LaCoO3/SBA-15 as a high surface area catalyst to activate peroxymonosulfate for degrading atrazine in water.

An efficient perovskite-based heterogeneous catalyst is highly desired to activate peroxymonosulfate (PMS) for removing organic pollutants in water. A high surface area PMS-activator was fabricated by loading LaCoO3 on SBA-15 to degrade atrazine (ATR) in water. The LaCoO3/SBA-15 depicted better textural properties and higher catalytic activity than LaCoO3. In 6.0 min, atrazine (ATZ) degradation in the selected LaCoO3/SBA-15/PMS system, LaCoO3, adsorption by LaCoO3/SBA-15, sole PMS processes reached approximately 100%, 55.15%, 12.80%, and 16.65 % respectively. Furthermore, 0.04 mg L-1 Co was leached from LaCoO3/SBA-15 during PMS activation by LaCoO3/SBA-15. The LaCoO3/SBA-15 showed stable catalytic activity after reuse. The use of radical scavengers and electron paramagnetic resonance spectroscopy (EPR) demonstrated that ROS such as 1O2, O2•-, •OH, and SO4•- were generated by PMS activated by LaCoO3/SBA-15 owing to redox reactions [Co2+/Co3+, and O2-/O2]. EPR, XPS, ATR-FTIR, EIS, LSV, and chronoamperometric measurements were used to explain the catalytic mechanism for PMS activation. Excellent atrazine degradation was due to high surface area, porous nature, diffusion-friendly structure, and ROS. Our investigation proposes that perovskites with different A and B metals and modified perovskites can be loaded on high surface area materials to activate PMS into ROS.

Redox mediators boost NOx reduction via trade-off electron charges using a cube-shaped (cMn@rGO) catalyst; mechanism and electrochemical study.

Gaseous pollutants like sulfur dioxide and nitrogen oxide(s) (SO2, NOx) have been increasing exponentially for the last two decades, which have had adverse effects on human health, aquatic life, and the environment. Recently, for air pollution taming, manganese/oxide (Mn/MnO) has become a very promising heterogeneous catalyst due to its environment-friendly, low-price, and remarkable catalytic abilities for toxic gases. In this work, cube-shaped Mn nanoparticles (cMn NPs) were decorated on the surface of reduced graphene oxide (rGO) by the solvothermal method. The resulting cMn@rGO composite was employed for electrochemical NOx reduction. However, the microscopic (TEM/HRTEM) and structural analysis were utilised to investigate the morphology and characteristics of the cMn@rGO composite. This electrochemical-based treatment for NOx reduction is employed by using electron shuttle or redox mediators. Here, four distinct redox mediators are used to address electrochemical obstacles, which effectively facilitate electron transportation and promoted NOx reduction on the electrode surface. These mediators not only significantly enhanced the NOx conversion into valuable products, i.e., N2 and N2O, but also made the process smooth with high performance. Among these mediators, neutral red (N.R) exhibited extraordinary potential in enhancing NOx reduction. The obtained results indicated that the remarkable catalytic performance (∼93%) of the cMn@rGO can be attributed to several factors, including the catalyst's three-dimensional architecture structure and abundant active sites. The designed catalyst (cMn@rGO) is not only cost-effective and sustainable but also exhibits excellent potential in effectively reducing NOx, which could be beneficial for large-scale NOx abatement.

Synthesis of a Novel Dithiocarbamate Surfactant Derivative Adsorbent for Efficient Removal of Heavy Metal Ions.

In this work, a novel heavy metal chelating agent (DTC-SDS) containing dithiocarbamate (DTC) was synthesized using sodium dodecyl sulfate (SDS), formaldehyde, and carbon disulfide. DTC-SDS has excellent trapping performance under pH 1-7 and initial concentrations 100-500 mg/L. With the increase in adsorbent dose, the adsorption amount of DTC-SDS increases and then decreases, and the optimized dosage of DTC-SDS is 0.02 g. The DTC-SDS adsorbent exhibits superior adsorption capacity (191.01, 111.7, and 79.14 mg/g) and high removal rates (97.99%, 98.48%, and 99.91%) for Mn2+, Zn2+, and Pb2+ respectively, in wastewater. Such remarkable adsorption performance could be attributed to the strong trapping effect on heavy metal ions by the C-S bond of DTC-SDS. The liquid adsorbent was in full contact with heavy metal ions, which further enhanced the complexation of heavy metal ions. The adsorption isothermal model showed that the adsorption process was typical of Langmuir monomolecular layer adsorption. Kinetic studies showed that the pseudo-second-order kinetic model fits the experimental adsorption data better than the pseudo-first-order kinetic model. In the ternary metal species system (Mn2+, Zn2+, and Pb2+), DTC-SDS preferentially adsorbed Pb2+ due to its highest covalent index. The main controlling step is the chemical interaction between the active groups of DTC-SDS and the heavy metal ions. This work provides valuable insights into the adsorption of heavy metal ions onto dithiocarbamate, which could guide the development of other heavy metal chelating agents and be beneficial for developing novel treatments of wastewater contaminated with heavy metals.

