Utilization of Passion Fruit Skin By-Product as Lead(II) Ion Biosorbent

The impact of three commercially available nanoparticles (NPs) on trichloroethylene (TCE) adsorption onto granular activated carbon (GAC) was investigated. TCE adsorption isotherm and column breakthrough experiments were conducted in the presence and absence of silicon dioxide, titanium dioxide, and iron oxide nanoparticles. A rapid small-scale column test (RSSCT) was assessed for its ability to predict TCE adsorption in pilot-scale GAC in the presence and absence of NPs. Zeta potential of the three NPs and the GAC were measured. Particle size distribution of the NP dispersions was analyzed as a function of time. The surface area and the pore size distribution of the virgin and the exhausted GAC were obtained along with transmission electron microscopy and Fourier transform infrared spectroscopy analysis. The effect of NPs was found to be a function of their zeta potential, concentration, and particle size distribution. Due to their electrical charge, NPs attached to the GAC and blocked the pores and thus reduced the access to the internal pore structure. However, due to the fast adsorption kinetics of TCE, no effect from the three NPs was observed in the isotherm and kinetic studies. The RSSCT, on the other hand, accurately predicted the pilot-column TCE breakthrough in the presence of NPs.     

Pb(II) Removal Using TiO<Subscript>2</Subscript>-Embedded Monolith Composite Cryogel as an Alternative Wastewater Treatment Method

Different from direct application of free nanoparticles (NPs) in water treatment, a composite material is used to reduce the release and potential toxic effects of NPs with maintained adsorption capacity and kinetics. Novel monolithic composites with TiO₂ NPs incorporated into the walls of macroporous cryogels were synthesized and evaluated for material characteristics and their efficiency for removal of Pb(II) from aqueous solution in batch test and continuous mode. The uniformly distributed 6% TiO₂-cryogel is shown to be optimal for minimizing TiO₂ NP losses while maximizing Pb(II) removal. Under (25.0 ± 0.1) °C with the initial Pb(II) concentration of 10 mg/l, TiO₂-cryogels exhibit excellent adsorption characteristic for Pb(II) removal with adsorption capacity up to 23.27 mg/g TiO₂, which is even a little higher than that of TiO₂ NPs (21.58 mg/g TiO₂), and the results fit well with Langmuir–Freundlich isotherm. Both adsorbents work well in higher pH range with the highest removal rate at pH 6 for TiO₂-cryogel, and the adsorption mechanism might be strong chemical interaction. Pseudo-second-order process can better describe the adsorption process rather than pseudo-first-order for both adsorbents. The external mass transfer process of Pb(II) on TiO₂ NPs is much faster than that on TiO₂-cryogel, and the ultimate equilibrium time is about the same (3 h) on both adsorbents. The synthesized composites could also withstand a continuous treatment, and the effect of competing and co-existing constituents such as Cd²⁺, SO₄ ^2? and dissolved organic matter (DOM) is almost negligible. The composite design with small particles embedded into cryogels is proved to successfully keep the adsorption activity of TiO₂ NPs and prevent them from releasing into the environment in engineering practice.     

Effects of sediment components and TiO2 nanoparticles on perfluorooctane sulfonate adsorption properties

Purpose

Here, the roles of sediment components in perfluorooctane sulfonate (PFOS) adsorption onto aquatic sediments and relevant adsorption mechanisms were investigated in terms of adsorption isotherms and influences of TiO₂ nanoparticles (NPs) contamination.

Materials and methods

Due to the complexity of the sediments, instead of randomly selecting different component sediments, the selective dissolution method was used to better explore the effects of sediment compositions, such as sediment organic matter (SOM) and ferric oxides (dithionite–citrate–bicarbonate [DCB] Fe), and TiO₂ NPs pollution on PFOS adsorption. Mathematical equations (Freundlich, Langmuir, and Temkin) were used to describe the adsorption behavior of PFOS on different sediments and adsorption mechanisms of multiple pollutant interactions. Moreover, the characterization methods of zeta potential, nitrogen (N₂) adsorption–desorption, and scanning electron microscopy (SEM) analysis, as well as Fourier transform infrared (FT-IR) spectroscopy, explained effects of the sediment components and TiO₂ NPs on PFOS adsorption properties in view of physicochemical theories.

