辽东湾入海河流水质时空变化与污染物来源分析

吴光红; 邱梦璇; 李建玲; 罗维

doi:10.12284/hyxb2023110

辽东湾入海河流水质时空变化与污染物来源分析

doi: 10.12284/hyxb2023110

1.
天津师范大学天津市水资源与水环境重点实验室，天津 300387
2.
中国科学院生态环境研究中心固体废弃物处理与资源化实验室，北京 100085

基金项目: 国家自然科学基金（41571479）。

详细信息

作者简介:
吴光红（1971-），男，福建省尤溪县人，博士，教授，主要从事水环境地球化学研究。E-mail：wuguanghong@tjnu.edu.cn

中图分类号: P734.2⁺1
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出版历程
- 收稿日期: 2023-01-16
- 修回日期: 2023-04-13
- 网络出版日期: 2023-08-29
- 刊出日期: 2023-09-30

Spatial-temporal variation of water quality and pollutant source analysis in rivers along Liaodong Bay

1.
Tianjin Key Laboratory of Water Resources and Environment, Tianjin Normal University, Tianjin 300387, China
2.
Laboratory of Solid Waste Treatment and Recycling, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China

摘要

摘要: 基于辽东湾入海河流120个监测断面（含16个入海断面）的水质数据，采用主成分分析−多元线性回归模型等方法，研究其有机物、营养盐和重金属等的污染特征和入海通量，并分析其可能来源。结果表明，水质超标指标主要是高锰酸盐指数（COD_Mn）、氨氮（AN）浓度、总磷（TP）浓度和总氮（TN）浓度，其他指标符合I类地表水水质标准。TN/TP比值较高，严重偏离Redfield比值，陆源高含量氮和低含量磷的输入是造成渤海海水TN/TP升高的主要因素。非汛期的溶解氧（DO）浓度、电导率（EC）、AN浓度和TN浓度显著高于汛期，而非汛期的pH、浊度、COD_Mn和TP浓度显著低于汛期。2021年河口有机物和营养盐浓度受河流穿行农业区等因素的影响，重金属浓度则与域内工业企业分布有关。TN、TP、化学需氧量（COD）、AN和石油类年入海通量分别为3.63 × 10⁴ t、1 608.5 t、14.8 ×10⁴ t、3 086.6 t和221.9 t，Hg、Cd、Pb、As和Cr⁶⁺分别为0.264 t、0.253 t、1.978 t、20.434 t和31.651 t。研究区主要的污染源按照其贡献大小依次为生活污水和工业废水、水动力条件等水文因素所致的污染源、水−气界面物质交换及二次转化源和农田地表径流与交通运输产生的非点源。
- 水质 /
- 来源分析 /
- PCA-MLR模型 /
- 入海通量 /
- 辽东湾
Abstract: Based on the dataset of 120 water quality monitoring sites (including 16 coastal sites) in rivers along Liaodong Bay, the principal component analysis-multiple linear regression (PCA-MLR) model was used to study the pollution characteristics and flux of organic matter, nutrients and heavy metals, and analyze their possible sources. The pollutants exceeding the first grade of Environmental Quality Standards for Surface Water were COD_Mn, AN concentration. TP concentration and TN concentration, and other water quality parameters met the standard. The TN/TP ratios were high and seriously deviated from the Redfield ratio. The input of high N and low P load from terrestrial sources was the main factor causing the increase of TN/TP in Bohai Sea. DO concentration, EC, AN concentration and TN concentration in non-flood season increased significantly than in flood season, while pH, turbidity, COD_Mn and TP concentration in non-flood season decreased significantly than in flood season. The concentrations of organic matter and nutrients in estuaries were affected by factors such as the agricultural areas that rivers flowed, while the concentrations of heavy metals were related to the distribution of industrial enterprises in the region. The annual fluxes of TN, TP, COD, AN and petroleum pollutant into Liaodong Bay were 3.63 × 10⁴ t, 1 608.5 t, 14.8 ×10⁴ t, 3 086.6 t and 221.9 t, respectively, and the fluxes of Hg, Cd, Pb, As and Cr⁶⁺ were 0.264 t, 0.253 t, 1.978 t, 20.434 t and 31.651 t, respectively. According to their contribution, the main pollution sources were domestic sewage and industrial wastewater, sources caused by hydrological factors (hydrodynamic conditions, etc.), water-gas interface pollutants exchange and secondary sources, non-point sources of farmland runoff and transportation.
- water quality /
- sources analysis /
- PCA-MLR model /
- flux /
- Liaodong Bay

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图 1 辽河流域及监测断面示意图

Fig. 1 The Liao River Basin and water quality monitoring sites

下载: 全尺寸图片幻灯片

图 2 主要水质指标的Spearman相关关系

*代表p ≤ 0.05；**代表p ≤ 0.01；***代表p ≤ 0.001

Fig. 2 Spearman correlation among major pollutants in surface water

* Indicates p ≤ 0.05; ** indicates p ≤ 0.01; *** indicates p ≤ 0.001

下载: 全尺寸图片幻灯片

图 3 汛期和非汛期主要污染物指标

*和***分别表示p < 0.1和p < 0.001显著性水平

Fig. 3 Indicators of major pollutants in the wet and dry season

* and *** indicate the significance level of p < 0.1 and p < 0.001, respectively

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图 4 不同水系的主要河流污染物指标

字母相同表示差异不显著，字母不同表示差异显著（p < 0.05）

Fig. 4 Index in main rivers in pollutants different water system

Same uppercase letters indicate no significant differences and different uppercase letters indicate significant differences (p < 0.05)

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图 5 旋转后的成份载荷（a）和前3个主成分的载荷（b）

