Determining distribution coefficients for low cost adsorbents

As with other construction materials, coal fly ash contains trace metals that can leach into the natural environment. As part of a broader effort to encourage appropriate coal combustion product use in infrastructure applications (e.g., road construction, stabilization, and structural fill), this study evaluated traditional and low‐cost adsorbent alternatives for their capacity to attenuate trace metals. Batch sorption tests were used as a preliminary screen for a wide variety of low cost (e.g., steel byproducts, rubber dust, and compost) and innovative materials (e.g., kudzu, biofilm, and pond weed) as well as conventional materials (activated carbon, alumina, and zeolites). The removal rates were demonstrated in this study by observing the calculated distribution coefficient (K_d) which were determined using a program called MATLAB. Limestone and steel byproducts were found to be particularly effective with large K_d values of 15,740, 1,520, and 540 L kg^?1 for cadmium, chromium, and selenium and, for ladle refractory and mill scale, K_d values of 3,910, 670, and 1,760 L kg^?1 were observed. Among the three metals tested for this study, it was observed that most low cost and innovative materials removed cadmium quite efficiently; however, the removal of selenium and chromium depended on the substrate and prevailing pH. In general, these results suggest that alternative materials may have relevance in niche applications where leaching is a concern that can be addressed through enhanced attenuation capacity via blending or layering of adsorbents.     

Wastewater Fines Influence the Adsorption Behavior of Pollutants onto Microplastics

Millions of tons of microplastics (MPs) enter the wastewater collection systems every day and interact with raw sewage. In addition to MPs, varieties of organic and inorganic fines from urban effluents release into the sewer system and provide suitable surfaces for adsorption. To better understand the quantitative assessment of MPs sorption in wastewater and the role of fines, batch reactor experiments were performed using synthetic wastewater solutions containing organic, inorganic, and mixed organic–inorganic fines, and the results compared to a solution without fines. The MPs were two types of clean polypropylene (PP) particles, isotactic (iPP) and atactic (aPP). The results showed in all applied solutions the adsorption of pollutants was higher for the aPP averaging 1.3 mg/g compared with 0.5 mg/g for iPP, indicating that the adsorption varies with the type of polymer and surface properties. Further experiments also revealed a decrease in the sorption values of MPs for solutions containing inorganic fines, measured as the partition coefficient (K_d) and adsorbed concentration at equilibrium (q_e). The result of the measured reference conductivity (к₂₅) of the solutions for the same tests showed similar trends indicating that the magnitude of pollution adsorption onto MPs surfaces is controlled by the surface charge potential of the fine particles. The relationship between the qualitative assessments of ion removal, measured in terms of к₂₅, and their quantitative assessment of adsorption values in terms of K_d in several identical tests, verifying that the conductivity of the solution was modified after adsorption of wastewater constituents onto the MPs.

     

Diffusion coefficients of organics in high density polyethylene (HDPE)

Only limited data are available on the diffusion of volatile organic solvents through flexible membrane liners (FMLs) used for lining impoundments and landfills. To expand this database, a rapid, inexpensive method is needed to measure the diffusion coefficients of volatile organic solvents through FML materials. An absorption method has been developed to determine the diffusion coefficients of volatile organic solvents through FML materials. The method is based on the depletion of an organic compound from an aqueous solution due to absorption by a submerged sample of FML. A numerical solution of Fick's second law of diffusion was used to develop a graph which can be used to determine the diffusion coefficient from the time dependent concentration data. The diffusion coefficients obtained from the absorption tests were validated by comparing them with coefficients determined using a two chamber diffusion cell. The diffusion coefficients determined for toluene and xylene in high density polyethylene (HDPE) were 5.1 × 10⁻⁹ cm²s⁻¹ and 1.0 × 10⁻⁹ cm²s⁻¹ by the two methods, respectively. The data indicate that the coefficient of distribution (K_d) between the FML and the organic solution, a value which is needed to calculate the diffusion coefficient from the data, can be estimated from the log of the octanol-water partition coefficient (K_ow), a commonly measured and reported value for many chemicals.     

