响应面分析法优化稀土废水MAP沉淀法脱氮

经过预处理后的稀土生产废水,其氨氮浓度大幅降低,但并未达到中华人民共和国《稀土工业污染物排放标准》（GB26451-2011）中氨氮浓度限值。实验通过响应面分析法中的Box-Behnken实验设计（BBD）,取pH、n（Mg）：n（N）、n（P）：n（N）3因素,采用Design-Expert 8.0.6,建立合适的剩余氨氮浓度及剩余总磷浓度模型,得到回归方程,并分析模型各项指标,各因素及其相互作用对剩余氨氮浓度及剩余总磷浓度的影响。利用预测模型预测最佳实验条件,在最佳实验条件下验证预测结果,并对沉淀物进行X射线衍射（XRD）分析。结果显示,二次响应模型适用于剩余氨氮浓度及剩余总磷浓度,2个模型均拥有较好的拟合程度、可信度及精密度,最优反应条件为：pH=9.88、n（Mg）：n（N）=1.50：1、n（P）：n（N）=1.38：1时,剩余氨氮浓度为46.58 mg/L,剩余总磷浓度为7.85 mg/L。在最优条件下所得到的沉淀物并非纯净的MgNH₄PO₄·6H₂O,还有Mg₃（PO₄）₂·22H₂O生成。     

O3/BAF工艺系统中有机物生物降解数学模型

研究臭氧预氧化/曝气生物滤池（O₃/BAF）联合工艺深度处理实际城市污水二级出水过程中,后续BAF系统中有机物的生物降解数学模型。以有机底物浓度、填料层高度两个基本变量为控制条件,研究BAF的总体运行常数和填料特性常数,得出BAF有机物生物降解动力学方程为S_e/S₀=exp(－Kh/qSⁿ₀)。出水与进水COD浓度比值（S_e/S₀）的对数与反应器填料高度（h）之间可表达成一次函数关系。在不同的进水浓度（S₀）下,根据ln（S_e/S₀）~h和关系式m=K/qSⁿ₀,得到方程ln(q_m)=－nln(S₀)+lnK。BAF总体运行常数K和填料特性常数n分别为1.708和0.5063。该模型对BAF工艺有如下指导意义：可以根据设计流量、进水有机物浓度和出水浓度,初步确定BAF的尺寸（如横截面积、高度等）。     

碳酸根对磷酸钙沉淀反应回收磷的影响简

以模拟的厌氧消化液为处理对象,通过小试实验,考察不同初始磷浓度C_P、Ca/P物质的量比、pH和温度下,碳酸根（CO₃^2-）对磷酸钙沉淀反应回收磷的影响;利用扫描电镜（SEM）、X射线衍射仪（XRD）和傅里叶变换红外光谱（FTIR）对沉淀产物进行表征。结果表明,高浓度的CO₃^2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大;C_P相同时,CO₃^2-浓度（C_CO3^2-）越大,P的去除率越低,低C_P（20 mg/L）时尤为显著;当C_CO3^2-相同时,随着C_P的增大,反应速率加快,P的去除率逐渐升高,但升高幅度越来越小;增大Ca/P比和pH能提高P的去除率,降低CO₃^2-对磷酸钙沉淀反应的抑制作用,综合考虑实际效果,应选择Ca/P比为3.33,pH为9.0作为适宜的反应条件;升高温度对降低CO₃^2-对磷酸钙沉淀反应的抑制作用贡献不大。在C_P为60 mg/L,Ca/P比为1.67,pH为9.0,温度为20℃的条件下,当C _CO3^2-为0时,得到的沉淀产物主要为羟基磷灰石HAP;当C _CO3^2-为30 mmol/L时,得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

污泥活性炭的表征及其对 Cr( VI) 的吸附特性

以城市污水处理厂污泥为原料,采用磷酸活化-微波热解法制备得到污泥活性炭,并将其用于吸附水溶液中的Cr（Ⅵ）。分别采用元素分析仪（Vario EL cube）、比表面积孔径分布测定仪（ASAP2020）、扫描电镜（SEM）和傅里叶红外光谱（FT-IR）等仪器对原污泥及污泥活性炭的表面组成和结构进行表征,探讨污泥活性炭的孔隙结构参数和表面化学性能。通过静态吸附实验,考察了溶液初始pH,接触时间,初始Cr（Ⅵ）浓度对污泥活性炭吸附Cr（Ⅵ）效果的影响,并探讨了污泥活性炭去除Cr（Ⅵ）的机理。实验结果表明,pH越低吸附效果越好,吸附平衡时间为100 h。不同温度下吸附过程均符合Langmuir等温吸附模型,30℃时最大吸附容量为27.55 mg/g;吸附动力学过程符合准二级速率方程（R2>0.99）;污泥活性炭对Cr（Ⅵ）的去除是一个吸附-还原耦合的过程。     

