A Bayesian hierarchical framework for calibrating aquatic biogeochemical models

Model practitioners increasingly place emphasis on rigorous quantitative error analysis in aquatic biogeochemical models and the existing initiatives range from the development of alternative metrics for goodness of fit, to data assimilation into operational models, to parameter estimation techniques. However, the treatment of error in many of these efforts is arguably selective and/or ad hoc. A Bayesian hierarchical framework enables the development of robust probabilistic analysis of error and uncertainty in model predictions by explicitly accommodating measurement error, parameter uncertainty, and model structure imperfection. This paper presents a Bayesian hierarchical formulation for simultaneously calibrating aquatic biogeochemical models at multiple systems (or sites of the same system) with differences in their trophic conditions, prior precisions of model parameters, available information, measurement error or inter-annual variability. Our statistical formulation also explicitly considers the uncertainty in model inputs (model parameters, initial conditions), the analytical/sampling error associated with the field data, and the discrepancy between model structure and the natural system dynamics (e.g., missing key ecological processes, erroneous formulations, misspecified forcing functions). The comparison between observations and posterior predictive monthly distributions indicates that the plankton models calibrated under the Bayesian hierarchical scheme provided accurate system representations for all the scenarios examined. Our results also suggest that the Bayesian hierarchical approach allows overcoming problems of insufficient local data by “borrowing strength” from well-studied sites and this feature will be highly relevant to conservation practices of regions with a high number of freshwater resources for which complete data could never be practically collected. Finally, we discuss the prospect of extending this framework to spatially explicit biogeochemical models (e.g., more effectively connect inshore with offshore areas) along with the benefits for environmental management, such as the optimization of the sampling design of monitoring programs and the alignment with the policy practice of adaptive management.     

Separation of dissolved iron from the aqueous system with excess ligand

A new technique for the separation and pre-concentration of dissolved Fe(III) from the ligand-rich aqueous system is proposed. A solid phase extraction (SPE) system with an immobilized macrocyclic material, commonly known as molecular recognition technology (MRT) gel and available commercially, was used. Synthetic Fe(III) solution in aqueous matrices spiked with a 100-fold concentration of EDTA was used. Dissolved iron that was ‘captured’ by the MRT gel was eluted using hydrochloric acid and subsequently determined by graphite furnace atomic absorption spectrometry. The effect of different variables, such as pH, reagent concentration, flow rate and interfering ions, on the recovery of analyte was investigated. Quantitative maximum separation (∼100%) of the dissolved Fe(III) from synthetic aqueous solutions at a natural pH range was observed at a flow rate of 0.2 mL min^-1. The extraction efficiency of the MRT gel is largely unaltered by the coexisting ions commonly found in natural water. When compared with different SPE materials, the separation performance of MRT gel is also much higher.     

Mn(Ⅱ)液强化电晕放电烟气脱硫效果

建立了线筒式电晕放电反应器,测定了其放电特性,研究了电压、水流量、Mn2+浓度和SO2浓度等对电晕放电与Mn(Ⅱ)液相催化协同脱硫效果的影响,并探讨了协同脱硫的反应机理.结果表明,脱硫效率随着放电电压、水流量和Mn2+浓度的增加而增加,SO2浓度的影响不明显.电晕放电与Mn(Ⅱ)液相催化协同能够加强SO2的氧化作用,提...     

不同来源废水COD、TOC与Cl^-的关系

通过对含盐化工废水（A）、受潮汐影响的河流水（B）、城市生活污水处理厂排水（C）、采油废水（D）4种不同来源废水进行为期15 d的采样监测,测定了其COD、TOC和Cl^-浓度,分析比较了3种废水指标之间的关系,其中COD分别使用重铬酸钾法、氯气校正法和碘化钾碱性高锰酸钾法3种方法进行测定。实验结果表明,4种废水Cl^-浓度差异较大,盐化工废水A（21749 mg/L）〉采油废水D（7013 mg/L）〉受潮汐影响的河流水B（1807 mg/L）〉城市生活污水处理厂排水C（977 mg/L）;在15 d的监测周期内,盐化工废水（A）的TOC波动较大,其余3种废水的TOC浓度基本保持稳定,与Cl^-浓度变化没有直接的关系;4种不同废水的COD与Cl^-浓度之间具有显著的正相关性。通过分析比较表明,碘化钾碱性高锰酸钾法比较适合于盐化工废水（A）和采油废水（D）的测定,氯气校正法比较适合于城市生活污水处理厂排水（C）和采油废水（D）的测定,受潮汐影响的河流水样（B）波动较大,3种方法测得的COD浓度与Cl^-浓度的变化趋势没有显著差异。TOC较适合表征水质有机污染程度。     

Reducing Streamflow Forecast Uncertainty: Application and Qualitative Assessment of the Upper Klamath River Basin,Oregon1

Abstract: The accuracy of streamflow forecasts depends on the uncertainty associated with future weather and the accuracy of the hydrologic model that is used to produce the forecasts. We present a method for streamflow forecasting where hydrologic model parameters are selected based on the climate state. Parameter sets for a hydrologic model are conditioned on an atmospheric pressure index defined using mean November through February (NDJF) 700‐hectoPascal geopotential heights over northwestern North America [Pressure Index from Geopotential heights (PIG)]. The hydrologic model is applied in the Sprague River basin (SRB), a snowmelt‐dominated basin located in the Upper Klamath basin in Oregon. In the SRB, the majority of streamflow occurs during March through May (MAM). Water years (WYs) 1980‐2004 were divided into three groups based on their respective PIG values (high, medium, and low PIG). Low (high) PIG years tend to have higher (lower) than average MAM streamflow. Four parameter sets were calibrated for the SRB, each using a different set of WYs. The initial set used WYs 1995‐2004 and the remaining three used WYs defined as high‐, medium‐, and low‐PIG years. Two sets of March, April, and May streamflow volume forecasts were made using Ensemble Streamflow Prediction (ESP). The first set of ESP simulations used the initial parameter set. Because the PIG is defined using NDJF pressure heights, forecasts starting in March can be made using the PIG parameter set that corresponds with the year being forecasted. The second set of ESP simulations used the parameter set associated with the given PIG year. Comparison of the ESP sets indicates that more accuracy and less variability in volume forecasts may be possible when the ESP is conditioned using the PIG. This is especially true during the high‐PIG years (low‐flow years).     

