Kinetic research on the sorption of aqueous lead by synthetic carbonate hydroxyapatite

The sorption of aqueous lead on carbonate-hydroxyapatite (CHAp) is a complicated non-homogeneous solid/water reaction, which from the kinetic point of view has two stages. In the first stage, the reaction rate is so fast and the kinetic pathway so intricate that further research is required. In the second stage, the reaction rate slows down and the reaction process follows that of a first-order kinetic equation. Experimental results show that the relationship between the reaction rate constant k(1) and temperature T agrees with the Arrhenius equation, and that the activation energy of sorption (E(a)) is 11.93 kJ/mol and the frequency factor (A) is 2.51/s. The reaction rate constant k(1) increases with the Pb(2+) initial concentration and decreasing pH, but with increasing CHAp dosage. X-ray diffraction (XRD), scanning electron microscopy with energy dispersion spectrum (SEM-EDS) and toxicity characteristic leaching procedure (TCLP) tests indicate that the main sorption mechanism is dissolution-precipitation, in conjunction with surface sorption.     

Designing reverse-flow packed bed reactors for stable treatment of volatile organic compounds

Reverse-flow packed bed reactors can be used to treat gaseous pollutants from chemical plants. This article describes the design and operation of a modified reverse-flow reactor (MRFR) which has a recuperator on each end of the reactor and a reaction zone in the middle. The recuperators have low thermal dispersion and the reaction zone has a high thermal dispersion, obtained by placing metal inserts into the bed, parallel with the gas flow. Performance of the MRFR during extended lean and rich conditions is determined with analytical analysis and compares well with numerical simulations of CO oxidation; however, the theory is expected to be useful for any reaction kinetics. A major advantage of this MRFR design is an extended time for the reactor to extinguish during lean conditions. This work also describes MRFR performance with internal reactor cooling, which can be used as a control mechanism to maintain reactor temperature for proper removal of volatile organic compounds.     

UV-H_2O_2联用工艺去除水中阿特拉津的研究

采用间歇式反应器考察了UV-H2O2高级氧化技术去除水中阿特拉津的效果及其影响因素,并进行了相关的反应动力学研究。结果表明,在pH值6.9,阿特拉津初始浓度500μg/L,紫外辐照强度172μW/cm2时,H2O2投加量50mg/L,反应10min后,阿特拉津的去除率90%。UV-H2O2联用工艺对阿特拉津的降解符合一级反应动力学。H2O2在该联用工艺降解阿特拉津中具有双重作用,一方面,当H2O2投加量较小时,一级反应速率常数随H2O2投加量的增加基本呈现线性增加的趋势;另一方面,当H2O2浓度增加到一定程度(90mg/L)后,阿特拉津的降解速率随H2O2浓度的变化已不明显,而H2O2浓度为102mg/L时,则出现了抑制作用。     

高铁酸钾氧化去除弱碱性地下水中低浓度石油类污染物实验研究

研究一般地下水弱碱性水溶液中,高铁酸钾对低浓度石油烃类污染物的氧化去除率。采用0#柴油模拟石油类污染物试验水样,氧化反应在200mL烧杯中模拟完全混合状态完成。实验分析浓度分别为5.02mg/L、2.05mg/L、1.01mg/L和0.52mg/L 4个水样石油类污染物氧化去除率。实验研究显示,石油类污染浓度与高铁酸钾浓度分别按1∶1、1∶2和1∶3投加进行配比,最大氧化去除率97.51%,平均氧化去除率89.46%,氧化反应结束时间为25T。采用乙酸等效计算的导致溶液p H降低小分子有机酸累积量较小;在高铁酸钾过量条件下,石油类污染物氧化反应近似为一级反应。     

Field dissipation of acetochlor in two New Zealand soils at two application rates