Effect of soil solids concentration in batch tests on the partition coefficients of organic pollutants in landfill liner-soil materials

 The effect of the soil solids concentration in batch tests on the measured values of the partition coefficient (K _p) of organic pollutants in landfill liner-soil material was investigated. Since this study was based on the results of batch and column tests conducted independently, there were limitations to the conclusions derived. The organic compounds tested were benzene, methylene chloride, toluene, trichloroethylene, and p-xylene. The results of this study showed that as soil solids concentrations increased, the measured K _p values of these organic compounds strongly decreased. The observed values of K _p stabilized when the soil solids concentration was above a certain value. Typical K _p values obtained from batch tests conducted under high soil solids concentrations were close to those obtained from column tests. It was concluded that the K _p values of organic compounds measured under low soil solids concentrations, i.e., less than 100 g/l, may not correctly simulate the field situation. Consequently, the values of K _p obtained with low soil solids concentrations can result in an overestimation of the retardation factor of the landfill liner material. Received: March 14, 2002 / Accepted: August 25, 2002     

Dry-thermophilic anaerobic digestion of organic fraction of municipal solid waste: methane production modeling

The influence of particle size and organic matter content of organic fraction of municipal solid waste (OFMSW) in the overall kinetics of dry (30% total solids) thermophilic (55 °C) anaerobic digestion have been studied in a semi-continuous stirred tank reactor (SSTR). Two types of wastes were used: synthetic OFMSW (average particle size of 1 mm; 0.71 g Volatile Solids/g waste), and OFMSW coming from a composting full scale plant (average particle size of 30 mm; 0.16 g Volatile Solids/g waste).A modification of a widely-validated product-generation kinetic model has been proposed. Results obtained from the modified-model parameterization at steady-state (that include new kinetic parameters as K, Y_pMAX and θ_MIN) indicate that the features of the feedstock strongly influence the kinetics of the process. The overall specific growth rate of microorganisms (μ_max) with synthetic OFMSW is 43% higher compared to OFMSW coming from a composting full scale plant: 0.238 d⁻¹ (K = 1.391 d⁻¹; Y_pMAX = 1.167 L CH₄/gDOC_c; θ_MIN = 7.924 days) vs. 0.135 d⁻¹ (K = 1.282 d⁻¹; Y_pMAX = 1.150 L CH₄/gDOC_c; θ_MIN = 9.997 days) respectively.Finally, it could be emphasized that the validation of proposed modified-model has been performed successfully by means of the simulation of non-steady state data for the different SRTs tested with each waste.     

Eco-Friendly, Vascular Shape and Interpenetrating Poly (Acrylic Acid) Grafted Pectin Hydrogels; Biosorption and Desorption Investigations

The synthesis and characterization of poly (acrylic acid) grafted pectin hydrogel followed by biosorption and desorption characteristics of cadmium, as a model heavy metal, have been studied. The grafted eco-friendly pectin based interpenetrating hydrogel was prepared in the presence of gluteraldehyde crosslinker under N₂ atmosphere and characterized using ¹H-NMR, FTIR, TGA and SEM techniques. Gluteraldehyde was found to form one-arm and two-arm crosslinks in the copolymer. Upon grafting, two-dimensional sheet structures bounded to tubular and vascular cylindrical rods were observed. The biosorption and desorption data, determined experimentally, were fitted to pseudo-second order reaction kinetics. At higher ionic strength values, the maximum metal uptake value (q _max) was lowered and pseudo-second order rate constant (k ₂) was increased. Whereas, at higher pH values the maximum metal uptake value (q _max) was increased and Pseudo-second order rate constant (k ₂) was decreased. 0.1?M HCl solution was a suitable eluent to regenerate the hydrogel surface and recover the adsorbed cadmium metal ions. Pectin based copolymer could be used as an efficient candidature biosorbent for the recovery of cadmium metal ions from aqueous solutions.     

