Low-cost adsorbents from bio-waste for the removal of dyes from aqueous solution

Activated carbons (ACs) were developed from bio-waste materials like rice husk and peanut shell (PS) by various physicochemical activation methods. PS char digested in nitric acid followed by treatment at 673 K resulted in high surface area up to ～585 m²/g. The novelty of the present study is the identification of oxygen functional groups formed on the surface of activated carbons by infrared and X-ray photoelectron spectroscopy and quantification by using temperature programmed decomposition (TPD). Typical TPD data indicated that each activation method may lead to varying amounts of acidic and basic functional groups on the surface of the adsorbent, which may be a crucial factor in determining the adsorption capacity. It was shown that ACs developed during the present study are good adsorbents, especially for the removal of a model textile dye methylene blue (MB) from aqueous solution. As MB is a basic dye, H₂O₂-treated rice husk showed the best adsorption capacity, which is in agreement with the acidic groups present on the surface. Removal of the dye followed Langmuir isotherm model, whereas MB adsorption on ACs followed pseudo-second-order kinetics.     

Quantitative evaluation of the chilled-ammonia process for CO2 capture using thermodynamic analysis and process simulation

There is strong world-wide interest in developing new and improved processes for post-combustion capture of CO₂, often using chemical absorption. Developers of new processes make positive claims for their proposals in terms of low energy consumption, but these are usually difficult to validate. This paper demonstrates that rigorous application of thermodynamic analysis and process simulation provides a powerful way to quantitatively estimate the energy requirements of CO₂-capture processes by applying the methodology to the analysis and evaluation of the chilled-ammonia process.     

Preparation and characterization of green bricks using pharmaceutical industrial wastes

This paper reports on recycling of industrial wastes (three pharmaceutical industrial sludges) into environmental friendly value-added materials. Stabilization/Solidification (S/S or bricks) process was applied to make a safer way for the utilization of pharmaceutical waste. The additives in this study include binders (cement, lime and bentonite) and strengthening material (pulverized fuel ash (PFA), silica fume and quarry dust) was used at different compositions. Bricks were cured for 28 days, and the following analysis-like compressive strength, leachability of heavy metals, mineralogical phase identity by X-ray diffraction (XRD) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermal behaviour by thermogravimetric-differential thermal analysis (TG-DTA) had done. All the bricks were observed to achieve the standard compressive strength as required for construction according to BIS standards. Metal concentration in the leachate has reached the dischargeable limits according to Brazilian standards. Results of this study demonstrate that production of bricks is a promising and achievable productive use of pharmaceutical sludge.     

COALBED METHANE PRODUCT WATER CHEMISTRY IN THREE WYOMING WATERSHEDS1

ABSTRACT: The Powder River Basin in Wyoming has become one of the most active areas of coalbed methane (CBM) development in the western United States. Extraction of methane from coalbeds requires pumping of aquifer water, which is called product water. Two to ten extraction wells are manifolded into one discharge point and product water is released into nearby unlined holding ponds. The objective of this study was to evaluate the chemistry, salinity, and sodicity of CBM product water at discharge points and associated holding ponds as a function of watershed. The product water samples from the discharge points and associated holding ponds were collected from the Cheyenne River (CHR), Belle Fourche River (BFR), and Little Powder River (LPR) watersheds during the summers of 1999 and 2000. These samples were analyzed for pH, electrical conductivity (EC), total dissolved solids (TDS), alkalinity, sodium (Na), calcium (Ca), magnesium (Mg), potassium (K), sulfate (SO₄^2‐), and chloride (C^1‐). From the chemical data, practical sodium adsorption ratio (SARp) and true sodium adsorption ratio (SARt) were calculated for the CBM discharge water and pond water. The pH, EC, TDS, alkalinity, Na, Ca, Mg, K, SARp, and SARt of CBM discharge water increased significantly moving north from the CHR watershed to the LPR watershed. CBM discharge water in associated holding ponds showed significant increases in EC, TDS, alkalinity, Na, K, SARp, and SARt moving north from the CHR to the LPR watershed. Within watersheds, the only significant change was an increase in pH from 7.21 to 8.26 between discharge points and holding ponds in the LPR watershed. However, the LPR and BFR exhibited larger changes in mean chemistry values in pH, salinity (EC, TDS), and sodicity (SAR) between CBM product water discharges and associated holding ponds than the CHR watershed. For instance, the mean EC and TDS of CBM product water in LPR increased from 1.93 to 2.09 dS/m, and froml,232 to 1,336 mg/L, respectively, between discharge and pond waters. The CHR exhibited no change in EC, TDS, Na, or SAR between discharge water and pond water. Also, while not statistically significant, mean alkalinity of CBM product water in BFR and LPR watersheds decreased from 9.81 to 8.01 meq/L and from 19.87 to 18.14 meq/L, respectively, between discharge and pond waters. The results of this study suggest that release of CBM product water onto the rangelands of BFR and LPR watersheds may precipitate calcium carbonate (CaCO₃) in soils, which in turn may decrease infiltration and increase runoff and erosion. Thus, use of CBM product water for irrigation in LPR and BFR watersheds may require careful planning based on water pH, EC, alkalinity, Na, and SAR, as well as local soil physical and chemical properties.     