Multimodal energy harvesting and catalysis of piezoelectric nanosheets for efficient and round-the-clock wastewater treatment.

Solar-driven pollutants degradation is an important way for green wastewater treatment, but it is still limited by the intermittent solar flux. Here, we have prepared piezoelectric Bi4Ti3O12 (BTO) nanosheets with abundant physical properties, which can convert extensive solar energy, mechanical energy and temperature variation energy into electrical and chemical energy. It can be used for round-the-clock wastewater treatment by harvesting multi-modal energy. More importantly, the degradation rate of piezoelectric nanosheets can reach 153.4 × 10-3 min-1, and nanosheets can degrade many organic pollutants. In addition, we fabricate porous foam catalysts based on BTO-polydimethylsiloxane (PDMS) composite to prevent secondary contamination. Our results suggest that BTO nanosheets with photoelectric, piezoelectric and pyroelectric catalysis offer a potential approach for round-the-clock wastewater degradation by harvesting solar energy, ambient mechanical energy, and cyclic thermal energy.

Heterogeneous photo-Fenton degradation of acid orange 7 activated by red mud biochar under visible light irradiation.

The heterogeneous photo-Fenton process is an effective technology for degrading organic contaminants in wastewater, and Fe-based catalysts are recently preferred due to their low biotoxicity and geological abundance. Herein, we synthesized a Fe-containing red mud biochar (RMBC) via one-step co-pyrolysis of red mud and shaddock peel as a photo-Fenton catalyst to activate H2O2 and degrade an azo dye (acid orange 7, AO7). RMBC showed excellent AO7 removal capability with a decolorization efficiency of nearly 100% and a mineralization efficiency of 87% in the heterogeneous photo-Fenton process with visible light irradiation, which were kept stable in five successive reuses. RMBC provided Fe2+ for H2O2 activation, and the light irradiation facilitated the redox cycle of Fe2+/Fe3+ in the system to produce more reactive oxygen species (ROS, i.e., •OH) for AO7 degradation. Further investigation revealed that •OH was the predominant ROS responsible for AO7 degradation in the light-free condition, while more ROS were produced in the system with light irradiation, and 1O2 was the primary ROS in the photo-Fenton process for AO7 removal, followed by •OH and O2•-. This study provides insight into the interfacial mechanisms of RMBC as a photo-Fenton catalyst for treating non-degradable organic contaminants in water through advanced oxidation processes under visible light irradiation.

Development of novel K0.8Ni0.4Ti1.6O4 nano bamboo leaves, microstructural characterization, double absorption, and photocatalytic removal of organic pollutant.

Novel K0.8Ni0.4Ti1.6O4 (KNTO) nano bamboo leaves were prepared for the first time under a simple hydrothermal method with 3 M KOH at 320 °C over 80 min. Highly pure KNTO possessing layered structure was determined by X-ray diffraction (XRD) and high-resolution transmission electron microscope (HRTEM). Double absorption feature of KNTO semiconductor was revealed at band energies of 1.88 and 2.08 eV by the UV-vis diffuse reflectance spectra and confirmed by the photoluminescence (PL) spectra. The photocatalytic activity was explored by the photodegradation of MB organic dye. KNTO not only exhibits strong adsorptive ability on methylene blue (MB) in dark environment, but also possesses good photodegradation capability of 94% degradation in 60 min. Degradation mechanism revealed that the photogenerated holes play an essential role in the MB degradation process, which is confirmed by trapping experiments. The recycling experiments demonstrated very high recycling ability and durability of KNTO nano bamboo leaves, suggesting KNTO is a potential candidate for high efficiency organic pollutant removal in the wastewater treatment.

Synthesis of manganese incorporated hierarchical mesoporous silica nanosphere with fibrous morphology by facile one-pot approach for efficient catalytic ozonation.

