Comparative removal of hazardous cationic dyes by MOF-5 and modified graphene oxide.

Among cationic dyes, malachite green (MG) is commonly used for dying purposes and also as an inhibitor in aquaculture, food, health, and chemical industries due to its cytotoxic effects. Therefore, MG removal is essential to keep the ecosystem and human health safety. Adsorption is a viable and versatile option and exploring efficient adsorbents have high priority. Herein, MOF-5 and aminated corn Stover reduced graphene oxide (ACS-RGO) of typical adsorbents of metal-organic-frameworks (MOFs) and carbon-based classes were studied for MG removal. MOF-5 and ACS-RGO had a specific surface area and total pore volume of 507.4 and 389.0 m2/g, and 0.271 cm3/g and 0.273 cm3/g, respectively. ACS-RGO was superior for MG adsorption and the kinetic rate coefficient for ACS-RGO was ~ 7.2 times compared to MOF-5. For ACS-RGO, MG removal remained high (> 94%) in a wide range of pH. However, dye removal was pH-dependent for MOF-5 and increased from ~ 32% to ~ 67% by increasing pH from 4 to 12. Increasing dye concentration from 25 mg/L to 100 mg/L decreased adsorption by MOF-5 and ACS-RGO for ~ 30% and 7%, respectively. Dye removal was evident in a few tens of seconds after adding ACS-RGO at doses above 0.5 g/L. A significant loss of 46% in adsorption was observed by decreasing MOF-5 mass from 1 to 0.1 g/L. ACS-RGO removed MG in multilayer with an exceptional adsorption capacity of 1088.27 mg/g. In conclusion, ACS-RGO, and MOF-5 showed promising kinetic rates and adsorption capacities toward MG.

Distributing and assessing fluoride health risk in urban drinking water resources in Fars Province, Iran, using the geographical information system.

Excessive fluoride intake has been reported in many studies, which can lead to diseases such as autism, mental retardation, low birth weight, reproductive disorder, as well as dental and bone fluorosis. The potential risk assessment of fluoride intake for the health of people living in Fars Province, Iran, is investigated. Hence, 1700 drinking water samples were taken from April 2018 to March 2020 in four seasons in 29 cities of Fars Province and were analyzed. Non-carcinogenic health risks of exposure to fluoride through drinking water were evaluated. Moreover, the spatial distribution maps of fluoride and hazard quotient (HQ) risk index were prepared using GIS software. The results showed that the concentration of fluoride in the drinking water of the studied area was in the range of 0.086 to 2.61 mg/L. Accordingly, in 48.27% of the cities, fluoride was in the range below the national and international standards, 34.48% of the cities were in the permissible range of 0.5 to 1.5 mg/L, and 17.24% of the urban areas of the province had fluoride contents above the permissible range. Hazard quotient index had the health risk of HQ > 1 in 27.58% of children, 17.24% of teenagers, and 10.34% of adults in the urban areas of Fars Province. In the cities with HQ > 1, there was risk of diseases associated with excessive fluoride intake. Therefore, it is necessary to replace water supply sources in these cities.

Defluoridationof drinking water by metal impregnated multi-layer green graphene fabricated from trees pruning waste.

A novel adsorbent with excellent adsorptive properties for fluoride was prepared through a green and cheap synthesis route. Populus caspica pruning wastes, a cheap agri-waste material, were reduced to multi-layer green graphene (MLG) and then post-modified to aluminum/iron modified multi-layer green graphene (AMLG and IMLG). Batch experiments revealed the effect of pH (3-11), contact time (0.5-12 h), and initial fluoride concentration (5-40 mg/L). The conversion of raw material to MLG increased the specific surface area about 120 times (from 4 to 475 m2/g). Furthermore, a significant improvement in zero points of charge (pHzpc) was attained for IMLG (7.1) and AMLG (8) compared with pristine MLG (4.3). Fluoride showed superior affinity to AMLG and IMLG compared with MLG. Fluoride removal increased gradually by pH from 3 to 8 and then decreased sharply up to pH 11. The study of process dynamics demonstrated the monolayer fluoride adsorption onto AMLG and IMLG controlled by the chemisorptions. The highest predicted adsorption capacities based on the Langmuir model were 31.52, 47.01, and 53.76 mg/g for MLG, IMLG, and AMLG, respectively. Considering economic and technical feasibility presents AMLG and IMLG as a promising candidate against water contamination by elevated fluoride. Graphical abstract.

Modified wheat straw-derived graphene for the removal of Eriochrome Black T: characterization, isotherm, and kinetic studies.

