Adsorption of cadmium by a high-capacity adsorbent composed of silicate-titanate nanotubes embedded in hydrogel chitosan beads.

In this study, we developed a nanoparticle-based mesoporous composite that consisted of silicate-titanate nanotubes (STNTs) supported in hydrogel chitosan beads (STNTs-Ch beads) and was studied for Cd2+ adsorption. By using Fourier-transform infrared spectroscopy, transmission and scanning electron microscopy coupled to an energy-dispersive X-ray spectrometer, we could determine that the hollow STNTs were highly dispersed in the walls of the hollow beads. The dispersion was attributed to the effect of pH when the composite was prepared and we observed a non-interaction between STNTs and chitosan. The adsorption studies of Cd2+ showed that the kinetic rate (k 2) increased 3-fold and that the diffusion rate (K d) increased 2-fold after the embedment. Moreover, the maximum capacity of adsorption of STNTs-Ch beads was 2.3 times higher than that of STNTs alone. The treatment of a synthetic Cd2+ solution and a real leachate in continuous mode showed two phases in which it was observed higher removed fractions of transition metal ions (Cd2+, Co2+, Ni2+, Zn2+ and Cu2+) and the post-transition metal ion Pb2+, in comparison to the removed fractions of alkali and alkali-earth metal ions (Ca2+, K+, Mg2+). The composite was successfully reused four times when adsorbing Cd2+, saving three times the needed amounts of TiO2, SiO2 and chitosan for the production of the material. This composite was produced in a simple way and shows the potential for wastewater treatment.

Two analytical approaches quantifying the electron donating capacities of dissolved organic matter to monitor its oxidation during chlorination and ozonation.

Electron-donating activated aromatic moieties, including phenols, in dissolved organic matter (DOM) partially control its reactivity with the chemical oxidants ozone and chlorine. This comparative study introduces two sensitive analytical systems to directly and selectively quantify the electron-donating capacity (EDC) of DOM, which corresponds to the number of electrons transferred from activated aromatic moieties, including phenols, to the added chemical oxidant 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonate) radical cation (i.e., ABTS•+). The first system separates DOM by size exclusion chromatography (SEC) followed by a post-column reaction with ABTS•+ and a spectrophotometric quantification of the reduction of ABTS•+ by DOM. The second system employs flow-injection analysis (FIA) coupled to electrochemical detection to quantify ABTS•+ reduction by DOM. Both systems have very low limits of quantification, allowing determination of EDC values of dilute DOM samples with <1 mg carbon per liter. When applied to ozonated and chlorinated model DOM isolates and real water samples, the two analytical systems showed that EDC values of the treated DOM decrease with increasing specific oxidant doses. The EDC decreases detected by the two systems were in overall good agreement except for one sample containing DOM with a very low EDC. The combination of EDC with UV-absorbance measurements gives further insights into the chemical reaction pathways of DOM with chemical oxidants such as ozone or chlorine. We propose the use of EDC in water treatment facilities as a readily measurable parameter to determine the content of electron-donating aromatic moieties in DOM and thereby its reactivity with added chemical oxidants.

Ozone and chlorine reactions with dissolved organic matter - Assessment of oxidant-reactive moieties by optical measurements and the electron donating capacities.