Results and discussion

The adsorption isotherms of PFOS on six tested sediments were all nonlinear (Freundlich model, R² = 0.992~1.000). The Freundlich sorption affinities (K_F) of PFOS on S (original sediments), S1 (sediment organic matter (SOM)-removed S), and S2 (ferric oxides (DCB Fe)-removed S1) were 0.232, 0.179, and 0.120, respectively. Both SOM and DCB Fe influenced the physicochemical properties of the sediments, e.g., zeta potential, specific surface area, and permanent negative charge. The addition of TiO₂ NPs increased the K_F of PFOS for S, S1, and S2 by approximately 9.9%, 14.5%, and 26.7%, respectively, by increasing the zeta potential and specific surface area (S_BET, S_ext, and S_micro) and by changing the water and oil properties of the three sediments. However, the addition of TiO₂ NPs decreased the linearity of the sorption isotherm (1/n). FT-IR spectroscopy showed that hydrophobicity, ion exchange, surface complexation, and hydrogen bonding interactions (non-fingerprint region) could all play a role in PFOS sorption onto tested sediments. However, the hypothesis of hydrogen bonding to promote PFOS adsorption on sediment layer silicates (fingerprint region) should be studied further.

Conclusions

The content of both SOM and DCB Fe affected the physicochemical properties of sediment. Both SOM and DCB Fe showed a positive relationship with sorption of PFOS on sediment. The addition of TiO₂ NPs increased PFOS sorption by altering the sediment surface properties. Hydrophobic interactions certainly impelled and ligand and ion exchange and hydrogen bonding (non-fingerprint region) could promote PFOS sorption on the sediments.

     

Adsorption-desorption of trichloroethylene in granular media

Sorption studies were conducted to determine the adsorption and desorption characteristics of a common synthetic chemical, trichloroethylene (TCE) in four granular media; sandy loam soil, organic top soil, peat moss and granular activated carbon (GAC). The results showed that the Freundlich Isotherm satisfactorily represents adsorption and desorption of dissolved TCE in these media and that the organic carbon content is an important factor in both processes. The soil-water partition coefficient (K _oc) for TCE suggests that it will migrate quickly through soil.     

Titanium Dioxide Nanoparticle Circulation in an Aquatic Ecosystem

Nanotechnology is a dynamically developing field of scientific and industrial interest across the entire world, and the commercialization of nanoparticles (NPs) is rapidly expanding. Incorporation of nanotechnologies into a range of manufactured goods results in increasing concern regarding the subsequent release of engineered NPs into the environment. One of the biggest threats of using NPs is the transfer and magnification of these particles in the trophic chain. The aim of the studies was the evaluation of the distribution of TiO₂ NP contamination in the aquatic ecosystem under laboratory conditions. Bioaccumulation of TiO₂ NPs by plants (Elodea canadensis) and fish (Danio rerio) in the source of contamination was investigated. The studies were focused on the consequences of short-term water contamination with TiO₂ NPs and the secondary contamination of the components of the investigated model ecosystem (plants, sediments). It was found that in the fish and the plants exposed to NP contamination, the amount of Ti was higher than in the control, indicating an effective bioaccumulation of NPs or ions originating from NPs. It was clearly shown that the NPs present in the sediments are available to plants and fish. Additionally, the aquatic plants, an important trophic level in the food chain, can accumulate NPs and be a source of NPs for higher organisms. It was concluded that even an incidental contamination of water by NPs may result in long-term consequences induced by the release of NPs.     

Enhanced Accumulation of Arsenate in Carp in the Presence of Titanium Dioxide Nanoparticles

