Riverine Nutrients Export and its Biogeochemical Behavior in the Jiulong Estuary under Subtropical Storm Events

由于气候变化（极端暴雨事件增加）和人类活动干扰（人为氮磷输入增加），亚热带流域-近海生物地球化学过程与通量受到显著影响。本研究选取九龙江流域-河口系统作为整体研究对象，以九龙江河流-河口混合区作为重点研究对象，开展常态和暴雨事件河流-河口营养盐（氮、磷、硅）和悬浮颗粒物的综合观测，分析暴雨事件河流营养盐输出过程、通量及主要控制因素，探讨河口营养盐生地化行为对河流输入的响应关系。主要研究结论如下： （1）常态下九龙江两大干流（北溪、西溪）的营养盐氮磷时空分布受污染分布和类型、大坝滞留和水文条件的综合影响，溶解硅（DSi）的分布由地质背景和土地利用共同控制。含量与组分上，北溪输出更多的NO23-...Nutrient biogeochemical process and fluxes from watershed to coast in the subtropical region are likely to be significantly influenced by the dual effects of global climate change (more extreme storm events) and human perturbation (increased anthropogenic nutrient input). The Jiulong River-Estuary was selected as a system to carry out a multiple-survey along river to estuary during various storm e...学位：理学硕士院系专业：环境与生态学院_环境管理学号：3312012115162

大孔吸附树脂分离纯化龙胆药材中龙胆苦苷和马钱子苷酸的研究

目的:建立利用大孔吸附树脂对龙胆药材中龙胆苦苷和马钱子苷酸进行富集和分离纯化的方法。方法:采用加速溶剂萃取法对龙胆药材中两种有效成分进行高效提取,比较了D301,AB-8,D101,XDA-1四种大孔树脂对龙胆苦苷和马钱子苷酸的吸附性能,最终确定采用D301型大孔对脂对二者进行富集吸附,对其工艺参数进行优化,全程采用高效液相色谱进行目标化合物浓度检测。结果:化优后的工艺参数为:上样浓度:0.2 g/mL,最大上样量:0.25 g龙胆药材/g树脂,最佳静态吸附时间:8 h,采用8%和55%的乙醇溶液对龙胆苦苷和马钱子苷酸分别进行洗脱;龙胆苦苷和马钱子苷酸分别富集在8%和55%的乙醇洗脱液中,洗脱液浓缩后冷冻干燥,可得到纯度分别为74.3%和80.9%的粗产物,龙胆苦苷和马钱子苷酸的回收率分别为70.11%和67.82%。结论:此法效率较高,操作简便,即可用于实验室制备少量的难以购置的标准品,也可进行放大研究,用于工业生产。国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 共建生物医药研发测试中心(LS-05-KJZX-76)资

Linking Watershed Nutrient Loads and Riverine Export to Reservoir Eutrophication:The Case of Shanzai Reservoir, Fujian Province

