accumulation index
图 4 DOM组分光谱图
a，b. 激发/发射波长与负载量曲线；c. C1组分光谱图；d. C2组分光谱图；e. C3组分光谱图；f. C4组分光谱图
Fig. 4. DOM component spectra
图 5 研究区沉积物DOM组分Fmax (a)和Fmax占比(b)分布图
Fig. 5. Distribution of sediment DOM fractions Fmax(a) and Fmax share in the study area(b)
图 6 表层沉积物重金属和DOM组分的Pearson分析
**.在0.01水平（双侧）.上显著相关；*. 在0.05水平（双侧）上显著相关
Fig. 6. Pearson analysis of heavy metals and DOM fractions in surface sediments
表 1 表层沉积物基本理化性质和重金属含量
Table 1. Basic physicochemical properties and heavy metal content of surface sediments
pH Ec（μs/cm） 重量含水率（%） Cr(mg/kg) Cu(mg/kg) Zn(mg/kg) As(mg/kg) Pb(mg/kg) 最小值 6.30 19.10 20.8 43.54 11.49 25.28 6.23 15.22 最大值 8.99 1 287 65.1 159.33 40.84 117.69 19.40 37.43 平均值 7.68 444.7 45.5 87.54 29.56 73.69 13.88 25.89 标准差 0.62 326.5 12.5 26.05 7.30 23.11 3.06 5.51 变异系数(%) 8.04 73.4 27.4 29.80 24.70 31.40 22.00 21.30 胶州湾背景值(刘兆庆, 2017) - - - 67.96 19.13 56.80 8.28 17.97 超背景值比例(%) - - - 28.80 54.50 29.70 67.60 44.10 超标率(%) - - - 90 90 75 90 90 
下载: 导出CSV
表 2 单因子污染指数和综合污染指数分级标准
Table 2. Single-factor pollution index and comprehensive pollution index classification criteria
分级 单因子污染指数分级标准 综合内梅罗指数分级标准 污染指数 污染等级 污染指数 污染等级 1级 Pi≤1 清洁 P≤0.7 安全 2级 1 < Pi≤2 轻污染 0.7 < P≤1 警戒 3级 2 < Pi≤3 中污染 1 < P≤2 轻污染 4级 Pi > 3 重污染 2 < P≤3 中污染 5级 - - P≥3 重污染
下载: 导出CSV
表 3 沉积物中4种DOM组分光谱特征
Table 3. Spectral characteristics of the four DOM components in the sediment
荧光组分 Ex/Em(nm) 荧光类型 同类研究比较(nm) C1 < 250/428 陆地类富里酸 < 250/426(Thibault et al., 2017)；250/436(Nicolás et al., 2017) C2 260/484 陆地类腐殖质 < 250/494(Brogi et al., 2020)； < 250/464(Murphy et al., 2011) C3 315/400 微生物源腐殖质 305/394(Cawley et al., 2012)；310/400(Gao and Gueguen, 2018) C4 270/334 类色氨酸 275/341(Brogi et al., 2019)；275/328(Zhou et al., 2019)
下载: 导出CSV
-
Bellir, K., Bencheikh-Lehocine, M., Meniai, A. H., et al., 2005. Study of the Retention of Heavy Metals by Natural Material Used as Liners in Landfills. Desalination, 185(1/2/3): 111-119. https://doi.org/10.1016/j.desal.2005.03.074 Brogi, S. R., Derrien, M., Hur, J., 2019. In-Depth Assessment of the Effect of Sodium Azide on the Optical Properties of Dissolved Organic Matter. Journal of Fluorescence, 29(4): 877-885. https://doi.org/10.1007/s10895-019-02398-w Brogi, S. R., et al., 2020. Time Resolved Data Unveils the Complex DOM Dynamics in a Mediterranean River. Science of the Total Environment, 733: 139212. https://doi.org/10.1016/j.scitotenv.2020.139212 Cao, H. H., 2018. Observation and Study on Current Characteristics andAssessment of Water Exchange Capacityin the Northern Bohai Sea(Dissertation), Shanghai Ocean University, Shanghai(in Chinese with English abstract). Cawley, K. M., Butler, K. D., Aiken, G. R., et al., 2012. Identifying Fluorescent Pulp Mill Effluent in the Gulf of Maine and Its Watershed. Marine Pollution Bulletin, 64(8): 1678-1687. https://doi.org/10.1016/j.marpolbul.2012.05.040 Chen, P. Y., 1982. Purification of Chromium-Containing Wastewater. Environmental Science & Technology, (1): 36-43(in Chinese with English abstract). Chen, W., Peng, L., Hu, K. R., et al., 2020. Spectroscopic Response of Soil Organic Matter in Mining Area to Pb/Cd Heavy Metal Interaction: A Mirror of Coherent Structural Variation. Journal of Hazardous Materials, 393(4): 