The persistence of pesticides in soils has both economic and environmental significance and is often used as a key parameter in pesticide risk assessment. Persistence of acetochlor [2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetylanilide] in two New Zealand field soils was measured over two years and the data were used to identify models that adequately describe acetochlor persistence in the field. Acetochlor was sprayed onto six fallow plots (3 x 9 m each) at each site at the recommended rate (2.5 kg a.i. ha(-1)) and at twice that rate. Acetochlor concentrations were measured in soil cores. Simple first-order kinetics (Model 1) adequately described acetochlor persistence in Hamilton clay loam soil (Humic Hapludull, Illuvial Spadic) at the high application rate, but overestimated it at the low application rate. A quadratic model (Model 2), a first-order double-exponential model (Model 3), a first-order biphasic model (Model 4), or a two-compartment model (Model 5) better described acetochlor persistence at the low application rate. The time for 50% (DT50) and 90% (DT90) of initial acetochlor loss was approximately 9 and 56 d, and 18 and 63 d at low and high application rates, respectively. The more complex Models 2 through 5 also better described the biphasic dissipation of acetochlor in Horotiu sandy loam soil (Typic Orthic Allophanic) than Model 1, with Model 1 significantly underestimating acetochlor concentrations on the day of application at both application rates. The DT50 and DT90 values were 5 and 29 d and 7 and 31 d at low and high application rates, respectively. Overall, application rate significantly affected the DT50 and DT90 values in the Hamilton soil, but not in the Horotiu soil. Faster acetochlor loss in the Horotiu soil possibly resulted from the higher soil organic carbon content that retained more acetochlor near the soil surface where higher temperature and photolysis accelerated the loss.     

A Sensitivity and Error Analysis Framework for Lake Eutrophication Modeling1

ABSTRACT: A framework for sensitivity and error analysis in mathematical modeling is described and demonstrated. The Lake Eutrophication Analysis Procedure (LEAP) consists of a series of linked models which predict lake water quality conditions as a function of watershed land use, hydrolgic variables, and morphometric variables. Specification of input variables as distributions (means and standard errors) and use of first-order error analysis techniques permits estimation of output variable means, standard errors, and confidence ranges. Predicted distributions compare favorably with those estimated using Monte-Carlo simulation. The framework is demonstrated by applying it to data from Lake Morey, Vermont. While possible biases exist in the models calibrated for this application, prediction variances, attributed chiefly to model error, are comparable to the observed year-to-year variance in water quality, as measured by spring phosphorus concentration, hypolimnetic oxygen depletion rate, summer chlorophyll-a, and summer transparency in this lake. Use of the framework provides insight into important controlling factors and relationships and identifies the major sources of uncertainty in a given model application.     

S-TE剩余污泥溶解过程中VSS的变化研究

从土壤中筛选出1株能分泌胞外酶、促进污泥溶解的嗜热脂肪芽孢杆菌Bacillus stearothermophilusAT07-1,将AT07-1培养液接种到不同浓度（TSS约为7.5、14.5、20.5 g/L）的剩余污泥中,于65℃进行嗜热菌溶解试验,并与未接种试验进行对比。结果表明,接种嗜热菌AT07-1促进了污泥中悬浮固体的溶解。60h时接种试验VSS的溶解率分别为61.41%、53.79%、41.86%,比不接种试验同期分别提高了27.57%、25.24%、16.26%。试验条件下VSS溶解过程在初始阶段（t=3d）符合一级反应动力学模型,接种后溶解速率常数Kd显著提高,从0.12 d-1、0.08 d-1、0.09 d^-1分别增加到0.27 d^-1、0.24 d^-1、0.13 d^-1。     

USE OF FIRST-ORDER UNCERTAINTY ANALYSIS TO OPTIMIZE SUCCESSFUL STREAM WATER QUALITY SIMULATION1

ABSTRACT: A first-order uncertainty technique is developed to quantify the relationship between field data collection and a modeling exercise involving both calibration and subsequent verification. A simple statistic (LTOTAL) is used to quantify the total likelihood (probability) of successfully calibrating and verifying the model. Results from the first-order technique are compared with those from a traditional Monte Carlo simulation approach using a simple Streeter-Phelps dissolved oxygen model. The largest single difference is caused by the filtering or removal of unrealistic outcomes within the Monte Carlo framework. The amount of bias inherent in the first-order approach is also a function of the magnitude of input variability and sampling location. The minimum bias of the first-order technique is approximately 20 percent for a case involving relatively large uncertainties. However the bias is well behaved (consistent) so as to allow for correct decision making regarding the relative efficacy of various sampling strategies. The utility of the first-order technique is demonstrated by linking data collection costs with modeling performance. For a simple and inexpensive project, a wise and informed selection resulted in an LTOTAL value of 86 percent, while an uninformed selection could result in an LTOTAL value of only 55 percent.     