Manganese incorporated fibrous silica nanosphere (MnOx-0.013/KCC-1) was synthesized by one step hydrothermal method for the first time and its catalytic activity for ozonation of oxalic acid was studied. For comparison, manganese loaded MCM-41 (MnOx-0.013/MCM-41) was prepared by impregnation method. Various characterizations showed that the morphological, structural and textural properties of MnOx-0.013/KCC-1 were well preserved. Ozonation and catalytic ozonation by MnOx-0.013/KCC-1 and MnOx-0.013/MCM-41 led to 4, 85 and 60% reduction in TOC respectively. Furthermore, 0.05 and 1.2mgL(-1) leaching of Mn was detected from MnOx-0.013/KCC-1 and MnOx-0.013/MCM-41, which are approximately 2.0 and 42.0% of the total Mn present in MnOx-0.013/KCC-1 and MnOx-0.013/MCM-41 respectively. The high catalytic activity was attributed to the generation of hydroxyl radical. Surface hydroxyl groups investigated by using phosphates and ATR-FTIR were believed to be the active sites. Our proposed method of synthesis can be generalized for the synthesis of other metal oxides incorporated fibrous silica for environmental catalysis and other catalytic reactions.

Enhanced anaerobic fermentation with azo dye as electron acceptor: simultaneous acceleration of organics decomposition and azo decolorization.

Accumulation of hydrogen during anaerobic processes usually results in low decomposition of volatile organic acids (VFAs). On the other hand, hydrogen is a good electron donor for dye reduction, which would help the acetogenic conversion in keeping low hydrogen concentration. The main objective of the study was to accelerate VFA composition through using azo dye as electron acceptor. The results indicated that the azo dye serving as an electron acceptor could avoid H2 accumulation and accelerate anaerobic digestion of VFAs. After adding the azo dye, propionate decreased from 2400.0 to 689.5mg/L and acetate production increased from 180.0 to 519.5mg/L. It meant that the conversion of propionate into acetate was enhanced. Fluorescence in situ hybridization analysis showed that the abundance of propionate-utilizing acetogens with the presence of azo dye was greater than that in a reference without azo dye. The experiments via using glucose as the substrate further demonstrated that the VFA decomposition and the chemical oxygen demand (COD) removal increased by 319.7mg/L and 23.3% respectively after adding the azo dye. Therefore, adding moderate azo dye might be a way to recover anaerobic system from deterioration due to the accumulation of H2 or VFAs.

Enhanced anaerobic digestion of organic contaminants containing diverse microbial population by combined microbial electrolysis cell (MEC) and anaerobic reactor under Fe(III) reducing conditions.

Microbial electrolysis cell (MEC) devices are efficient for wastewater treatment, but its application was limited due to low anode oxidation rate. The objective of this study was to improve anode performance of a MEC combined anaerobic reactor (R1) for high concentration industrial wastewater treatment via dosing Fe(OH)3. For the first 53 days without power, the addition of Fe(OH)3 in R1 enhanced the degradation of reactive brilliant red X-3B dye and sucrose. Applying a voltage of 0.8 V in R1 resulted in a higher decolorization and COD removal through driving the redox reactions at electrodes under Fe(III)-reducing conditions. Real-time PCR and enzyme activity analysis showed that the abundance and azoreductase activity of bacteria were improved in R1. Pyrosequencing revealed that dominant populations in anode biofilm and R1 were more diverse and abundant than the common anaerobic reactor (R2), and there was a significant distinction among anode film, R1 and R2 in microbial community structure.

Fate of carbosulfan and monocrotophos in sandy loam soils of Pakistan under field conditions at different watertable depths.

Information regarding pesticide mobility is critical for the evaluation of pesticide management practices. For this purpose, lysimetric studies were conducted to develop assessment schemes to protect groundwater from unacceptable effects caused by pesticide use. By using these studies, specific monitoring actions and prevention measures for the protection of waters can be studied, and the results thus obtained can provide the local authorities and the decision makers with an identification tool for demarcating risk areas. Pesticide residues were found at the bottom of lysimeters in the following pattern i.e., 1.52 > 2.1 > 2.74 m which could represent an "index of risk" for groundwater pollution. Regressions built for carbofuran and monocrotophos against watertable depths showed a decreasing trend of pesticide in higher watertable treatments. These findings support the existence of a significant role for chromatographic flow in sandy texture soil. Moreover, the higher values of pesticide residue at the bottom of lysimeters reflect that chromatographic flow as well as preferential flow pattern prevails during higher precipitation events. The precipitation received during the study was higher than the 10 year average and can be considered relatively as a worst case scenario. Finally, the authors have recommended a standardized pesticide monitoring scheme for groundwater in accordance with the already validated generic schemes in developed countries.

Pesticides exposure in Pakistan: a review.

