HNO_3在气相及SiO_2表面的紫外光解反应

利用紫外及红外吸收光谱等分析手段对365 nm光照下HNO3在气相与SiO2表面的光解反应进行了研究.考察了HNO3浓度、光照时间、相对湿度等条件对反应的影响.结果表明:随着HNO3浓度及光照时间的增加,光解产生的NO2和NO浓度均呈指数增加;无水汽情况下,400 Pa的HNO3光解45 min后,产生NO2及NO浓度比气相光解产生的分别高约3及1.7倍.HNO3光解产生的HONO的浓度随相对湿度的增加而呈线性增加,在SiO2颗粒物表面光解产生的NO2浓度随着相对湿度的增加而减少,而NO浓度则随之增大.400 Pa的HNO3光照45 min后,SiO2表面光解产生的HONO浓度是气相光解的3倍、SiO2表面暗反应的约30倍.     

黄壤表面电场作用下Cu~(2+)与Zn~(2+)的吸附/解吸动力学研究

利用静态恒流法研究了黄壤表面电场作用下Cu2+与Zn2+的吸附/解吸动力学.结果发现:考虑黄壤表面电场作用下,Cu2+和Zn2+的吸附实验呈现初期强吸附作用下的零级动力学过程和一定时间之后弱吸附作用下的一级动力学过程,与理论预期一致;在Cu2+和Zn2+的解吸实验中,只有前期出现了弱吸附作用下的一级动力学过程,实验结果与理论预期存在差别,原因在于专性吸附的Cu2+、Zn2+很难被解吸下来;在交换/吸附实验中,Cu2+的吸附速率值和平衡吸附量均大于Zn2+,且Cu2+-K+体系的表面电化学参数φ0、σ0、E0均大于Zn2+-K+体系中的对应值,证明了黄壤颗粒表面对Cu2+的吸附作用强于Zn2+;在交换/解吸实验中,Zn2+的解吸速率值和平衡解吸量均大于Cu2+,Zn2+-K+体系的表面电化学参数φ0、σ0、E0均大于Cu2+-K+体系中的对应值,证明Zn2+-K+体系中Zn2+的解吸作用比Cu2+-K+体系中的Cu2+解吸作用强.     

钱塘江(杭州段)水中有机氯农药残留污染特征及健康风险评价

利用气相色谱法对采集于2013年5月、7月和11月的钱塘江(杭州段)表层水中10种有机氯农药(OCPs)残留进行了分析,初步明确其组成特征及来源,并对其健康风险进行了评价.结果表明,钱塘江(杭州段)水体中检出5种微量的OCPs,检出频率最高的是β-HCH和δ-HCH.14个采样点均有不同浓度检出,钱塘江干流∑OCPs的浓度范围在1.31~6.68 ng·L-1,属低污染水平,3条主要支流∑OCPs的浓度范围则是1.32~4.23 ng·L-1.钱塘江(杭州段)水体中OCPs污染空间分布各异,上游兰江点位及桐庐县、富阳市境内各点位总体浓度相对较高.通过特征组分比例可确认HCHs污染主要源于农田中使用有机氯类农药的降解残留及新的林丹污染输入,且非固定污染源输入.利用EPA推荐方法对通过饮水和皮肤接触途径摄入钱塘江水体中OCPs的健康风险进行评价:非致癌健康风险指数介于8.56×10-5~1.82×10-3,根据评价标准均未超标;致癌健康风险指数在3.96×10-8~1.93×10-7,均位于可忽略风险范围内.结果表明钱塘江(杭州段)作为饮用水水源,其水体中OCPs残留引起对人体产生的致癌、非致癌健康危害可忽略.     

人工湿地常用生物陶粒基质LDHs覆膜改性及其除磷效果研究

分别利用3种二价金属化合物和3种三价金属化合物,采用水热共沉淀法在碱性条件下对人工湿地中常用的生物陶粒基质进行层状双金属氢氧化物(LDHs)覆膜改性,并将9种不同类型的LDHs覆膜改性生物陶粒基质和普通生物陶粒基质分别填充于10个垂直流人工湿地模拟实验柱中,进行除磷净化实验.结果表明,9种不同类型的改性生物陶粒基质均能有效提高磷素的净化效果;Zn系LDHs改性生物陶粒对总磷、溶解性总磷、磷酸盐均有很好的处理效果,其中Zn Fe-LDHs、Zn Co-LDHs和Zn Al-LDHs对总磷的平均去除率均在92%以上,对溶解性总磷和磷酸盐的平均去除率均超过95%;其对磷素的净化机理主要集中于物理化学作用,同时还应与其对微生物生长的促进作用有关.     

基于水域面积法的山区河流水电站下游生态流量定值研究

水电站的大量兴建导致下游河道萎缩退化甚至断流,如何改变水电站运行调度方式,维持下游河道一定的生态流量、保障河流健康成为国内外普遍关注的问题.本文在传统水文学方法的基础上融入生物栖息地法思想,以河流生态系统的生物多样性为功能目标,用河道流量反映河流的水文过程,河道水域面积反映河流生态系统的生物多样性,创新性地提出考虑河道水文生态特性的生态流量定值方法——水域面积法.以北江上游浈江二级支流罗坝水为例进行分析计算.计算结果表明:枯水年罗坝水生态流量为2.26 m3·s-1,占多年平均流量的25.97%;平水年生态流量分月控制,生态流量过程与建站前流量过程基本一致.根据枯水年的生态流量值和平水年各月份的生态流量值,结合水电站的运行调度规则,换算成一定时期内的径流量来确定该时期内水电站需释放的水量,进而对水电站下游河道的生态功能进行保护和修复.     