Oxidation processes are impacted by the type, concentration and reactivity of the dissolved organic matter (DOM). In this study, the reactions between various types of DOM (Suwannee River fulvic acid (SRFA), Nordic Reservoir NOM (NNOM) and Pony Lake fulvic acid (PLFA)) and two oxidants (ozone and chlorine) were studied in the pH range 2-9 by using a combination of optical measurements and electron donating capacities. The relationships between residual electron donating capacity (EDC) and residual absorbance showed a strong pH dependence for the ozone-DOM reactions with phenolic functional groups being the main reacting moieties. Relative EDC and absorbance abatements (UV254 or UV280) were similar at pH 2. At pH 7 or 9, the relative abatement of EDC was more pronounced than for absorbance, which could be explained by the formation of UV-absorbing products such as benzoquinone from the transformation of phenolic moieties. An increase in fluorescence abatement with increasing pH was also observed during ozonation. The increase in fluorescence quantum yields could not be attributed to formation of benzoquinone, but related to a faster abatement of phenolic moieties relative to fluorophores with low ozone reactivity. The overall •OH yields as a result of DOM-induced ozone consumption increased significantly with increasing pH, which could be related to the higher reactivity of phenolic moieties at higher pH. The •OH yields for SRFA and PLFA were proportional to the phenolic contents, whereas for NNOM, the •OH yield was about 30% higher. During chlorination of DOM at pH 7 an efficient relative EDC abatement was observed whereas the relative absorbance abatement was much less pronounced. This is due to the formation of chlorophenolic moieties, which exert a significant absorbance, and partly lose their electron donating capacity. Pre-ozonation of SRFA leads to a decrease of chloroform and haloacetic acid formation, however, only after a threshold of > ∼50% abatement of the EDC and under conditions which are not precursor limited. The decrease in chloroform and haloacetic acid formation after the threshold EDC abatement was proportional to the relative residual EDC.

Arsenic adsorption by iron-aluminium hydroxide coated onto macroporous supports: Insights from X-ray absorption spectroscopy and comparison with granular ferric hydroxides.

This paper evaluates the arsenic adsorption characteristics of a macroporous polymer coated with coprecipitated iron-aluminium hydroxides (MHCMP). The MHCMP adsorbent-composite fits best with a pseudo-second order model for As(III) and a pseudo-first order kinetic model for As(V). The MHCMP shows a maximum adsorption capacity of 82.3 and 49.6 mg As/g adsorbent for As(III) and As(V) ions respectively, and adsorption followed the Langmuir model. Extended X-ray absorption fine structure showed that binding of As(III) ions were confirmed to take place on the iron hydroxides coated on the MHCMP, whereas for As(V) ions the binding specificity could not be attributed to one particular metal hydroxide. As(III) formed a bidentate mononuclear complex with Fe sites, whereas As(V) indicated on a bidentate binuclear complex with Al sites or monodentate with Fe sites on the adsorbent. The column experiments were run in a well water spiked with a low concentration of As(III) (100 µg/L) and a commercially available adsorbent (GEH(®)102) based on granular iron-hydroxide was used for comparison. It was found that the MHCMP was able to treat 7 times more volume of well water as compared to GEH(®)102, maintaining the threshold concentration of less than 10 µg As/L, indicating that the MHCMP is a superior adsorbent.

Production of raw starch-degrading enzyme by Aspergillus sp. and its use in conversion of inedible wild cassava flour to bioethanol.

The major bottlenecks in achieving competitive bioethanol fuel are the high cost of feedstock, energy and enzymes employed in pretreatment prior to fermentation. Lignocellulosic biomass has been proposed as an alternative feedstock, but because of its complexity, economic viability is yet to be realized. Therefore, research around non-conventional feedstocks and deployment of bioconversion approaches that downsize the cost of energy and enzymes is justified. In this study, a non-conventional feedstock, inedible wild cassava was used for bioethanol production. Bioconversion of raw starch from the wild cassava to bioethanol at low temperature was investigated using both a co-culture of Aspergillus sp. and Saccharomyces cerevisiae, and a monoculture of the later with enzyme preparation from the former. A newly isolated strain of Aspergillus sp. MZA-3 produced raw starch-degrading enzyme which displayed highest activity of 3.3 U/mL towards raw starch from wild cassava at 50°C, pH 5.5. A co-culture of MZA-3 and S. cerevisiae; and a monoculture of S. cerevisiae and MZA-3 enzyme (both supplemented with glucoamylase) resulted into bioethanol yield (percentage of the theoretical yield) of 91 and 95 at efficiency (percentage) of 84 and 96, respectively. Direct bioconversion of raw starch to bioethanol was achieved at 30°C through the co-culture approach. This could be attractive since it may significantly downsize energy expenses.