尿素/三乙醇胺吸收烟气NOx的实验研究

以尿素作为吸收液,与NO_x反应生成N₂和CO₂,脱除烟气中的氮氧化物。以一套双级串连的填料塔为主体反应器,分别对气速、液气比、反应物浓度、添加剂浓度和反应温度等参数对尿素溶液吸收NO_x反应的影响进行了实验研究,获得了优化实验工况,研究结果显示,在气速为0.1 m/s、液气比为16 L/m³、三乙醇胺为0.01%(质量比)、尿素浓度为13%（质量比）工况下, 反应温度为30~70℃,脱硝总效率可达50％以上,且随着NO_x体积分数增加而提高。     

Evaluation of Dynamically Dimensioned Search Algorithm for Optimizing SWAT by Altering Sampling Distributions and Searching Range

The primary advantage of Dynamically Dimensioned Search (DDS) algorithm is that it outperforms other optimization techniques in both convergence speed and searching ability for parameter sets that satisfy statistical guidelines while requiring only one algorithm parameter (perturbation factor) in the optimization process. Conventionally, a default value of 0.2 is used as the perturbation factor, where a normal distribution is applied with mean sampling distribution of zero and variance of one. However, the perturbation factor sensitivity to the performance of DDS for watershed modeling is still unknown. The fixed‐form sampling distribution may result in finding parameters at the local scale rather than global in the sampling space. In this study, the efficiency of DDS was evaluated by altering the perturbation factor (from 0.05 to 1.00) and the selection of sampling distribution (normal and uniform) on hydrologic and water quality predictions in a lowland agricultural watershed in Texas, United States. Results show that the use of altered perturbation factor may cause variations in convergence speed or the ability to find better solutions. In addition, DDS results were found to be very sensitive to sampling distribution selections, where DDS‐N (normal distribution) outperformed DDS‐U (uniform distribution) in all case scenarios. The choice of sampling distributions could be the potential major factor to be attributed for the performance of auto‐calibration techniques for watershed simulation models.     

纳米腐植酸基复合树脂的制备及其对Ni~(2+)和Cd~(2+)的吸附

采用水溶液聚合法,以丙烯酸、丙烯酰胺及改性蒙脱土为原料,纳米腐植酸为基体,N,N’-亚甲基双丙烯酰胺为交联剂,过二硫酸钾为引发剂,制备了丙烯酸-蒙脱土-丙烯酰胺/纳米腐植酸复合树脂(简称复合树脂)。考察了溶液pH、吸附时间、吸附温度、初始离子浓度等因素对复合树脂分别吸附Ni~(2+)和Cd~(2+)的影响。实验结果表明:在吸附温度35℃、吸附时间90 min、溶液pH为7、初始Ni~(2+)和Cd~(2+)的浓度分别为0.02 mol/L、复合树脂加入量16.7 g/L的条件下,Ni~(2+)和Cd~(2+)的吸附量分别为383.02 mg/g和359.27 mg/g;复合树脂吸附Ni~(2+)和Cd~(2+)的吸附等温线均满足Langmuir等温吸附方程;吸附过程均符合准二级动力学方程;复合树脂重复使用6次,其对Ni~(2+)和Cd~(2+)的吸附量分别降低了17.1%和9.3%。     

臭氧氧化结合碱液吸收法烟气脱硝的工艺研究

利用臭氧将烟气中溶解度较小的NO氧化成NO2,再结合尿素、氢氧化钠、氢氧化钙溶液吸收脱除臭氧氧化产物,重点考察了O3与NO反应的摩尔比、进口NO浓度、烟气中SO2浓度和相对湿度等工艺参数对NO氧化的影响,并探明不同的吸收液脱除臭氧氧化产物的特性。结果显示O3与NO反应的最佳摩尔比为1.02,随着进口NO浓度的增加氧化效率下降,而烟气中的SO2和相对湿度对NO氧化影响较小。通过对氢氧化钙吸收臭氧氧化产物的特性分析得出,碱液对NO的吸收率相对较小,而对NO2的吸收率达到80%以上。     

Evaluation of the MIKE SHE Model for Application in the Loess Plateau,China1

Abstract: Quantifying the hydrologic responses to land use/land cover change and climate variability is essential for integrated sustainable watershed management in water limited regions such as the Loess Plateau in Northwestern China where an adaptive watershed management approach is being implemented. Traditional empirical modeling approach to quantifying the accumulated hydrologic effects of watershed management is limited due to its complex nature of soil and water conservation practices (e.g., biological, structural, and agricultural measures) in the region. Therefore, the objective of this study was to evaluate the ability of the distributed hydrologic model, MIKE SHE to simulate basin runoff. Streamflow data measured from an overland flow‐dominant watershed (12 km²) in northwestern China were used for model evaluation. Model calibration and validation suggested that the model could capture the dominant runoff process of the small watershed. We found that the physically based model required calibration at appropriate scales and estimated model parameters were influenced by both temporal and spatial scales of input data. We concluded that the model was useful for understanding the rainfall‐runoff mechanisms. However, more measured data with higher temporal resolution are needed to further test the model for regional applications.