九江市是长江大保护战略实施的首批试点城市之一，成都是长江流域范围内重要城市，经济发展的同时水生态环境污染严重。本研究以长江流域部分典型城市河流（沱江流域成都段、九江市十里河）为研究对象，结合现场监测与实验室分析模拟，以生化需氧量（COD）、氨氮（NH₃-N）、总氮（TN）等污染物为重点考察指标，研究了长江流域部分典型城市河流污染物的降解系数，探明了溶解氧（DO）和温度（T）等影响因素与降解系数之间的关系；并采用紫外吸收光谱（UV-Vis）、三维荧光光谱-平行因子分析（EEMs-PARAFAC）等方法，分析了河流中溶解性有机质（DOM）的含量、组分以及来源的时空分布特征，并探讨分析了初期雨水径流对溶解性有机质的影响，主要结论如下：

（1）当DO浓度为3~5和>7 mg/L时，COD的降解系数（K）分别为0.17057 d^-1和0.40047 d^-1； 分别为0.06623 d^-1和0.09012 d^-1； 分别为0.04743 d^-1和0.10736 d^-1。在<2 mg/L、3~5 mg/L和>7 mg/L条件下 分别为0.14049 d^-1、0.15786 d^-1和0.19106 d^-1，随着DO浓度下降，K减少。当T为15 ℃、20 ℃和25 ℃时， 分别为0.10275 d^-1、0.19558 d^-1、0.27228 d^-1， 分别为0.13459 d^-1、0.18837 d^-1、0.2496 d^-1， 降解系数分别为0.15302 d^-1、0.16978 d^-1、0.19297 d^-1，随着T的升高污染物的K呈升高趋势。DO浓度和T升高有利于污染物的降解。

（2）通过对阿累尼乌斯（Ar-rhenius）关系式的转化，确定温度与COD、NH₃-N、TN和TP降解系数值之间的经验公式，分别为 ； ； ； 。现场原位实验中上、中游各月份COD降解系数值相对中下游采样点降解系数值较高，上、下游中5、6月份NH₃-N降解系数值高于其他月份降解系数值，下游采样点表现更明显；上游6月TN降解系数较高，6月TN的降解系数值上游>中游>下游，TP则相反。原位监测降解系数与环境参数相关性分析表明氧化还原电位、T分别是COD、NH₃-N降解快慢的主要影响因素。

（3）沱江流域上、下层水溶解性有机碳（DOC）变化范围分别为2.90~11.48 mg/L、2.83~6.91 mg/L、0.23~4.93 mg/L和0.88~4.78 mg/L。十里河上游6月DOC浓度变化为降解前（3.59 mg/L）高于降解后（2.66 mg/L）；中游中4月降解前后DOC浓度变化不大，5月呈降解后（3.47 mg/L）低于降解前（4.15 mg/L）；下游各月份DOC浓度均呈现降解后高于降解前，原因可能是水体中颗粒态有机质（POC）转化为溶解态有机质（DOC），且增加的DOC含量高于因降解减少的DOC量，使得降解后DOC含量增高。EEMs-PARAFAC分析，结果表明沱江流域成都段中荧光组分为UVA类腐殖质（C1）、类酪氨酸（C2）、类腐殖质（C3）和类色氨酸（C4），类蛋白C2是河流DOM主要成分，受内源影响较大；水体中DOM来源受陆源与内源共同影响；上下层水腐殖化指数（HIX）变化较小，腐殖化程度变化较大，表明以自生源为主。确定十里河水体中含有E_x/E_m位于255/420 nm类腐殖质（C1），2类色氨酸（C2、C3）和1类酪氨酸（C4），类色氨酸（C2、C3）分别在5月和6月微生物活跃。C4整体降解前后组分占比小，变化较小。十里河荧光指数（FI）差异较小、HIX均较低，生物指数（BIX）降解前后存在部分差异，主要还是以生物内源为主。

（4）雨水径流导致十里河水中COD，NH₃-N，TN和TP浓度增加。光学分析表明，初始雨水径流导致DOM在河水中的浓度增加，但DOM腐殖化程度变化不大，说明DOM主要以内源为主，初始雨水径流对其特性的影响不大。使用PARAFAC模型鉴定了DOM的三种腐殖质（类腐殖酸A、类富里酸A和类富里酸C）和两种蛋白质（类色氨酸T1和类色氨酸T2）组分。相关性分析表明，三种腐殖质样组分的来源是一致的，与蛋白质样组分C4的来源不同。水质参数（COD、NH₃-N）与组分C1~C5呈显著正相关，表明组分可以较好地反映水质的各项指标。

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Jiujiang City is one of the first pilot cities for the implementation of the Yangtze River protection strategy, and Chengdu is an important city within the Yangtze River basin, where economic development is accompanied by serious pollution of the water ecology and environment. In this study, the degradation coefficients of pollutants in some typical urban rivers in the Yangtze River basin (Chengdu section of the Tuo River basin and Shili River in Jiujiang City) were investigated by combining field monitoring and laboratory analysis and simulation, with COD, NH₃-N, TN and other pollutants as key indicators. The relationships between the influencing factors such as DO, T and degradation coefficients were explored. The content, fractions and spatial and temporal distribution characteristics of the sources of DOM in rivers were analysed UV- Vis and EEMs-PARAFAC, and the effect of initial stormwater runoff on DOM was explored and analysed. The main conclusions are as follows.