Synthesis and in vitro anti-inflammatory activity of novel benzo[d] imidazolyl dihydrospiro[indoline-3,1′-isoindole]-2,4′,7′-triones

Synthesis of novel benzo[d]imidazolyldihydrospiro[indoline-3,1′-isoindole]-2,4′,7′-triones has been described. The key intermediate 2-[(2-sulfanyl-1H-benzo[d]imidazol-5-yl)amino]acetic acid is obtained by reacting 5-amino-2-mercapto benzimidazole and chloroacetic acid. The three-component reaction of 2-[(2-sulfanyl-1H-benzo[d]imidazol-5-yl)amino]acetic acid with isatin and 1,4-benzoquinone in the presence of 10 mol% of L-proline at ambient temperature afforded 2′-(2-mercapto-1H-benzo [d] imidazol-5-yl)-3′,3a′-dihydrospiro[indoline-3,1′-isoindole]-2,4′,7′(2′H,7a′H)-triones. All the synthesized compounds were evaluated for in vitro anti-inflammatory activity.     

Heavy metal bioaccumulation in selected medicinal plants collected from Khetri copper mines and comparison with those collected from fertile soil in Haridwar,India

Heavy metal distribution in medicinal plants is gaining importance not only as an alternative medicine, but also for possible concern due to effects of metal toxicity. The present study has been focused on emphasizing the heavy metal status and bioaccumulation factors of V, Mn, Fe, Co, Cu, Zn, Se (essential metals) and Cr, Ni, Cd, As and Pb (potentially toxic metals) in medicinal plants grown under two different environmental conditions e.g., near to Khetri copper mine and those in fertile soils of Haridwar, both in India, using Instrumental Neutron Activation Analysis (relative method) and Atomic Absorption Spectrometry. The copper levels in the medicinal plants from Khetri were found to be 3-4 folds higher (31.6–76.5 mg kg^?1) than those from Haridwar samples (7.40–15.3 mg kg^?1), which is correlated with very high copper levels (763 mg kg^?1) in Khetri soil. Among various heavy metals, Cr (2.60–5.92 mg kg^?1), Cd (1.47–2.97 mg kg^?1) and Pb (3.97–6.63 mg kg^?1) are also higher in concentration in the medicinal plants from Khetri. The essential metals like Mn (36.4–69.3 mg kg^?1), Fe (192–601 mg kg^?1), Zn (24.9–49.9 mg kg^?1) and Se (0.13–0.91 mg kg^?1) and potentially toxic metals like Ni (3.09–9.01 mg kg^?1) and As (0.41–2.09 mg kg^?1) did not show much variations in concentration in the medicinal plants from both Khetri and Haridwar. The medicinal plants from Khetri, e.g., Ocimum sanctum, Cassia fistula, Withania somnifera and Azadirachta Indica were found rich in Ca and Mg contents while Aloe barbadensis showed moderately high Ca and Mg. Higher levels of Ca-Mg were found to correlate with Zn (except Azadirachta Indica). The bioaccumulation factors (BAFS) of the heavy metals were estimated to understand the soil-to-plant transfer pattern of the heavy metals. Significantly lower BAF values of Cu and Cr were found in the medicinal plants from Khetri, indicating majority fraction of these metals are precipitated and were immobilized species unsuitable for plant uptake. Overall, Withania somnifera (Ashwagandha) showed very high metal bioaccumulation.     