122425. https://doi.org/10.1016/j.jhazmat.2020.122425 Chen, Z. H., Wang, B. G., Zhao, J. F., 2022. Adsorption and Desorption Characteristics of Cd in Upland and Paddy Soil of Jianghan Plain. Earth Science, 47(2): 544-555(in Chinese with English abstract). Cory, R. M., McKnight, D. M., 2005. Fluorescence Spectroscopy Reveals Ubiquitous Presence of Oxidized and Reduced Quinones in Dissolved Organic Matter. Environmental Science & Technology, 39(21): 8142-8149. https://doi.org/10.1021/es0506962 Cui, B., Gao, H. J., Zheng, Z. P., et al., 2021. Applying EEM Coupled with 2D-COS to Character Structural Composition of DOM and Its SpatialVariations in an Urban River. Journal of Ecology and Rural Environment, 37(3): 369-377(in Chinese with English abstract). Daniel, G., Garrido-Pérez, M. C., Nebot-Sanz, E., et al., 2011. Source and Fate of Heavy Metals in Marine Sediments from a Semi-Enclosed Deep Embayment Subjected to Severe Anthropogenic Activities. Water, Air, & Soil Pollution, 221(1/2/3/4): 191-202. https://doi.org/10.1007/s11270-011-0782-0 Deng, B., Zhang, J., Zhang, G. R., et al., 2010. Enhanced Anthropogenic Heavy Metal Dispersal from Tidal Disturbance in the Jiaozhou Bay, North China. Environmental Monitoring and Assessment, 161(1/2/3/4): 349-358. https://doi.org/10.1007/s10661-009-0751-x Gao, Z. Y., Guéguen, C., 2018. Distribution of Thiol, Humic Substances and Colored Dissolved Organic Matter during the 2015 Canadian Arctic GEOTRACES Cruises. Marine Chemistry, 203: 1-9. https://doi.org/10.1016/j.marchem.2018.04.001 Guo, J. M., Liu, H., Fu, H., et al., 2022. WoS and CNKl Database-Based Analysis of Advance on Coastal Eco-environment Research. Environmental Ecology, 4(1): 49-58(in Chinese with English abstract). Hu, R., 2021. Distribution Pattern and Risk Assessment for Heavy Metals in the Surface Sedimentsof Jiaozhou Bay. Marine Geology Frontiers, 37(11): 11-21(in Chinese with English abstract). Ishii, S. K. L., Boyer, T. H., 2012. Behavior of Reoccurring PARAFAC Components in Fluorescent Dissolved Organic Matter in Natural and Engineered Systems: A Critical Review. Environmental Science & Technology, 46(4): 2006-2017. https://doi.org/10.1021/es2043504 Li, H., Wang, J. H., Zhao, B. Y., et al., 2018. The Role of Major Functional Groups: Multi-Evidence from the Binding Experiments of Heavy Metals on Natural Fulvic Acids Extracted from Lake Sediments. Ecotoxicology and Environmental Safety, 162: 514-520. https://doi.org/10.1016/j.ecoenv.2018.07.038 Li, J. H., 2021. Effect of Phosphate on the Complexation Properties of Fulvic Acid with Heavy Metals before and after Fractionation on Hydrous Iron Ore(Dissertation). South China University of Technology, Guangdong(in Chinese with English abstract). Li, J. J., Peng, E. Z., 2005. Summarization on the Existing Form and Transferring Rules of Chromium in Soil. Industrial Safety and Environmental Protection, (3): 31-33(in Chinese with English abstract). Li, M. M., Kong, F. L., Li, Y., et al., 2020a. Ecological Indication Based on Source, Content, and Structure Characteristics of Dissolved Organic Matter in Surface Sediment from Dagu River Estuary, China. Environmental Science and Pollution Research, 27(36): 