超重力-磷酸钠法脱除低浓度SO2

为开发脱硫率高、成本低、可回收SO₂的脱硫技术,以旋转填料床为吸收设备,磷酸钠溶液为吸收剂,系统开展了液气比L/G、转速N、气体中SO₂浓度CSO₂,in、吸收剂磷酸浓度CL和初始pH等工艺参数和溶液再生循环次数对脱硫率η影响的实验研究。结果表明,η随L/G、N、CL和初始pH的增加而增大,且它们的值越低时,η增加越明显;受G和CSO₂,in影响较小。在适宜操作条件下,脱硫率达99%以上,出口SO₂浓度低于100 mg/m³。磷酸钠溶液可再生循环使用,脱硫率稳定在99%以上。表明超重力-磷酸钠法脱硫技术在小的液气比下即可达到高的脱硫率,吸收剂循环使用,可实现低成本并达标治理SO₂废气,且适用范围宽,具有良好的工业应用前景。     

PAC-chitosan复合絮凝剂中铝形态

以不同碱化度(B)的聚合氯化铝(PAC)和不同粘度的壳聚糖为原料制备出一系列PAC-chitosan复合絮凝剂。采用Al-Ferron逐时络合比色法研究了PAC-chitosan复合絮凝剂中铝的形态分布,探讨了PAC的B值、壳聚糖的含量（C）和粘度（η）对复合絮凝剂中铝的形态分布的影响。结果表明：壳聚糖与PAC之间发生了一定的相互作用,通过试验结果推断出当B=1.5,壳聚糖粘度η=800 Pa·s,C=0.6 mg/mL絮凝效果最佳。并用某造纸废水进行了烧杯絮凝试验。絮凝试验结果与推断结果相一致。     

超细粉煤灰基成型吸附剂的动态吸附实验

以粉煤灰为原料制备成型吸附剂,对水溶液中亚甲基蓝和Cr⁶⁺进行动态吸附研究,绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式C_t=A₁－A₂〖〗1+(t/t₀)^p+A₁。结果表明,初始浓度C₀=25 mg/L,填料高度不同时,达到穿透点的时间随填料高度的增加而增加;填料高度h=200 mm,初始浓度不同时,达到穿透点的时间随初始浓度的增加而减小;该吸附剂对有机染料和重金属离子均有较好的吸附性能;穿透曲线通式的回归线性相关系数表明,该通式可很好地反映超细粉煤灰成型吸附剂的动态吸附过程。     

小型燃油锅炉NOx的排放特征与管理控制

以68台燃油锅炉（≤10.5 MW）NO_x排放实测数据为基础,通过统计分析方法,研究了NO_x的排放特征;通过对比分析,探讨了我国燃油锅炉NO_x排放控制与管理现状,讨论了进一步加强我国燃油锅炉NO_x排放管理控制的可能性与可行性,并提出了相应的管理控制建议。结果表明,NO_x平均排放浓度为318.2 mg/m³,     

河北廊坊地区大气污染物变化特征与来源追踪

为了解河北省廊坊地区大气污染水平、变化特征以及污染物来源,2009年7月—2010年6月对该地区大气中NO、NO_x（NO_x=NO+NO₂）、O₃、SO₂和PM₁₀进行了连续在线观测,并用统计方法和后向轨迹模拟对所获数据进行分析。结果表明,一次污染物NO、NO_x、SO₂和PM₁₀浓度具有相似的季变化和日变化,冬季浓度最高,季节日均值分别为（57±53）、（127±84）、（69±340）和（181±129）μg/m³;二次污染物O₃夏季浓度最高,日小时均值最高值季节日平均为（99±39）μg/m³。一次污染物浓度日变化呈早晚双峰型,冬季,变化幅度最大;二次污染物日变化为单峰型,最大值出现在夏季午后。夏季受东南气流影响,往往造成该地区O₃超标;冬季,廊坊和天津污染具有较高一致性,出现区域性大气复合污染。廊坊地区大气污染除受本地排放影响,还受到周边地区污染物输送的影响,其在京津两大城市间对大气污染的缓冲作用也不可小觑。     

钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量,有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性,增加了烟草叶中Cd的吸收量,有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。     