This is the first systematic review of studies done since 1960, and to give an integrated picture of pesticides exposure to humans, animals, plants, waters, soils/sediments, atmosphere etc. in Pakistan. Authors have extracted data from different departments, published literature in research journals and National reports. Although the wide-spread usage of pesticides in Pakistan has controlled the pests, but like other countries, it has started causing environmental problems in the area. In some areas of Punjab and Sindh groundwater has been found contaminated and is constantly being under the process of contamination due to pesticide use. There is considerable evidence that farmers have overused and misused pesticides especially in cotton-growing areas. It is evident from the biological monitoring studies that farmers are at higher risk for acute and chronic health effects associated with pesticides due to occupational exposure. Furthermore, the intensive use of pesticides (higher sprays more than the recommended dose) in cotton areas involves a special risk for the field workers, pickers, and of an unacceptable residue concentration in cottonseed oil and cakes. The authors have also discussed the merits and demerits of different studies. The review will set the future course of action of different studies on pesticide exposure in Pakistan. Data limitations are still the major obstacle towards establishing clear environmental trends in Pakistan. The authors suggest that a reliable monitoring, assessment and reporting procedures shall be implemented in accordance with appropriate environmental policies, laws and regulations in order to minimize the pesticides exposure.

Degradation and persistence of cotton pesticides in sandy loam soils from Punjab, Pakistan.

The present study evaluated the influence of temperature, moisture, and microbial activity on the degradation and persistence of commonly used cotton pesticides, i.e., carbosulfan, carbofuran, lambda-cyhalothrin, endosulfan, and monocrotophos, with the help of laboratory incubation and lysimeter studies on sandy loam soil (Typic Ustocurepts) in Pakistan. Drainage from the lysimeters was sampled on days 49, 52, 59, 73, 100, 113, and 119 against the pesticide application on days 37, 63, 82, 108, and 137 after the sowing of cotton. Carbofuran, monocrotophos, and nitrate were detected in the drainage samples, with an average value, respectively, of 2.34, 2.6 microg/L, and 15.6 mg/L for no-tillage and 2.16, 2.3 microg/L, and 13.4 mg/L for tillage. In the laboratory, pesticide disappearance kinetics were measured with sterile and nonsterile soils from 0 to 10 cm in depth at 15, 25, and 35 degrees C and 50% and 90% field water capacities. Monocrotophos and carbosulfan dissipation followed first-order kinetics while others followed second-order kinetics. The results of incubation studies showed that temperature and moisture contents significantly reduced the t(1/2) (half-life) values of pesticides in sterile and nonsterile soil, but the effect of microbial activity was nearly significant that might be due to less organic carbon (0.3%). The presence of carbofuran and monocrotophos in the soil profile (0-10, 10-30, 30-60, 60-90, 90-150 cm) and the higher concentrations of endosulfan and lambda-cyhalothrin in the top layer (0-10 cm) showed the persistence of the pesticides. The detection of endosulfan and lambda-cyhalothrin in the 10-30 cm soil layer might be due to preferential flow. The data generated from this study could be helpful for risk assessment studies of pesticides and for validating pesticide transport models for sandy loam soils in cotton-growing areas of Pakistan.

Pesticides in shallow groundwater of Bahawalnagar, Muzafargarh, D.G. Khan and Rajan Pur districts of Punjab, Pakistan.

In Pakistan there is little data on environmental contamination of rural water sources by pesticides. This study evaluated pesticide contamination of groundwater in four intensive cotton growing districts. Water samples were collected from 37 rural open wells in the areas of Bahwalnagar, Muzafargarh, D.G. Khan and Rajan Pur districts of Punjab and analysed for eight pesticides which are mostly used. Information on types of pesticide used and distance to nearest pesticide mixing area and application areas was obtained for each site. From the eight pesticides analysed, six pesticides were detected in the water samples. Only cypermethrin and cabosulfan were not detected. The percentage of detection of bifenthrin, lambda-cyhalothrin, carbofuran, endosulfan, methyl parathion and monocrotophos was, respectively 13.5%, 5.4%, 59.4%, 8%, 5.4% and 35.1% in July; 16.2%, 13.55%, 43.2%, 8%, N.D. (not detected) and 24.3% in October. Maximum contamination levels (MCLs) established by the U.S. Environmental Protection Agency for drinking water were not exceeded. The study has shown the need for monitoring pesticide contamination in rural water resources, and the development of drinking water quality standards for specific pesticides in Pakistan. The conclusions and recommendations will be disseminated to senior decision makers in central and local governments, extension agents and farmers.