Simulation of Nitrogen Dynamics and Fluxes in Contrasting Catchments in Norway by Applying the Integrated Nitrogen Model for Catchments (INCA)

The process-based INCA model was applied to Dalelva Brook (3.2 km²) and the Bjerkreim River (685 km²) including several subcatchments, in order to test the model's ability to simulate streamwater nitrate (NO₃ ^-) dynamics and output fluxes under highly contrasting climatic conditions and nitrogen (N) loading. The simulated runoff volumes and mean NO₃ ^- concentrations at Dalelva and Bjerkreimwere within +2 to +10% of the measured average during 1993–1995 (–19 to +31% within individual years). INCA to a great extent also reproduced the observed streamwater flow dynamics at both study sites (coefficient of determination, r ² > 0.70). Temporal variation of streamwater NO₃ ^- during 1993–1995 was captured quite well by the model, especially at small catchments with a distinct seasonal NO₃ ^- pattern (r ² = 0.46–0.68). At the Bjerkreim River outlet, the relationship were somewhat weaker (r ² = 0.26, p < 0.01). Despite a few situations where the model failed to capturethe streamwater NO₃ ^- dynamics, INCA proved to be a quite robust tool for simulating NO₃ ^- dynamics and output fluxes in the two study catchments.     

Response surface analysis of effects of hydraulic retention time and influent feed concentration on performance of an UASFF bioreactor

The interactive effects of hydraulic retention time (HRT) and influent chemical oxygen demand (COD_in) on the performance of an up-flow anaerobic sludge fixed film (UASFF) bioreactor treating palm oil mill effluent (POME) was studied. Anaerobic digestion of POME was modeled and analyzed with two variables i.e. HRT and COD_in. Experiments were conducted based on a general factorial design and analyzed using response surface methodology (RSM). The region of exploration for digestion of POME was taken as the area enclosed by HRT (1–6 days) and COD_in (5260–34,725 mg/l) boundaries. Eight dependent parameters were either directly measured or calculated as response. Increase in the variables resulted in decrease in COD removal efficiency, solid retention time (SRT) and sludge retention factor (SRF) and increase of COD removal rate, volatile fatty acid to alkalinity ratio (VFA/Alk), CO₂ percentage in biogas and methane production rate. The value of the maximum specific microbial growth rate (μ_m) determined through the equation that correlated organic loading rate (OLR) and μ (calculated by quadratic model for SRF) was found to be 0.153 d^?1. This value was close to that obtained using Chen and Hashimoto kinetic equation (0.207 d^?1) in a previous study. The present study provides valuable information about interrelations of quality and process parameters in POME digestion using a UASFF bioreactor.     

The effect of bed properties on methane removal in an aerated biofilter--model studies

The capacity of laboratory-scale aerated biofilters to oxidize methane was investigated. Four types of organic and mineral-organic materials were flushed with a mixture of CH₄, CO₂ and air (1:1:8 by volume) during a six-month period. The filter bed materials were as follows: (1) municipal waste compost, (2) an organic horticultural substrate, (3) a composite of expanded perlite and compost amended with zeolite, and (4) the same mixture of perlite and compost amended with bentonite. Methanotrophic capacity during the six months of the experiment reached maximum values of between 889 and 1036 g m⁻² d⁻¹. Batch incubation tests were carried out in order to determine the influence of methane and oxygen concentrations, as well as the addition of sewage sludge, on methanotrophic activity. Michaelis constants K_M for CH₄ and O₂ were 4.6-14.9%, and 0.7-12.3%, respectively. Maximum methanotrophic activities V_max were between 1.3 and 11.6 cm³ g⁻¹ d⁻¹. The activity significantly increased when sewage sludge was added. The main conclusion is that the type of filter bed material (differing significantly in organic matter content, water-holding capacity, or gas diffusion coefficient) was not an important factor in determining methanotrophic capacity when oxygen was supplied to the biofilter.     

