加拿大东部农田流域颗粒态磷的输出及藻类有效性研究
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摘要
农业非点源污染对水环境的恶化有着十分显著的贡献,农田流域内径流磷素流失与受纳淡水水体(湖泊、河流、水库、溪流等)的富营养化现象的发生有着密切的关系。在农田流域中,径流磷素以溶解态和颗粒态(或者泥沙结合态)两种形态损失,但以泥沙结合态为主。大部分溶解态磷可被藻类直接利用,泥沙携带的部分颗粒态磷则是淡水水体浮游生物长期的潜在可利用磷源。进入水体后,流域内的溪流沟渠系统是磷素的主要运移通道,磷素在溪流沟渠内的持留和释放将影响污染物向下游的迁移形态和输出的时空变化。本论文研究了加拿大东部典型农田流域融雪期内悬浮泥沙和磷素的输出情况及影响因子,以及无雪期内溪流或人工湿地内悬浮泥沙和底泥沉积物中磷素的富集、藻类有效性、释放潜能及主要影响因子。本论文的结果将有助于评估融雪期内流域尺度的土壤侵蚀和磷素流失风险、以及无雪期内溪流泥沙磷素的藻类有效性及其对受纳水体生态平衡的潜在影响,并制订相应的最佳养分管理措施,以减少农田生态系统中磷的输出。主要研究结果如下：
1.本实验基于水文条件(降雨、雪水当量、径流)、土壤冻融程度和流域出口水质监测数据分析了加拿大东部两农田流域(BHW和BBW)在2007-2009年雪融期内的土壤侵蚀及磷素流失情况和影响因子。结果表明在两个流域内均存在明显的融雪发生条件及土壤侵蚀和磷素流失的年间差异。在2007和2009年融雪期内,两农田流域内大约80%的表层土壤处于冰冻状态,而在2008年由于异常丰厚的积雪的保温作用,只有低于50%的表层土壤处于冰冻状态。在流域BHW内,2008年融雪过程中溪水悬浮泥沙(SS)、总磷(TP)、溶解态磷(DP)和泥沙结合态磷(PP)的中值含量均明显高于其他两个年份的观测数据；溶解态磷和泥沙结合态磷的比值因径流事件变异极其显著,但是其中值接近1表明总体上溶解态磷和泥沙结合态磷的流失量相当。在流域BBW内,2008年融雪过程中溪水溶解态活性磷(DRP)也明显高于2009年的观测数据,泥沙结合态磷则是磷素的主要流失形态。本研究还表明融雪期间悬浮泥沙和磷素流失的年间变化是积雪厚度、土壤冻融程度和降雨情况综合作用的结果；最严重的土壤侵蚀和泥沙结合态磷的流失主要与发生在冻土上的降雨事件有关。基于径流和水体磷的监测数据,我们估计在BHW内有大约20%的年度总磷流失发生在融雪期,在BBW内有大约12%的年度溶解态活性磷流失发生在融雪期。因此,我们建议在这两个流域内采取相应的最佳养分管理措施以减少融雪期土壤侵蚀和磷素输出。
2.本实验比较了两农田小流域——处理流域(Intervention)和对照流域(Control)出口处、以及处理流域内部两支流(Br14和Br15)底泥沉积物和悬浮泥沙及中磷素的富集、富集、藻类有效性、释放潜能并探讨了主要影响因子。研究表明,在底泥沉积物中,1)总磷(TP)和藻类有效态磷(AAP)在两个小流域出口处含量相当,但在Br15中的含量显著高于另一支流Br14中的含量；总的说来,藻类有效态磷占总磷的大约10%。2)在所有采样点,弱吸附态磷(P1)不足总磷的1%,而多于60%的总磷以钙结合态磷(P4)存在。对照流域出口处底泥沉积物中弱吸附态磷(P1)、可还原态磷(P2i)和非活性有机磷(P5)含量显著高于处理流域出口处的观测数据,而铝铁结合态的有机磷(P3o)则相反；Br15底泥沉积物中弱吸附态磷(P1)、可还原态磷(P2i)、有机磷(P2o)和钙结合态磷(P4)含量显著高于Brl4的观测数据。3)对照流域出口处底泥沉积物中磷饱和指数高于环境阈值15%并且显著高于其在处理流域出口处的对应值,表明在对照流域出口处底泥沉积物更倾向于向水体释放磷,而在处理流域出口处底泥沉积物要持留水体中的磷。悬浮泥沙中磷素分析结果表明,1)总磷(TP)和藻类有效态磷(AAP)在两个流域出口处所收集悬浮泥沙中的含量相当,但在Br15中的含量显著高于另一支流Br14中的含量；藻类有效态磷占悬浮泥沙总磷的大约10-30%。2)对照流域出口处悬浮泥沙所含弱吸附态磷(P1)、可还原态磷(P2i)、有机磷(P2o)含量显著高于其在处理流域的对应值；除了这三种形态的磷,Br15还有显著高于Br14的铝铁结合态有机磷(P3o)。3)在所有采样点,大多数磷饱和指数远低于环境阈值15%,表明在大多数条件下悬浮泥沙主要持留水体中的磷而不是向水体释放磷。值得注意的是,虽然Br15中悬浮泥沙还有底泥沉积物仍具有很高的持续持留水体磷的能力,但是Br15中两种泥沙的总磷和藻类有效态磷甚至高于对照流域的对应含量,表明现有的在处理流域实施的最佳养分管理措施还存在不足,尤其是在Br15的流经区域内存在很高的土壤侵蚀和磷素流失风险。因此今后的管理措施应该重点加强Br15流经区域农田的磷素管理。此外,本研究表明泥沙性状(有机质含量,交换态铝和交换态钙)和土壤发生分类解释了大多数或者部分的泥沙磷素特征的空间变异。本实验还初步探讨了氧化还原状况对Br14和Br15底泥沉积物磷的释放的影响,发现处于缺氧状况下的地下水补给并未导致Br14底泥沉积物中可还原态磷释放至水体中,一方面可能因为Br14中底泥沉积物可还原态磷含量很低,另一方面也可能因为水沙界面的氧化层持留了向上迁移的自由磷离子。
3.本实验研究了农田流域-河流交界之处三个人工湿地(B1,B2和B3)底泥沉积物磷素的富集、富集、藻类有效性、释放潜能及其主要影响因子。三个人工湿地底泥沉积物中总磷(TP)含量没有显著的差异,但是藻类有效态磷(AAP)在B1和B2中显著高于在B3中的观测值。藻类有效态磷(AAP)占了总磷的9-20%,表明底泥沉积物中有很大一部分磷可以作为藻类可利用的磷源。相对比较稳定的钙磷(P4)最主要的磷的赋存形态。磷饱和指数均低于5%,进一步说明这些人工湿地的底泥沉积物主要在持留水体中的磷,而不是向水体中释放。但这只是一个短期效应,随着接纳的农业径流的增多以及底泥沉积物磷素吸附位点被充满,这些人工湿地除磷的功效将大大降低。此外,本研究还表明有机物是所研究人工湿地底泥沉积物中藻类有效态磷的重要控制因子。
