Sorption of metal ions from aqueous solution using bone char

The sorption of cadmium, copper and zinc from aqueous solutions onto bone char has been studied in both single and binary multi-component systems. Equilibrium experimental studies have been performed to determine the sorption capacity of bone char for each metal ion. The isotherm results have been analysed using single and multi-component equilibrium models. The rate of sorption of the metal ions onto bone char has been studied using an agitated batch adsorber. The concentration versus time decay curves have been measured and a number of mass transfer models have been developed and tested based on diffusion controlled sorption. The results of the equilibrium and rate studies are presented and discussed in the paper. The possible mechanisms of metal sorption are also discussed. Finally a series of fixed bed column studies have been performed and analysed using a diffusion mass transport model. The experimental results show a displacement effect for the binary metal ion breakthrough curves.     

Sorption behavior of selenium on humic acid under increasing selenium concentration or increasing solid/liquid ratio

The sorption of selenium (Se) on humic acid (HA) was investigated in order to better understand the fate of stable and radioactive Se in soils and sediments. An ultrafiltration technique was used to determine size distributions of HA-sorbed-Se when increasing Se concentration and solid/liquid ratio. The results showed that the Se sorption onto HA followed the Freundlich isotherm. No solid/liquid ratio-dependence was observed especially when <3 kDa molecular size fraction was used from solid/liquid separation. The Freundlich isotherm parameters K(F) and n obtained using the <3 kDa molecular size fraction for solid/liquid separation were 3.7 x 10(2) and 0.82, respectively. In addition, since dissolved HA increased with decreased ionic strength in the HA suspension, ionic strength could promote aggregation of HA. The conformational change of HA could affect the sorption behavior of Se on HA.     

Adsorption of thorium from aqueous solutions by perlite

The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 ± 1 °C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as ΔG^o, ΔH^o and ΔS^o were calculated as a function of temperature.     

Biogeocomposite material and its heavy metal adsorption potential from aqueous solutions

Biosorption process is emerging as a potential alternative for the heavy metal removal from aqueous solutions. A packed bed column containing biomaterials like papaya leaf powder and paddy straw powder was used for copper removal from aqueous solutions. The breakthrough curve was having an S-shaped profile and the breakthrough time became less with increase in initial concentration. Percentage removal of copper was around 85% and 77% for papaya leaf powder and paddy straw powder, respectively for a contact time of 120 minutes and initial concentration of 10 mg/L. A biogeocomposite material was developed to test the enhancement in adsorption using layers of non-woven geotextile material and a significant increase in adsorption was obtained. With the addition of geotextile material in between papaya powder layer and paddy straw powder, there was an average increase of 12.66% and 11.98%, respectively for the removal. A biocomposite material was developed with a mixture of the two biosorbents and the adsorption value of the biocomposite material was in between the two biosorbents. The applicability of Yoon Nelson model and Adam Bohart model were also evaluated and the most suitable model came out to be Yoon and Nelson model.     

Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6 ± 2.1 and 94.7 ± 3.3% was observed for an initial concentration of 50 and 100 mg L⁻¹, respectively at pH 6.0 and an adsorbent dose of 2.0 g L⁻¹. Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68 ± 5.04 mg g⁻¹. An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (≅100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.     

Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect

This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Sorption and transport of radionuclides by tumbleweeds from two plastic-lined radioactive waste ponds

Previous research has examined the uptake of radionuclides by tumbleweeds growing in contaminated soils, but none has heretofore examined the sorption of radionuclides to tumbleweeds blowing into radioactively contaminated water. Three tumbleweed species; Russian thistle (Salsola kali), Jim Hill mustard (Sisymbrium altissimum) and summer cypress (Kochia scoparia) blow in, and out of, two plastic-lined radioactive wastewater ponds, constructed in 1993 on the US Department of Energy's Idaho National Engineering and Environmental Laboratory in southeast Idaho. This research quantified radionuclide sorption to tumbleweeds, tumbleweed movement from the ponds, and determined radionuclide transport from the ponds. Average plant/water concentration factors associated with tumbleweeds taken from the ponds ranged from 5 for 152Eu to over 9000 for 54Mn. Based on changes in tumbleweed numbers and average concentrations associated with them, 66.2 MBq were estimated to have been transported from the ponds via tumbleweeds between 18 October 1994 and 8 November 1996. This amounts to about 0.01% of the non-tritium and 0.0002% of the tritium activity released to the ponds through 8 November 1996. A power function best described the radionuclide buildup curve for tumbleweeds submerged in the ponds. Visually marked tumbleweeds traveled from the ponds in the predominant wind direction a maximum of 737 m. Management practices which may reduce the number of tumbleweeds blowing both into and out of contaminated ponds are discussed.     

Sorption behaviour of Am on marl groundwater colloids.