In this study adsorption of arsenic (As) onto TiO₂ nanoparticles and the facilitated transport of As into carp (Cyprinus carpio) by TiO₂ nanoparticles was examined. Adsorption kinetics and adsorption isotherm were conducted by adding As(V) to TiO₂ suspensions. Facilitated transport of As by TiO₂ nanoparticles was assessed by accumulation tests exposing carp to As(V) contaminated water in the presence of TiO₂ nanoparticles. The results showed that TiO₂ nanoparticles had a significant adsorption capacity for As(V). Equilibrium was established within 30 min and the isotherm data was described by Freundlich isotherm. The K_F and 1/n were 20.71 mg/g and 0.58, respectively. When exposed to As(V)-contaminated water in the presence of TiO₂ nanoparticles, carp accumulated considerably more As, and As concentration in carp increased by 132% after 25 days exposure. Considerable As and TiO₂ accumulated in intestine, stomach and gills of the fish, and the lowest level of accumulation was found in muscle. Accumulation of As and TiO₂ in stomach, intestine and gills are significant. Arsenic accumulation in these tissues was enhanced by the presence of TiO₂ nanoparticles. TiO₂ nanoparticles that have accumulated in intestine and gills may release adsorbed As and As bound on TiO₂ nanoparticles which cannot be released maybe transported by TiO₂ nanoparticles as they transferred in the body. In this work, an enhancement of 80% and 126% As concentration in liver and muscle after 20 days of exposure was found.     

An improved method for determining the specific surface areas of topsoils with varied organic matter content, texture and clay mineral composition

Measuring the specific surface area (SSA) of soils that contain much organic matter (OM) is problematic. The adsorption of p-nitrophenol (pNP) from xylene at room temperature yielded realistic values for the SSA of a wide range of clays, oxides and subsoils. Here we have extended the same measurement to some topsoils with varied OM content, texture and clay mineral composition. Specifically, we have compared the surface areas measured by adsorption of N₂, and, applying the BET equation, with the values obtained by adsorption of pNP, before and after treatment of the samples with hydrogen peroxide. In all instances, the removal by H₂O₂ of organic matter – albeit in part only – led to a marked increase in the SSAs measured by nitrogen because of the exposure of micropores previously blocked or covered by OM. The surface areas measured by pNP were appreciably larger than those obtained by the standard BET equation, and showed little change after removal of organic matter. However, the surface area of two smectite-rich samples measured by pNP increased substantially after peroxidation, presumably because smectite crystals decomposed during treatment with H₂O₂. The results suggest that, under the experimental conditions used, pNP could diffuse without hindrance into and through organic matter, enabling it to adsorb on to micropore surfaces within clay aggregates (domains). In keeping with this suggestion, the relation between the surface areas measured by pNP and the corresponding values calculated from the clay and OM contents, and clay mineral composition, of the soils was close to 1:1. An even stronger relation was observed between the measured and calculated values for cation exchange capacity.     

Effects of TiO<Subscript>2</Subscript> Nanoparticles on the Neotropical Cladoceran <Emphasis Type="Italic">Ceriodaphnia silvestrii</Emphasis> by Waterborne and Dietary Routes

The impact of nanoparticles (NPs) in zooplankton is poorly studied, particularly when organisms are exposed through diet. Food, constituted mainly by unicellular algae, can act as an important route of contamination for zooplankton. Since unicellular algae have a high surface area in relation to their volume, NPs can interact with their cell membranes and walls, as well as with exopolysaccharides secreted by them. In the present research, we investigated both the acute effects of waterborne titanium dioxide nanoparticles (TiO₂ NPs), and its chronic effects via dietary exposure on the Neotropical freshwater zooplankton Ceriodaphnia silvestrii Daday, 1902 (Crustacea: Cladocera). The observed acute effects served as support for chronic tests, in which we investigated the effects of TiO₂ NPs on survival and life history parameters (body length, numbers of eggs, and neonates produced) of cladoceran adult females, using the freshwater cosmopolitan chlorophycean Raphidocelis subcapitata as source of contamination of TiO₂ NPs for zooplankton. R. subcapitata cells were exposed to concentrations of 0, 0.01, 1, and 10 mg L^?1 of TiO₂ NPs for 96 h, and then provided as food for females of C. silvestrii until the third brood was released. Significant toxic effects were observed in body length and total number of neonates and eggs produced by females of C. silvestrii at concentrations of 1 and 10 mg L^?1 of TiO₂ NPs. Survival was the most sensitive parameter when exposure was given via food. From the concentration of 0.01 mg L^?1 of TiO₂ NPs, there was a decrease in the survival of C. silvestrii females. The quantification of TiO₂ NPs in algae evidenced that they have retained NPs in their cells, being, therefore, an important route of exposure and toxicity of TiO₂ NPs to the studied microcrustacean.     

