莱州湾入海河流河口氮来源及转化过程的同位素解析

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摘要为解决莱州湾氮污染问题,本文开展了莱州湾入海河流氮来源及转化过程研究.通过分析水质参数、氮含量、水和硝酸盐的稳定同位素,以明确河流河口水体氮来源及其关键过程.结果表明:水的δD和δ¹⁸O与盐度之间具有较好的时空变化一致性,表明入海河口受到较强的海水混合作用影响,并向河流上游显著减弱.丰水期和枯水期NO₃^--N占TN比例除个别点较低外,大部分都在37.2%~ 81.7%和29.5 % ~ 95.9%内,表明在大部分河段NO₃^--N是主要的无机氮形态;枯水期ρ(TN) 和ρ(NH₄⁺-N)在部分样点出现极值,显著高于丰水期,部分水体ρ(NH₄⁺-N)在2mg/L以上,属劣Ｖ类水质.2005-2023年间的ρ(NO₃^--N)的变化表明,莱州湾入海河流NO₃^--N浓度呈“先上升,后下降”趋势.总体上,水体中δ¹⁵N-NO₃^-在丰水期和枯水期的变化范围分别为+5.7‰~+18.6‰和+4.5‰~+20.0‰;δ¹⁸O-NO₃^-为+4.2‰~+13.8‰和-0.5‰~+20.1‰,均无明显季节变化.硝酸盐同位素结果表明莱州湾入海河流主要受硝化作用影响,同时部分河段样点受到反硝化作用影响.枯水期低盐度采样点NO₃^--N主要来自于粪肥和污水,丰水期河口大部分采样点受咸潮回溯的影响,并且大部分河段水体受农业施肥影响明显.本研究明确了莱州湾海岸带入海河流河口氮污染源的排放特征和时空差异性,所取得的认识可以为未来环渤海入海河流氮污染的防控和治理提供研究示范和数据参考.

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	张璐瑶
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	马卓妮
	弓耀奇
	刘小龙

关键词 ：同位素, 氮来源, 莱州湾, 入海河流

Abstract：To understand nitrogen pollution and sources of Laizhou Bay, nitrogen sources and transformation processes in the coastal rivers entering the sea of Laizhou Bay were studied. Water quality parameters, nitrogen content, and stable isotopes were used to clarify the sources and key processes in river estuary. The results indicate strong temporal and spatial consistency between δD and δ¹⁸O of water, EC, and salinity, suggesting significant seawater mixing effects in the estuary, which was significantly weakened upstream of the river. NO₃^--N was found to be the dominant form to inorganic nitrogen in most reaches of the river during high flow and low flow seasons, ranging from 37.2% to 81.7% and 29.5% to 95.9%, respectively, except for a few sites. Furthermore, extreme values of ρ(TN) and ρ(NH₄⁺-N) values were observed at some sample sites during low flow season, which were significantly higher than those during the high flow season. Some water samples had ρ(NH₄⁺-N) values exceeding 2mg/L, resulting in an inferior Category V water quality. The long-term variation of ρ(NO₃^--N) from 2005 to 2023 showed an initial increase followed by a decrease in rivers entering Laizhou Bay. The δ¹⁵N-NO₃^- varied from +5.7‰ to +18.6‰ and from +4.5‰ to +20.0‰ during the high flow and low flow seasons, respectively, while the δ¹⁸O-NO₃^- varied from +4.2‰ to +13.8‰ and from -0.5‰ to +20.1‰, with no obvious seasonal variations. The nitrate isotope results showed that nitrification was major process affecting riverine nitrogen entering Lanzhou Bay, and that some river samples were also influenced by denitrification. During low flow season, NO₃^--N at the low salinity sampling sites was mainly sourced from manure and sewage, while most estuary sites during the high flow season were affected by the salty tide backflow, and agricultural fertilization impacted most river sections. This study provides insights into the emission characteristics of nitrogen pollution sources and spatial and temporal variability in Laizhou Bay’s coastal zone estuaries, offering valuable research demonstrations and data references for future prevention, control, and management efforts for nitrogen pollution in rivers entering the sea around the Bohai Sea.

