Removal of Methylene Blue Dye from Aqueous Solutions Using Polymer Inclusion Membrane Containing Calix[4]pyrrole.

The effective purification of aqueous solutions of methylene blue dye was tested using polymer inclusion membranes (PIMs) that contained cellulose triacetate (CTA) as a polymer base, o-nitrophenyl octyl ether (o-NPOE) as a plasticizer, and meso-tetra methyl tetrakis-[methyl-2-(4-acetlphenoxy)] calix[4]pyrrole (KP) as a carrier. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy were used to define the microstructure and surface of PIMs. Experimental results showed that, with an increased concentration of methylene blue in an aqueous solution, the removal percentage also increased. Further observation showed that the flux increased with the rise in the source phase pH values from 3 to 10. The carrier and plasticizer content in the membrane significantly influenced the membrane's transport properties. The optimal composition of the membrane in percent by weight for KP was 74% plasticizer; 18% support, and 8% carrier. The maximum MB removal (93.10%) was achieved at 0.10 M HCl solution as the receiving phase. It was shown that the membrane with optimal composition showed good reusability and enabled the easy and spontaneous separation of methylene blue from aqueous solutions.

Evaluating low-cost permeable adsorptive barriers for the removal of benzene from groundwater: Laboratory experiments and numerical modelling.

Permeable adsorptive barriers (PABs) consisting of individual (compost, zeolite, and brown coal) and composite (brown coal-compost and zeolite-compost) adsorbents were evaluated for their hydraulic performance and effectiveness in removing aqueous benzene using batch and column experiments. Different adsorption isotherms and kinetic models and different formulations of the equilibrium advection-dispersion equation (ADE) were evaluated for their capabilities to describe the benzene sorption in the media. The batch experiments showed that the adsorption of benzene by the adsorbents was favourable and could be adequately described by the Freundlich and Langmuir isotherms and the pseudo-second-order kinetic model. Particle attrition and structural reorganization occurred in the columns, possibly introducing preferential flow paths and resulting in slight changes in the final hydraulic conductivity values (4.3 × 10-5 cm s-1-1.7 × 10-3 cm s-1) relative to the initial values (4.2 × 10-5 cm s-1-2.14 × 10-3 cm s-1). Despite the fact that preferential flow appeared to have an impact on the performance of the investigated adsorbents, the brown coal-compost mixture proved to be the most effective adsorbent. It significantly delayed benzene breakthrough (R = 29), indicating that it can be applied as a low-cost effective adsorbent in PABs for sustainable remediation of benzene-contaminated groundwater. The formulated transport models could fairly describe the behaviour of benzene in the investigated media under dynamic flow conditions; however, model refinement and additional experimental studies are needed before pilot/full-scale applications to improve the fits and verify the benzene removal processes. Our results generally demonstrate how such studies can be useful in evaluating potential reactive barrier materials.

Ecotoxicity and bioremediation potential assessment of soil from oil refinery station area.

Purpose: The aim of the present study was to evaluate the toxicity and biodegradation potential of oil hydrocarbons contaminated soil samples obtained from different depths at an oil refinery station area. An approach involving chemical, microbiological, respirometry and ecotoxicity assessment of soil polluted by oil hydrocarbons was adopted, in order to determine the biodegradability of pollutants and ecotoxicological effects of natural attenuation strategy. Methods: The ecotoxicity of soil samples was evaluated using an ostracod test kit and a seed germination test. The results of the phytotoxicity assay were expressed as a percentage of seedling emergence and as the relative yield of fresh and dry biomass compared to control plants. The intrinsic biodegradation potential of the contaminated soil was examined using a Micro-Oxymax respirometer. Intrinsic biodegradation rates were estimated from the slopes of linear regressions curves plotted for cumulative O2 uptake. The obtained values were then entered in the mass balance equation for the stoichiometric reaction of hydrocarbon decomposition and converted per kg of soil per day. Results: Although the tested contaminants were biodegradable in the respirometric assay, they were slightly to moderately toxic to plants and extremely toxic to ostracods. The noxious effects raised with the increased concentration of contaminants. The monocotyledonous oat was more tolerant to higher concentrations of oil hydrocarbons than the other test plants, indicating its greater suitability for soil reclamation purposes. Conclusion: By assessing phytotoxicity and effect on ostracod mortality and progress of soil self-decontamination process, proper approach of reclamation of demoted area can be provided.