Cryogel-supported titanate nanotubes for waste treatment: Impact on methane production and bio-fertilizer quality.

By reducing the cadmium (Cd(2+)) content in biomass used for bio-based products such as biogas, a less toxic bio-based fertilizer can be obtained. In this work, we demonstrate how a macroporous polymer can support titanate nanotubes, and we take advantage of its known selective adsorption behavior towards Cd(2+) in an adsorption process from real nutrient-rich process water from hydrolysis of seaweed, a pollutant-rich biomass. We show that pretreatment steps involving alteration in area-to-volume ratio performed in aerated and acidic conditions release the most Cd(2+) from the solid material. By integrating an adsorption step between hydrolysis and the biomethane, we show that it was possible to obtain high Cd(2+) removal (ca. 94%) despite molar excess (between 100 and 500) of co-present ions (e.g., Mg(2+), Ca(2+), Na(+), K(+)) and with maintained total phosphorous content. The bio-methane potential did not significantly decrease as compared to a process without cadmium removal and the yielded bio-fertilizer followed Swedish guideline values. This study provides a sound and promising alternative for a novel remediation step, enabling higher use of otherwise tricky and to some extent overlooked biomass sources.

A GH57 4-α-glucanotransferase of hyperthermophilic origin with potential for alkyl glycoside production.

4-α-Glucanotransferase (GTase) enzymes (EC 2.4.1.25) modulate the size of α-glucans by cleaving and reforming α-1,4 glycosidic bonds in α-glucans, an essential process in starch and glycogen metabolism in plants and microorganisms. The glycoside hydrolase family 57 enzyme (GTase57) studied in the current work catalyzes both disproportionation and cyclization reactions. Amylose was converted into cyclic amylose (with a minimum size of 17 glucose monomers) as well as to a spectrum of maltodextrins, but in contrast to glycoside hydrolase family 13 cyclodextrin glucanotransferases (CGTases), no production of cyclodextrins (C6-C8) was observed. GTase57 also effectively produced alkyl-glycosides with long α-glucan chains from dodecyl-ß-D-maltoside and starch, demonstrating the potential of the enzyme to produce novel variants of surfactants. Importantly, the GTase57 has excellent thermostability with a maximal activity at 95 °C and an activity half-life of 150 min at 90 °C which is highly advantageous in this manufacturing process suggesting that enzymes from this relatively uncharacterized family, GH57, can be powerful biocatalysts for the production of large head group glucosides from soluble starch.

Improved arsenic(III) adsorption by Al2O3 nanoparticles and H2O2: evidence of oxidation to arsenic(V) from X-ray absorption spectroscopy.

We have investigated the oxidation of inorganic As(III) with H2O2 catalysed by Al2O3, using X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. The effects of different reaction conditions (pH, time and initial H2O2 concentration) were also studied as were the kinetics of the oxidation reaction. We demonstrated that As(III) was oxidized to As(V) in the presence of H2O2 and Al2O3. Furthermore, all arsenic species found on the Al2O3 surface were in the As(V) state. The presence of both Al2O3 and H2O2 was necessary for oxidation of As(III) to take place within the period of time studied. The oxidation kinetics indicate a mechanism where reversible As(III) binding to the alumina surface is followed by irreversible oxidation by H2O2 leading to strongly bound As(V). Results from this study indicate that there is a surface-catalysed oxidation of As(III) on Al2O3 by H2O2, a reaction that can take place in nature and can be of help in the development of novel treatment systems for As(III) removal.

Γ-Al2O3-based nanocomposite adsorbents for arsenic(V) removal: assessing performance, toxicity and particle leakage.

