Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Hydrate formation during CO2 transport: Predicting water content in the fluid phase in equilibrium with the CO2-hydrate

In order to evaluate the risk of hydrate formation in CO₂ transport one has to be able to predict the water content in the fluid phase in equilibrium with the CO₂-hydrate. A literature review has identified some knowledge gaps, for example, there are no results available at temperatures lower than 243.15 K (?30 °C); and none of the models found in literature predicts the water content with high accuracy. A model based on equality of water fugacity in fluid and hydrate phase is presented here and used for the predictions of water content in equilibrium with hydrates. Although this model gives better accuracy in the overall temperature and pressure ranges of measurements than the models found in the literature, it is not accurate enough to satisfy the requirements of CO₂ transport. The simulation results also show that it is possible to form hydrate at low water content, such as x_w = 50 vppm, if temperature is low enough. In order to verify the results and improve the model accuracy further, more experimental data in a larger temperature and pressure region are required.     

Resampling methods for evaluating classification accuracy of wildlife habitat models

Predictive models of wildlife-habitat relationships often have been developed without being tested The apparent classification accuracy of such models can be optimistically biased and misleading. Data resampling methods exist that yield a more realistic estimate of model classification accuracy These methods are simple and require no new sample data. We illustrate these methods (cross-validation, jackknife resampling, and bootstrap resampling) with computer simulation to demonstrate the increase in precision of the estimate. The bootstrap method is then applied to field data as a technique for model comparison We recommend that biologists use some resampling procedure to evaluate wildlife habitat models prior to field evaluation.     

Empirical Comparison of Temperature-Distribution Models for Energy and Exergy Analyses of Stratified Thermal Energy Storages

Five previously developed temperature-distribution models are compared using data from actual thermal energy storage (TES) systems, and the advantages and disadvantages of each model are identified. These models are used for evaluating the energy and exergy in a TES. Furthermore, the accuracy and simplicity of the temperature-distribution models (Linear, Stepped, Continuous-linear, Three-zone and General-linear) are compared in order to determine which model has the greatest accuracy and simplicity regarding computational effort, while providing physical understanding. After fitting the models to temperature data for 35 stratified TES samples, it was observed that some models are easy to use but relatively inaccurate, while others are relatively accurate but complicated to use. As a trade-off, the Three-zone model provides physical understanding, yields acceptable accuracy and is relatively simple to use, especially in computing the parameters needed for energy and exergy assessments of stratified TESs.     

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.     

Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions

For immobilization technologies to be successful, the use of readily available and cost advantageous amendment is important when the remediation targets vast amounts of contaminated soils. The objectives of this study were to investigate whether the byproduct-synthesized hydroxyapatite can be used as an immobilizing amendment for dissolved Pb from a shooting range soil, and to model the kinetic data collected from dissolution experiments. A soil–solution kinetic experiment was conducted under fixed pH conditions as a function of time. A Pb-contaminated soil was reacted with various hydroxyapatite amendments to determine the dissolution rate and mineral products of soil Pb. Three types of amendments used were pure hydroxyapatite (HA), and poorly crystalline hydroxyapatites synthesized from gypsum waste (CHA), and synthesized from incinerated poultry litter (PHA). The dissolved Pb concentration decreased with the addition of amendments at pH 3–7. Both CHA and PHA were more effective than HA for attenuating Pb dissolution at pH 6 and above. According to the thermodynamic calculation at pH 6, the dissolved Pb concentration for CHA and PHA treatments was predicted to be 66% and 50% lower than that of HA treatment, respectively. A better Pb immobilization effect demonstrated by CHA and PHA resulted in their greater solubility at higher pH, which may promote the formation of chloropyromorphite precipitates. Dissolution kinetics of soil Pb was adequately explained by pseudo-first order and pseudo-second order equations in acid pH ranges. According to the ion exchange model, an adequate agreement between the experimental data and regression curves was shown in the initial 40 min of the reaction process, but the accuracy of model predictability decreased thereafter. According to kinetic models and dissolution phenomena, CHA and PHA amendments had better Pb sorption capacity with rapid kinetics than pure hydroxyapatite at weak acid to neutral pH.     

