1. Introduction
Water resources are an important basis for the survival of terrestrial organisms, but the amount of water available for biological use is very low [
1]. More importantly, water resources also show regional imbalances across the world, especially in arid and semi-arid areas, and are very scarce [
2,
3]. The permanent surface area of the water of downstream countries affected by water scarcity has decreased over time in Central Asia [
4]. The research conducted by Rockstroem et al. showed that by 2050, approximately 60% of the world’s population could face surface water shortages in relation to water stemming from lakes, rivers, and reservoirs [
5]. The question of how to manage water resources has become one of the major challenges in the 21st century [
6]. In fact, global population growth and economic development have had serious impacts on the aquatic environment [
7]. In recent decades, the development of industry and agriculture has caused surface water pollution [
8,
9,
10]. The shortage of water resources and water pollution are interrelated in that water pollution reduces the supply of water [
11,
12]. The pollution of rivers and lakes in the United States generally originates from agriculture, which mainly increases the content of nitrogen and phosphorus [
13]. The excessive use of chemical fertilizers and pesticides has caused serious non-point source water pollution [
14]. Industrially polluted rivers have increased concentrations of heavy metal ions, sulfides, organic compounds, etc. [
10,
15]. The same process has occurred in other parts of the world [
16,
17,
18]. In addition, climate change precipitates water quality problems, accentuates water level fluctuations and loss of biodiversity, and induces the destruction of habitats, eventually leading to the death of fish [
19]. In sub-basins, land use patterns and landscape patterns have significant impacts on water quality changes [
20]. Water pollution has exacerbated water conflicts in arid areas [
21]. Therefore, water pollution remains one of the key focuses of global interest and research.
China is a country with scarce water resources and serious water pollution [
21,
22]. The results of research have indicated that most of its regions mainly rely on surface water, which accounts for less than 50% of the surface water supply situated in only four provinces of China [
23]. As its water bodies became increasingly polluted, studies found that in some parts of China, the pollution level exceeded the national drinking water standard for nitrate (45 mg/L) [
24]. According to the statistics of the Ministry of Ecology and Environment of China (
http://mee.gov.cn/ (accessed on 28 May 2022)), water pollution mainly originates from agricultural production, and the main pollutants are measured by chemical oxygen demand (COD) and include nitrogen and phosphorus. The emissions of COD, total nitrogen, and total phosphorus in China’s water bodies were 1324.09 × 10
4 t, 270.46 × 10
4 t, and 28.47 × 10
4 t, respectively, in 2010. This research has shown that the total amount of agricultural N emissions in water bodies in the Haihe Basin was 1079 Gg N in 2012, of which cropland contributed 54%, while the total amount of agricultural P emissions in these water bodies was 208 Gg P, of which livestock contributed 78% [
25]. Facing severe water pollution, the Chinese government has taken active measures to reduce the discharge of pollutants [
26,
27]. Compared with those in 2010, the total amounts of water pollution emissions of COD, nitrogen, and phosphorus decreased by 19.4%, 47.79%, and 25.53, respectively, in 2017. Pan et al. (2022) found that China’s Environmental Protection Interview led to an average reduction in water pollution of 14.5%, and this effect persisted in the long term [
28]. However, the research of Wu et al. (2022) demonstrated that in the Yongan River watershed of eastern China, although chemical N fertilizer use decreased by 49% and the number of domestic animals decreased by 73% from 2000–2019, flow-normalized riverine TN and NO
3− concentrations progressively increased by 161% and 232%, respectively, from 1980–2019 [
29]. Therefore, in general, China’s water environment is improving, but there is still a risk of water quality deterioration in some areas.