Adsorption of Nonylphenol onto Granular Activated Carbon

The applicability of granular activated carbon (GAC)filtration for the removal of the xeno-estrogenicmicropollutant nonylphenol (NP) is evaluated using batchadsorption data. From the obtained adsorption data, it wasapparent that with contact times of 4 d and 24 hr and GACdosages of 1 and 0.1 g L^-1 no saturationof the GAC could be obtained with NP total contaminantloadings up to 10 000 μg L^-1.Higher NP concentrations could not be applied due to its lowwater solubility (～5 mg L^-1). The influence of temperature(4 or 28 °C) on NP sorption onto GAC was negligible.The results showed that the sorption capacity of GAC for NPwas at least 100 mg g^-1 GAC. According to thesedata it can be concluded that a full-scale GACfilter unit will be sufficient to remove environmentallyrelevant NP concentrations of 10 μg L^-1.Consequently, the existing GAC treatment technology indrinking water treatment should protect the consumer from theintake of the xeno-estrogenic micropollutant NP via drinkingwater. The sorption capacity of dissolved humic acids (DHA)for NP is considerable at liquid NP concentrations of 10 μgL^-1 and the affinity of DHA for GAC is not significant.These observations suggest that interference on removal of NP onGAC, due to the presence of DHA, can be expected at microgramper liter concentrations of NP. They may warrant the removalof humic substances in treatment steps preceding GAC-filtration.     

Effect of Soil Organic Matter on Adsorption and Insecticidal Activity of Toxins from Bacillus thuringiensis

With the large-scale cultivation of transgenic crops expressing Bacillus thuringiensis (Bt) insecticidal toxin in the world, the problem of environmental safety caused by these Bt crops has received extensive attention. The effects of soil organic matter (SOM) on the adsorption and insecticidal activity of Bt toxin in variable- and constant-charge soils (red and brown soils, respectively) were studied. Organic carbon in the soils was removed using hydrogen peroxide (H_2O_2). After H_2O_2 treatment, the SOM in the red and brown soils decreased by 71.26% and 82.82%, respectively. Mineral composition of the H_2O_2-treated soils showed no significant changes,but soil texture showed a slight change. After SOM removal, the cation exchange capacity (CEC) and pH decreased, while the specific surface area (SSA), point of zero charge (PZC), and zeta potential increased. The adsorption isotherm experiment showed that the Bt toxin adsorption on the natural and H_2O_2-treated soils fitted both the Langmuir model (R~2≥ 0.985 7) and the Freundlich model (R~2≥ 0.984 1), and the amount of toxin adsorbed on the H_2O_2-treated soils was higher than that on the natural soils. There was a high correlation between the maximum adsorption of Bt toxin and the PZC of soils (R~2= 0.935 7); thus, Bt toxin adsorption was not only influenced by SOM content, but also by soil texture, as well as the SSA, CEC, PZC, and zeta potential. The LC_(50) (lethal concentration required to kill 50% of the larvae) values for Bt toxin in the H_2O_2-treated soils were slightly lower than those in the natural soils, suggesting that the environmental risk from Bt toxin may increase if SOM decreases. As the measurement of insecticidal activity using insects is expensive and time consuming, a rapid and convenient in vitro method of enzyme-linked immunosorbent assays is recommended for evaluating Bt toxin degradation in soils in future studies.     

Effect of individual and combined exposure of Fe2O3 nanoparticles and oxytetracycline on their bioaccumulation by rice (Oryza sativa L.)

Purpose

It has been reported the bioaccumulation of γ-ferric oxide nanoparticles (Fe₂O₃ NPs) or oxytetracycline (OTC) in crops. However, there have been little references investigating their uptake and bioaccumulation in crops after the combined exposure. The present study focused on Fe₂O₃ NPs and OTC accumulation on root surface and in the tissues of rice (Oryza sativa L.) seedlings under combined exposure. And, the interactive influence mechanism was also discussed.

Materials and methods

Hydroponic experiments were conducted to investigate the Fe and OTC accumulation on root surface and in rice tissues under individual and combined exposure of Fe₂O₃ NPs and OTC. The dynamic change of particulate Fe, ionic Fe, and Fe plaque concentrations on root surface was determined under the influence of OTC from Fe₂O₃ NPs and Fe-EDTA exposure. Fe²⁺ from Fe-EDTA was selected in order to compare the Fe bioaccumulation from ionic Fe and nanoparticle Fe exposure. Hydrodynamic diameter and ζ-potential of Fe₂O₃ NPs in solution were investigated when OTC was present or not, and the changes of OTC concentrations were also determined during hydroponic culture. SEM, XRD, and TEM were used to analyze Fe₂O₃ NP distribution on root surface and inside root under the influence of OTC.