Development of a highly sensitive extractive spectrophotometric method for the determination of nickel(II) from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone

Nickel(II) reacts with N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) and forms a yellow colored complex, which was extracted into n-butanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-ECCT complex was measured at different intervals of time at 400nm, to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72h. The system obeyed Beer's law in the concentration range of 1.2-5.6mugml(-1) of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.114x10(4)Lmol(-1)cm(-1) and 5.29x10(-3)mugcm(-2) at 400nm, respectively. Hence, a detailed study of the extraction of nickel(II) with ECCT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.     

Intracellular biosynthesis of Au and Ag nanoparticles using ethanolic extract of Brassica oleracea L. and studies on their physicochemical and biological properties

In this present study, we reported broccoli (Brassica oleracea L.) as a potential candidate for the synthesis of gold and silver nanoparticles (NPs) in green chemistry method. The synthesized metal nanoparticles are evaluated their antimicrobial efficacy against different human pathogenic organisms. The physico-chemical properties of gold nanoparticles were analyzed using different analytical techniques such as a UV–Vis spectrophotometer, Field Emission Scanning Electron Microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and a Fourier Transform Infrared spectrophotometer. In addition, gold and silver NP antimicrobial efficacy was checked by disc diffusion assay. UV–Vis color intensity of the nanoparticles was shown at 540 and 450 nm for gold and silver nanoparticles respectively. Higher magnification of the Field Emission Scanning Electron Microscopy image shows the variable morphology of the gold nanoparticles such as spherical, rod and triangular shapes and silver nanoparticles were seen in spherical shapes. The average spherical size of the particles was observed in 24–38 nm for gold and 30–45 nm for silver NPs. X-ray diffraction pattern confirmed the presence of gold nanoparticles and silver nanoparticles which were crystalline in nature. Additionally, the functional metabolites were identified by the Fourier Transform Infrared spectroscopy. IR spectra revealed phenols, alcohols, aldehydes (sugar moieties), vitamins and proteins are present in the broccoli extract which are accountable to synthesize the nanoparticles. The synthesized gold and silver NPs inhibited the growth of the tested bacterial and fungal pathogens at the concentration of 50 μg/mL respectively. In addition, broccoli mediated gold and silver nanoparticles have shown potent antimicrobial activity against human pathogens.     

Dual mechanochemical immobilization of heavy metals and decomposition of halogenated compounds in automobile shredder residue using a nano-sized metallic calcium reagent

Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90–100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45–1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L⁻¹; Cr 1.5 mg L⁻¹; Fe, Pb, and Zn 3.0 mg L⁻¹; Mn and Ni 1 mg L⁻¹) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.

     

Electroosmotic dewatering of dredged sediments: bench-scale investigation

The Indiana Harbor (Indiana, USA) has not been dredged since 1972 due to lack of a suitable disposal site for dredged sediment. As a result of this, over a million cubic yards of highly contaminated sediment has accumulated in the harbor. Recently, the United States Army Corps of Engineers (USACE) has selected a site for the confined disposal facility (CDF) and is in the process of designing it. Although dredging can be accomplished rapidly, the disposal in the CDF has to be done slowly to allow adequate time for consolidation to occur. The sediment possesses very high moisture content and very low hydraulic conductivity, which cause consolidation to occur slowly. Consolidation of the sediment is essential in order to achieve adequate shear strength of sediments and also to provide enough air space to accommodate the large amount of sediment that requires disposal. Currently, it has been estimated that if a one 3-foot (0.9-m) thick layer of sediment was disposed of at the CDF annually, it would take approximately 10 years to dispose of all the sediment that is to be dredged from the Indiana Harbor. This study investigated the feasibility of using an electroosmotic dewatering technology to accelerate dewatering and consolidation of sediment, thereby allowing more rapid disposal of sediment into the CDF. Electroosmotic dewatering essentially involves applying a small electric potential across the sediment layer, thereby inducing rapid flow as a result of physico-chemical and electrochemical processes. A series of bench-scale electrokinetic experiments were conducted on actual dredged sediment samples from the Indiana Harbor to investigate dewatering rates caused by gravity alone, dewatering rates caused by gravity and electric potential, and the effects of the addition of polymer flocculants on dewatering of the sediments. The results showed that electroosmotic dewatering under an applied electric potential of 1.0VDC/cm could increase the rate of dewatering and consolidation by an order of magnitude as compared to gravity drainage alone. Amending the sediment with polymers at low concentrations (0.5-1% by dry weight) will enhance this dewatering process; however, the optimal polymer concentration and the cost-effectiveness of using polymers should be investigated further.