The Yellow River Basin covers a total of 752,400 km
2, spanning nine provinces in northern China, and it is an important area of economic development and ecological protection. Similarly, with the development of industry and agriculture, the shortage of water resources and water pollution in the Yellow River Basin has become increasingly prominent [
30]. The research of Lu et al. (2021) found that the polymeric state of dissolved copper in the Yellow River tends to be stable [
31]. Xia et al. (2022) concluded that nitrate concentrations have a pronounced influence of human activities in the Yellow River Delta [
32]. Hong et al. (2020) found that the concentration of heavy metals in the Yellow River was affected by runoff, and the concentration of heavy metals was the lowest in the wet season [
33]. Wang et al. (2009) found that there was a significant difference in water pollution between the tributaries and the main stream of the Yellow River that and SO
42−, NO
3−, and Cl
− were present in the main stream [
34]. In the Lanzhou section of the upper reaches of the Yellow River, the concentrations of total PAHs in the porewaters ranged from 48.2 to 206 μg/L and were positively correlated with the sediment content in the water [
35]. In addition, some studies showed that the water quality in the upper reaches of the Yellow River Basin was better than that in the lower reaches [
36]. One study also showed that the water pollution in the Yellow River Basin is due to agricultural (planting, animal husbandry, and aquaculture), industrial, and domestic pollution [
37]. The research of Zuo et al. (2016) showed that there is a mid- to high-risk level of Cd in the upper Yellow River [
38]. In the small areas where the tributaries of the middle and upper reaches of the Yellow River Basin flow, agriculture is the main industry. Therefore, water pollution mainly originates from agriculture in these regions. Kang et al. (2015) suggested that there was non-point source pollution in the Anjiagou watershed in the upper reaches of the Yellow River, and the main pollutants were COD
Mn, BOD
5, and TP derived from agricultural land and forested land [
39].
As illustrated by the abovementioned studies, water pollution has become a problem that cannot be ignored with regard to the utilization of water resources in the Yellow River Basin. Changes in water quality in the Yellow River Basin are very important for the social development and ecological protection of the region. Therefore, it is necessary to analyze changes in water quality in the Yellow River Basin and study the factors affecting the changes in water pollutants. In this study, we selected the Zuli River Basin in the upper reaches of the Yellow River Basin as an area to study temporal changes in surface water quality. The goals of this study were to (1) analyze the change trend of pollutants in the Zuli River Basin from 2001 to 2021; (2) detect the change cycle of water pollutants in the Zuli River Basin; and (3) identify the factors affecting the changes in water pollutants in the Zuli River Basin. This study will contribute to the protection, scientific development, and utilization of water resources in the upper reaches of the Yellow River Basin.
4. Discussion
To better explain the relationships between water quality and environmental factors, the main variation cycles of the water quality indicators were compared with those of three environmental factors (precipitation, runoff, and sediment) in the Zuli River Basin from 2001 to 2021 (
Figure 8). In
Figure 8, because the cycles of most of the water quality indicators (except for TP) and runoff are relatively similar, the variations in runoff and the water quality indicators show obvious similarities or dissimilarities. For instance, the variation trends of DO and runoff were similar, while those of BOD
5 and runoff were in opposition to the main variation cycle. Additionally, in relation to the main variation cycle, the variation trends of most of the water quality indicators except for DO, TP, and NO
3-N were opposite to those of runoff after 2010. It seems that the variation in runoff may have affected the water quality of the Zuli River, especially after 2010. Precipitation and runoff may increase or decrease the level of pollutants in rivers through the transportation of surface pollutants into rivers via surface runoff. Surface pollutants adhere to the soil and enter the river through heavy precipitation and surface runoff [
52]; however, increased precipitation can increase runoff, and increased runoff enhances the potency of dilution and reduces the residence time of pollutants in rivers [
31,
53,
54,
55]. Therefore, the quality of water in a river also depends on other environmental factors, such as landscape patterns and land use types [
56]. For example, due to the low vegetation coverage of the surface during the dry season, surface runoff after rain is more likely to transport pollutants from soil into the Changle River watershed [
57]. Forest land was found to reduce the content of pollutants in rivers compared to cultivated land in the Jiulong River Basin [
58]. In the Zuli River Basin, more vegetation measures have been applied for soil erosion control in the watershed area, thereby reducing the erosion of soil and its transfer into rivers through surface runoff, since the 1980s [
39,
40]. In
Figure 4, one can see that the sediment content in the Zuli River has continued to decline, indicating that the soil erosion in the entire basin has decreased; thus, the pollutants accompanying the soil may have also decreased from 2001 to 2021. Therefore, reduced soil erosion and increased runoff may be the main reasons for the decrease in the content of pollutants in the Zuli River Basin after 2011.