Fenton试剂对亚甲基蓝氧化褪色的反应动力学实验研究

为了提高Fenton试剂处理有机污染物的效率,探索最佳处理条件,以亚甲基蓝溶液为模型污水,进行了Fenton试剂氧化亚甲基蓝褪色反应的影响因素实验。对不同条件下的时间过程进行了在线动力学跟踪、拟合和比较。研究发现:Fenton试剂高级氧化的反应动力学过程可分为三阶段。反应前期符合一级动力学,后期符合二级动力学,两者之间存在一个过渡性阶段。一级动力学期的反应速度快,氧化能力高,对于污染物的化学处理是比较合理的,实验还确认了反应前期的Fe(II)浓度对过程的支配作用。     

A screening model for fate and transport of biodegradable polyesters in soil

A numerical model for predicting the fate and transport of biodegradable polyester residues in soil, following successive applications of mulch film, was developed and applied. The polymer, applied on surface soil, was assumed to be converted into by-products (monomers), according to a first order kinetics with constant K(1deg). The monomers released were assumed to sorb on soil organic matter (according to a first-order kinetics with constant K(s)), to be leached with the seepage water, through vertical advection and hydrodynamic dispersion, and biodegraded (according to a first-order kinetics with constant K(b)). Results suggested that, to assess a possible build-up of mulch film (as a polymer) on the surface soil, the degradation constant K(1deg) relating the polymer conversion to by-products should be known, whereas the biodegradation constant K(b) indicates there is no danger of groundwater pollution. Likewise, on the basis of by-product concentration in deep soil, soil pollution should not occur.     

组合人工湿地对化工园区尾水COD的去除及其模拟

采用组合人工湿地中试试验对工业园区污水厂尾水进行处理,研究了3种不同的水力负荷(10cm/d,20cm/d和25cm/d)下COD的去除,并用一级动力学模型对组合人工湿地及其各个湿地单元的COD的去除进行了模拟。结果表明组合人工湿地对COD的去除受水力负荷影响有限,去除率基本都在60%以上,系统出水COD浓度在40mg/L以下,并且夏季的去除效果最佳。对数学模拟的结果进行分析,发现一、二级潜流湿地对COD去除贡献较大,另外组合人工湿地系统对COD的去除效果也优于单个的湿地。系统最终出水中的COD模拟结果和实测值相接近,说明基于一级动力学模型的组合人工湿地数学模拟对实际运行有指导意义。     

Effects of environmental factors on 1,3-dichloropropene hydrolysis in water and soil

Hydrolysis is the major pathway for fumigant 1,3-dichloropropene (1,3-D) degradation in water and soil, yet the process is not well understood. Experiments were conducted to investigate the effect of various environmental factors on the rate of 1,3-D hydrolysis. Cis-, trans-1,3-D and their isomeric mixture were spiked into water and Arlington soil (coarse-loamy, mixed, thermic Haplic Durixeralfs) and incubated under different conditions. The rate of 1,3-D hydrolysis in water and soil were evaluated based on its residual amount and Cl- release, respectively. 1,3-D hydrolyzed rapidly in deionized water, with a half-life of 9.8 d at 20 degrees C. The hydrolysis was pH dependent, with low pH inhibiting and high pH favoring the reaction. Other factors such as isomeric differences, photo irradiation, suspended particles, and small amounts of co-solutes had little effect on the reaction. In soil, 1,3-D hydrolyzed following pseudo first-order kinetics. The hydrolysis rate constant increased with soil moisture content and decreased with the initial 1,3-D concentration. At 20 degrees C, > 60% of the 1,3-D applied at < 0.61 g kg(-1) in 10% moisturized soil hydrolyzed within 30 d. The soil particle size and mineralogy had little effect on the reaction rate. Organic matter promoted 1,3-D degradation via direct substitution reactions, and the trans-isomer showed preference over the cis- to react with certain organic molecules. Microbial contributions were initially insignificant, and became important as soil microorganisms adapted to the fumigant. The results suggest that to accelerate 1,3-D degradation, pH, soil moisture, and organic amendment should be considered.     

Kinetic effect of humic acid on alachlor degradation by anodic Fenton treatment

Contamination of water often results from the heavy use of agricultural chemicals, and the disposal of aqueous pesticide waste is a concern. Anodic Fenton treatment (AFT) has been shown to be a successful remediation method for pesticides in solution, but the effect of soil on the degradation kinetics of pesticides using this method has not been determined. The purpose of this study was to study the effect of humic acid, as a soil surrogate, on the degradation kinetics of alachlor [2-chloro-N-(2,6-diethylphenyl-N-(methoxymethyl) acetamide], a heavily used herbicide that has been studied in pure aqueous solution by AFT. The AFT consists of a controlled constant delivery of Fenton reagents, using an electrochemical half-cell to deliver ferrous iron. Alachlor was quickly degraded by AFT, and the kinetics were found to obey the previously developed AFT model well. Degradation of alachlor by AFT in humic acid slurry showed that when the amount of humic acid was increased, alachlor degradation was significantly slowed down and the degradation kinetics were shifted from the AFT model to a first-order model. Further experimentation indicated that humic acid not only competes with alachlor for hydroxyl radicals, reducing the degradation rate of the target compound, but also buffers the slurry at near neutral pH, blocking regeneration of ferrous ion from ferric ion and subsequently shifting the kinetics to first order. Degradation of several other pesticides in humic acid slurry also followed first-order kinetics. These results imply that higher concentrations of Fenton reagents will be required for soil remediation.     