微波诱导热解法制备落叶吸附剂及其工艺优化

采用微波诱导热解法制备低成本落叶吸附剂,以实现落叶的资源化利用.以碘吸附值为响应值,采用响应面分析法研究了微波诱导热解法制备落叶吸附剂的工艺条件.结果表明,热解时间与微波功率之间存在交互作用,当热解功率增加时,可适当缩短热解时间.落叶吸附剂的最佳制备工艺条件为:热解时间4.04 min,微波功率488.72W,氯化锌质量分数27％.落叶吸附剂以微孔吸附为主,BJH孔径分布较窄,孔容最高峰对应的孔径在1.9 nm左右,Langmuir比表面积为769.61 m2/g.     

地表载荷对硬岩区埋地管道应力应变影响分析

为研究地表载荷对硬岩区埋地管道力学性能的影响,建立了管-土耦合三维数值模型,分析了地表载荷大小、作用面积、管道压力、管道径厚比及回填土弹性模量对管道应力分布、塑性应变、椭圆度的影响。结果表明:地表压载作用下,高应力区首先出现在管道顶部且呈椭圆形;随着地表载荷及其作用面积的增大,管道高应力区逐渐扩大,管道截面左右两侧也出现应力集中;随着回填土弹性模量、管道壁厚及内压的增加,管道顶部高应力区及最大等效应力均减小。塑性应变首先出现在管顶,且塑性区随地表载荷、载荷作用长度增加而增大,随回填土体弹性模量及管道壁厚增大而逐渐减小;当内压为0~4MPa时,管道塑性应变及塑性区随内压的增大而减小。管道椭圆度随回填土体弹性模量、管道内压、壁厚增加而逐渐减小,随地表压载增大而增大。     

Development and Operational Testing of a Super‐Ensemble Artificial Intelligence Flood‐Forecast Model for a Pacific Northwest River

Coastal catchments in British Columbia, Canada, experience a complex mixture of rainfall‐ and snowmelt‐driven contributions to flood events. Few operational flood‐forecast models are available in the region. Here, we integrated a number of proven technologies in a novel way to produce a super‐ensemble forecast system for the Englishman River, a flood‐prone stream on Vancouver Island. This three‐day‐ahead modeling system utilizes up to 42 numerical weather prediction model outputs from the North American Ensemble Forecast System, combined with six artificial neural network‐based streamflow models representing various slightly different system conceptualizations, all of which were trained exclusively on historical high‐flow data. As such, the system combines relatively low model development times and costs with the generation of fully probabilistic forecasts reflecting uncertainty in the simulation of both atmospheric and terrestrial hydrologic dynamics. Results from operational testing by British Columbia's flood forecasting agency during the 2013‐2014 storm season suggest that the prediction system is operationally useful and robust.     

Using GIS to Delineate Headwater Stream Origins in the Appalachian Coalfields of Kentucky

Headwater streams have a significant nexus or physical, chemical, and/or biological connection to downstream reaches. Generally, defined as 1st‐3rd order with ephemeral, intermittent, or perennial flow regimes, these streams account for a substantial portion of the total stream network particularly in mountainous terrain. Due to their often remote locations, small size, and large numbers, conducting field inventories of headwater streams is challenging. A means of estimating headwater stream location and extent according to flow regime type using publicly available spatial data is needed to simplify this complex process. Using field‐collected headwater point of origin data from three control watersheds, streams were characterized according to a set of spatial parameters related to topography, geology, and soils. These parameters were (1) compared to field‐collected point of origin data listed in three nearby Jurisdictional Determinations, (2) used to develop a geographic information system (GIS)‐based stream network for identifying ephemeral, intermittent, and perennial streams, and (3) applied to a larger watershed and compared to values obtained using the high‐resolution National Hydrography Dataset (NHD). The parameters drainage area and local valley slope were the most reliable predictors of flow regime type. Results showed the high‐resolution NHD identified no ephemeral streams and 9 and 65% fewer intermittent and perennial streams, respectively, than the GIS model.     

Environmental behaviors of phoxim with two formulations in bamboo forest under soil surface mulching

Phoxim (emulsifiable concentrate (EC) and granules (G)) has been widely used in bamboo forests. The persistence and magnitude of phoxim residues in the crop and soil must be investigated to ensure human and environmental safety. The environmental behaviors of the two formulations were investigated in a bamboo forest under soil surface mulching conditions (CP) and non-covered cultivation conditions (NCP). The half-lives of phoxim in soil under the two conditions in soil were 4.1–6.2 days (EC) and 31.5–49.5 days (G), respectively. Phoxim in EC could be leached from the topsoil into the subsoil. A minimized leaching effect was observed for G under NCP. Inversely, an enhanced leaching effect was observed for G under CP. The G formulation resulted in more parent compound (in bamboo shoots) and metabolite (in soil) residues of phoxim than in the case of EC, especially under CP conditions. In addition, the intensity and duration of the formulation effect on soil pH adjustment from G were more obvious than that from EC. Results showed that the environmental behaviors (distribution, degradation, residue) of phoxim in the bamboo forest were significantly influenced by the type of formulation. The prolongation effect from phoxim G might cause persistence and long-term environmental risk. However, bamboo shoot consumption could be considered relatively safe after applying the recommended dose of the two phoxim formulations.