Agricultural production and livestock breeding can increase the number of pollutants in surface water. The use of chemical fertilizers increases the content of nitrogen and phosphorus in surface water, resulting in poor water quality [
59,
60]. Farmed animal waste not only increases the content of pollutants in surface water but also leads to an increase in chemical oxygen demand, leading to poor water quality [
61]. However, in this study, we found that an increase in the number of sheep had a significant negative correlation with the concentration of pollutants in the water of the Zuli River Basin after 2011. In order to identify the reason for this trend, the main variation cycles of water quality indicators were compared with those of four social factors (fertilizer, large cattle, pigs, and sediment) in the Zuli River Basin from 2001 to 2021 (
Figure 9). It was found that the number of sheep and the concentrations of DO and NO
3-N were at high peaks, while the other water quality indicators were at a low peak after 2011. This may be the reason for the extremely significant negative correlation between the number of sheep and water quality indicators (except for DO and NO
3-N) presented in
Table 7. The reason why there was little correlation between the social factors and water quality indicators after 2011 may be that (1) the slow growth of fertilizer use and aquaculture in the Zuli River Basin and the implementation of more environmentally friendly operation methods did not increase the discharge of pollutants or that (2) the increase in runoff reduced the content of pollutants in the river.
5. Conclusions
In this study, the water quality indicators of DO, BOD5, NH3-N, CODMn, VP, TP, F−, and NO3-N were selected for an analysis of the Zuli River Basin. We studied the change trends and main variation cycles of these water quality indicators and analyzed the factors affecting them. The results are as follows:
Six water quality indicators, excepting DO and F−, showed an increasing trend before 2011, of which NO3-N and BOD5 had the fastest growth rates, reaching 3.83 mg/L × a−1 and 1.1 mg/L × a−1, respectively. DO showed an extreme, significant downward trend, with a rate of 0.34 mg/L × a−1. The water quality of the Zuli River Basin continued to deteriorate from 2001–2011.
There was an extreme, significant upward trend in DO at a rate of 0.63 mg/L × a−1 after 2011, while there were extreme, significant downward trends in CODMn, VP, and F- at rates of 1.21 mg/L × a−1, 0.0021 mg/L × a−1, and 0.056 mg/L × a−1, respectively. BOD5 and NH3-N significantly decreased at rates of 2.3 mg/L × a−1 and 0.55 mg/L × a−1, respectively. The water quality of the Zuli River Basin gradually improved after 2011.
DO, BOD5, VP, and NO3-N all had 10-year main variation cycles; NH3-N and CODMn both had 7-year main variation cycles; TP had a 3-year main variation cycle; and F− had an 8-year main variation cycle. According to the main variation cycles of the other water quality indicators, the water quality of the Zuli River Basin may gradually improve in the short term after 2021.
Through Spearman correlation analysis and a comparison of the major periodic changes, it was found that the reasons for these water quality changes in the Zuli River Basin are complex. Before 2011, social factors may have been the main reasons for the poor water quality in the Zuli River Basin, especially the increase in the content of pollutants in the water caused by chemical fertilizers and aquaculture, resulting in a decrease in the DO content. In contrast, environmental factors may be the main reasons for the improvement of the water quality in the Zuli River Basin after 2011, mainly the increase in precipitation and runoff, which has reduced the content of pollutants in the water.
Therefore, the overall water quality of the Zuli River Basin has gradually improved since 2011. This may be due to (1) increased precipitation and runoff, diluting the concentrations of pollutants in the river, or (2) decreased content of pollutants entering the river with decreasing soil erosion.