Fluoride removal by a continuous flow electrocoagulation reactor

Long-term consumption of water containing excessive fluoride can lead to fluorosis of the teeth and bones. Electrocoagulation (EC) is an electrochemical technique, in which a variety of unwanted dissolved particles and suspended matter can be effectively removed from an aqueous solution by electrolysis. Continuous flow experiments with monopolar aluminium electrodes for fluoride removal were undertaken to investigate the effects of the different parameters such as: current density (12.5-50A/m(2)), flow rate (150-400 mL/min), initial pH (4-8), and initial fluoride concentration (5-25mg/L). The highest treatment efficiency was obtained for the largest current and the removal efficiency was found to be dependent on the current density, the flow rate and the initial fluoride concentration when the final pH ranged between 6 and 8. The composition of the sludge produced was analysed using the X-ray diffraction (XRD) spectrum. The strong presence of the aluminium hydroxide [Al(OH)(3)] in the above pH range, which maximizes the formation of aluminium fluoride hydroxide complex [Al(n)F(m)(OH)(3n-m)], is the main reason for defluoridation by electrocoagulation. The results obtained showed that the continuous flow electrocoagulation technology is an effective process for defluoridation of potable water supplies and could also be utilized for the defluoridation of industrial wastewater.     

Zerovalent iron nanoparticles for treatment of ground water contaminated by hexachlorocyclohexanes

Ground water and aquifer samples from a site contaminated by hexachlorocyclohexanes (HCHs; C(6)H(6)Cl(6)) were exposed to nanoscale iron particles to evaluate the technology as a potential remediation method. The summed concentration of the HCH isomers in ground water was approximately 5.16 micromol L(-1) (1500 microg L(-1)). Batch experiments with 2.2 to 27.0 g L(-1) iron nanoparticles showed that more than 95% of the HCHs were removed from solution within 48 h. Using a pseudo first-order kinetics model, the HCH isomers were removed in accordance with the trend gamma congruent with alpha > beta > delta. This seems to be correlated with the orientation (axial vs. equatorial) of the chlorine atoms lost in the dihaloelimination steps. Although the reactivity of the HCH isomers has been investigated in the classical organic chemistry literature, the present study was the first in the environmental remediation arena. The rate of removal is directly correlated to the number of axial chlorines. The observed rate constant varied from 0.04 to 0.65 h(-1), and the rate constant normalized to the iron surface area concentration ranged from 5.4 x 10(-4) to 8.8 x 10(-4) L m(-2) h(-1). Post-test extractions of the reactor contents detected little HCH remaining in solution or on the iron surfaces, reinforcing the contention that reaction rather than sorption was the operative mechanism for the HCH removal. Together with previously published work on a wide variety of chlorinated organic solvents, this work further demonstrates the potential of zerovalent iron nanoparticles for treatment and remediation of persistent organic pollutants.     

Simple models for phosphorus loss from manure during rainfall

Mechanistic, predictive equations for phosphorus (P) transport in runoff from manure-applied fields constitute a critical knowledge gap for developing nonpoint-source pollution models. We derived two simple equations to describe the P release from animal manure during a rainfall event-one based on first-order P desorption kinetics and one based on second-order kinetics. The manure characteristics needed in the two kinetic equations are the maximum amount of water-extractable phosphorus (WEP) and a characteristic desorption time. Water-extractable P can be measured directly but currently the characteristic time can only be obtained by fitting experimental data. In addition, we evaluated two models usually used to estimate P loss from soil, the Elovitch equation and power function, both of which relate P loss to time. The models were tested against previously published data of P release from different manures under laboratory conditions. All equations fit the data well. Of the two kinetic equations, the second-order model showed better agreement with the data than the first-order model; for example, maximum relative differences between the model results and measured data were 2.6 and 4.7%, respectively. The characteristic times varied between 20 min for dairy manure and almost 100 min for poultry manure. The characteristic time did not appear to change with flow rate but decreased with smaller manure aggregates. The parameters for power-function relationships could not be related to measured manure characteristics. These results provide the first step to process-based approximations for predicting P release from manure with time during rainfall shortly after land application, when P losses are the greatest.     