Separation of Mercury(II) from Industrial Wastewater through Polymer Inclusion Membranes with Calix[4]pyrrole Derivative.

Polymer membranes with immobilized ligands are encouraging alternatives for the removal of toxic metal ions from aquatic waste streams, including industrial wastewater, in view of their high selectivity, stability, removal efficacy and low energy demands. In this study, polymer inclusion membranes (PIMs) based on cellulose triacetate, with a calix[4]pyrrole derivative as an ion carrier, were tested for their capability to dispose mercury (Hg(II)) ions from industrial wastewater. The impacts were assessed relative to carrier content, the quantity of plasticizer in the membrane, the hydrocholoric acid concentration in the source phase, and the character of the receiving phase on the performance of Hg(II) elimination. Optimally designed PIMs could be an interesting option for the industrial wastewater treatment due to the high removal efficiency of Hg(II) and great repeatability.

Fate of selected neonicotinoid insecticides in soil-water systems: Current state of the art and knowledge gaps.

The occurrence of emerging contaminants, such as: personal care products, medicines, pharmaceuticals, pesticides, and their transformation products in the environment is of concern for human health and aquatic ecosystems due to their high persistence, toxicity and potential to bioaccumulation. Among pesticides, the main attention and thus our focus is on neonicotinoids: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam, which are widely used classes of insecticides in agriculture. Determining the associated risk to humans and ecosystems from neonicotinoid insecticides requires detailed understanding of their fate and transport in the environment which is complex and includes diverse pathways and processes depending on environmental compartments in which they occur. This paper critically reviews the current state of the art about processes, parameters and phenomena influencing the fate of neonicotinoid insecticides in soil-water systems (i.e. soil and groundwater), and reveals existing knowledge gaps. Sorption, biodegradation, chemical transformations of neonicotinoid insecticides in the soil and leaching to the groundwater, as well as groundwater/surface water interactions are highlighted, as they determine their further migration from sources, through soils to groundwater systems and then to other environmental compartments posing ecological and human risks. A number of key knowledge gaps in fate of neonicotinoid insecticides in soil-water systems are identified, that concern mostly processes and pathways occurring in the groundwater, and require further research to assess the associated risk to humans and ecosystems.

Restoration of soil quality using biochar and brown coal waste: A review.

Soils in intensively farmed areas of the world are prone to degradation. Amendment of such soils with organic waste materials attempts to restore soil quality. Organic amendments are heterogeneous media, which are a source of soil organic matter (SOM) and maintain or restore chemical, physical, biological and ecological functionality. More specifically, an increase in SOM can influence the soil microclimate, microbial community structure, biomass turnover and mineralisation of nutrients. The search is on-going for locally sourced alternatives as many forms may be costly or geographically limiting. The present review focuses on a heterogeneous group of amendments i.e. biochar and brown coal waste (BCW). Both biochar (made from a variety of feedstocks at various temperatures) and BCW (mined extensively) are options that have worldwide applicability. These materials have very high C contents and soil stability, therefore can be used for long-term C sequestration to abate greenhouse gas emissions and as conditioners to improve soil quality. However, biochar is costly for large-scale applications and BCW may have inherently high moisture and pollutant contents. Future studies should focus on the long-term application of these amendments and determine the physicochemical properties of the soil, bioavailability of soil contaminants, diversity of soil communities and productivity of selected crops. Furthermore, the development of in situ technologies to lower production and processing costs of biochar and BCW would improve their economic feasibility for large-scale application.

Assessment of zeolite and compost-zeolite mixture as permeable reactive materials for the removal of lead from a model acidic groundwater.