Results and discussion

OTC promoted surface-Fe and shoot-Fe accumulation in Fe₂O₃ NPs treatments, which was just an opposite result from Fe-EDTA treatments. Upon Fe₂O₃ NP exposure, Fe plaque was formed through the direct adsorption of NPs on the outside root surface and then incorporated into plaque as its crystalline components. OTC elevated notably surface-Fe accumulation mainly through increasing adsorption and precipitation of Fe₂O₃ NPs on the root surface due to low repulsive electrostatic interaction between NPs and the root surface after adding OTC. Fe₂O₃ NPs increased surface-OTC and root-OTC levels. Compared to Fe-EDTA, surface-Fe from NP treatments can hold strongly OTC due to Fe₂O₃ particle precipitated on root surface with high specific surface area. NPs reduced shoot-OTC under 25 mg L^?1 OTC, but not under 100 mg L^?1 OTC.

Conclusions

This study clearly demonstrates that Fe/OTC accumulation in rice was always in the order root surface > shoot > root, whether Fe₂O₃ NPs/OTC was individual or combined exposure. The combined exposure will increase their root surface distribution comparing with individual exposure, and Fe₂O₃ NPs increased also root-OTC levels, which could pose a potential risk to food safety in subsequent growth of rice.

     

Titanium oxide nanoparticle effects on composition of soil microbial communities and plant performance

We examined the effect of TiO₂ nanoparticles (NPs) on the growth of maize and soybean plants and associated soil microbial communities. Plants were grown in a greenhouse, and low levels of undoped or nitrogen-doped TiO₂ NPs were applied. Plant growth and nutrient content were determined, and effects of NPs on composition of soil microbial communities were examined using terminal restriction fragment length polymorphism analysis (TRFLP) of rDNA. We found no significant effects of TiO₂ NPs on plant growth, nutrient content, or the composition of bacterial communities within the rhizosphere. However, arbuscular mycorrhizal fungal communities were affected by application of undoped and nitrogen-doped TiO₂ NPs. This observation may be partially attributed to the small but significant TiO₂ NP uptake levels in the root tissues of both plants. Our results suggest that even low concentrations of TiO₂ NPs may influence some important groups of soil microbes, such as mycorrhizal fungi, but changes in the composition of microbial communities may not affect plant growth under conditions of adequate moisture and nutrients.     

Trihalomethanes Adsorption on Activated Carbon Fiber and Granular Activated Carbon

Isotherms and the effects on activated carbon fiber (ACF), compared with granular activated carbon (GAC), adsorption of trihalomethans (THMs) in water were studied. It was found that the isotherms for ACF or GAC were not agree to Langmuir equation well, but successfully correlated by Freundlich equation, and the coefficients of Freundlich isotherm were given and compared to isotherms reported in the literatures for THMs. ACF and GAC adsorbing THMs was exothermic, isotheric heats of adsorption were calculated and increased with increasing bromine substitution in CHCl₃. The adsorptive capacity of ACF was about two-fold greater than that of GAC, and increased with THMs more hydrophobic or bromine substitution. pH value and temperature had no significant effect on the adsorptive capacity of ACF. The adsorptive capacity of GAC was decreased with temperature slightly. The adsorptive capacities of ACF or GAC was increased with the THMs initial concentration rising. Fixed-bed reactor studies were measured, the amount of THMs adsorbed on ACF column at saturation was much greater than that of GAC at the same operating conditions, and the running time of ACF column was two-fold longer than that of GAC column. The mass transfer zones of ACF column were less than those of GAC column and decreased as the chlorine atoms in CHCl₃ substituted by bromine atoms, while the mass transfer zones of GAC column were quite uniform.     