The sorption of americium on marl colloids is studied in a comprehensive way. In Na-HCO3 groundwater conditions, americium in the concentration range 3 x 10(-11)-3 x 10(10) M sorbs onto groundwater colloids. In these tests, the colloid concentration is rather high, i.e. Ccoll 1.7+/-1.3 mg l(-1) for sizes 505000 nm or Ncoll (1.7+/-0.1) x 10(11) l(-1) for sizes larger than 100 nm. These colloids are mainly chlorite and smectite/illite with an average size smaller than 500 nm. For the groundwater (pH 8.6, [Na+]-[HCO3]-2 x 10(-2) M), Kd values in the range 1-3 x 10(6)mlg(-1) are measured. These values are compared with experimental and modelled values reported earlier in the literature.     

Sorption of volatile organic compounds on typical carpet fibers

Measurements of adsorption isotherms for three volatile organic compounds (VOCs) (toluene, 1,2-dichlorobenzene and 1,1,1-trichloroethane) on polyacrylonitrile carpet fibers over the temperature range 25-45 degrees C were carried out in a thermogravimetric analyzer (TGA). Linear isotherms were observed in all cases with values of the Henry coefficient ranging from 0.063 to 0.941 mm. The results of additional experiments carried out in a simple test chamber containing a single source of VOC showed that the carpet fibers acted as a significant sink causing a prolonged elevation of VOC concentration in the air within the chamber. An unsteady-state model is presented, which adequately described the adsorption and desorption phenomena occurring in the test chamber and yielded realistic values of the adsorption and desorption rate constants. There was good agreement between the equilibrium and kinetic constants obtained in the TGA and test chamber experiments.     

Biological activity and environmental impact of anionic surfactants

The newest results concerning the biological activity and environmental fate of anionic surfactants are collected and critically evaluated. The chemical and physicochemical parameters related to the biological activity and the field of application are briefly discussed. Examples on the effect of anionic surfactants on the cell membranes, on the activity of enzymes, on the binding to various proteins and to other cell components and on their human toxicity are presented and the possible mode of action is elucidated. The sources of environmental pollution caused by anionic surfactants are listed and the methods developed for their removal from liquid, semiliquid and solid matrices are collected. Both the beneficial and adversary effects of anionic surfactants on the environment are reported and critically discussed. It was concluded that the role of anionic surfactants in the environment is ambiguous: they can cause serous environmental pollution with toxic effect on living organisms; otherwise, they can promote the decomposition and/or removal of other inorganic and organic pollutants from the environment. The relationship between their chemical structure, physicochemical parameters, biological activity and environmental impact is notwell understood. A considerable number of data are needed for the development of new anionic surfactants and for the successful application of the existing ones to reduce the adversary and to promote beneficial effects.     

Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd_sorption) over that of the desorption (Kd_desorption). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10⁻³, 1 × 10⁻⁶ and 1 × 10⁻⁸ mol L⁻¹). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd_sorption > 100 to 1 × 10⁴ L kg⁻¹) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd_sorption 52 L kg⁻¹), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd_sorption 4 L kg⁻¹). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd_sorption was low (8 L kg⁻¹) compared to soil Bu (pH 8) (70 L kg⁻¹). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10⁻³ mol L⁻¹, due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.     

The bioavailability of selenium and risk assessment for human selenium poisoning in high-Se areas,China

Enshi prefecture of Hubei Province is well known for human selenium (Se) poisoning in the early 1960s in China. Sporadic cases of Se poisoning in livestocks are still being found. In this study, Se levels in water, cropland soils and various crops from high-Se areas of Enshi were measured to investigate the distribution and bioavailability of Se in the environments, as well as probable daily intake (PDI) of Se for local residents. The total Se in surface water ranged from 2.0 to 519.3 μg/L with a geometric mean of 46.0 ± 127.8 μg/L (n = 48), 70.5–99.5% of which was present in the form of Se(VI). The soil Se concentration varied from 2.89 to 87.3 μg/g with a geometric mean of 9.36 ± 18.6 μg/g (n = 45), and most of Se was associated with organic matter (OM-Se). The total Se in rice, corn, and vegetable samples were 2.11 ± 2.87 μg/g (n = 21), 3.76 ± 11.6 μg/g (n = 16), and 2.09 ± 3.38 μg/g (n = 25), respectively. Stream water Se is likely leached from carbonaceous shale and mine wastes, leading to Se accumulation in paddy soils. OM-Se may play an important role in Se uptake by rice plant in high-Se area of Enshi.The PDI of Se is approximately 2144 μg/day, and Se concentration in blood is estimated at about 3248 μg/L, posing a potential chronic Se poisoning risk to local residents. Cereal consumption (48.5%) makes a great contribution to human daily Se intake, followed by vegetables (36.6%), meats (8.5%), and drinking water (6.4%). However, when assessing health risk on human in high-Se areas, the contribution of drinking water to daily Se intake cannot be ignored due to high Se content and dominant Se(VI) species. Local inhabitants should be advised not to grow crops in high-Se lands or irrigate using high-Se water. If possible, they should drink pipe water and consume foods mixed with those from outside the high-Se areas.     

Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes

Over the past few years, pharmaceuticals are considered as an emerging environmental problem due to their continuous input and persistence to the aquatic ecosystem even at low concentrations. Advanced oxidation processes (AOPs) are technologies based on the intermediacy of hydroxyl and other radicals to oxidize recalcitrant, toxic and non-biodegradable compounds to various by-products and eventually to inert end-products. The environmental applications of AOPs are numerous, including water and wastewater treatment (i.e. removal of organic and inorganic pollutants and pathogens), air pollution abatement and soil remediation. AOPs are applied for the abatement of pollution caused by the presence of residual pharmaceuticals in waters for the last decade. In this light, this paper reviews and assesses the effectiveness of various AOPs for pharmaceutical removal from aqueous systems.     

Kinetics of radiocesium released from contaminated soil by fertilizer solutions

(137)Cs is one of the major artificial radionuclides found in environments; but the mechanisms behind fertilizer-induced (137)Cs desorption from soil remain unknown. This study aimed to investigate the kinetics and mechanisms underlying the various cations and anions that cause Cs release from soil under acidic conditions. NH(4)H(2)PO(4) (1M), 0.5M (NH(4))(2)SO(4), 1M NH(4)Cl, 1M KCl or 1M NaCl solutions were added to (137)Cs-contaminated soil. The power function model well described the short term (137)Cs desorption with the solutions. The rate coefficients for (137)Cs release from soil in NH(4)H(2)PO(4), (NH(4))(2)SO(4), NH(4)Cl, and KCl solutions were 7.7, 7.3, 6.8, and 6.1 times higher than the rate observed in a NaCl solution, respectively. The NH(4)H(2)PO(4) and (NH(4))(2)SO(4) solutions induced significantly greater (137)Cs release from the contaminated soil than the NH(4)Cl, KCl and NaCl solutions. After four times repeated extractions with the fertilizer solutions, the total amount of (137)Cs extracted by (NH(4))(2)SO(4) and NH(4)Cl solutions reached equilibrium, while that extracted using an NH(4)H(2)PO(4) solution continued to increase. The combined effect of phosphate and protons was the major mechanism behind (137)Cs release from contaminated soils, when an NH(4)H(2)PO(4) solution was used.     

Removal of nitrogen oxides with organic amines and metal complexes

Aqueous solutions containing organic amines and metal complexes were applied for the removal of nitrogen oxides. Organic amines were effective for the removal of the mixture composed of nitric oxide and nitrogen dioxide. In particular, methyl and ethyl amines removed these species with 1 : 1 ratio from the mixture at fairly rapid rates. Dinitrogen trioxide (N₂O₃) was suggested to be involved in the course of the removal.Metal complexes removed nitrogen dioxide efficiently. As has been previously reported for a number of inorganic or organic redox systems, it was concluded that the removal of nitrogen dioxide by metal complexes proceeded also by the redox mechanism.Iron (ii) chelate complexes were highly effective for the removal of nitric oxide and this was attributed to a reversible coordination to the complex.     

Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.     

Spatial variation of carbon monoxide and oxides of nitrogen concentrations inside residences

A spatial comparison of pollutant concentrations within the residential environment is undertaken, comparing pollutant concentrations from three indoor sampling locations (zones). The indoor air quality base was obtained from sampling the indoor air of 12 residential sites and two office buildings in the metropolitan Boston area. Each residential site was monitored continuously for two weeks, and data were reduced into hourly averages. Interzonal comparisons of the mean of hourly averages, 24-h averages, and daily maximum hourly concentrations were made at all sites. Linear regressions were computed between daily maximum hourly concentrations and mean 24-h concentrations of NO, NO₂, and CO for kitchens to determine whether maximum hourly concentrations could be predicted from the 24-h concentration. These pollutants show interzonal statistical differences in residences with gas-fired cooking facilities but not in residences with electric cooking facilities. It was determined that, while one indoor sampling zone is not sufficient to specify indoor pollutant concentration maxima in residences having indoor sources of pollution, the daily mean of hourly pollutant concentrations obtained from one indoor zone can adequately describe the indoor environment. In addition, the maximum indoor hourly concentration for NO, NO₂, and CO can be estimated for residences with all electric facilities, by using the mean 24-h concentration. The reliability of similar estimates for NO, NO₂, and CO in residences with unvented gas appliances is reduced because of substantially more scatter in the paired data point, particularly at higher pollutant concentrations.     

Aluminum, iron, and lead content of respirable particulate samples from a personal monitoring study

Samples of respirable particulate matter collected during a personal monitoring study in Topeka, KS, were analyzed for iron, aluminum, and lead content. The sampling protocol and instrumentation are described in detail. Lead indoor concentrations (median = 79 ng/m³) were found to be less than both personal (median = 112 ng/m³) and outdoor lead concentrations (median = 106 ng/m³). The indoor, outdoor, and personal levels of iron and aluminum were not significantly different. In addition, it was determined that outdoor respirable particulate mass does not correlate well with the personal or indoor metal concentrations, and that the amount of time spent in motor vehicles is a relatively good indicator of lead exposures. The relationships between indoor, outdoor, and personal lead are discussed in greater detail, with references to supporting evidence from other studies.