Key words： isotopes nitrogen sources Laizhou Bay coastal rivers

收稿日期: 2024-07-16

PACS:

X52

基金资助:国家自然科学基金资助项目(42293262);国家科技基础资源调查专项项目(2021FY101001)

通讯作者: 岳甫均,副教授,fujun_yue@tju.edu.cn;李军,副研究员,lijun5931@163.com E-mail: fujun_yue@tju.edu.cn;lijun5931@163.com

作者简介: 张璐瑶(2000-),女,山东东营人,天津师范大学硕士研究生,研究方向为流域污染物溯源分析.zly13205481219@163.com.

引用本文:

张璐瑶, 岳甫均, 李军, 简锐风, 马卓妮, 弓耀奇, 刘小龙. 莱州湾入海河流河口氮来源及转化过程的同位素解析[J]. 中国环境科学, 2025, 45(2): 981-990. ZHANG Lu-yao, YUE Fu-jun, LI Jun, JIAN Rui-feng, MA Zhuo-ni, GONG Yao-qi, LIU Xiao-long. Isotopic analysis of nitrogen sources and transformation processes in the coastal river estuaries of Laizhou Bay. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(2): 981-990.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2025/V45/I2/981

[1] 张晓丽,姚瑞华,徐昉.陆海统筹协调联动助力渤海海洋生态环境保护 [J]. 环境保护, 2019,47(7):13-16.Zhang X L, Yao R H, Xu F. Coordination and linkage of land and sea to promote the marine eco-environment protection in Bohai Sea [J]. Environmental Protection, 2019,47(7):13-16.
[2] Schindler W D, Hecky E R, et al. Eutrophication: more nitrogen data needed [J]. Science, 2009,324(5928):721-722.
[3] Carey R O, Migliaccio K W, Brown M T. Nutrient discharges to Biscayne Bay, Florida: Trends, loads, and a pollutant index [J]. Science of the Total Environment, 2011,409(3):530-539.
[4] Camargo J A, Alonso Á. Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: A global assessment [J]. Environment International, 2006,32(6):831-849.
[5] 吴亚丽,亢晓琪,牛远,等.基于氮氧同位素的深水湖泊硝酸盐来源辨析 [J]. 中国农村水利水电, 2022,(4):106-113.Wu Y L, Kang X Q, Niu Y, et al. An analysis of nitrate sources in deep lake based on nitrogen and oxygen isotopes [J]. China Rural Water and Hydropower, 2022,(4):106-113.
[6] Kendall C. Tracing nitrogen sources and cycling in catchments [M] // Isotope tracers in catchment hydrology, Elsevier, 1998:519-576.
[7] Kohl D H, Shearer G B, Commoner B. Fertilizer nitrogen: contribution to nitrate in surface water in a corn belt watershed [J]. Science, 1971, 174(4016):1331-1334.
[8] Heaton T H. Isotopic studies of nitrogen pollution in the hydrosphere and atmosphere: a review [J]. Chemical Geology: Isotope Geoscience Section, 1986,59:87-102.
[9] Amberger A, Schmidt H L. Natürliche isotopengehalte von Nitrat als Indikatoren für dessen Herkunft [J]. Geochimica et Cosmochimica Acta, 1987,51(10):2699-2705.
[10] 任奕蒙,岳甫均,徐森,等.利用氮氧同位素解析赤水河流域水体硝酸盐来源及其时空变化特征 [J]. 地球与环境, 2019,47(6):820-828.Ren Y M, Yue F J, Xue S, et al. Temporal and spatial variation of nitrate sources in the Chishui River watershed based on isotope approach [J]. Earth and Environment, 2019,47(6):820-828.
[11] 邢萌,刘卫国,胡婧.浐河、涝河河水硝酸盐氮污染来源的氮同位素示踪 [J]. 环境科学, 2010,31(10):2305-2310.Xing M, Liu W G, Hu J. Using nitrate isotope to trace the nitrogen pollution in Chanhe and Laohe River [J]. Environmental Science, 2010,31(10):2305-2310.