Integrating Environmental and Socio-Economic Indicators of a Linked Catchment–Coastal System Using Variable Environmental Intensity

Can we develop land use policy that balances the conflicting views of stakeholders in a catchment while moving toward long term sustainability? Adaptive management provides a strategy for this whereby measures of catchment performance are compared against performance goals in order to progressively improve policy. However, the feedback loop of adaptive management is often slow and irreversible impacts may result before policy has been adapted. In contrast, integrated modelling of future land use policy provides rapid feedback and potentially improves the chance of avoiding unwanted collapse events. Replacing measures of catchment performance with modelled catchment performance has usually required the dynamic linking of many models, both biophysical and socio-economic—and this requires much effort in software development. As an alternative, we propose the use of variable environmental intensity (defined as the ratio of environmental impact over economic output) in a loose coupling of models to provide a sufficient level of integration while avoiding significant effort required for software development. This model construct was applied to the Motueka Catchment of New Zealand where several biophysical (riverine water quantity, sediment, E. coli faecal bacteria, trout numbers, nitrogen transport, marine productivity) models, a socio-economic (gross output, gross margin, job numbers) model, and an agent-based model were linked. An extreme set of land use scenarios (historic, present, and intensive) were applied to this modelling framework. Results suggest that the catchment is presently in a near optimal land use configuration that is unlikely to benefit from further intensification. This would quickly put stress on water quantity (at low flow) and water quality (E. coli). To date, this model evaluation is based on a theoretical test that explores the logical implications of intensification at an unlikely extreme in order to assess the implications of likely growth trajectories from present use. While this has largely been a desktop exercise, it would also be possible to use this framework to model and explore the biophysical and economic impacts of individual or collective catchment visions. We are currently investigating the use of the model in this type of application.     

Thermogravimetric pyrolysis of waste polyethylene-terephthalate and polystyrene: A critical assessment of kinetics modelling

Pyrolysis is considered as possible technique to thermally convert waste plastics into chemicals and energy. Literature on experimental findings is extensive, although experiments are mostly performed in a dynamic heating mode, using thermogravimetric analysis (TGA) and at low values of the heating rate (mostly below 30 K/min). The present research differs from literature through the application of far higher heating rates, up to 120 K/min. The use of these dynamic results to define the reaction kinetics necessitates the selection of an appropriate reaction mechanism, and 21 models have been proposed in literature considering the rate limiting step being diffusion, nucleation or the reaction itself.The current research studied the cracking of PET and PS by TGA at different heating rates (temperature ramps). Results were used to check the validity of the proposed mechanisms. Several conclusions are drawn: (i) to obtain fair results, the heating ramp should exceed a minimum value, calculated at 30 K/min for PET and 80 K/min for PS; (ii) application of the majority of the models to experimental findings demonstrated that they do not meet fundamental kinetic considerations and are questionable in their use; and (iii) simple models, with reaction order 1 or 2, provide similar results of the reaction activation energy.A further comparison with literature data for dynamic and isothermal experiments confirms the validity of these selected models. Since TGA results are obtained on a limited amount of sample, with results being a strong function of the applied heating rate, the authors believe that isothermal experiments, preferably on a large scale both towards equipment and/or sample size, are to be preferred.     

Comparative Evaluation of Three River Water Quality Models1

Abstract: Selection of a biochemical oxygen demand (BOD) reaction model to incorporate into dissolved oxygen (DO) water quality models is an overlooked choice available to river water quality modelers. Data from rivers can serve in screening methods to discriminate between competing water quality models. In this study, 15 published BOD and DO datasets based on a 7 year long study of the Bormida River in Italy are used to calibrate three‐multiorder BOD models: first‐order, three‐halves order, and second‐order, which are then included in three corresponding DO models which incorporate these BOD models. The adequacy of the first‐order, three‐halves order and second‐order BOD models was evaluated by calculating the root mean square error between a model and data. A similar procedure was followed to evaluate three DO models, each of which incorporated one of the three BOD models. The first‐order BOD model most frequently fit the river data best, followed by the three‐halves order and the second‐order BOD models. The DO model incorporating a first‐order BOD model most frequently fit the data best, followed by the DO order incorporating second‐order BOD and the DO model incorporating three‐halves order BOD.     