Streambed Sediment Geochemical Controls on In-Stream Phosphorus Concentrations during Baseflow

A spatially extensive geochemical data set of stream water and bed sediment composition across the Tamar catchment in south-west England was analysed to identify the key bed sediment properties that control the in-stream dissolved reactive phosphorus (DRP) concentrations during baseflow conditions. Linear regression analysis of the streamwater DRP concentrations and the distribution coefficient K _d for DRP revealed that the former is positively correlated with total SiO₂ and Al₂O₃, and negatively correlated with K₂O. The primary control on these major element distributions is the dominant bedrock geology. The data suggest that streamwater DRP concentrations are mainly controlled by adsorption to clay minerals. Where P concentrations in streamwater were considerably elevated by inputs from point sources, DRP concentrations are also controlled by precipitation of hydroxyapatite.     

Extracellular Biopolymer Production by Aureobasidium pullulans MTCC 2195 Using Jackfruit Seed Powder

In this present paper, statistical screening and optimization of jackfruit seed powder based medium components were investigated for pullulan production from Aureobasidium pullulans. Seven medium variables jackfruit seed powder, K₂HPO₄, yeast extract, (NH₄)₂SO₄, NaCl, MgSO₄·7H₂O and ZnSO₄·7H₂O were screened by employing Plackett–Burman (PB) method. PB method showed jackfruit seed powder, ZnSO₄·7H₂O, K₂HPO₄ and yeast extract were significant. Central composite design of response surface method applied to optimize the significant variables identified from the PB experiment. Statistical analysis of the experimental results showed optimal values were found to be jackfruit seed powder 2 % (w/v), K₂HPO₄ 0.55 % (w/v), yeast extract 0.30 % (w/v) and ZnSO₄·7H₂O 0.006 % (w/v) with maximum pullulan concentration of 18.76 (g/L). Maximum pullulan concentration of 17.95 (g/L) was observed in the validation experiment. This experimental result explained the model was fitted 96 % as compare with the result predicted by response surface method.     

The biogenic content of process streams from mechanical–biological treatment plants producing solid recovered fuel. Do the manual sorting and selective dissolution determination methods correlate?

The carbon emissions trading market has created a need for standard methods for the determination of biogenic content (χ_B) in solid recovered fuels (SRF). We compare the manual sorting (MSM) and selective dissolution methods (SDM), as amended by recent research, for a range of process streams from a mechanical–biological treatment (MBT) plant. The two methods provide statistically different biogenic content values, as expressed on a dry mass basis, uncorrected for ash content. However, they correlate well (r² > 0.9) and the relative difference between them was <5% for χ_B between 21% ^w/w_d and 72% ^w/w_d (uncorrected for ash content). This range includes the average SRF biogenic content of ca. 68% ^w/w_d. Methodological improvements are discussed in light of recent studies. The repeatability of the SDM is characterised by relative standard deviations on triplicates of <2.5% for the studied population.     

Simulation of substrate degradation in composting of sewage sludge

To simulate the substrate degradation kinetics of the composting process, this paper develops a mathematical model with a first-order reaction assumption and heat/mass balance equations. A pilot-scale composting test with a mixture of sewage sludge and wheat straw was conducted in an insulated reactor. The BVS (biodegradable volatile solids) degradation process, matrix mass, MC (moisture content), DM (dry matter) and VS (volatile solid) were simulated numerically by the model and experimental data. The numerical simulation offered a method for simulating k (the first-order rate constant) and estimating k₂₀ (the first-order rate constant at 20 °C). After comparison with experimental values, the relative error of the simulation value of the mass of the compost at maturity was 0.22%, MC 2.9%, DM 4.9% and VS 5.2%, which mean that the simulation is a good fit. The k of sewage sludge was simulated, and k₂₀, k_20s (first-order rate coefficient of slow fraction of BVS at 20 °C) of the sewage sludge were estimated as 0.082 and 0.015 d^?1, respectively.     