建立流域氮磷输出、河流输送与入库通量的分析方法,以福建省山仔水库为例,基于gIS技术分析乡镇、子流域的氮磷污染分布和来源构成,识别关键源区并探讨库区水质与流域污染输出和河流输送之间的关联性。结果表明,2009年山仔流域单位面积总氮输出负荷为13.4 kg n·HM-2·A-1(生活污水和化肥流失占64%),总磷输出负荷为0.82 kg P·HM-2·A-1(畜禽养殖和生活污水占90%),入库氮、磷负荷分别为3248 T n·A-1和192 T P·A-1,其中河流输入占62%和89%,环库区面源污染贡献小于2%;不同乡镇单位面积氮输出负荷为3.54~20.0 kg n·HM-2,磷输出负荷为0.38~2.50 kg P·HM-2,其中日溪乡和霍口乡临近库区,化肥流失与畜禽养殖污染最重。上游乡镇污染较轻,但生活污水比重大(42%~84%)。皇帝洞溪子流域污染最重(19.4 kg n·HM-2;1.95 kg P·HM-2),其次是霍口溪中下游和日溪子流域。库区总氮高值出现在坝区和日溪湾汊,总磷高值在小沧至霍口溪七里入口之间,水质有明显分区,与流域污染分布、河流输送和库区沉积物的释放相关联,河流输入对库区富营养化起决定性作用。流域氮磷输出负荷比值平均为16,库区水中氮磷比值在15~20之间,意味着该生态系统处于磷的弱限制,水华爆发风险较大,建议采取“分区整治流域污染、氮磷联合削减、畜禽养殖和磷肥流失优先控制“的富营养化防控策略。A quantitative analysis of watershed nitrogen(N)and phosphorus(P)loads,riverine export and other inputs to reservoir was conducted for Shanzai reservoir in Fujian Province.Spatial variation of N and P pollution and major components were interpreted at town and sub-watershed scale using GIS techniques,and the critical source area(CSA)was indentified.The linkage between reservoir water quality and watershed nutrients loading and riverine export fluxes was examined.Results revealed that total N and P loads per unit area of the Shan zai watershed were 13.4 kg N·hm-2·a-1and 0.82 kg P·hm-2·a-1,respectively.Domestic sewage and fertilizer runoff accounted for 64% of total N load,and livestock waste and domestic sewage shared 90% of total P load.Total N and P loads to the Shanzai reservoir were 3248 t N·a-1 and 192 t P·a-1,62% and 89% of which were through riverine transport and the remainder mostly from sediment release.Less than 2% of in puts were from non-point sources in the surrounding area.Town-level N and P loads per unit area ranged from 3.54~20.0 kg N·hm-2and 0.38~2.50 kg P·hm-2,respectively.Two towns(Rixi and Huokou) adjacent to the reservoir were identified as CSA of fertilizer runoff and livestock waste,while human sewage dominated the nutrient load(42%~84% of total)in other towns in the upstream area.Huangdidong subwatershed was the most polluted catchment(19.4 kg N·hm-2;1.95 kg P·hm-2),followed by the lower reaches of Huokou River and Rixi subwatershed.The high value of total N concentration was observed near the dam head and Rixi inlet,whereas high total P concentration was found in channel from Huokuo inlet to Xiaocang.The spatial variation of the nutrients level in the reservoir was highly associated with watershed nutrient loads,riverine export and sediment-water exchange,indicating that riverine input is the decisive factor contributing to eutrophication of the reservoir.The average N∶P ratio of the nutrient load was calculated as 16 for the whole watershed,which combined with the TN∶ TP ratio of 15~20 observed in reservoir surface water suggested that the reservoir ecosystem was weakly limited by P and tended to stimulate algal bloom.To mitigate eutrophication,reduction of both N and P pollution should be considered in those CSAs,with a priority given to P pollution from livestock and phosphate fertilizer loss.公益类科研院所专项(2011R1004-2); 中央高校基本科研业务费专项(厦门大学基础创新科研基金项目)(2012121053

Sediment-water Flux and Processes of Nutrients and Gaseous Nitrogen Release in a China River Reservoir

以九龙江北溪西陂电站库区为例,于2013年不同季节开展原状泥柱静态培养、气态氮水柱剖面观测和通量模拟实验,结合水和沉积物理化参数和微生物参数,研究河流库区沉积物-水界面营养盐及气态氮的释放过程和通量.结果表明,库区沉积物nH+4和PO3-4总体表现为释放行为[平均nH+4通量(480±675)Mg·(M2·d)-1,平均PO3-4通量(4.56±0.54)Mg·(M2·d)-1],而nO-3和nO-2表现为吸附行为.洪水季节带来大量的有机质沉积在库区,造成枯水期沉积物无机氮磷向上覆水体释放.湖泊区气态氮释放以n2为主(>98%),沉积物-水界面n2释放通量平均为(15.8±12.5)Mg·(M2·d)-1.水柱n2净增量有明显的空间差异和垂向分布规律,受沉积物-水界面生地化过程(反硝化和厌氧氨氧化作用)和流动水团的综合影响.下游站位存在较强的硝化作用,n2O相对富集,主要受水中氨氮占无机氮的比例控制.The key processes and fluxes of nutrients( N and P) and gaseous N( N2 and N2O) across the sediment-water interface in a river reservoir( Xipi) of the Jiulong River watershed in southeast China were studied.Intact core sediment incubation of nutrients exchange,in-situ observation and lab incubation of excess dissolved N2 and N2O( products of nitrification,denitrification and Anammox),and determination of physiochemical and microbe parameters were carried out in 2013 for three representative sites along the lacustrine zone of the reservoir.Results showed that ammonium and phosphate were generally released from sediment to overlying water [with averaged fluxes of N( 479.8 ± 675.4) mg·( m2·d)- 1and P( 4.56 ± 0.54) mg·( m2·d)- 1],while nitrate and nitrite diffused into the sediment.Flood events in the wet season could introduce a large amount of particulate organic matter that would be trapped by the dam reservoir,resulting in the high release fluxes of ammonium and phosphate observed in the following low-flow season.No clear spatial variation of sediment nutrient release was found in the lacustrine zone of the reservoir.Gaseous N release was dominated by excess dissolved N2( 98% of total),and the N2 flux from sediment was( 15.8 ± 12.5) mg·( m2·d)- 1.There was a longitudinal and vertical variation of excess dissolved N2,reflecting the combined results of denitrification and Anammox occurring in anoxic sediment and fluvial transport.Nitrification mainly occurred in the lower lacustrine zone,and the enrichment of N2 O was likely regulated by the ratio of ammonium to DIN in water.国家自然科学基金项目(41076042;41376082); 中央高校基本科研业务费专项(2012121053); 中国科学院城市环境与健康重点实验室(城市环境研究所)开放基金项目(KLUEH201008