[12] 王诗绘,马玉坤,沈珍瑶.氮氧稳定同位素技术用于水体中硝酸盐污染来源解析方面的研究进展 [J]. 北京师范大学学报(自然科学版), 2021,57(1):36-42.Wang S H, Ma Y K, Shen,Z Y. Identification of nitrate source in receiving water with dual isotopes (δ(¹⁵N) and δ(¹⁸O)) [J]. Journal of Beijing Normal University (Natural Science), 2021,57(1):36-42.
[13] 刘静,刘录三,郑丙辉.入海河口区水环境管理问题与对策 [J]. 环境科学研究, 2017,30(5):645-653.Liu J, Liu L S, Zheng B H. Problems and countermeasures of water environmental management in estuaries [J]. Research of Environmental Sciences, 2017,30(5):645-653.
[14] 姜会超,王玉珏,李佳蕙,等.莱州湾营养盐空间分布特征及年际变化趋势 [J]. 海洋通报, 2018,37(4):411-423.Jiang H C, Wang Y J, Li J H, et al. Annual variation and spatial distribution of nutrients in the Laizhou Bay [J]. Marine Science Bulletin, 2018,37(4):411-423.
[15] 童钧安.莱州湾主要污染物来源及分布特征 [J]. 黄渤海海洋, 1994, (4):16-20.Tong J A. The main source and distribution characteristics of pollutants in Laizhou Bay [J]. Journal of Oceanography of Huanghai & Bohai Seas, 1994,(4):16-20.
[16] 马绍赛,辛福言,崔毅,等.黄河和小清河主要污染物入海量的估算 [J]. 海洋水产研究, 2004,(5):47-51.Ma S S, Xin F Y, Cui Y, et al. Assessment of main pollution matter volume into the sea from Yellow River and Xiaoqing River [J]. Marine Fisheries Research, 2004,(5):47-51.
[17] 王一诺,关纬城,邹立,等.环莱州湾主要河口氮磷组成特征及其输送贡献 [J]. 海洋环境科学, 2023,42(5):684-692.Wang Y N, Guan W C, Zou L, et al. Composition and transport of nitrogen and phosphorus in the main estuaries around Laizhou Bay [J]. Marine Environmental Science, 2023,42(5):684-692.
[18] 刘娟.渤海化学污染物入海通量研究 [D]. 青岛:中国海洋大学, 2006:9-77.Liu J. Study on the main pollutant fluxes flowing into the Bohai [D]. Qingdao: Ocean University of China, 2006:9-77.
[19] 毛绪美,罗泽娇,刘存富,等.细菌反硝化法同时分析天然水中硝酸盐氮、氧同位素组成研究 [J]. 地质科技情报, 2006,(5):97-100.Mao X M, Luo Z J, Liu C F, et al. A method of nitrogen and oxygen isotopic analysis of nitrate in water with bacterial denitrificati on at one time [J]. Geological Science and Technology Information, 2006, (5):97-100.
[20] 岳甫均,李思亮,刘丛强,等.利用反硝化细菌法测试水体硝酸盐氮氧同位素 [J]. 生态学杂志, 2012,31(8):2152-2157.Yue F J, Li S L, Liu C Q, et al. Measurement of waters nitrate dual isotopes based on denitrifier method [J]. Chinese Journal of Ecology, 2012,31(8):2152-2157.
[21] 杨巧凤,王瑞久,徐素宁,等.莱州湾南岸卤水的稳定同位素与地球化学特征 [J]. 地质论评, 2016,62(2):343-352.Yang Q F, Wang R J, Xu S N, et al. Hydrogeochemical and stable isotopic characteristics of brine in Laizhou Bay [J]. Geological Review, 2016,62(2):343-352.
[22] 李志林,姜会超,张娟,等.山东近岸海域夏季pH分布特征及影响因素分析 [J]. 海洋环境科学, 2023,42(2):193-199.Li Z L, Jiang H C, Zhang J, et al. Distributions and influencing factors of pH in Shandong coastal area in summer [J]. Marine Environmental Science, 2023,42(2):193-199.
[23] 周国华,孙彬彬,曾道明,等.中国东部主要入海河流河口区地球化学特征:理化指标与水溶态元素浓度 [J]. 中国地质, 2012,39(2):283-294.Zhou G H, Sun B B, Zeng D M, et al. Hydrogeochemical characteristics of major estuaries in eastern China: Physicochemical indicators and soluble element concentrations of river water [J]. Geology in China, 2012,39(2):283-294.