Phosphorus (P) inputs from agricultural sources have been identified as the primary contributor to eutrophication of fresh waters. Sediment associated P is the dominant form of P lost from agricultural lands. This thesis involved three projects being undertaking in three typical agricultural catchments in Eastern Canada and investigated the sediment and P losses during the snowmelt period, and the sediment P storage, algal availability, release potential and possible controlling factors during snow/ice free periods in streams and constructed wet ponds. This knowledge would help us assess the magnitude of soil erosion and P loss at catchment scale and develop beneficial management practices (BMPs) to conserve soil fertility and to reduce water contamination risk during snowmelt period. A further look into the sediment P characteristics in receiving waters during snow free period will help us better understand the fate of sediment P and their role in contributing to the aquatic ecology. The main conclusions are as following:
1. Using two agricultural catchments in Eastern Canada, the suspended solids (SS) and P losses during the snowmelt period was quantified to investigate how snowmelt contributes SS and P loss. Water samples were collected from the outlets of the Bras d'Henri Catchment (BHW,2007-2009) and Black Brook Catchment (BBW,2008-2009) and measured for SS and P concentrations. Hydrological parameters (precipitation, snow water equivalent, and runoff discharge), soil frozen status and soil temperature were also measured. Results revealed inter-annual variation of snowmelt conditions and SS and P losses in each catchment. The 2008 snowmelt in BHW and BBW mainly occurred on unfrozen soils, while the 2007 and 2009 snowmelts in BHW and 2009 snowmelt in BBW mainly on frozen soils. In BHW,2008 snowmelt caused much higher median concentrations of SS, total P (TP), dissolved P (DP) and particulate P (PP) in steam water than 2007 and 2009; ratios of PP fractions in TP were variable with events but the median values were similar, suggesting both DP and PP important contrubutor to TP loss. In BBW, the median concentration of dissolved reactive phosphorus (DRP) in stream water was greater in 2008 snowmelt than in 2009 snowmelt; PP dominated TP loss. This study also suggests that soil state (i.e. frozen status) and rainfall were the most important factors influencing SS and P losses during snowmelt. Furthermore, snowmelt P export represented more than 20% of the total annual P export in BHW, and more than 12% of the annual DRP export in BBW. Thus, we strongly recommend adopting Best Management Practices (BMPs) that specifically target sediment and P loss during snowmelt.