Geographic information systems (GIS) based model of dairy manure transportation and application with environmental quality consideration

Survey information was used to develop a minimum cost spatial dairy manure transportation model where environmental quality and crop nutrient requirements were treated as constraints. The GIS model incorporated land use types, exact locations of dairy farms and farmlands, road networks, and distances from each dairy farm to receiving farmlands to identify dairy manure transportation routes that minimized costs relative to environmental and other constraints. Our analyses indicated that the characteristics of dairy manure, its bulk and relatively low primary N, P₂O₅ and K₂O nutrient levels limit the distribution areas or distances between the farms and the land over which the manure can be economically spread. Physical properties of the land limit the quantities of nutrients that can be applied because of excess nutrient buildup in soil and potential to harm nearby waterbodies and downstream people and places. Longer distances between dairy and farmland favor the use of commercial fertilizers due to the high cost of manure transportation. At $0.08 per ton per km transportation cost, the optimal cut-off distances for dairy manure application is 30 km for N and 15 km each for P₂O₅ and K₂O consistent rules. An analysis of dairy manure application to different crop types suggest that, on average, 1 ha of land requires 61 tons of dairy manure to meet the recommended N, P₂O₅ and K₂O needs.     

New Numerical Model Study on a Tidal Flat System – Seasonal,Daily and Tidal Variations

We developed a new numerical model to investigate the dynamics of tidal flat ecosystems and their role in water quality in terms of the carbon cycle. This model was applied to Isshiki, a natural tidal flat area, which is the largest in Mikawa Bay, Japan.This model dealt with variations of biochemical or physical interaction among dissolved oxygen and C–N–P species (comprised of carbon, nitrogen, and phosphorus elements) both on a short-time scale (<24 h) as well as over a long-time scale (seasonal variation). The model indicated that the time dependence on phytoplankton, NH₄–N, NO_x–N, and PO₄–P are more sensitive to daily environmental variation than to seasonal environmental variation. This means that the rotation speed of these materials in the tidal flat area is fast. Here, we defined the rotation speed as the ratio of total fluxes of substance to the mass of the substance. Phytoplankton with a high rotation speed in the tidal flat area means that the tidal flat has the potential to recover from rapidly increasing phytoplankton: red tide. The model also indicated that the peculiar feature of the tidal flat is the mineralization of organic material. The effect on a long term base, is that it prevents the accumulation of sediment, which results in controlling the increase of oxygen consumption in benthic system, which is the cause of oxygen depleted water.     

Integration of the Pesticide Impact Rating Index with a Geographic Information System for the Assessment of Pesticide Impact on Water Quality

The pesticide impact rating index (PIRI) has been integrated with a Geographic Information System (GIS) to enable regional assessment of pesticide impact on groundwater and surface water resources. The GIS version of PIRI (PIRI-GIS) was used to assess the impact of pre-planting atrazine use in the pine plantations on the Gnangara Mound, Western Australia. The impact on groundwater was found to be spatially variable, mainly dependent on soil type and depth to groundwater, because land use variables were spatially constant. Areas with the greatest impact on groundwater were those where the soil had a low sorption capacity for atrazine. Knowledge of the spatial distribution of the sorption coefficient based on organic carbon (K _oc) for atrazine was found to significantly improve the results from PIRI-GIS. Average values for K _oc (i.e. based on overseas data) were too low for most of the local soil types, resulting in a general overestimation of pesticide impact on groundwater resources, but an underestimation of impact in areas that should be of greatest concern (i.e. where the soil has a low sorption capacity for atrazine).     

Compost mixture influence of interactive physical parameters on microbial kinetics and substrate fractionation

Composting is a feasible biological treatment for the recycling of wastewater sludge as a soil amendment. The process can be optimized by selecting an initial compost recipe with physical properties that enhance microbial activity. The present study measured the microbial O₂ uptake rate (OUR) in 16 sludge and wood residue mixtures to estimate the kinetics parameters of maximum growth rate μ_m and rate of organic matter hydrolysis K_h, as well as the initial biodegradable organic matter fractions present. The starting mixtures consisted of a wide range of moisture content (MC), waste to bulking agent (BA) ratio (W/BA ratio) and BA particle size, which were placed in a laboratory respirometry apparatus to measure their OUR over 4 weeks. A microbial model based on the activated sludge process was used to calculate the kinetic parameters and was found to adequately reproduced OUR curves over time, except for the lag phase and peak OUR, which was not represented and generally over-estimated, respectively. The maximum growth rate μ_m, was found to have a quadratic relationship with MC and a negative association with BA particle size. As a result, increasing MC up to 50% and using a smaller BA particle size of 8–12 mm was seen to maximize μ_m. The rate of hydrolysis K_h was found to have a linear association with both MC and BA particle size. The model also estimated the initial readily biodegradable organic matter fraction, MB₀, and the slower biodegradable matter requiring hydrolysis, MH₀. The sum of MB₀ and MH₀ was associated with MC, W/BA ratio and the interaction between these two parameters, suggesting that O₂ availability was a key factor in determining the value of these two fractions. The study reinforced the idea that optimization of the physical characteristics of a compost mixture requires a holistic approach.     