[24] Turekian K. Geochemical distribution of elements [J]. Encyclopedia of science and technology, 1977,4:627-630.
[25] 王莹.基于环境同位素的胶莱平原地下水补给来源研究 [D]. 烟台:鲁东大学, 2021:13-65.Wang Y. Study on groundwater recharge sources based on environmental isotope in Jiaolai Plain [D]. Yantai: Ludong University, 2021:13-65.
[26] 杨巧凤,王瑞久,徐素宁,等.莱州湾白浪河河水和河口海水的水化学和氢氧稳定同位素特征 [J]. 水文地质工程地质, 2016,43(5):48-55.Yang Q F, Wang R J, Xu S N, et al. Hydrochemical and stable isotopic characteristics of estuarial seawater and river water of Bailang River in Laizhou Bay [J]. Hydrogeology & Engineering Geology, 2016,43(5): 48-55.
[27] Xia B, Zhang L. Carbon distribution and fluxes of 16 rivers discharging into the Bohai Sea in summer [J]. Acta Oceanologica Sinica, 2011,30:43-54.
[28] 张龙军,夏斌,桂祖胜,等.2005年夏季环渤海16条主要入海河流的污染状况 [J]. 环境科学, 2007,(11):2409-2415.Zhang L J, Xia B, Gui Z S, et al. Contaminative conditions evaluation of sixteen main rivers flowing into sea around Bohai Sea, in summer of 2005 [J]. Environmental Science, 2007,(11):2409-2415.
[29] 蔡林颖,杨丽标,刘树庆,等.枯水期环渤海16条河流N₂O释放通量研究 [J]. 环境科学与技术, 2014,37(12):89-95.Cai L Y, Yang L B, Liu S Q, et al. Emission flux of N₂O in 16 rivers flowing into Bohai Sea during dry season [J]. Environmental Science & Technology, 2014,37(12):89-95.
[30] Yu J, Zhang W, Tan Y, et al. Dual-isotope-based source apportionment of nitrate in 30rivers draining into the Bohai Sea, north China [J]. Environmental Pollution, 2021,283:117112.
[31] 陆庆沅.基于海陆协同调查的莱州湾主要化学污染物入海通量和时空演变特征研究 [D]. 上海:上海海洋大学, 2022:12-73.Lu Q Y. Study on the fluxes and temporal and spatial evolution characteristics of major chemical pollutants in Laizhou Bay based on sea-land collaborative survey [D]. Shanghai: Shanghai Ocean University, 2022:12-73.
[32] 王修林,崔正国,李克强,等.环渤海三省一市溶解态无机氮容量总量控制 [J]. 中国海洋大学学报(自然科学版), 2008,(4):619-622,626.Wang X L, Cui Z G, Li K Q, et al. Study on the gross control of DIN environmental capacity in the peripheral zone of the Bohai Sea [J]. Periodical of Ocean University of China, 2008,(4):619-622,626.
[33] 鹿红.我国海洋生态文明建设研究 [D]. 大连:大连海事大学, 2018:15-169.Lu H. Research on the construction of marine ecological civilization in our country [D]. Dalian: Dalian Maritime University, 2018:15-169.
[34] Mueller C, Zink M, Samaniego L, et al. Discharge driven nitrogen dynamics in a mesoscale river basin as constrained by stable isotope patterns [J]. Environmental Science & Technology, 2016,50(17):9187-9196.
[35] Anornu G, Gibrilla A, Adomako D. Tracking nitrate sources in groundwater and associated health risk for rural communities in the White Volta River basin of Ghana using isotopic approach (δ¹⁵N, δ¹⁸ONO₃ and 3H) [J]. Science of the Total Environment, 2017,603: 687-698.
[36] Li S L, Liu C Q, Li J, et al. Assessment of the sources of nitrate in the Changjiang River, China using a nitrogen and oxygen isotopic approach [J]. Environmental Science & Technology, 2010,44(5):1573-1578.