2. Suspended and streambed sediments were collected from four sites (the outlets of the intervention and control catchments in Bras d'Henri River Catchment, and two branches within the intervention catchment) and from June 2008 to December 2009 and November 2007 to November 2009 respectively. The objective of this study is to assess the role of stream sediments in controlling stream water P by investigating the sediment P storage, algal availability and possible affecting factors. Streambed sediment analysis showed that: (1) the average concentration of TP and AAP (0.1M NaOH extractable P) in Streambed sediments were comparable in intervention and control outlets, but were significantly higher in Brl5 than in Brl4; AAP accounted for approximately 10% of the sediment TP. (2) In all the four sites, the immediately available P (P1) represented less than 1% of the TP in streambed sediments, while more than 60% of the TP presented in the form bound to carbonate and apatite-P (P4). Intervention and control outlets exhibited distinctive concentration differences in P forms—P1, P2i (redox-sensitive P), P3o (P in microorganisms) and P5 (organic and refractory P), with P1, P2i and P5 greater in the control outlet than in the intervention outlet, but in the opposite for P3o. Br15 had significantly greater amounts of P1, P2i, P2o, P3o and P4 in streambed sediments than Br14 did. (3) P saturation index (PSI) were more than 15% and significantly greater in control outlet than in the sites within the intervention catchment (the outlet, Brl4 and Br15), indicating that streambed sediments in control outlet likely acted as a source of stream water P while those in intervention catchment mainly as a sink. P analysis in suspended sediments showed that:(1) TP and AAP in suspended sediments were also comparable between intervention and control outlets, but was significantly higher in Br15 than in Brl4. AAP accounted for 10-30% of the sediment TP. (2) P1, P2i and P2o in intervention suspended sediments were significantly lower than in the control outlet. Br15 had significantly greater amounts of P1, P2i, P2o and P3o than Branch 14 did. (3) PSI values suggested in most of the occasions suspended sediments from all the sites likely acted as a sink of stream water P. Despite of mainly acting as a P sink, the streambed and suspended sediments in Br15 had even greater amounts of TP and AAP than those in the control catchment. This highlighted the high risk of P loss in Br15 draining area and thus BMPs targeting this loss should be implemented in this area in the future.
Sediment properties (OM, M3A1 and M3Ca) and the pedology of source soils mainly or partly explained the spatial variations in sediment P characteristics. Redox potential in the sediment-water interface was presumed to be an important factor influencing sediment P characteristics because of groundwater recharge, but pipe and seepage meter experiments in Br14 and Br15 during the base flow period indicated a minor contribution of sediment reducible P release to stream water P in Br14 where anoxic ground water recharge occurred. This was due partly to the low reduction of P-containing Fe/Mn compounds under anaerobic conditions and partly to the poor hydrological connectivity at the sediment-water interface.
