Assessing the abundance, sources, and potential ecological risk assessment of microplastics using their particle and mass units in Uiam lake, South Korea.

Microplastics (MPs) enter lakes through various pathways, including effluents from wastewater treatment plants (WWTPs), surface runoff, and improperly disposed of plastic waste. In this study, the extent of MPs pollution in Uiam Lake in fall of 2022 and spring of 2023 was assessed by determining both the number (n/m3) and mass concentrations (µg/m3) of MPs. Moreover, the correlation between water quality parameters and MP properties was analyzed, and an ecological risk assessment was conducted. MPs abundance was higher in spring than in fall, probably due to the lifting of coronavirus disease-19 restrictions, melting of ice, higher rainfall, and faster wind speed. Fragment was the dominant shape of the MPs collected, while polyvinyl chloride (PVC) and polyester/polyethylene terephthalate were the frequently detected polymer types of MPs in fall and spring, respectively. There was a moderate positive correlation between the number concentration of MPs and the total nitrogen, total phosphorus (T-P), and total organic carbon levels; in contrast, there was no significant relationship between the mass concentration of MPs and all water quality parameters. However, the abundance (µg/m3) of PVC and polymethyl methacrylate MPs were positively correlated with T-P and electrical conductivity. The pollution load index, polymer hazard index, and potential ecological risk index (PERI) were generally higher when the mass unit of MPs was used due to the presence of large-sized MPs composed of highly hazardous polymers (e.g., polyurethane, PVC, and alkyd). For instance, the PERI value of the WWTP effluent was at the very high level (> 1200) in both seasons, regardless of the abundance unit of MPs. Therefore, WWTP effluents may have increased the ecological toxicity of MPs pollution in Uiam Lake.

Synthesis of recyclable and light-weight graphene oxide/chitosan/genipin sponges for the adsorption of diclofenac, triclosan, and microplastics.

Emerging micropollutants, such as pharmaceuticals and microplastics (MPs), have become a pressing water environmental concern. The aim of this study is to synthesize chitosan sponges using graphene oxide (GO) and genipin (GP) for the removal of pharmaceuticals (diclofenac (DCF) and triclosan (TCS)) and MPs, verify their adsorption mechanisms, evaluate the effects of temperature, pH, and salinity on their adsorption capacities, and determine their reusability. The GO5/CS/GP sponge exhibited a macroporous nature (porosity = 95%, density = 32.6 mg/cm3). GO and cross-linker GP enhanced the adsorption of DCF, TCS, and polystyrene (PS) MPs onto the CS sponges. The adsorption of DCF, TCS, and PS MPs involved multiple steps: surface diffusion and pore diffusion of the sponge. The adsorption isotherms demonstrated that Langmuir model was the most fitted well model to explain adsorption of TCS (qm = 7.08 mg/g) and PS MPs (qm = 7.42 mg/g) on GO5/CS/GP sponge, while Freundlich model suited for DCF adsorption (qm = 48.58 mg/g). DCF adsorption was thermodynamically spontaneous and endothermic; however, the adsorption of TCS and PS MPs was exothermic (283-313 K). The optimal pH was 5.5-7 due to the surface charge of the GO5/CS/GP sponge (pHzpc = 5.76) and ionization of DCF, TCS, and PS MPs. As the salinity increased, DCF removal efficiency drastically decreased due to the weakening of electrostatic interactions; however, TCS removal efficiency remained stable because TCS adsorption was mainly caused by hydrophobic and π-π interactions rather than electrostatic interaction. The removal of PS MPs was enhanced by the electrostatic screening effects of high Na+ ions. PS nanoplastics (average size = 26 nm) were removed by the GO5/CS/GP sponge at a rate of 73.0%, which was better than that of PS MPs (41.5%). In addition, the GO5/CS/GP sponge could be recycled over five adsorption-desorption cycles.

Recent advances in microbial and enzymatic engineering for the biodegradation of micro- and nanoplastics.