45499-45512. https://doi.org/10.1007/s11356-020-10456-1 Li, S. D., Hou, X., Shi, Y., et al., 2020b. Rapid Photodegradation of Terrestrial Soil Dissolved Organic Matter (DOM) with Abundant Humic-Like Substances under Simulated Ultraviolet Radiation. Environmental Monitoring and Assessment, 192(2): 15. https://doi.org/10.1007/s10661-019-7945-7 Liu, D. P., 2021. Characterization of DOM in Urban Polluted River Bottom Sediment and Its Complexation Mechanism with Heavy Metals(Dissertation). Chinese Research Academy of Environmental Sciences, Beijing(in Chinese with English abstract). Liu, Z. Q., 2017. Environmental Background Values and Contamination Assessment of Heavy Metals in Sediments of Jiaozhou Bay Catchment(Dissertation), China University of Petroleum(East China), Qiongdao(in Chinese with English abstract). Murphy, K. R., Hambly, A., Singh, S., et al., 2011. Organic Matter Fluorescence in Municipal Water Recycling Schemes: Toward a Unified PARAFAC Model. Environmental Science & Technology, 45(7): 2909-2916. https://doi.org/10.1021/es103015e Nicolás, M. P., Sidhu, B. S., Legge, R. L., et al., 2017. Investigation of Ozone and Peroxone Impacts on Natural Organic Matter Character and Biofiltration Performance Using Fluorescence Spectroscopy. Chemosphere, 172(10): 225-233. https://doi.org/10.1016/j.chemosphere.2016.12.118 Ren, H. Y., Ma, F. Y., Yao, X., et al., 2020. Multi-Spectroscopic Investigation on the Spatial Distribution and Copper Binding Ability of Sediment Dissolved Organic Matter in Nansi Lake, China. Journal of Hydrology, 591(1): 125289. https://doi.org/10.1016/j.jhydrol.2020.125289 Shang, S. B., 2008, Study on the Impact of Soil Colloid on Heavy Metals Migrationin Vadose Zone(Dissertation), Jilin University, Changchun(in Chinese with English abstract). Thibault, L., Bouillon, S., Darchambeau, F., et al., 2017. Effects of Human Land Use on the Terrestrial and Aquatic Sources of Fluvial Organic Matter in a Temperate River Basin (The Meuse River, Belgium). Biogeochemistry, 136(2): 191-211. https://doi.org/10.1007/s10533-017-0387-9 Tian, Y. Y., Wu, Y., Peng, Y. Y., et al., 2021. Study on the Complexation of Heavy Metals Onto Biogas Slurry DOM Using Two-Dimensional Correlation Spectroscopy Combined with the Log-Transformed Synchronous Fluorescence Spectroscopy. Environmental Science and Pollution Research, 28(18): 22878-22885. https://doi.org/10.1007/s11356-021-12401-2 Wang, Z. G., Cao, J., Meng, F. G., 2015. Interactions between Protein-Like and Humic-Like Components in Dissolved Organic Matter Revealed by Fluorescence Quenching. Water Research, 68(4): 404-413. https://doi.org/10.1016/j.watres.2014.10.024 Xiao, C. L., Chen, L. F., Li, Y. B., 2017. Distribution Characteristics and Potential Risk Assessment of Heavy Metals in the Sediment of Jiaozhou Bay. China Sciencepaper, 12(9): 1079-1086(in Chinese with English abstract). Xu, H. C., Guo, L. D., 2018. Intriguing Changes in Molecular Size and Composition of Dissolved Organic Matter Induced by Microbial Degradation and Self-Assembly. Water Research, 135: 187-194. https://doi.org/10.1016/j.watres.2018.02.016 Xu, H. C., Zou, L., Guan, D. X., et al., 2019. Molecular Weight-Dependent Spectral and Metal Binding Properties of Sediment