3. Bottom sediments were regularly taken from three constructed wet ponds to investigate P storage, algal availability and release potential in order to provide information for evaluating the wet ponds'function as a nutrients remover. The sediment TP concentrations hadn't varied significantly among the ponds, while the algal available fractions (AAP and M3P) were significantly greater in ponds B1 and B2 than in pond B3. The relative contribution of AAP to TP varied from 9% to 20% indicating that a considerable part of the TP could be algal available. The majority of sediment P was closely associated with carbonate and apatite (P4) which was relatively stable, while P1 and P2o accounted for the least parts. The maximum PSI values being less than 5% further implied that the three ponds sediments potentially act as a P sink rather than a source in the short-term. In the long term, as long as there is the incoming agricultural runoff, the bottom sediments eventually may play a limited role in removing P from water column due to P sorption sites saturation. This study also indicated the importance of organic matter in controlling the algal availability of sediment P in studied wet ponds.
1.本实验基于水文条件(降雨、雪水当量、径流)、土壤冻融程度和流域出口水质监测数据分析了加拿大东部两农田流域(BHW和BBW)在2007-2009年雪融期内的土壤侵蚀及磷素流失情况和影响因子。结果表明在两个流域内均存在明显的融雪发生条件及土壤侵蚀和磷素流失的年间差异。在2007和2009年融雪期内,两农田流域内大约80%的表层土壤处于冰冻状态,而在2008年由于异常丰厚的积雪的保温作用,只有低于50%的表层土壤处于冰冻状态。在流域BHW内,2008年融雪过程中溪水悬浮泥沙(SS)、总磷(TP)、溶解态磷(DP)和泥沙结合态磷(PP)的中值含量均明显高于其他两个年份的观测数据；溶解态磷和泥沙结合态磷的比值因径流事件变异极其显著,但是其中值接近1表明总体上溶解态磷和泥沙结合态磷的流失量相当。在流域BBW内,2008年融雪过程中溪水溶解态活性磷(DRP)也明显高于2009年的观测数据,泥沙结合态磷则是磷素的主要流失形态。本研究还表明融雪期间悬浮泥沙和磷素流失的年间变化是积雪厚度、土壤冻融程度和降雨情况综合作用的结果；最严重的土壤侵蚀和泥沙结合态磷的流失主要与发生在冻土上的降雨事件有关。基于径流和水体磷的监测数据,我们估计在BHW内有大约20%的年度总磷流失发生在融雪期,在BBW内有大约12%的年度溶解态活性磷流失发生在融雪期。因此,我们建议在这两个流域内采取相应的最佳养分管理措施以减少融雪期土壤侵蚀和磷素输出。
2.本实验比较了两农田小流域——处理流域(Intervention)和对照流域(Control)出口处、以及处理流域内部两支流(Br14和Br15)底泥沉积物和悬浮泥沙及中磷素的富集、富集、藻类有效性、释放潜能并探讨了主要影响因子。研究表明,在底泥沉积物中,1)总磷(TP)和藻类有效态磷(AAP)在两个小流域出口处含量相当,但在Br15中的含量显著高于另一支流Br14中的含量；总的说来,藻类有效态磷占总磷的大约10%。2)在所有采样点,弱吸附态磷(P1)不足总磷的1%,而多于60%的总磷以钙结合态磷(P4)存在。对照流域出口处底泥沉积物中弱吸附态磷(P1)、可还原态磷(P2i)和非活性有机磷(P5)含量显著高于处理流域出口处的观测数据,而铝铁结合态的有机磷(P3o)则相反；Br15底泥沉积物中弱吸附态磷(P1)、可还原态磷(P2i)、有机磷(P2o)和钙结合态磷(P4)含量显著高于Brl4的观测数据。3)对照流域出口处底泥沉积物中磷饱和指数高于环境阈值15%并且显著高于其在处理流域出口处的对应值,表明在对照流域出口处底泥沉积物更倾向于向水体释放磷,而在处理流域出口处底泥沉积物要持留水体中的磷。悬浮泥沙中磷素分析结果表明,1)总磷(TP)和藻类有效态磷(AAP)在两个流域出口处所收集悬浮泥沙中的含量相当,但在Br15中的含量显著高于另一支流Br14中的含量；藻类有效态磷占悬浮泥沙总磷的大约10-30%。2)对照流域出口处悬浮泥沙所含弱吸附态磷(P1)、可还原态磷(P2i)、有机磷(P2o)含量显著高于其在处理流域的对应值；除了这三种形态的磷,Br15还有显著高于Br14的铝铁结合态有机磷(P3o)。3)在所有采样点,大多数磷饱和指数远低于环境阈值15%,表明在大多数条件下悬浮泥沙主要持留水体中的磷而不是向水体释放磷。值得注意的是,虽然Br15中悬浮泥沙还有底泥沉积物仍具有很高的持续持留水体磷的能力,但是Br15中两种泥沙的总磷和藻类有效态磷甚至高于对照流域的对应含量,表明现有的在处理流域实施的最佳养分管理措施还存在不足,尤其是在Br15的流经区域内存在很高的土壤侵蚀和磷素流失风险。因此今后的管理措施应该重点加强Br15流经区域农田的磷素管理。此外,本研究表明泥沙性状(有机质含量,交换态铝和交换态钙)和土壤发生分类解释了大多数或者部分的泥沙磷素特征的空间变异。本实验还初步探讨了氧化还原状况对Br14和Br15底泥沉积物磷的释放的影响,发现处于缺氧状况下的地下水补给并未导致Br14底泥沉积物中可还原态磷释放至水体中,一方面可能因为Br14中底泥沉积物可还原态磷含量很低,另一方面也可能因为水沙界面的氧化层持留了向上迁移的自由磷离子。