[37] 嵇晓燕,王姗姗,杨凯,等.2016~2020年中国地表水中总氮浓度时空变化特征分析 [J]. 生态环境学报, 2022,31(6):1184-1192.Ji X Y, Wang S S, Yang K, et al. Temporal and spatial variation characteristics of total nitrogen concentration in surface water from 2016 to 2020 in China [J]. Ecology and Environmental Sciences, 2022, 31(6):1184-1192.
[38] 王兰海.昌邑市潍河防潮蓄水闸除险加固措施 [J]. 山东水利, 2019, (8):53-54.Wang L H. De-risking and reinforcement measures for Weifang river Tide-proof storage lock in Changyi [J]. Shandong Water Resources, 2019,(8):53-54.
[39] Shi W M, Zhang Y, Zhang C Q, et al. Sources and health risks of nitrate pollution in surface water in the Weihe River watershed, China [J]. Journal of Mountain Science, 2022,19(8):2226-2240.
[40] 赵娟娟,谷文文,王韵,等.盐度增加对不同反硝化系统脱氮效能的影响及碳排放对比研究 [J]. 环境科学学报, 2024,44(8):181-189.Zhao J J, Gu W W, Wang Y, et al. A comparative study on the effect of increasing salt concentration on denitrification efficiency and carbon emissions of different denitrification systems [J]. Acta Scientiae Circumstantiae, 2024,44(8):181-189.
[41] Kendal C, Elliot E M, Wankel S D. Tracing anthropogenic inputs of nitrogen to ecosystems [J]. Stable isotopes in ecology and environmental science, 2007:375-449.
[42] Xue D, Botte J, De Baets B, et al. Present limitations and future prospects of stable isotope methods for nitrate source identification in surface-and groundwater [J]. Water research, 2009,43(5):1159-1170.
[43] Kool D M, Wrage N, Oenema O, et al. Oxygen exchange with water alters the oxygen isotopic signature of nitrate in soil ecosystems [J]. Soil Biology and Biochemistry, 2011,43(6):1180-1185.
[44] Sigman D M, Difiore P J, Hain M P, et al. The dual isotopes of deep nitrate as a constraint on the cycle and budget of oceanic fixed nitrogen [J]. Deep Sea Research Part I: Oceanographic Research Papers, 2009,56(9):1419-1439.
[45] Keeling R F. The atmospheric oxygen cycle: The oxygen isotopes of atmospheric CO₂ and O₂ and the O₂/N₂ ratio [J]. Reviews of Geophysics, 1995,33(S2):1253-1262.
[46] Tian S, Gaye B, Tang J, et al. A nitrate budget of the Bohai Sea based on an isotope mass balance model [J]. Biogeosciences, 2022,19(9): 2397-2415.
[47] Isnansetyo A, Getsu S, Seguchi M, et al. Independent effects of temperature, salinity, ammonium concentration and pH on nitrification rate of the Ariake seawater above mud sediment [J]. Hayati Journal of Biosciences, 2014,21(1):21-30.
[48] 李荣富,罗跃辉,曾洪玉,等.稳定同位素技术在环境水体氮的生物地球化学循环研究中的应用 [J]. 南京大学学报(自然科学), 2016,52 (1):16-26.Li R F, Luo Y H, Zeng H Y, et al. Review on applications of stable isotope techniques in studying biogeochemical cycle of nitrogen in environmental water [J]. Journal of Nanjing University (Natural Sciences), 2016,52(1):16-26.