Dissolved Organic Matter from Different Origins. Science of The Total Environment, 665: 828-835. https://doi.org/10.1016/j.scitotenv.2019.02.186 Yan, R, D., Li, Y., Kong, F. L., et al., 2020. Source, Structural Characteristics and Ecological Indication of Dissolved Organic Matter Extracted from Sediments in the Primary Tributaries of the Dagu River. Ecological Indicators, 109: 105776. https://doi.org/10.1016/j.ecolind.2019.105776 Yang, L. Q., Hu, M., Wang, P. J., et al., 2021. Pollution Characteristics and Ecological Risk Assessment of Sediment in Zhongba River, Beijing. Acta Scientiae Circumstantiae, 41(1): 181-189(in Chinese with English abstract). Yao, C. H., Zhang, C. R., Li, S. Y., et al., 2021. Spatial Distribution and Ecological Risk Assessment of Heavy Metals in Soils along the Coast of Jiaozhou Bay. China Sciencepaper, 16(1): 112-120(in Chinese with English abstract). Yi, C, L., Meng, F. P., Du, Y. X., et al., 2016. Distribution, Speciation, and Ecological Risk Assessment of Heavy Metals in Surface Sediments of Jiaozhou Bay, China. Human and Ecological Risk Assessment: An International Journal, 22(5): 1253-1267. https://doi.org/10.1080/10807039.2016.1159503 Zhou, Y. L., Martin, P., Müller, M., 2019. Composition and Cycling of Dissolved Organic Matter from Tropical Peatlands of Coastal Sarawak, Borneo, Revealed by Fluorescence Spectroscopy and Parallel Factor Analysis. Biogeosciences, 16(13): 2733-2749. https://doi.org/10.5194/bg-16-2733-2019 Zuo, W. P., 2022. Assessment of Heavy Metal Pollution and Health Risk in Farmland in the Volcanic Weathering Area: a Case Study in Jiangdong New District of Haikou. Earth Science, 1-15(in Chinese with English abstract). 陈孜涵, 汪丙国, 赵建芳, 2022. 江汉平原旱地和水田土壤镉的吸附与解吸特征及影响因素. 地球科学, 47(2): 544-555. doi: 10.3799/dqkx.2021.108 曹慧慧, 2018. 渤海北部海流特征观测研究及水交换能力评估(博士毕业论文). 上海: 上海海洋大学. 崔兵, 高红杰, 郑昭佩, 等, 2021. 基于三维荧光和二维相关光谱的城市河流溶解性有机质组成及其空间分异特征. 生态与农村环境学报, 37(3): 369-377. https://www.cnki.com.cn/Article/CJFDTOTAL-NCST202103014.htm 陈丕亚, 1982. 含铬废水的净化. 湖北环境保护, (1): 36-43. https://www.cnki.com.cn/Article/CJFDTOTAL-FJKS198201006.htm 郭京梅, 刘宏伟, 付豪, 等, 2022. 基于WoS与CNKI数据库分析海岸带生态环境研究进展. 环境生态学, 4(1): 49-58. https://www.cnki.com.cn/Article/CJFDTOTAL-HJSX202201008.htm 胡睿, 2021. 胶州湾海域表层沉积物重金属元素分布特征与风险评价. 海洋地质前沿, 37(11): 11-21. https://www.cnki.com.cn/Article/CJFDTOTAL-HYDT202111002.htm 刘兆庆, 2017. 胶州湾流域沉积物重金属元素背景值及其污染评价(博士毕业论文). 青岛: 中国石油大学(华东). 李晶晶, 彭恩泽, 2005. 综述铬在土壤和植物中的赋存形式及迁移规律. 工业安全与环保, (3): 31-33. https://www.cnki.com.cn/Article/CJFDTOTAL-GYAF200503012.htm 刘东萍, 2021. 城市污染河流底泥DOM特征及其与重金属络合机制研究(博士毕业论文). 北京: 中国环境科学研究院. 李俊辉, 2021. 磷酸根对富里酸在水铁矿上分馏前后与重金属络合特性的影响(博士毕业论文). 广州: 华南理工大学. 商书波, 2008. 包气带中的土壤可移动胶体及对重金属迁移影响的研究(博士毕业论文). 长春: 吉林大学. 肖彩玲, 陈路锋, 李雁宾, 2017. 胶州湾沉积物重金属分布特征及生态风险评价. 中国科技论文, 12(9): 1079-1086. https://www.cnki.com.cn/Article/CJFDTOTAL-ZKZX201709019.htm 姚春卉, 张春荣, 李少勇, 等, 2021. 胶州湾沿岸土壤重金属元素分布特征及其生态风险评价. 中国科技论文, 16(1): 112-120. https://www.cnki.com.cn/Article/CJFDTOTAL-ZKZX202101017.htm 杨兰琴, 胡明, 王培京, 等, 2021. 北京市中坝河底泥污染特征及生态风险评价. 环境科学学报, 41(1): 181-189. https://www.cnki.com.cn/Article/CJFDTOTAL-HJXX202101020.htm 左文萍, 2022. 火山岩风化区农田重金属污染及健康风险评价——以海口江东新区为例. 地球科学, 1-15. -
点击查看大图
图(6) / 表(3)
计量
- 文章访问数: 312
- HTML全文浏览量: 182
- PDF下载量: 48
- 被引次数: 0