Suitability of different erosivity models used in RUSLE2 for the South West Indian region

RUSLE2 is the most used soil erosion model in practice. The rainfall-erosivity factor (R) is one of the six factors that is taken into consideration while estimating soil loss at a hill slope profile. R is determined using rainfall data collected from any region making use of basic rainstorm kinetic energy versus rainfall intensity relationships, which are variable for different geographic regions. Indian researchers used a specific erosivity model for building an iso-erosivity map for India. Many other erosivity models around the world are now available. However, it is not clear whether one can replace RUSLE2 recommended model by the ones derived in other geographic regions for using in Indian soil erosion studies. This has been examined here on south-western Indian data. Various models derived in diverse places were analyzed and compared with the RUSLE2 recommended relationship; and found that, a few could very well replace the usual RUSLE2 recommended expression.     

Ecosystem Manipulation Experimentation as a Means of Testing a Biogeochemical Model

2 concentration, and global or regional temperature change. Such model projections are frequently used as the basis or justification for public policy decisions and legislation. A substantial need has therefore arisen to test and substantiate the veracity of mathematical model projections. Unfortunately, environmental models can never be truly validated because natural systems are never closed and model solutions are always nonunique. Partial model confirmation is possible, however, and entails demonstration of agreement between prediction and observation. Experimental ecosystem manipulation provides one of the best, and in many cases only, available basis for model confirmation. The use and potential misuse of data from experimental ecosystem manipulations for model testing is explored using examples drawn from the application of an acid–base chemistry model, MAGIC. As model projections provide an increasingly important basis for public policy decisions, and as both the scientific questions and the models become increasingly complex, it will become critical to provide data from a suite of well-designed ecosystem manipulation experiments in order to evaluate the quality and uncertainty of those model projections and the models upon which they are based.     

Adsorption studies of hazardous malachite green onto treated ginger waste

Adsorption of malachite green (MG) from aqueous solution onto treated ginger waste (TGW) was investigated by batch and column methods. The effect of various factors such as initial dye concentration, contact time, pH and temperature were studied. The maximum adsorption of MG was observed at pH 9. Langmuir and Freundlich isotherms were employed to describe the MG adsorption equilibrium. The monolayer adsorption capacities were found to be 84.03, 163.9 and 188.6 mg/g at 30, 40 and 50 °C, respectively. The values of thermodynamic parameters like ΔG°, ΔH° and ΔS° indicated that adsorption was spontaneous and endothermic in nature. The pseudo second order kinetic model fitted well in correlation to the experimental results. Rechienberg's equation was employed to determine the mechanism of adsorption. The results indicated that film diffusion was a major mode of adsorption. The breakthrough capacities were also investigated.     

Application of cupuassu shell as biosorbent for the removal of textile dyes from aqueous solution

The cupuassu shell (Theobroma grandiflorum) which is a food residue was used in its natural form as biosorbent for the removal of C.I. Reactive Red 194 and C.I. Direct Blue 53 dyes from aqueous solutions. This biosorbent was characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption/desorption curves. The effects of pH, biosorbent dosage and shaking time on biosorption capacities were studied. In acidic pH region (pH 2.0) the biosorption of the dyes were favorable. The contact time required to obtain the equilibrium was 8 and 18 h at 298 K, for Reactive Red 194 and Direct Blue 53, respectively. The Avrami fractionary-order kinetic model provided the best fit to experimental data compared with pseudo-first-order, pseudo-second-order and chemisorption kinetic adsorption models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Radke-Prausnitz isotherm models. For both dyes the equilibrium data were best fitted to the Sips isotherm model.     

ACCURACY AND PRECISION OF NRCS MODELS FOR SMALL WATERSHEDS1

ABSTRACT: In the last 30 years, the National Resource Conservation Service's TR‐55 and TR‐20 models have seen a dramatic increase in use for stormwater management purposes. This paper reviews some of the data that were originally used to develop these models and tests how well the models estimate annual series peak runoff rates for the same watersheds using longer historical data record lengths. The paper also explores differences between TR‐55 and TR‐20 peak runoff rate estimates and time of concentration methods. It was found that of the 37 watersheds tested, 25 were either over‐ or under‐predicting the actual historical watershed runoff rates by more than 30 percent. The results of this study indicate that these NRCS models should not be used to model small wooded watersheds less than 20 acres. This would be especially true if the watershed consisted of an area without a clearly defined outlet channel. This study also supports the need for regulators to allow educated hydrologists to alter pre‐packaged model parameters or results more easily than is currently permitted.     