(1)At 3~5 and >7 mg/L, it was 0.17057 d^-1 and 0.40047 d^-1, respectively.  was 0.06623 d^-1, and 0.09012 d^-1, respectively.  was 0.04743 d^-1, and 0.10736 d^-1, respectively.  was 0.14049 d^-1, 0.15786 d^-1, and 0.19106 d^-1 at <2 mg/L, 3~5 and >7 mg/L, respectively. As DO concentration decreases, K decreases. At 15 °C, 20 °C and 25 °C,  was 0.10275 d^-1, 0.19558 d^-1, and 0.27228 d^-1, respectively.  was 0.13459 d^-1, 0.18837 d^-1, and 0.2496 d^-1, respectively.  was 0.15302 d^-1, 0.16978 d^-1, and 0.19297 d^-1, respectively. The K of pollutants tends to increase with increasing T. The DO concentration and T increase favor the degradation of pollutants.

（2）Through the transformation of the Ar-rhenius relationship, the empirical formulas between temperature and the values of COD, NH₃-N, TN, and TP degradation coefficients were determined, respectively. ; ; ； . In the on-site in situ experiment, the COD degradation coefficient values of the upper and midstream months were higher than those of the middle and lower sampling points, and the NH₃-N degradation coefficient values in May and June in the upper and lower reaches were higher than the degradation coefficient values in other months, and the performance of the downstream sampling points was more obvious; the TN degradation coefficient in the upstream June was higher, and the degradation coefficient value of the TN in June was higher in the upstream > the downstream of the middle >, and the opposite was true in TP. Correlation analysis between in situ monitoring degradation coefficient and environmental parameters showed that the redox potential and T were the main influencing factors of COD and NH3-N degradation, respectively.

（3）The variation range of DOC in the upper and lower waters of the Tuojiang River Basin was 2.90~11.48 mg/L, 2.83~6.91 mg/L, 0.23~4.93 mg/L, and 0.88~4.78 mg/L, respectively. The DOC concentration in the upper reaches of the Shili River changed in June from before degradation (3.59 mg/L) higher than after degradation (2.66 mg/L), and the DOC concentration in the middle reaches of the midstream before and after degradation in April was not much, and the degradation rate in May was lower than that before degradation (4.15 mg/L), and the DOC concentration in all downstream months was higher than before degradation. The reason may be that POC in the water body is converted to DOC, and the increased DOC content is higher than the amount of DOC reduced due to degradation, resulting in an increase in the DOC content after degradation. EEMs-PARAFAC analysis showed that the fluorescent components in the Chengdu section of the Tuojiang River Basin were divided into UVA -like humic substances (C1), tyrosine-like (C2), humic substances (C3) and tryptophan-like (C4). The protein C2 was the main component of the river DOM and was greatly affected by endogenous sources. The DOM source in a water body is influenced by both terrestrial and endogenous sources. The HIX of upper and lower water has little change and the degree of humification varies greatly, indicating that it is mainly autologous. It was determined that the water body of the Shili River contained Ex/Em at 255/420 nm humus (C1), class 2 tryptophan (C2, C3) and class 1 tyrosine (C4), and tryptophan (C2, C3) was active in May and June, respectively. The proportion of components before and after the overall degradation of C4 is small and the change is small. The difference in FI of the Shili River is small, the HIX is low, and there are some differences before and after the degradation of BIX, mainly based on biological endogenous sources.

（4）Stormwater runoff leads to increased concentrations of COD, NH₃-N, TN and TP in the Shili River. Optical analysis showed that the initial rainwater runoff led to an increase in the concentrations of DOM in the river water, but the degree of DOM humification did not change much, indicating that the DOM was mainly based on internal sources, and the initial rainwater runoff had little effect on its characteristics. Three humic substances (humic acid-like A, fulvic acid-like A and fulvic acid-like C) and two protein (tryptophan-like T1 and tryptophan-like T2) of the DOM were identified using the PARAFAC model. Correlation analysis showed that the sources of the three humic-like components were consistent, different from those of protein-like component C4. The water quality parameters (COD, NH₃-N) were significantly positively correlated with components C1~C5, indicating that the components could better reflect the various indicators of water quality.

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