Competitive Adsorption of Some Hazardous Organic Pollutants from their Binary and Ternary Solutions onto Granular Activated Carbon Columns

Competitive adsorption of some priority pollutants, namely phenol, o-cresol, p-nitrophenol, m-methoxyphenol, benzoic acid and salicylic acid from their aqueous solutions onto granular activated carbon (GAC) column was studied. Experiments were carried out to determine the breakthrough curves for adsorbates when present in aqueous solutions as single-, bi- and tri-solute system to evaluate the competitive adsorption phenomenon. Results indicate that in single-solute-GAC systems, p-nitrophenol is most strongly adsorbed as compared to other phenol derivatives studied. The substituted phenols were found to adsorb to a greater extent than phenol itself. The GAC-bisolute and GAC-trisolute systems clearly show the competitive or preferential adsorption of one solute over the other, as the solutes are competing for the available GAC surface for adsorption. Initially, all the adsorbates are taken up by the GAC surface, but near the breakthrough point the more adsorbable solute is able to desorb the less adsorbable one.     

Effects of coated and non-coated ZnO nano particles on cucumber seedlings grown in gel chamber

Zinc oxide-engineered nanoparticles (ZnO ENPs) have received the most attention in recent years. This increasing interest has been directed towards studying the environmental fate and effects of ZnO ENPs on ecological terrestrial species. In this study, ZnO NPs were synthesized by atmospheric pressure solution evaporation method and were coated or uncoated with humic acid (HA). The root uptakes of uncoated and HA-coated ZnO NPs and zinc (Zn) were investigated by gel-grown cucumber. Two ZnO levels (1 and 200 µM) were applied in the form of coated (T₃) and non-coated (T₂) NPs or bulk particles (T₁). The results showed that coating NPs by HA increases zeta potential of NPs and decreases their aggregation size due to the increase in the repulsion forces among the particles. Addition of 1 mgL^?1 ZnO into gel chamber enhanced root and shoot biomass; however, the shoot growth was higher in the presence of NPs compared to its bulk counterpart. Moreover, greater phytotoxicity of ZnO from the source of NPs than bulk particles in shoot was observed. Scanning electron microscopy results showed a clear evidence of the penetration of NPs into root cells.     

Pedotransfer function for estimation of soil-specific surface area using soil fractal dimension of improved particle-size distribution

The specific surface area (SSA) of a soil is crucial for the interface of ions and water molecules with the soil particles. Therefore, many physical and chemical properties of a soil are determined using its total SSA. Measurement of SSA is time-consuming and laborious, and its estimation using pedotransfer functions is therefore preferred. The objectives of this study were to: (1) analyze the pore–solid interface fractal dimension (D) in soils with different textures from thesouthern part of Iran using estimated improved particle-size distribution (PSD) from the soil primary particles, i.e. clay, silt and sand; (2) develop a multivariate pedotransfer function to estimate D based on PSD; and (3) develop a multivariate pedotransfer function to link the values of D to the SSA. As a result, two pedotransfer functions are presented for estimation of D and SSA. To estimate SSA, the value of D is first obtained using the presented pedotransfer function and these estimated D values are then used in another pedotransfer function to estimate SSA. The pedotransfer functions were validated and it is concluded that they are able to predict the values of D and SSA accurately.     

Characteristics of Biochemical and Fractal Structure of Activated Sludge with Thermochemical Lysis

In this study, we investigated the structural characteristic and biochemical properties of waste-activated sludge after thermochemical pretreatment. The results show that with the increase dosage of hydrochloric acid or sodium hydroxide, the concentration of suspended solid (SS) and volatile suspended solids (VSS) declined, especially at pH 12 + H (“H” means heating). At the same time, soluble chemical oxygen demand (SCOD) all increased as well, especially at pH 12, the greatest lysis effect appeared. Protein and polysaccharide presented a similar law with SCOD. Furthermore, the specific surface area (SSA), two-dimensional fractal dimension (D ₂), and three-dimensional fractal dimension (D ₃) all increased to a certain degree with acid/alkali pretreatment whether or not heating. Otherwise, the median particle size (d _0.5) and zeta potential decreased leading to more compact and stable floc structure and reduction effect compared with the original sludge. In Pearson correlation analysis, SSA and SS, SSA and VSS, zeta potential and SCOD, and zeta potential and protein have significant negative correlations; D ₃ and SSA have a significant correlation with SS, VSS, SCOD, and protein. Consequently, measuring the structural parameters D ₃ and SSA online can reflect the effects of sludge lysis indirectly, which will be helpful to guide the practical application.     