Column experiments were performed to assess the effectiveness of zeolite and compost-zeolite mixture in removing dissolved lead (Pb2+) from acidic water of pH 2.4. The acid neutralizing ability and hydraulic performance of the materials were also studied. Fitting the advection-dispersion equation (ADE) and mathematical models (i.e. the Dose-Response, Adams-Bohart, and Yoon-Nelson models) to the Pb2+ experimental breakthrough curves (BTCs) was also performed. The compost-zeolite mixture proved to be better than zeolite alone both: in removing Pb2+ and in buffering the acidic pH. The maximum adsorption capacity, qo obtained for zeolite was 0.097 mg/g and 0.151 mg/g for the compost-zeolite mixture, respectively. Lead removal was attributed to ion exchange and adsorption. Observed Pb2+ BTCs demonstrated sorption-related nonequilibrium effects in the columns. The hydraulic conductivity of zeolite decreased by 2% and by 28.8% in the case of compost-zeolite mixture at the end of the experiment. The entire experimental BTC of Pb2+ was well described by the Dose-Response model while the Adams-Bohart model was better in describing only the initial part of the lead BTCs.

Immobilized materials for removal of toxic metal ions from surface/groundwaters and aqueous waste streams.

Heavy metals from industrial processes are of special concern because they produce chronic poisoning in the aquatic environment. More strict environmental regulations on the discharge of toxic metals require the development of various technologies for their removal from polluted streams (i.e. industrial wastewater, mine waters, landfill leachate, and groundwater). The separation of toxic metal ions using immobilized materials (novel sorbents and membranes with doped ligands), due to their high selectivity and removal efficiency, increased stability, and low energy requirements, is promising for improving the environmental quality. This critical review is aimed at studying immobilized materials as potential remediation agents for the elimination of numerous toxic metal (e.g. Pb, Cd, Hg, and As) ions from polluted streams. This study covers the general characteristics of immobilized materials and separation processes, understanding of the metal ion removal mechanisms, a review of the application of immobilized materials for the removal of toxic metal ions, as well as the impacts of various parameters on the removal efficiency. In addition, emerging trends and opportunities in the field of remediation technologies using these materials are addressed.

Geochemical modelling for predicting the long-term performance of zeolite-PRB to treat lead contaminated groundwater.

The feasibility of using geochemical modelling to predict the performance of a zeolite-permeable reactive barrier (PRB) for treating lead (Pb(2+)) contaminated water was investigated in this study. A short-term laboratory column experiment was first performed with the zeolite (clinoptilolite) until the elution of 50 PV (1 PV=ca. 283 mL). Geochemical simulations of the one-dimensional transport of the Pb(2+), considering removal processes including: ion-exchange, adsorption and complexation; the concomitant release of exchangeable cations (Ca(2+), Mg(2+), Na(+), and K(+)) and the changes in pH were subsequently performed using the geochemical model PHREEQC. The results showed a reasonable agreement between the experimental results and the numerical simulations, with the exception of Ca(2+) for which a great discrepancy was observed. The model also indicated the formation of secondary mineral precipitates such as goethite and hematite throughout the experiment, of which the effect on the hydraulic conductivity was found to be negligible. The results were further used to extrapolate the long-term performance of the zeolite. We found the capacity would be completely exhausted at PV=250 (ca. 3 days). The study, thus, generally demonstrates the applicability of PHREEQC to predict the short and long-term performance of zeolite-PRBs. Therefore, it can be used to assist in the design and for management purposes of such barriers.

An overview of permeable reactive barriers for in situ sustainable groundwater remediation.

Permeable reactive barriers (PRBs) are one of the innovative technologies widely accepted as an alternative to the 'pump and treat' (P&T) for sustainable in situ remediation of contaminated groundwater. The concept of the technology involves the emplacement of a permeable barrier containing reactive materials across the flow path of the contaminated groundwater to intercept and treat the contaminants as the plume flows through it under the influence of the natural hydraulic gradient. Since the invention of PRBs in the early 1990s, a variety of materials has been employed to remove contaminants including heavy metals, chlorinated solvents, aromatic hydrocarbons, and pesticides. Contaminant removal is usually accomplished via processes such as adsorption, precipitation, denitrification and biodegradation. Despite wide acknowledgment, there are still unresolved issues about long term-performance of PRBs, which have somewhat affected their acceptability and full-scale implementation. The current paper presents an overview of the PRB technology, which includes the state of art, the merits and limitations, the reactive media used so far, and the mechanisms employed to transform or immobilize contaminants. The paper also looks at the design, construction and the long-term performance of PRBs.