This review examines the escalating issue of plastic pollution, specifically highlighting the detrimental effects on the environment and human health caused by microplastics and nanoplastics. The extensive use of synthetic polymers such as polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS) has raised significant environmental concerns because of their long-lasting and non-degradable characteristics. This review delves into the role of enzymatic and microbial strategies in breaking down these polymers, showcasing recent advancements in the field. The intricacies of enzymatic degradation are thoroughly examined, including the effectiveness of enzymes such as PETase and MHETase, as well as the contribution of microbial pathways in breaking down resilient polymers into more benign substances. The paper also discusses the impact of chemical composition on plastic degradation kinetics and emphasizes the need for an approach to managing the environmental impact of synthetic polymers. The review highlights the significance of comprehending the physical characteristics and long-term impacts of micro- and nanoplastics in different ecosystems. Furthermore, it points out the environmental and health consequences of these contaminants, such as their ability to cause cancer and interfere with the endocrine system. The paper emphasizes the need for advanced analytical methods and effective strategies for enzymatic degradation, as well as continued research and development in this area. This review highlights the crucial role of enzymatic and microbial strategies in addressing plastic pollution and proposes methods to create effective and environmentally friendly solutions.

Coupled adsorption-photocatalysis process for the removal of diclofenac using magnetite/reduced graphene oxide nanocomposite.

Diclofenac (DCF) is frequently detected in water bodies (ng/L to g/L) as it is not completely removed by conventional wastewater treatment plants. Adsorption and photocatalysis have been studied as promising methods for treating DCF; however, both processes have limitations. Thus, in this study, the removal efficiency of DCF is evaluated using a magnetite/reduced graphene oxide (Fe3O4/RGO) nanocomposite via a coupled adsorption-catalysis process. The Fe3O4/RGO nanocomposite was successfully synthesized using a microwave-assisted solvothermal method and exhibited a bandgap of 2.60 eV. The kinetic data best fitted the Elovich model (R2 = 0.994, χ2 = 0.29), indicating rapid adsorption. The maximum DCF adsorption capacity calculated using the Langmuir model was 80.33 mg/g. An ultraviolet C (UVC) light source and 0.1 g/L of Fe3O4/RGO nanocomposite were the optimum conditions for the removal of DCF (C0 = 30 mM) by a coupled adsorption-photocatalysis process (first-order rate constant (k) = 0.088/min), which was greater than the single adsorption (k = 0.029/min) and pre-adsorption and post-photocatalysis (k = 0.053/min) processes. This indicates that the adsorbed DCF did not hamper the photocatalytic reaction of the Fe3O4/RGO nanocomposite, but rather enhanced the coupled adsorption-photocatalytic reaction. DCF removal efficiency was higher at acidic conditions (pH 4.3-5.0), because high H+ promotes the generation of certain reactive oxygen species (ROS) and increases of electrostatic interaction. The presence of NaCl and CaCl2 (10 mM) did not notably affect the total DCF removal efficiency; however, Ca2+ affected the initial DCF adsorption affinity. Scavenger experiments demonstrated O2∙- and h+ play a key ROS than ·OH to degrade DCF. The acute toxicity of DCF towards Aliivibrio fischeri gradually decreased with increasing treatment time.

Water quality seasonal variation assessment of the Gongji and Yaksa streams, Chuncheon, South Korea.

Gongji Stream flows into Lake Uiam, a potable water source for the capital region of Chuncheon, South Korea. Algal blooms often occur downstream of the Gongji stream in combination with drastic flow rate variations. Downstream water quality may also be affected by Yaksa stream. Yaksa stream joins Gongji stream before it reaches Uiam Lake, which is a drinking water source for the city. Limited data exists on the Yaksa stream water quality. Therefore, water quality parameters (pH, electrical conductivity (EC), biological oxygen demand (BOD), total nitrogen (T-N), total phosphorous (T-P), chlorophyll-a (Chl-a), total coliforms, and Escherichia coli (E. coli) concentration) were sampled from Gongji (at sites GJ1 and GJ2) and Yaksa (at sites YS1 and YS2) streams from May to September, 2022. The results revealed the overall water quality of both streams was good (BOD = 0.27-3.66 mg/L; TP = 0.003-0.074 mg/L), except on August 3. On August 3, the concentrations of BOD, TP, total coliforms, and E. coli were elevated, with the highest concentrations in samples from GJ2. The recent heavy rainfall potentially caused sewage inflows near GJ2. The correlation analysis revealed positive linear relationships in the 1-day cumulative precipitation with BOD (r = 0.503), total coliforms (r = 0.547), and TP (r = 0.814). The Yaksa stream may be an Anabaena sp. source, which contaminated samples from YS1, YS2, and GJ2, but not at GJ1 (upstream of the tributary).

Adsorption behavior of triclosan on microplastics and their combined acute toxicity to D. magna.

