济南泉域岩溶水系统溶解性有机质的光谱特性及指示作用

刘丹; 田婵娟; 陈学群; 徐丹丹; 管清花; 辛光明

doi:10.11932/karst2024y022

济南泉域岩溶水系统溶解性有机质的光谱特性及指示作用

doi: 10.11932/karst2024y022

刘丹^{1, 2,},
田婵娟^{1, 2},
陈学群^{1, 2, ,},
徐丹丹^{1, 2},
管清花^{1, 2},
辛光明^{1, 2}

1.
山东省水利科学研究院, 山东济南 250014
2.
山东省水资源与水环境重点实验室, 山东济南 250014

基金项目: 山东省自然科学基金项目（ZR2021QD021，ZR2021MD086）；水利技术示范项目（SF-202210）；山东省水利科学研究院自选课题（SDSKYZX202121-1）

详细信息

作者简介:
刘丹（1991－），女，工程师，博士，研究方向为环境水文地质、岩溶地下水与泉水保护。E-mail：liudan9192@126.com

通讯作者:
陈学群（1979－），男，研究员，硕士，研究方向为水资源与水环境、地下水资源保护。E-mail：cxq1115@126.com。

中图分类号: P641.3
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出版历程
- 收稿日期: 2023-04-28
- 网络出版日期: 2024-08-15
- 刊出日期: 2024-06-25

Spectral characteristics and indication of dissolved organic matter in the karst water system of Jinan

LIU Dan^{1, 2
,},
TIAN Chanjuan^{1, 2},
CHEN Xuequn^{1, 2
, ,},
XU Dandan^{1, 2},
GUAN Qinghua^{1, 2},
XIN Guangming^{1, 2}

1.
Water Resources Research Institute of Shandong Province, Jinan, Shandong 250014, China
2.
Shandong Province Key Laboratory of Water Resources and Environment, Jinan, Shandong 250014, China

摘要

摘要: 选取济南泉域岩溶水系统为研究对象，在分析水化学特征的基础上，采用紫外—可见光光谱、三维荧光光谱和平行因子分析方法，识别岩溶水系统中溶解性有机质（DOM）的组分、来源及其空间分布特征，探讨影响DOM分布特征的控制因素及其指示作用。结果表明：识别出的岩溶水系统中3种主要荧光组分分别为腐殖质物质、类蛋白色氨酸和类蛋白酪氨酸，间接补给区以腐殖质物质组分为主（31%），直接补给区和汇集排泄区以类蛋白色氨酸物质为主(48.5%和45.6%)。岩溶地下水DOM处于弱腐殖化水平，在微生物活动影响下以内源输入为主。腐殖质物质与TDS、Ec、K⁺、Mg²⁺等水化学指标显著相关；类蛋白色氨酸、类蛋白酪氨酸与微生物作用关系密切，可作为评价岩溶水系统生态及脆弱性的指标。
- 溶解性有机质 /
- 光谱特性 /
- 空间分布 /
- 荧光组分 /
- 济南泉域
Abstract: Dissolved organic matter (DOM) plays an important role in the biochemical cycle of karst water systems. In this paper, the karst water system of Jinan spring, a typical karst area in North China as well as an important source of drinking water in Jinan, was selected as the research area. In the southern part of the area, the metamorphic rocks of the Taishan Group of Archean Eonothem are exposed. The carbonate rock strata of the Cambrian and Ordovician, which incline toward the north with monoclinic structures and are hidden under the Quaternary in the north part, are located above the metamorphic rocks. The regional groundwater flows from south to north under the control of topography. The main aquifers in the sampling area of this study are the middle Cambrian Zhangxia Formation, the upper Cambrian Fengshan Formation and the Ordovician aquifers, which contain carbonate fissure water with lithology mainly composed of limestone, dolomite limestone and argillaceous limestone. According to the hydrogeological conditions in the source area and the formation process of the source, the study area was successively divided into the indirect recharge area (IRA), direct recharge area (DRA) and discharge area (DA) from south to north. The direct recharge area can directly be recharged by surface water leakage. In the indirect recharge area, recharged by atmospheric precipitation, surface water and groundwater flows into the direct recharge area in the form of surface and subsurface runoffs. Groundwater was blocked by magmatic rocks in the north, and fissures were developed in the contact zone between aquifers and the magmatic rocks, where karst groundwater rose and was exposed, and springs came into being.This study aims to investigate the spectral characteristics, spatial distribution and indicator of DOM in karst groundwater in recharge, runoff and discharge areas at a spring-area scale. The composition, source and spatial distribution in the karst water system of Jinan spring were analyzed by absorption spectrum, fluorescence spectrum and PARAFAC, combined with water chemical index and correlation analysis. In this study, three main fluorescence components have been identified in the Jinan spring area, namely, C1, C2 and C3, which are humus, protein-like tryptophan and protein-like tyrosine, respectively. Groundwater in the indirect recharge area is dominated by humic substances in low molecular weight, while groundwater in the direct recharge area and the confluence and discharge area are dominated by protein-like substances. In these two areas, the change in protein-like substances caused by microbial activities is the main driving force for the change in geochemical characteristics of DOM. The order of endogenous contributions is DA>DRA>IRA, which is consistent with the order of water circulation quantity in the karst water system. In this karst water system, aromatic substances are mainly present in hydrophobic components. The humus component C1 is an exogenous input, and is significantly positively correlated with the protein-like tryptophan component C2. These two components from different sources are subject to the same factors. The protein-like tyrosine component C3 has no obvious correlation with all indices. The humus component C1 and the total fluorescence intensity can be used as natural indicators to trace the karst water cycle. Besides, the protein-like tryptophan C2 and the protein-like tyrosine C3 may provide important biogeochemical information to evaluate the vulnerability of karst aquifers.
- dissolved organic matter /
- spectral characteristics /
- spatial distribution /
- fluorescent component /
- the Jinan spring area