A cost-effective and environment-benign adsorbent was prepared from an abundant agro-waste material. Wheat straw was reduced to graphene and then modified by crosslinking to epichlorohydrin. During the conversion process of wheat straw to graphene, the specific surface area increased more than 100 times (from 4 to 415 m2 g-1). The adsorption efficiency of raw wheat straw, graphene nanosheets, and modified graphene against Eriochrome Black T (EBT) were 8.0, 34.7, and 74.4%, respectively. The modified graphene was further investigated for the effect of environmental condition, i.e., pH (3 to 11), EBT concentration (25-100 mg L-1), adsorbent dosage (0.25-0.75 g L-1), contact time (5-60 min), and solution temperature (30-60 °C). The dye removal remained at a high level under a wide range of pH from 3 to 9. The EBT removal decreased from 87.3 to 54.5 by increasing dye concentration and increased from 38.2 to 85.4% by increasing adsorbent dose in the studied ranges. Dye removal also increased by mixing time from 5 to 30 min, whereas a slight drop was observed by continuing agitation up to 60 min. Conducting experiments at various temperatures revealed an endothermic process. Pseudo-first-order and pseudo-second-order models were adequate to represent the adsorption kinetics. Isotherm models suggest a multilayer adsorption of EBT molecules on heterogeneous modified graphene surface with a maximum adsorption capacity of 146.2 mg g-1. The present work demonstrated that the modified graphene obtained from available and low-cost agro-wastes could be used effectively as adsorbent against EBT from aqueous media.

Optimization of electro-kinetic process for remediation of soil contaminated with phenanthrene using response surface methodology.

The objective of this work was to investigate the modification of soil contaminated with phenanthrene (PHE) by electro-kinetic remediation (EKR) process using response surface methodology (RSM). The soil sample was obtained from the subgrades (0-30 cm) of an area close to Shahroud City, Northeast of Iran. The effect of variables such as initial pH, voltage, electrolyte concentration, and reaction time on PHE removal was studied. Based on the results obtained from the central composite design (CCD) experiment, the highest and lowest amount of PHE removal was 97 and 20%, respectively. In this study, the variables A, B, C, AB, AC, and C2 with a p value < 0.05 were significant model terms and the parameter of the lack of fit was not significant (p value = 0.0745). Findings indicated that the "predicted R-squared" of 0.9670 was in reasonable agreement with the "adj R-squared" of 0.9857 and the plot of residual followed a normal distribution and approximately linear. Also, the kinetic rates of the removal PHE by the EKR process best fitted with a first-order kinetic model (R2: 0.926). Results of the investigation of the effective variables showed that in values of pH 3, time of 168 h, voltage of 3 V, and electrolyte concentration of 4 mg/L, the removal efficiency of PHE reached 96.6%. Graphical abstract.

Modeling of chromium (VI) removal from aqueous solution using modified green-Graphene: RSM-CCD approach, optimization, isotherm, and kinetic studies.

BACKGROUND: The aim of this study was to investigate the removal of Cr (VI) using Green-Graphene Nanosheets (GGN) synthesized from rice straw. METHODS: Synthesis of the GGN was optimized using response surface methodology and central composite design (CCD). The effect of two independent variables including KOH-to-raw rice ash (KOH/RRA) ratio and temperature on the specific surface area of the GGN was determined. To have better removal of Cr (VI), GGN was modified using the grafting amine group method. In the Cr (VI) removal process, the effects of four independent variables including initial Cr (VI) concentration, adsorbent dosage, contact time, and initial solution pH were studied. RESULTS: The results of this study showed that the optimum values of the KOH/RRA ratio and temperature for the preparation of GGN were 10.85 and 749.61 °C, respectively. The maximum amount of SSA obtained at optimum conditions for GGN was 551.14 ± 3.83 m 2 /g. The optimum conditions for Cr (VI) removal were 48.35 mg/L, 1.46 g/L, 44.30 min, and 6.87 for Cr (VI) concentration, adsorbent dosage, contact time, and pH, respectively. Based on variance analysis, the adsorbent dose was the most sensitive factor for Cr (VI) removal. Langmuir isotherm (R2 = 0.991) and Pseudo-second-order kinetic models (R2 = 0.999) were the best fit for the study results and the Q max was 138.89 mg/g. CONCLUSIONS: It can be concluded that the predicted conditions from the GGN synthesis model and the optimum conditions from the Cr (VI) removal model both agreed with the experimental findings.

Valorization of biomass into amine- functionalized bio graphene for efficient ciprofloxacin adsorption in water-modeling and optimization study.

A green synthesis approach was conducted to prepare amine-functionalized bio-graphene (AFBG) as an efficient and low cost adsorbent that can be obtained from agricultural wastes. In this study, bio-graphene was successfully used to remove Ciprofloxacin (CIP) from synthetic solutions. The efficacy of adsorbent as a function of operating variables (i.e. pH, time, AFBG dose and CIP concentration) was described by a polynomial model. A optimal99.3% experimental removal was achieved by adjusting the mixing time, AFBG dose, pH and CIP concentration to 58.16, 0.99, 7.47, and 52.9, respectively. Kinetic model revealed that CIP diffusion into the internal layers of AFBG controls the rate of the process. Furthermore, the sorption process was in monolayer with a maximum monolayer capacity of 172.6 mg/g. Adsorption also found to be favored under higher CIP concentrations. The thermodynamic parameters (ΔG°<0, ΔH°>0, and ΔS°>0) demonstrated that the process is endothermic and spontaneous in nature. The regeneration study showed that the AFBG could simply regenerated without significant lost in adsorption capacity.