[49] 杨晓宇,孙晖,王岩,等.典型引调水受水流域氮时空分布特征及硝酸盐来源解析——以汾河水库上游流域为例 [J]. 中国环境科学, 2024,44(7):3823-3831.Yang X Y, Sun H, Wang Y, et al. Characterization of spatial and temporal distribution of nitrogen and source analysis of nitrate in a typical water diversion receiving basin: A case study on upper reaches of Fenhe Reservoir [J]. China Environmental Science, 2024,44(7): 3823-3831.
[50] 肖春艳,孙艺萌,赵同谦,等.丹江口水库淅川库区大气硝酸盐干沉降特征及源解析 [J]. 中国环境科学, 2024,44(3):1515-1525.Xiao C Y, Sun Y M, Zhao T Q, et al. Atmospheric nitrate-nitrogen dry deposition characteristics and source analysis in the Xichuan reservoir area of Danjiangkou Reservoir [J]. China Environmental Science, 2024,44(3):1515-1525.
[51] 王艳碧,周忠发,孔杰,等.基于水化学与氮氧同位素的喀斯特山区水体硝酸盐来源示踪与估算——以平寨水库为例 [J]. 中国环境科学, 2023,43(10):5265-5276.Wang Y B, Zhou Z F, Kong J, et al. Tracing and estimation of nitrate sources based on hydrochemistry and nitrogen and oxygen isotopes in karst mountainous water: A case study of the Pingzhai reservoir [J]. China Environmental Science, 2023,43(10):5265-5276.
[52] Zhang Y, Shi P, Song J, et al. Application of nitrogen and oxygen isotopes for source and fate identification of nitrate pollution in surface water: a review [J]. Applied sciences, 2018,9(1):18.
[53] 徐璐,蒋勇军,段世辉,等.基于双同位素(δ¹⁵N-NO₃^--δ¹⁸O-NO₃^-)和IsoSource模型的岩溶槽谷区地下水硝酸盐来源的定量示踪 [J]. 环境科学, 2020,41(8):3637-3645.Xu L, Jiang Y J, Duan S H, et al. Quantification of nitrate sources to groundwater in karst trough-valley areas based on dual stable isotopes of δ¹⁵N-NO₃^- and δ¹⁸O-NO₃^- and the IsoSource Model [J]. Environmental Science, 2020,41(8):3637-3645.
[54] Kruk M K, Mayer B, Nightingale M, et al. Tracing nitrate sources with a combined isotope approach (δ¹⁵N-NO₃^-, δ¹⁸O-NO₃^- and δ¹¹B) in a large mixed-use watershed in southern Alberta, Canada [J]. Science of the Total Environment, 2019,703:135043.
[55] Yang P, Li Y, Groves C, et al. Coupled hydrogeochemical evaluation of a vulnerable karst aquifer impacted by septic effluent in a protected natural area [J]. Science of the Total Environment, 2019,658:1475-1484.
[56] Xiao J, Lv G, Chai N, et al. Hydrochemistry and source apportionment of boron, sulfate, and nitrate in the Fen River, a typical loess covered area in the eastern Chinese Loess Plateau [J]. Environmental Research, 2022,206:112570.
[57] Wu H, Dong Y, Gao L, et al. Identifying nitrate sources in surface water, regolith and groundwater in a subtropical red soil Critical Zone by using dual nitrate isotopes [J]. Catena, 2021,198:104994.
[58] 于璐,郑天元,郑西来.地下水硝酸盐污染源解析及氮同位素分馏效应研究进展 [J]. 现代地质, 2022,36(2):563-573.Yu L, Zheng T Y, Zheng X L. Review of nitrate source apportionment and nitrogen isotope fractionation in groundwater [J]. Geoscience, 2022,36(2):563-573.
[59] 王辉,栾维新,康敏捷.渤海氮污染的来源结构与污染压力空间分布 [J]. 地理研究, 2020,39(1):186-199.Wang H, Luan W X, Kang M J. Nitrogen pollution source structure and spatial distribution of Bohai Sea [J]. Geographical Research, 2020,39(1):186-199.