Removal of toxic metal ions from landfill leachate by complementary sorption and transport across polymer inclusion membranes.

In this study, performance of a lab-scale two-step treatment system was evaluated for removal of toxic metal ions from landfill leachate. The technology of polymer inclusion membranes (PIMs) was the first step, while the second step of the treatment system was based on sorption on impregnated resin. The PIMs were synthesized from cellulose triacetate as a support, macrocyclic compound i.e. alkyl derivative of resorcinarene as a ionic carrier and o-nitrophenyl pentyl ether as a plasticizer. The transport experiments through PIM were carried out in a permeation cell, in which the membrane film was tightly clamped between two cell compartments. The sorption tests were carried out using a column filled with a resin impregnated with resorcinarene derivative. The obtained results show the good performance with respect to the removal of heavy metals from landfill leachate with the overall removal efficiency of 99%, 88% and 55% for Pb(II), Cd(II) and Zn(II) ions, respectively. Moreover the contents of metal ions in the leachate sample after treatment system were below permissible limit for wastewater according to the Polish Standards.

Ecotoxicological and environmental problems associated with the former chemical plant in Tarnowskie Gory, Poland.

The environmental problems related to the former chemical plant in Tarnowskie Gory, with respect to the Quaternary and Triassic groundwater as main receptors, are described and the eco-toxicological impact is discussed. The historical use of that site included industrial mining of ores (Ag, Pb, Zn) and use of Ba, B, Sr, Al, Cu during production of pigment. The majority of used and produced substances were toxic or hazardous. The applied technologies resulted in generation of waste which were mostly dumped without any elementary protection principles. Hydrodynamic modelling showed potential hazard to water-intakes. The variations of spatial distributions of selected contaminants within the Triassic carbonate series indicate that the chemical waste dumped in vicinity of the plant are the sources of groundwater contamination of boron. The results of soil and groundwater monitoring at the constructed landfill show significant contamination, mainly due to leaching from dumped waste, but also from infiltration of non-operating underground installations, and spills of toxic substances during the plant operation. The Quaternary aquifers are heavily contaminated due to the leaching out of chemical compounds from dumping sites. This is hazardous to the Triassic reservoirs--the main sources of potable water for the region. The characteristics of the key contaminants (As, B, Ba and Sr) are provided, including their transport, fate and toxicity. The spatial and temporal distribution of contaminants in groundwater is presented, and observed trends of groundwater quality decrease, mainly with respect to the Triassic aquifers, are discussed. The groundwater risk assessment being developed for the Tarnowskie Gory site should consider the present situation, and provide an approach towards evaluation and assessment of the required remediation measures.

Enhancing anaerobic fermentation of sewage sludge for increasing biogas generation.

The article presents results of biogas generation from sewage sludge after applying two pretreatment methods: sonification and thermal hydrolysis. Original results and literature data of the ultrasonic field influence on biogas generation were compared with literature data concerning effectiveness of the thermal hydrolysis. Sludge pretreatment by the ultrasonic field intensified the biogas production as the amounts of biogas was of ca. 20-24% higher, as compared to the nontreated sludge. The highest generation of biogas was observed after a shorter time. The degree of organic matter reduction was of 45-47%. The content of volatile fatty acids dropped down to 139 mg CH3COOH dm(-3) during 20 days. During the thermal pretreatment of sludge the amounts of generated biogas were ca. 25% higher, as compared to nontreated sludge. The maximum biogas production of 0.92 dm3 was observed in the day 9 of fermentation. To-date results indicate that efficiency of ultrasonic disintegration depends on sonification time, type of heads, as well as power and frequency transmitted to heads.