Modelling radionuclide transport for time varying flow in a channel network

Water flowrates and flow directions may change over time in the subsurface for a number of reasons. In fractured rocks flow takes place in channels within fractures. Solutes are carried by the advective flow. In addition, solutes may diffuse in and out of stagnant waters in the rock matrix and other stagnant water regions. Sorbing species may sorb on fracture surfaces and on the micropore surfaces in the rock matrix. We present a method by which solute particles can be traced in flowing water undergoing changes in flowrate and direction in a complex channel network where the solutes can also interact with the rock by diffusion in the rock matrix. The novelty of this paper is handling of diffusion in the rock matrix under transient flow conditions. The diffusive processes are stochastic and it is not possible to follow a particle deterministically. The method therefore utilises the properties of a probability distribution function for a tracer moving in a fracture where matrix diffusion is active. The method is incorporated in a three dimensional channel network model. Particle tracking is used to trace out a multitude of flowpaths, each of which consists of a large number of channels within fractures. Along each channel the aperture and velocity as well as the matrix sorption properties can vary. An efficient method is presented whereby a particle can be followed along the variable property flowpath. For stationary flow conditions and a network of channels with advective flow and matrix diffusion, a simple analytical solution for the residence time distribution along each pathway can be used. Only two parameter groups need to be integrated along each path. For transient flow conditions, a time stepping procedure that incorporates a stochastic Monte-Carlo like method to follow the particles along the paths when flow conditions change is used. The method is fast and an example is used for illustrative purposes. It is exemplified by a case where land rises due to glacial rebound. It is shown that the effects of changing flowrates and directions can be considerable and that the diffusive migration in the matrix can have a dominating effect on the results.     

Numerical calculation of flow and stack-gas concentration fluctuation around a cubical building

A numerical simulation model was developed to predict the instantaneous concentration fluctuation of a plume and applied to stack-gas diffusion around a cubical building. The flow field, including an instantaneous velocity component, was predicted using the large eddy simulation (LES) method in the developed numerical model. Then, the instantaneous concentration fluctuation was predicted using the obtained unsteady flow field. Concentration was calculated using the finite difference method, in which the LES is expanded for concentration, and the puff method, in which small volumes of the tracer gas are divided and combined according to the calculation mesh sizes. In order to avoid numerical viscous effects, a puff method and finite difference method were applied separately in the regions near and far from the stack-gas release point, respectively. Then, the flow field around a cubical building and the diffusion of stack-gas, emitted from an elevated point source at an upstream position of the building, were calculated using the model mentioned above. Numerical calculation results were compared with those obtained in wind tunnel experiments in which concentration fluctuation was measured using high-response flame ionization detectors. Although there were some discrepancies in the flow field between the calculated results and those of wind tunnel experiments, e.g., the calculated windward length of a cavity region behind the building, the calculated mean velocity and turbulent intensity showed good agreement with those of the wind tunnel experiments. Furthermore, the calculated concentration fluctuation showed good agreement with that in the wind tunnel, not only regarding the features of fluctuating concentration signals, but also statistic quantities, viz., mean concentration, fluctuation intensity and high-concentration values.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

An interpretation of potential scale dependence of the effective matrix diffusion coefficient

Matrix diffusion is an important process for solute transport in fractured rock, and the matrix diffusion coefficient is a key parameter for describing this process. Previous studies have indicated that the effective matrix diffusion coefficient values, obtained from a large number of field tracer tests, are enhanced in comparison with local values and may increase with test scale. In this study, we have performed numerical experiments to investigate potential mechanisms behind possible scale-dependent behavior. The focus of the experiments is on solute transport in flow paths having geometries consistent with percolation theories and characterized by multiple local flow loops formed mainly by small-scale fractures. The water velocity distribution through a flow path was determined using discrete fracture network flow simulations, and solute transport was calculated using a previously derived impulse-response function and a particle-tracking scheme. Values for effective (or up-scaled) transport parameters were obtained by matching breakthrough curves from numerical experiments with an analytical solution for solute transport along a single fracture. Results indicate that a combination of local flow loops and the associated matrix diffusion process, together with scaling properties in flow path geometry, seems to be an important mechanism causing the observed scale dependence of the effective matrix diffusion coefficient (at a range of scales).     

Localizing gaseous fugitive emission sources by combining real-time optical remote sensing and wind data

This paper presents a new approach to localize point emissions from ground-level fugitive gaseous air pollution sources. We estimate the crosswind plume's ground-level peak location downwind from the source by combining smooth basis functions minimization (SBFM) with pathintegrated optical remote sensing concentration data acquired along the crosswind direction in alternating beam path lengths. Peak location estimates, in conjunction with real-time measured wind direction data, are used to reconstruct the fugitive source location. We conducted a synthetic data study to evaluate the proposed peak location SBFM reconstruction. Furthermore, the methodology was validated with open-path Fourier transform infrared concentration data collected with wind direction data downwind from a controlled point source. This approach was found to provide reasonable estimates of point source location. The field study reconstructed source location was within several meters of the real source location.     