Content of gentiopicroside and loganic acid in Radix gentianae and their fingerprints

To develop a HPLC-DAD-ESI-TOF/MS analysis method for the determination of gentiopicroside and loganic acid in Radix gentianae samples and for the research of their fingerprints.The samples were extracted using ASE for 10 min under 100 ℃ and 9.65 MPa,and divided into water phase and chloroform phase and analyzed them with HPLC-DAD-ESI-TOF/MS method respectively.Based on this method,the HPLC fingerprints of Radix gentianae were established.Comparing the spectrogram and mass spectrum of the chromatogram peak with the reference value,three compounds in water phase were identified as gentiopicroside,asafetida acid and loganic acid.There is no report of the compounds in chloroform phase.The content of gentiopicroside and loganic acid in samples of different groups were determined,separately.The fingerprints were compared by the software of the similarity evaluation system for chromatographic fingerprint.The water phase fingerprint congruence coefficients of samples from six different areas were above 0.90,however,the chloroform phase fingerprint congruence coefficients were within 0.62-0.99.This method can be used for determination of potent component in Radix gentianae and its quality control.Radix gentianae from different producing areas have the largest diversities,and the diversities embodied in the content of chloroform phase compounds.青岛“2004将才计划”(04-3-JJ-11);; 国家海洋局青年基金资助项目(2005602);; 崂山区政府区校共建生物医药研发测试中心资助(LS-05-KJZX-76)

Determination of Gentiopicroside and Loganic Acid in Radix Gentianae by MEKC and MEEKC Mode

目的建立胶束电动毛细管色谱(MEKC)和微乳液毛细管电动色谱(MEEKC)分析龙胆药材中龙胆苦苷和马钱子苷酸含量的方法。方法采用加速溶剂萃取法(ASE)对龙胆药材进行提取,萃取温度:100℃,压力:9.65MPa,萃取时间:10min。采用未涂层熔融石英毛细管(内径75μm,有效长度50cm)。分别考察了两种分离模式下电泳介质的构成和电泳过程中的各操作参数对样品分离过程的影响,优化了MEKC和MEEKC的分析条件,在各自对应的缓冲液体系下,MEKC和MEEKC分离电压分别为30和22kV,柱温均为25℃,检测波长均为238nm。结果在选定的工作条件下,龙胆苦苷和马钱子苷酸与其他组分达到了基线分离,两种成分的浓度与其响应信号值之间具有较好的线性相关性,加标回收率在96.3%～105.1%之间,检测限均低于10mg·L-1,对6处不同产地的龙胆药材进行了分析,并对测定结果进行了t检验,结果表明,两种模式下,测定结果之间不存在显著性差异,而不同产地的龙胆药材的龙胆苦苷和马钱子苷酸含量之间存在较大差异。结论本方法简便,准确,快速,重现性较好,可用于龙胆药材有效成分的含量测定和质量控制。OBJECTIVE To develop MEKC and MEEKC modes for the determination of gentiopicroside and loganic acid in extracts of Radix Gentianae. METHODS The analyte was extracted from Radix Gentianae samples by accelerated solvent extraction, and the extraction conditions were optimized. Separation and determination were carried out on a bared fused silica capillary(50 cm×75 μm) with corresponding buffer. The run voltage of MEKC and MEEKC were 30kV and 22 kV respectively. Detection wavelength of DAD was at 238 nm and column temperature was 25 ℃. RESULTS The developed ASE-HPCE method was simple and reliable for the determination of gentiopicroside and loganic acid in Radix Gentianae samples with a broad linear dynamic range, a recovery range of 96.3%～105.16%,and the detection limit was below 10 mg·L-1. The contents of gentiopicroside and loganic acid in six samples from different regions were determined by the developed method in two modes. T-test value indicated that the determined contents of gentiopicroside and loganic acid by MEKC and MEEKC were consistent. CONCLUSION The method is simple,accurate,rapid and with good reproducibility.It can be used to determine active components in Radix Gentianae.国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 崂山区校区共建生物医药研发测试中心资助(LS-05-KJZX-76