3.本实验研究了农田流域-河流交界之处三个人工湿地(B1,B2和B3)底泥沉积物磷素的富集、富集、藻类有效性、释放潜能及其主要影响因子。三个人工湿地底泥沉积物中总磷(TP)含量没有显著的差异,但是藻类有效态磷(AAP)在B1和B2中显著高于在B3中的观测值。藻类有效态磷(AAP)占了总磷的9-20%,表明底泥沉积物中有很大一部分磷可以作为藻类可利用的磷源。相对比较稳定的钙磷(P4)最主要的磷的赋存形态。磷饱和指数均低于5%,进一步说明这些人工湿地的底泥沉积物主要在持留水体中的磷,而不是向水体中释放。但这只是一个短期效应,随着接纳的农业径流的增多以及底泥沉积物磷素吸附位点被充满,这些人工湿地除磷的功效将大大降低。此外,本研究还表明有机物是所研究人工湿地底泥沉积物中藻类有效态磷的重要控制因子。
Phosphorus (P) inputs from agricultural sources have been identified as the primary contributor to eutrophication of fresh waters. Sediment associated P is the dominant form of P lost from agricultural lands. This thesis involved three projects being undertaking in three typical agricultural catchments in Eastern Canada and investigated the sediment and P losses during the snowmelt period, and the sediment P storage, algal availability, release potential and possible controlling factors during snow/ice free periods in streams and constructed wet ponds. This knowledge would help us assess the magnitude of soil erosion and P loss at catchment scale and develop beneficial management practices (BMPs) to conserve soil fertility and to reduce water contamination risk during snowmelt period. A further look into the sediment P characteristics in receiving waters during snow free period will help us better understand the fate of sediment P and their role in contributing to the aquatic ecology. The main conclusions are as following:
1. Using two agricultural catchments in Eastern Canada, the suspended solids (SS) and P losses during the snowmelt period was quantified to investigate how snowmelt contributes SS and P loss. Water samples were collected from the outlets of the Bras d'Henri Catchment (BHW,2007-2009) and Black Brook Catchment (BBW,2008-2009) and measured for SS and P concentrations. Hydrological parameters (precipitation, snow water equivalent, and runoff discharge), soil frozen status and soil temperature were also measured. Results revealed inter-annual variation of snowmelt conditions and SS and P losses in each catchment. The 2008 snowmelt in BHW and BBW mainly occurred on unfrozen soils, while the 2007 and 2009 snowmelts in BHW and 2009 snowmelt in BBW mainly on frozen soils. In BHW,2008 snowmelt caused much higher median concentrations of SS, total P (TP), dissolved P (DP) and particulate P (PP) in steam water than 2007 and 2009; ratios of PP fractions in TP were variable with events but the median values were similar, suggesting both DP and PP important contrubutor to TP loss. In BBW, the median concentration of dissolved reactive phosphorus (DRP) in stream water was greater in 2008 snowmelt than in 2009 snowmelt; PP dominated TP loss. This study also suggests that soil state (i.e. frozen status) and rainfall were the most important factors influencing SS and P losses during snowmelt. Furthermore, snowmelt P export represented more than 20% of the total annual P export in BHW, and more than 12% of the annual DRP export in BBW. Thus, we strongly recommend adopting Best Management Practices (BMPs) that specifically target sediment and P loss during snowmelt.