Fig. 5 Component loadings after varimax rotation (a) and loading plots of the first three components (b)

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表 1 水质指标描述性统计

Tab. 1 Descriptive statistics of water quality parameters

	均值	标准误	偏度	峰度	Kolmogorov-Smirnov	Shapiro-Wilk
T	12.8	0.2	0.13	−1.35	0.00	0.00
pH	7.9	0.0	−0.11	0.75	0.00	0.00
DO浓度	10.0	0.1	0.33	−0.03	0.03	0.04
EC	219.4	13.8	6.12	51.47	0.00	0.00
浊度	32.4	2.1	4.94	31.24	0.00	0.00
COD_Mn	3.4	0.0	1.78	5.66	0.00	0.00
COD浓度	14.2	0.2	2.80	27.99	0.00	0.00
BOD₅浓度	2.1	0.0	1.67	4.72	0.00	0.00
AN浓度	0.26	0.01	4.58	42.31	0.00	0.00
TP浓度	0.079	0.002	6.27	104.62	0.00	0.00
TN浓度	5.4	0.1	2.30	9.11	0.00	0.00
Cu浓度	0.001 6	0.000 1	10.66	166.23	0.00	0.00
Zn浓度	0.017	0.001	6.42	66.06	0.00	0.00
F⁻浓度	0.401	0.009	1.29	1.74	0.00	0.00
Se浓度	0.000 2	0.000 0	8.48	81.61	0.00	0.00
As浓度	0.001 0	0.000 1	14.03	291.31	0.00	0.00
Hg浓度	0.000 02	0.000 00	3.33	10.74	0.00	0.00
Cd浓度	0.000 07	0.000 01	9.44	106.66	0.00	0.00
Cr⁶⁺浓度	0.003	0.000	5.39	33.16	0.00	0.00
Pb浓度	0.001	0.000	0.90	2.17	0.00	0.00
CN⁻浓度	0.002	0.000	10.02	127.46	0.00	0.00
挥发酚浓度	0.000 5	0.000 0	10.73	137.50	0.00	0.00
S²⁻浓度	0.003	0.000	15.19	267.18	0.00	0.00
石油类浓度	0.01	0.00	8.37	122.00	0.00	0.00
LAS浓度	0.03	0.00	3.28	12.12	0.00	0.00
注：T的单位为℃；EC得单位为μS/cm；浊度单位为NTU；pH无量纲；其他指标单位为mg/L。

下载: 导出CSV

表 2 2021年不同水区污染物浓度和入海通量

Tab. 2 Fluxes and concentrations of pollutants in the Liaohe River Basin in 2021

	辽河水系		浑太河水系		东北沿渤海诸河
	浓度/(mg·L⁻¹)	通量/t	浓度/(mg·L⁻¹)	通量/t	浓度/(mg·L⁻¹)	通量/t
COD	18.8 ± 1.3	59 760	19.7 ± 2.1	75 369	13.0 ± 0.9^a	12 602
TN	8.63 ± 0.90	9 309	4.00 ± 0.43	23 934	7.66 ± 0.90	3021
AN	0.46 ± 0.09	585.9	0.23 ± 0.03	2 355.9	0.60 ± 0.06	144.8
TP	0.124 ± 0.011	473.4	0.178 ± 0.020	1 053.6	0.135 ± 0.016	81.5
石油类	0.010 ± 0.002	67.7	0.023 ± 0.011	145.0	0.016 ± 0.002	9.21
Hg	0.000 02 ± 0.000 00	0.135	0.000 05 ± 0.000 01	0.103	0.000 69 ± 0.000 39	0.026
Cd	0.000 11 ± 0.000 06	0.059	0.000 02 ± 0.000 00	0.135	0.000 13 ± 0.000 07	0.059
Pb	0.000 17 ± 0.000 08	0.518	0.000 18 ± 0.000 07	1.201	0.001 39 ± 0.000 35	0.259
As	0.002 32 ± 0.000 31	6.828	0.001 24 ± 0.000 55	6.419	0.001 49 ± 0.000 58	7.187
Cr⁶⁺	0.014 1 ± 0.004 8	15.304	0.005 2 ± 0.002 0	12.425	0.003 0 ± 0.000 6	3.922
流域面积/km²	44 947		27 661		29 482
径流量/(10⁸ m³)	29.0		51.7		6.85

下载: 导出CSV

表 3 解释方差及累计解释方差

Tab. 3 Explained variance and accumulative explained variance

成份	初始特征值			提取平方和载入			旋转平方和载入
成份	合计	方差/%	累积/%	合计	方差/%	累积/%	合计	方差/%	累积/%
1	4.146	34.554	34.554	4.146	34.554	34.554	3.896	32.470	32.470
2	1.650	13.752	48.306	1.650	13.752	48.306	1.485	12.379	44.849
3	1.140	9.504	57.810	1.140	9.504	57.810	1.331	11.096	55.945
4	1.038	8.648	66.458	1.038	8.648	66.458	1.262	10.513	66.458
5	0.876	7.302	73.760
6	0.802	6.681	80.441
7	0.605	5.040	85.481
8	0.569	4.742	90.224
9	0.426	3.549	93.773
10	0.312	2.598	96.371
11	0.259	2.155	98.526
12	0.177	1.474	100.000

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表 4 主成分的回归系数

Tab. 4 Coefficients of regression analysis of PCs

	回归系数	标准化后回归系数	t值	p值	R²
常量	0.584	0.000	24.883	0.000 47	0.995
PC1	5.246	0.827	218.472	0.000 29
PC2	2.488	0.402	106.162	0.000 36
PC3	1.825	0.289	76.380	0.000 19
PC4	1.247	0.203	53.639	0.000 35

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