BMP estimation of landfilled municipal solid waste by multivariate statistical methods using specific waste parameters: case study of a sanitary landfill in Turkey

The main objective of this study was to determine whether methane potential of waste could be estimated more easily by a limited number of waste characterization variables. 36 samples were collected from 12 locations and 3 waste depths in order to represent almost all waste ages at the landfill. Actual remaining methane potential of all samples was determined by the biochemical methane potential (BMP) tests. The cumulative methane production of closed landfill (cLF) samples reached 75–125 mL at the end of experiment duration, while the samples from active landfill (aLF) produced in average 216–266 mL methane. The average experimental k and L ₀ values of cLF and aLF were determined by non-linear regression using BMP data with first-order kinetic equation as 0.0269 day^?1–30.38 mL/g dry MSW and 0.0125 day^?1–102.1 mL/g dry MSW, respectively. The principal component analysis (PCA) was applied to analyze the results for cLF and aLF along with BMP results. Three PCs for the data set were extracted explaining 72.34 % variability. The best MLR model for BMP prediction was determined for seven variables (pH–Cl–TKN–NH4–TOC–LOI–Ca). R ² and Adj. R ² values of this best model were determined as 80.4 and 75.3 %, respectively.     

Characterization and recycling of cadmium from waste nickel–cadmium batteries

A severe threat was posed due to improper and inefficient recycling of waste batteries in China. The present work considered the fundamental aspects of the recycling of cadmium from waste nickel–cadmium batteries by means of vacuum metallurgy separation in scale-up. In the first stage of this work, the characterization of waste nickel–cadmium batteries was carried out. Five types of batteries from different brands and models were selected and their components were characterized in relation to their elemental chemical composition and main phase. In the second stage of this work, the parameters affecting the recycling of cadmium by means of vacuum metallurgy separation were investigated and a L₁₆ (4⁴) orthogonal design was applied to optimize the parameters. With the thermodynamics theory and numerical analysis, it can be seen that the orthogonal design is an effective tool for investigating the parameters affecting the recycling of cadmium. The optimum operating parameters for the recycling of cadmium obtained by orthogonal design and verification test were 1073 K (temperature), 2.5 h (heating time), 2 wt.% (the addition of carbon powder), and 30 mm (the loaded height), respectively, with recycling efficiency approaching 99.98%. The XRD and ICP-AES analyzed results show that the condensed product was characterized as metallic cadmium, and cadmium purity was 99.99% under the optimum condition.     

Acid soluble bio-organic substances isolated from urban bio-waste. Chemical composition and properties of products

As previous work proposed commercial expectations for soluble bio-organic substances (SBO) isolated from compost of urban food, gardening and park trimming residues as chemical auxiliaries, nine urban bio-wastes (BW) treated by aerobic and anaerobic digestion for 0-360 days were used to extract SBO and investigate source variability effects on product chemical composition and properties. The bio-wastes were collected over a 13732 km² area populated by 2.9 millions from 565 municipalities. The SBO were characterized by their content of different C types and functional groups and by their distribution coefficient (K_PEGW) between polyethylene glycol and water. A significant linear correlation was found between K_PEGW and the lipophilic/hydrophilic C ratio. The investigated SBO exhibited up to sixfold change of K_PEGW demonstrating that BW available from densely populated urban areas are an interesting exploitable source of a wide variety of potential products for the chemical market.