Feasibility Assessment of Chromium Removal from Groundwater for Drinking Purposes by Sorption on Granular Activated Carbon and Strong Base Anion Exchange

The goal of this study was to compare the performances of strong base anion (SBA) exchange and activated carbon adsorption in the removal of hexavalent chromium, Cr(VI), from a real groundwater matrix exploited for drinking purposes. Two SBA resins and three granular activated carbons (GAC) were tested by batch experiments for kinetics and equilibrium isotherm determination. SBA resins showed higher affinity toward Cr(VI) (present in raw water at about 20 μg L^?1) with respect to the GACs, with faster kinetics and higher equilibrium adsorption capacities. Among GACs, vegetal-based carbons showed higher Cr(VI) removal efficiencies than the mineral-based carbon, which can be related to the more developed textural properties. SBA resins also displayed relevant removal capacities towards nitrate and sulfate (present at mg L^?1 concentration levels), while boron (present at about 60 μg L^?1) was effectively removed by GACs. Batch experiment results were elaborated to estimate the chromium throughputs for the studied materials, to preliminary compare their performances in a real-scale application. The monitoring of a real-scale GAC adsorption stage permitted to validate throughputs estimation and confirmed that, despite being effective toward synthetic organics, GAC adsorption is a not feasible solution for Cr(VI) removal, with extremely early breakthrough. SBA exchange process resulted to be the most suitable solution, providing the best sorbent usage rates. However, SBA resin usage rates can strongly increase when considering the removal of nitrate and sulfate ions, requiring much shorter cycle times.     

Toxicological effects of TiO2 and ZnO nanoparticles in soil on earthworm Eisenia fetida

Nanoparticles (NPs) of TiO₂ and ZnO are receiving increasing attention due to their widespread applications. To evaluate their toxicities to the earthworm Eisenia fetida (Savigny, 1826) in soil, artificial soil systems containing distilled water, 0.1, 0.5, 1.0 or 5.0 g kg⁻¹ of NPs were prepared and earthworms were exposed for 7 days. Contents of Zn and Ti in earthworm, activities of antioxidant enzymes, DNA damage to earthworm, activity of cellulase and damage to mitochondria of gut cells were investigated after acute toxicity test. The results from response of the antioxidant system combined with DNA damage endpoint (comet assay) indicated that TiO₂ and ZnO NPs could induce significant damage to earthworms when doses were greater than 1.0 g kg⁻¹. We found that Ti and Zn, especially Zn, were bioaccumulated, and that mitochondria were damaged at the highest dose in soil (5.0 g kg⁻¹). The activity of cellulase was significantly inhibited when organisms were exposed to 5.0 g kg⁻¹ of ZnO NPs. Our study demonstrates that both TiO₂ and ZnO NPs exert harmful effects to E. fetida when their levels are higher than 1.0 g kg⁻¹ in soil and that toxicity of ZnO NPs was higher than TiO₂.     

Adsorption of Cadmium and Zinc onto Micaceous Minerals: Effect of Siderophore Desferrioxamine B

The mobility, bioavailability, and environmental fate of heavy metals in soil are controlled by their adsorption onto soil minerals and solid organic matter. The adsorption is strongly affected by the presence of various low-molecular-weight organic acids. In this study, effect of hydroxamate siderophore desferrioxamine B (DFOB) on cadmium (Cd) and zinc (Zn) adsorption onto two micaceous clay minerals, muscovite and phlogopite, was evaluated in batch experiments. Results showed that the presence of DFOB diminished the adsorption of Cd and Zn onto both minerals, particularly under neutral to alkaline pH conditions. For instance, at pH 8.2, the presence of DFOB caused a decrease in the adsorption of Zn onto phlogopite by nearly 50%. The equilibrium adsorption of Cd and Zn was satisfactorily described using Freundlich isotherm. The adsorption isotherms showed that the affinity of Cd and Zn onto the minerals decreased in the presence of DFOB. For example, at pH 8.0, the presence of siderophore caused a decrease in the Freundlich adsorption isotherm coefficient K_F for Zn adsorption onto muscovite and phlogopite from 4.60 to 0.07 L g^-1 and from 3.56 to 0.36 L g^-1, respectively. These findings confirm the potential influence of siderophore on the fate of Cd and Zn in arid soils containing substantial contributions of micaceous silicate minerals.