The generation and development of effective adsorption materials for arsenic removal are urgently needed due to acute arsenic contamination of water sources in many regions around the world. In the search for these new adsorbents, the application of nanomaterials or nanocomposites, and especially the use of nanoparticles (NPs), has proven increasingly attractive. While the adsorptive performance of a range of nanocomposite and nanomaterial-based systems has been extensively reviewed in previously-published literature, the stability of these systems in terms of NP release, i.e. the ability of the nanomaterial or nanocomposite to retain incorporated NPs, is less well understood. Here we examine the performance of nanocomposites comprised of aluminium oxide nanoparticles (AluNPs) incorporated in macroporous polyacrylamide-based cryogels (n-Alu-cryo, where n indicates the percentage of AluNPs in the polymer material (n=0-6%, w/v)) for As(V) adsorption, and evaluate AluNP leakage before and after the use of these materials. A range of techniques is utilised and assessed (SEM, TEM, mass weight change, PIXE and in vitro toxicity studies). The 4-Alu-cryo nanocomposite was shown to be optimal for minimising AluNP losses while maximising As(V) removal. From the same nanocomposite we were further able to show that NP losses were not detectable at the AluNP concentrations used in the study. Toxicity tests revealed that no cytotoxic effects could be observed. The cryogel-AluNPs composites were not only effective in As(V) removal but also in immobilising the AluNPs. More challenging flow-through conditions for the evaluation of NP leakage could be included as a next step in a continued study assessing particle loss and subsequent toxicity.

Arsenite adsorption on cryogels embedded with iron-aluminium double hydrous oxides: possible polishing step for smelting wastewater?

Arsenic is among the most toxic elements and it commonly exists in water as arsenite (As(III)) and arsenate (As(V)) ions. As(III) removal often requires a pre-oxidation or pH adjustment step and it is a challenge to adsorb As(III) at circumneutral pH. In this study, iron-aluminium double hydrous oxides were synthesized and incorporated into cryogels. The resulting composite cryogels were evaluated for As(III) adsorption. Initial experiments indicated that the adsorbent showed similar adsorption kinetics for both As(V) and As(III) ions. The adsorption of As(III) best fit the Langmuir isotherm and the maximum adsorption capacity was 24.6 mg/g. Kinetic modeling indicated that the mechanism of adsorption was chemisorption, making the adsorbent-adsorbate interactions independent of charge and hence allowing the adsorbent to function equally efficient across pH 4-11. A Swedish smelting wastewater was used to evaluate the adsorption performance in continuous mode. The studies showed that the adsorbent was successful in reducing the arsenic concentrations below the European Union emission limit (0.15 mg/l) in a smelting wastewater collected after two precipitation processes. The arsenic removal was obtained without requiring a pH adjustment or a pre-oxidation step, making it a potential choice as an adsorbent for As(III) removal from industrial wastewaters.

Removal of heavy metals from water effluents using supermacroporous metal chelating cryogels.

Applications of IDA in, for example, immobilized metal ion affinity chromatography for purification of His-tagged proteins are well recognized. The use of IDA as an efficient chelating adsorbent for environmental separations, that is, for the capture of heavy metals, is not studied. Adsorbents based on supermacroporous gels (cryogels) bearing metal chelating functionalities (IDA residues and ligand derived from derivatization of epoxy-cryogel with tris(2-aminoethyl)amine followed by the treatment with bromoacetic acid (defined as TBA ligand)) have been prepared and evaluated on capture of heavy metal ions. The cryogels were prepared in plastic carriers, resulting in desired mechanical stability and named as macroporous gel particles (MGPs). Sorption and desorption experiments for different metals (Cu²+, Zn²+, Cd²+, and Ni²+ with IDA adsorbent and Cu²+ and Zn²+ with TBA adsorbent) were carried out in batch and monolithic modes, respectively. Obtained capacities with Cu²+ were 74 µmol/mL (TBA) and 19 µmol/mL gel (IDA). The metal removal was higher for pH values between pH 3 and 5. Both adsorbents showed improved sorption at lower temperatures (10°C) than at higher (40°C) and the adsorption significantly dropped for the TBA adsorbent and Zn²+ at 40°C. Desorption of Cu²+ by using 1 M HCl and 0.1 M EDTA was successful for the IDA adsorbent whereas the desorption with the TBA adsorbent needs further attention. The result of this work has demonstrated that MGPs are potential treatment alternatives within the field of environmental separations and the removal of heavy metals from water effluents.