A comparison of hydraulic and transport parameters measured in low-permeability fractured media

Data from 90 tracer experiments performed in low-permeability fractured media have been studied to explore correlations among parameters controlling flow and transport. The original data had been interpreted by different authors using different models, which prevents direct comparison of their estimated parameters. In order to produce comparable parameters, the data have been reexamined using simple models (homogeneous domain, steady-state flow regime, single porosity). Specifically, hydraulic conductivity has been derived as the ratio of water flux to head gradient and apparent porosity as the ratio of water velocity to water flux; the former estimated from both first and peak arrival times. Hydraulic conductivity and porosity correlate along a straight line of slope 1:3 in log scale. While the regression is too noisy to be of predictive use, it lends some support to the use of a generalized cubic law. The fact that correlation for first arrival time porosity (0.77) is larger than for peak arrival porosity (0.62) suggests that first arrival is controlled by the same flow paths as hydraulic conductivity. Apparent porosity derived from peak arrival time is found to grow with travel time along a line of 0.55 slope (again log scale). The correlation coefficient ranges between 0.73 and 0.80 (depending on the data set) for hard rocks. The fact that this correlation is maintained when varying the flow rate at a given site leads us to suggest that it is caused by diffusion mechanisms. This conclusion is further supported by the increase of apparent porosity with the matrix porosity of the rock on which the experiments were performed.     

Localizing Gaseous Fugitive Emission Sources by Combining Real-Time Optical Remote Sensing and Wind Data

ABSTRACT

This paper presents a new approach to localize point emissions from ground-level fugitive gaseous air pollution sources. We estimate the crosswind plume's ground-level peak location downwind from the source by combining smooth basis functions minimization (SBFM) with path-integrated optical remote sensing concentration data acquired along the crosswind direction in alternating beam path lengths. Peak location estimates, in conjunction with real-time measured wind direction data, are used to reconstruct the fugitive source location. We conducted a synthetic data study to evaluate the proposed peak location SBFM reconstruction. Furthermore, the methodology was validated with open-path Fourier transform infrared concentration data collected with wind direction data downwind from a controlled point source. This approach was found to provide reasonable estimates of point source location. The field study reconstructed source location was within several meters of the real source location.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

临江河回水区营养盐及富营养化特征分析

以2008年3～9月对库区次级河流临江河回水区水质的调查为依据,分析了临江河回水区氮、磷营养盐的污染分布及富营养化特征。结果表明,临江河回水区氨氮(NH₃-N)、总氮(TN)的浓度在7月中旬达到最小值,分别为1.963和5.128 mg/L, 之后在9月初出现峰值,而磷酸盐(PO^3-₄-P)和总磷(TP)的浓度却呈现出先增加后下降的变化规律;氮主要来自点源污染,而磷受面源污染影响较大;溶解性无机氮(DIN)和PO^3-₄-P是TN与TP的主要存在形态,平均分别占TN和TP的85.3%和77.8%,而DIN又以NH₃-N为主。营养盐浓度呈现出回水区中游最高,回水末端次之,河口处最低的空间分布特征。叶绿素a（Chl-a）的浓度在4月和9月出现峰值,其空间分布特征与营养盐的类似。研究表明,临江河回水区在重度污染的情况下,即便是河流型水体也可能发生富营养化;流速对Chl-a浓度的显著影响呈指数关系。     

A dynamic contaminant fate model of organic compound: a case study of Nitrobenzene pollution in Songhua River, China

A one-dimensional dynamic contaminant fate model, coupling kinematic wave flow option with advection-dispersion-reaction equation, has been applied to predict Nitrobenzene pollution emergency in Songhua River, China that occurred on November 13, 2005. The model includes kinetic processes including volatilization, photolysis and biodegradation, and diffusive mass exchange between water column and sediment layer as a function of particles settling and resuspension. Four kinds of quantitative statistical tests, namely Nash-Sutcliffe efficiency, percent bias, ratio of root-mean-square to the standard deviation of monitoring data and Theil’s inequality coefficient, are adopted to evaluate model performance. The results generally show that the modeled and detected concentrations exhibit good consistency. Flow velocity in the river is most sensitive parameter to Nitrobenzene concentration in water column based on sensitivity analysis of input parameters. It indicates flow velocity has important impact on both distribution and variance of contaminant concentration. The model performs satisfactory for prediction of organic pollutant fate in Songhua River, with the ability to supply necessary information for pollution event control and early warning, which could be applied to similar long natural rivers.