HTML

图 1 研究区及采样点位置分布图

Figure 1. Distribution of the study area and the location of sampling points

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图 2 济南岩溶水水化学Piper三线图

Figure 2. Piper diagram of hydrochemistry of karst water in Jinan

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图 3 紫外—可见吸收光谱参数图

Figure 3. Diagram of ultraviolet-visible absorption spectrum parameter

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图 4 DOM三种荧光组分三维荧光光谱图（左）及其激发/发射波长图（右）

Figure 4. Three-dimensional fluorescence spectra of the three fluorescence components of DOM (left) and their corresponding excitation/emission wavelength (right)

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图 5 荧光特征参数

Figure 5. Fluorescent characteristics of DOM

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图 6 不同荧光组分最大荧光强度（a）和相对含量（b）

Figure 6. Maximum fluorescence intensity (a) and relative content (b) of different fluorescence components

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图 7 DOM指标相关性热图

Figure 7. Heat map of DOM index correlation

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表 1 主要现场理化指标和DOC浓度

Table 1. Main on-site physical and chemical indicators and DOC concentrations

类型		编号	pH	TDS/mg·L⁻¹	Ec/μs·cm⁻¹	DO/mg·L⁻¹	DOC/mg·L⁻¹
地表水	间接补给区	SW-1	7.95	298	588	6.99	5.67
		SW-2	8.02	279	550	7.63	11.20
		SW-3	8.28	283	553	7.76	4.56
	直接补给区	SW-4	8.07	272	540	7.02	4.90
	直接补给区	SW-5	8.06	233	458	6.91	8.45
	汇集排泄区	SW-6	8.05	197	396	7.02	10.30
地下水	间接补给区	KG-1	7.50	420	813	7.31	5.51
		KG-2	7.92	270	539	7.38	4.90
		KG-3	7.86	2421	4137	7.79	2.67
		KG-4	7.63	175	342	6.44	7.31
	直接补给区	KG-5	7.93	401	786	5.45	5.52
	直接补给区	KG-6	7.72	446	872	5.08	10.40
	汇集排泄区	KG-7	7.38	496	992	7.11	7.32
		KG -8	7.71	369	688	6.18	4.09
		KG-9	7.89	319	628	6.69	3.59
		KG-10	7.52	506	972	6.20	3.78
		KG-11	7.78	266	524	7.23	2.76
		KG-12	8.01	266	526	7.52	4.62
		KG-13	7.87	427	846	7.14	4.50
		S-1	7.86	703	1239	6.79	2.46

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表 2 水体中主要荧光组分特征

Table 2. Characteristics of main fluorescence components in water

组分	激发波长/发射波长	指示类型	意义	参考文献
C1	250 nm /420 nm	腐殖质物质	陆源输入、内源性形成	240~270/370~440^[37] 235~255/410~450^[7]
C2	240(280) nm /350 nm	类蛋白色氨酸	内源性形成	225~237/340~381和375/340^[38]
C3	237(270) nm /330 nm	类蛋白酪氨酸	内源性形成	270~290/300~320^[37]

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