Degradation of soil fumigants as affected by initial concentration and temperature

Soil fumigation using shank injection creates high fumigant concentration gradients in soil from the injection point to the soil surface. A temperature gradient also exists along the soil profile. We studied the degradation of methyl isothiocyanate (MITC) and 1,3-dichloropropene (1,3-D) in an Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralf) at four temperatures and four initial concentrations. We then tested the applicability of first-order, half-order, and second-order kinetics, and the Michaelis-Menten model for describing fumigant degradation as affected by temperature and initial concentration. Overall, none of the models adequately described the degradation of MITC and 1,3-D isomers over the range of the initial concentrations. First-order and half-order kinetics adequately described the degradation of MITC and 1,3-D isomers at each initial concentration, with the correlation coefficients greater than 0.78 (r2> 0.78). However, the derived rate constant was dependent on the initial concentration. The first-order rate constants varied between 6 and 10x for MITC for the concentration range of 3 to 140 mg kg(-1), and between 1.5 and 4x for 1,3-D isomers for the concentration range of 0.6 to 60 mg kg(-1), depending on temperature. For the same initial concentration range, the variation in the half-order rate constants was between 1.4 and 1.7x for MITC and between 3.1 and 6.1x for 1,3-D isomers, depending on temperature. Second-order kinetics and the Michaelis-Menten model did not satisfactorily describe the degradation at all initial concentrations. The degradation of MITC and 1,3-D was primarily biodegradation, which was affected by temperature between 20 and 40 degrees C, following the Arrhenius equation (r2 > 0.74).     

A stochastic model for colloid transport and deposition

Profiles of retained colloids in porous media have frequently been observed to be hyper-exponential or non-monotonic with transport depth under unfavorable attachment conditions, whereas filtration theory predicts an exponential profile. In this work we present a stochastic model for colloid transport and deposition that allows various hypotheses for such deviations to be tested. The model is based on the conventional advective dispersion equation that accounts for first-order kinetic deposition and release of colloids. One or two stochastic parameters can be considered in this model, including the deposition coefficient, the release coefficient, and the average pore water velocity. In the case of one stochastic parameter, the probability density function (PDF) is characterized using log-normal, bimodal log-normal, or a simple two species/region formulation. When two stochastic parameters are considered, then a joint log-normal PDF is employed. Simulation results indicated that variations in the deposition coefficient and the average pore water velocity can both produce hyper-exponential deposition profiles. Bimodal formulations for the PDF were also able to produce hyper-exponential profiles, but with much lower variances in the deposition coefficient. The shape of the deposition profile was found to be very sensitive to the correlation of deposition and release coefficients, and to the correlation of pore water velocity and deposition coefficient. Application of the developed stochastic model to a particular set of colloid transport and deposition data indicated that chemical heterogeneity of the colloid population could not fully explain the observed behavior. Alternative interpretations were therefore proposed based on variability of the pore size and the water velocity distributions.     

Sulfadimethoxine degradation kinetics in manure as affected by initial concentration, moisture, and temperature

Sulfadimethoxine is a widely used sulfonamide veterinary antibiotic and could be a source of agricultural contamination. Therefore, information is needed about its degradation kinetics in manure under aerobic conditions. Based on the analysis of first-order kinetics and the assumption that sulfadimethoxine availability for degradation in manure could be limiting, a new kinetic model was developed and was found to fit the degradation kinetics well. The degradation rate in sterile manure was found to be much lower than in nonsterile manure, indicating that biodegradation was significant. In biologically active manure, the degradation rate constant decreased with increasing initial concentration of sulfadimethoxine, implying that the activity of the degrading microorganisms was inhibited. Increasing moisture or temperature was found to increase sulfadimethoxine degradation in manure. Mixing manure containing high levels of sulfadimethoxine with manure containing lower levels may result in more rapid degradation, thus greatly diminishing sulfadimethoxine contamination in manure and significantly reducing sulfadimethoxine inputs into the environment. During treatment, keeping the manure moist and storing in a moderately warm place under aerobic conditions may also help to diminish sulfadimethoxine contamination.     

蚯蚓有机废水土地处理试验研究

利用蚯蚓的有机废水土地处理是一种符合生态平衡的新的处理技术，在这种处理工艺中，含有蚯蚓的土壤对废水中的COD的吸附去除百分数和有机物负荷均比常规的污水土地处理高两倍以上。这一处理过程的机理符合吸附，再生过程的一级反应动力学。