基于水化学与氮氧同位素的丘陵区水库农业流域硝酸盐来源解析
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国家自然科学基金项目(42377077);济南市水务科技项目(JNSWKJ202202)


Nitrate source analysis in an agricultural basin of reservoir in hilly areas based on hydrochemistry, nitrogen and oxygen isotopes
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    摘要:

    硝酸盐污染是水库面临的主要环境问题之一。为解析丘陵区水库流域内硝酸盐来源,该研究选取以农业为主的乔店水库流域为研究区域,结合水化学分析、氮氧同位素示踪技术等方法,利用MixSIAR贝叶斯混合模型,定性和定量识别流域内硝酸盐来源及不同来源的贡献率。水化学分析结果表明,流域内干支流水体水化学类型以HCO3·SO4-Ca型为主,离子组成成分主要受岩石风化溶解控制。水中溶解无机氮的赋存形态主要为硝酸盐氮,硝酸盐氮浓度变化主要受水文气象条件、土地利用类型以及人类活动的影响,具体表现为冰封期>丰水期>消融期>枯水期>汛前期;中上游硝酸盐浓度受小流域内土地利用影响变化较大。水体的δ15N-NO3-均值表现为汛前期>消融期>枯水期>冰封期>丰水期;δ18O-NO3-均值表现为汛前期>枯水期>丰水期>冰封期>消融期。综合多种解析结果可知,土壤氮和粪便与污水是导致流域硝酸盐浓度变化的最主要因素。MixSIAR模型结果表明,冰封期、消融期和枯水期的硝酸盐主要源自土壤氮和粪便与污水,在冰封期和枯水期的土壤氮占比最高,贡献率分别为37%和36%。汛前期硝酸盐的来源中以粪便与污水为主,且大气沉降的占比增高,贡献率为13%。丰水期受农业面源污染最为严重,土壤氮和化肥对硝酸盐的贡献率分别为41%和31%,均为各时期最高。研究结果可为处于丘陵区的水库农业流域面源污染防控提供科学依据。

    Abstract:

    Nitrate pollution is one of the major environmental issues in reservoirs. Small and medium-sized reservoirs are the sources of drinking water more sensitive to seasonal variations in diffuse pollution. This study aims to analyze the changes in nitrate sources in a reservoir in a hilly watershed under agricultural cultivation in different periods. The Qiaodian Reservoir basin was selected as the study area. 16 sites were set to collect the water samples in January (freeze-up period), March (ablation period), June (pre-flood period), August (high water period), and November (low water period) in 2023. These samples were examined for water quality indicators, major ion compositions, and nitrogen and oxygen isotopes. Different sources of nitrate contamination in the water and their contributions were identified using hydrochemistry analysis, the nitrogen and oxygen isotope tracer technique, and the Bayesian stable isotope mixing model (MixSIAR). Hydrochemical analysis showed that the hydrochemistry was dominated by the HCO3·SO4-Ca type in the study area, where the dissolution of rock weathering seriously controlled the ionic composition. The ionic sources were enhanced by water-rock interaction during the abundant water period. There were relatively consistent trends in the TN and NO3--N concentrations, with NO3--N emerging as the primary form of dissolved inorganic nitrogen. Hydrometeorological conditions, land use patterns, and anthropogenic activities primarily contributed to the fluctuations in the nitrate concentrations. There was dry land (35.8% of the watershed area) with various crops. Livestock farming existed in the villages, where more animal manure was applied to the farmland. The rest types of land use were forest land and grassland, which accounted for 29.6% and 28.5% of the watershed area, respectively. Temporally, the nitrate concentrations declined in the descending order of freeze-up period (3.83 mg/L), high water period (3.57 mg/L), ablation period (3.51 mg/L), low water period (2.54 mg/L), pre-flood period (1.90mg/L). At the spatial scale, NO3--N concentrations were more variable in the upper and middle reaches of the watershed, while the downstream NO3--N concentrations were close to those in the reservoir area. The δ15N-NO3- mean values of nitrate were 9.61‰, 9.11‰, 8.1‰, 7.18‰, and 6.04 ‰ in the pre-flood, ablation, low water, freeze-up, and high water periods, respectively. The δ18O-NO3- mean values of nitrate were 9.52‰, 4.25‰, 3.74‰, 3.46‰, and 1.96 ‰ in the pre-flood, low water, high water, freeze-up, and ablation periods, respectively. The range of δ15N-NO3- and δ18O-NO3- values varied outstandingly in the different periods, indicating the multiple sources of nitrate. Various analyses showed that soil nitrogen, manure, and sewage were the pivotal contributors to nitrate concentration shifts within the reservoir basin. MixSIAR model was used to quantitatively assess the contribution rates of different nitrate sources. Nitrate was derived mainly from the soil nitrogen, manure, and sewage during the freeze-up, ablation, and low water periods. The proportions of nitrate sources were more consistent between the freeze-up and the low water period. Specifically, soil nitrogen contributed the highest proportion of nitrate to the watershed, 37% and 36%, respectively. Nitrate depended on the atmospheric deposition during the pre-flood period, accounting for 13%. There was the most severe loss of soil nitrogen during the high water period, when the highest contribution rates of nitrate from soil nitrogen and chemical fertilizer were 41% and 31%, respectively. This finding can provide a scientific basis for preventing and controlling surface pollution in the small and medium-sized reservoir watersheds in hilly agricultural areas.

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高艺雄,刘玉玉,刘爱华,王昊,王昕,姜欣,张保祥,魏开学.基于水化学与氮氧同位素的丘陵区水库农业流域硝酸盐来源解析[J].农业工程学报,2024,40(21):202-211. DOI:10.11975/j. issn.1002-6819.202405007

GAO Yixiong, LIU Yuyu, LIU Aihua, WANG Hao, WANG Xin, JIANG Xin, ZHANG Baoxiang, WEI Kaixue. Nitrate source analysis in an agricultural basin of reservoir in hilly areas based on hydrochemistry, nitrogen and oxygen isotopes[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE),2024,40(21):202-211. DOI:10.11975/j. issn.1002-6819.202405007

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  • 收稿日期:2024-05-04
  • 最后修改日期:2024-08-28
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  • 在线发布日期: 2024-11-01
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