2. Suspended and streambed sediments were collected from four sites (the outlets of the intervention and control catchments in Bras d'Henri River Catchment, and two branches within the intervention catchment) and from June 2008 to December 2009 and November 2007 to November 2009 respectively. The objective of this study is to assess the role of stream sediments in controlling stream water P by investigating the sediment P storage, algal availability and possible affecting factors. Streambed sediment analysis showed that: (1) the average concentration of TP and AAP (0.1M NaOH extractable P) in Streambed sediments were comparable in intervention and control outlets, but were significantly higher in Brl5 than in Brl4; AAP accounted for approximately 10% of the sediment TP. (2) In all the four sites, the immediately available P (P1) represented less than 1% of the TP in streambed sediments, while more than 60% of the TP presented in the form bound to carbonate and apatite-P (P4). Intervention and control outlets exhibited distinctive concentration differences in P forms—P1, P2i (redox-sensitive P), P3o (P in microorganisms) and P5 (organic and refractory P), with P1, P2i and P5 greater in the control outlet than in the intervention outlet, but in the opposite for P3o. Br15 had significantly greater amounts of P1, P2i, P2o, P3o and P4 in streambed sediments than Br14 did. (3) P saturation index (PSI) were more than 15% and significantly greater in control outlet than in the sites within the intervention catchment (the outlet, Brl4 and Br15), indicating that streambed sediments in control outlet likely acted as a source of stream water P while those in intervention catchment mainly as a sink. P analysis in suspended sediments showed that:(1) TP and AAP in suspended sediments were also comparable between intervention and control outlets, but was significantly higher in Br15 than in Brl4. AAP accounted for 10-30% of the sediment TP. (2) P1, P2i and P2o in intervention suspended sediments were significantly lower than in the control outlet. Br15 had significantly greater amounts of P1, P2i, P2o and P3o than Branch 14 did. (3) PSI values suggested in most of the occasions suspended sediments from all the sites likely acted as a sink of stream water P. Despite of mainly acting as a P sink, the streambed and suspended sediments in Br15 had even greater amounts of TP and AAP than those in the control catchment. This highlighted the high risk of P loss in Br15 draining area and thus BMPs targeting this loss should be implemented in this area in the future.
Sediment properties (OM, M3A1 and M3Ca) and the pedology of source soils mainly or partly explained the spatial variations in sediment P characteristics. Redox potential in the sediment-water interface was presumed to be an important factor influencing sediment P characteristics because of groundwater recharge, but pipe and seepage meter experiments in Br14 and Br15 during the base flow period indicated a minor contribution of sediment reducible P release to stream water P in Br14 where anoxic ground water recharge occurred. This was due partly to the low reduction of P-containing Fe/Mn compounds under anaerobic conditions and partly to the poor hydrological connectivity at the sediment-water interface.
3. Bottom sediments were regularly taken from three constructed wet ponds to investigate P storage, algal availability and release potential in order to provide information for evaluating the wet ponds'function as a nutrients remover. The sediment TP concentrations hadn't varied significantly among the ponds, while the algal available fractions (AAP and M3P) were significantly greater in ponds B1 and B2 than in pond B3. The relative contribution of AAP to TP varied from 9% to 20% indicating that a considerable part of the TP could be algal available. The majority of sediment P was closely associated with carbonate and apatite (P4) which was relatively stable, while P1 and P2o accounted for the least parts. The maximum PSI values being less than 5% further implied that the three ponds sediments potentially act as a P sink rather than a source in the short-term. In the long term, as long as there is the incoming agricultural runoff, the bottom sediments eventually may play a limited role in removing P from water column due to P sorption sites saturation. This study also indicated the importance of organic matter in controlling the algal availability of sediment P in studied wet ponds.
引文
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