Modeling Fire Susceptibility to Delineate Wildland–Urban Interface for Municipal-Scale Fire Risk Management

The wildland–urban interface (WUI) is the region where development meets and intermingles with wildlands. The WUI has an elevated fire risk due to the proximity of development and residents to wildlands with natural wildfire regimes. Existing methods of delineating WUI are typically applied over a large region, use proxies for risk, and do not consider site-specific fire hazard drivers. While these models are appropriate for federal and provincial risk management, municipal managers require models intended for smaller regions. The model developed here uses the Burn-P3 fire behavior model to model WUI from local fire susceptibility (FS) in two study communities. Forest fuel code (FFC) maps for the study communities were modified using remote sensing data to produce detailed forest edges, including ladder fuels, update data currency, and add buildings and roads. The modified FFC maps used in Burn-P3 produced bimodal FS distributions for each community. The WUI in these communities was delineated as areas within community bounds where FS was greater than or equal to ?1 SD from the mean FS value ( ${\text{WUI}} = {\text{FS}} \geqslant - 1 \, [\bar \chi - \sigma ]$ ), which fell in the trough of the bimodal distribution. The WUI so delineated conformed to the definition of WUI. This model extends WUI modeling for broader risk management initiatives for municipal management of risk, as it (a) considers site-specific drivers of fire behavior; (b) models risk, represented by WUI, specific to a community; and, (c) does not use proxies for risk.     

Multi-criteria risk management with the use of <Emphasis Type="Italic">DecernsMCDA</Emphasis>: methods and case studies

Emerging challenges of risk management, environmental protection, and land-use planning requires integration of stakeholder values and expert judgment. The process of decision making in situation of high uncertainty can be assisted through the use of decision support systems (DSSs). Such DSSs are often based on tools for spatial data representation (GIS) and environmental models that are integrated using multi-criteria decision analysis (MCDA). This paper presents DecernsMCDA implementing all major types of multi-criteria methods and tools (AHP, MAUT, Outranking) under the same user interface. In addition to providing ability for testing model uncertainty associated with selection of specific MCDA algorithms, DecernsMCDA implements new algorithms for parameter uncertainty analysis based on probabilistic approaches and fuzzy sets. The paper illustrates application of DecernsMCDA for selecting remedial alternative at radiologically contaminated sites.     

Oxidation of organic impurities in the recycle and reclaim loops of ultra-pure water plants

 The oxidation of trace organic impurities in ultrapure water by ultraviolet light (UV), ozone, and the combination of UV/ozone is investigated. The emphasis is on the development of a global model to simulate the process that take place in the typical oxidation reactors used in ultrapure water plants. The study also focuses on reaction mechanism for oxidation of multi-component organic impurities. Eighteen organic model compounds are chosen as representative contaminants. The results demonstrate and confirm a significant synergistic effect between UV and ozone oxidation. A mechanism for the synergistic oxidation of organic impurities is proposed and validated with experimental data. The combination of the reaction and the reactor models is used to determine the fundamental kinetic parameters involved in the three oxidation processes. Received: 3 July 1998 / Accepted: 4 September 1998     

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic,equilibrium, and thermodynamic studies

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4 h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.     

The Effects of Population Density on Juvenile Growth Rate in White-Tailed Deer

Animal body size is driven by habitat quality, food availability, and nutrition. Adult size can relate to birth weight, to length of the ontogenetic growth period, and/or to the rate of growth. Data requirements are high for studying these growth mechanisms, but large datasets exist for some game species. In North America, large harvest datasets exist for white-tailed deer (Odocoileus virginianus), but such data are collected under a variety of conditions and are generally dismissed for ecological research beyond local population and habitat management. We contend that such data are useful for studying the ecology of white-tailed deer growth and body size when analyzed at ordinal scale. In this paper, we test the response of growth rate to food availability by fitting a logarithmic equation that estimates growth rate only to harvest data from Fort Hood, Texas, and track changes in growth rate over time. Results of this ordinal scale model are compared to previously published models that include additional parameters, such as birth weight and adult weight. It is shown that body size responds to food availability by variation in growth rate. Models that estimate multiple parameters may not work with harvest data because they are prone to error, which renders estimates from complex models too variable to detect interannual changes in growth rate that this ordinal scale model captures. This model can be applied to harvest data, from which inferences about factors that influence animal growth and body size (e.g., habitat quality and nutritional availability) can be drawn.