Microplastics (MP) have been recently identified as emerging water contaminants in worldwide. Owing to its physicochemical properties, MP have been considered as a vector of other micropollutants and may affect their fate and ecological toxicity in the water environment. In this study, triclosan (TCS), which is a widely-used bactericide, and three frequently found types of MP (PS-MP, PE-MP, and PP-MP) were investigated. The adsorption behavior of TCS on MP was investigated by the effect of reaction time, initial concentration of TCS, and other water chemistry factors. Elovich model and Temkin model are the most fitted well with kinetics and adsorption isotherms, respectively. The maximum TCS adsorption capacities were calculated for PS-MP (9.36 mg/g), PP-MP (8.23 mg/g), and PE-MP (6.47 mg/g). PS-MP had higher affinity to TCS owing to hydrophobic and π-π interaction. The TCS adsorption on PS-MP was inhibited by decreasing concentrations of cations, and increasing concentration of anion, pH, and NOM concentration. At pH 10, only 0.22 mg/g of adsorption capacity was obtained because of the isoelectric point (3.75) of PS-MP and pKa (7.9) of TCS. And almost no TCS adsorption occurred at NOM concentration of 11.8 mg/L. Only PS-MP had no acute toxic effect on D. magna, whereas TCS showed acute toxicity (EC50,24h of TCS = 0.36 ± 0.4 mg/L). Although survival rate increased when TCS with PS-MP due to lower the TCS concentration in solution via adsorption, PS-MP was observed in intestine and body surface of D. magna. Our findings can contribute to understanding the combined potential effects of MP fragment and TCS to aquatic biota.

Adsorption of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose beads: Characterization, toxicity tests, and adsorption experiments.

Mercury (Hg) is widely used in many industrial processes and is released into the environment. Therefore, efficient removal of Hg from water is of vital importance worldwide. Here, we explored the adsorption characteristics of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose (PEI-CMC) beads and studied the toxicity of the beads toward Daphnia magna and Pseudokirchneriella subcapitata. The PEI-CMC beads had an average particle size of 2.04 ± 0.25 mm, a point of zero charge (pHpzc) of 5.8, and a swelling ratio of 2.45. Acute toxicity tests demonstrated that the PEI-CMC beads had no toxic effects on D. magna. The growth inhibition tests revealed that growth inhibition of P. subcapitata could be attributed to adsorption of trace elements in growth media on the PEI-CMC beads. The adsorption experiments exhibited that the Matthews and Weber model best described the kinetic data, whereas the Redlich-Peterson model was well fitted to the isotherm data. The theoretical maximum Hg(II) adsorption capacity of the PEI-CMC beads was 313.1 mg/g. The thermodynamic experiments showed endothermic nature of the Hg(II) adsorption on the PEI-CMC beads at 10-40 °C. The adsorption experiments exhibited that the Hg(II) adsorption capacity decreased gradually as pH increased from 2 to 12. The adsorption of Hg(II) on the PEI-CMC beads can occur through chelation and electrostatic attraction. The FTIR and XPS spectra before and after Hg(II) adsorption confirmed that chelation of neutral Hg(II) species (HgCl2, HgClOH, and Hg(OH)2) can occur with amino and oxygen-containing functional groups on the PEI-CMC beads. Considering species distribution of Hg(II) and the pHpzc of the PEI-CMC beads, electrostatic attraction between the positively-charged beads and anionic Hg(II) species (HgCl3- and HgCl42-) can take place in highly acidic solutions. The PEI-CMC beads were regenerated and reused for Hg(II) adsorption using 0.1 M HCl.

Degradation of oxytetracycline and doxycycline by ozonation: Degradation pathways and toxicity assessment.

Tetracyclines are one of the antibiotics widely employed worldwide and frequently detected in surface waters because of incomplete removal from wastewater treatment. Various advanced oxidation processes have been investigated for tetracyclines degradation and their transformation products (TPs) have recently gained more attention. Studies on ozonation are however seldom for the degradation of oxytetracycline (OTC) and doxycycline (DTC). In the present study, a lower O3 inlet gas concentration (4.67 ± 0.13 mg/L), supplied at a flow rate of 0.27 L/min, was shown to be more effective at removing OTC than the same dose of ozone applied at higher inlet gas concentration (up to 6.29 mg/L) over a shorter time at the same flow rate. The use of pCBA and t-BuOH indicated that ozone plays a more important role in the degradation of OTC than HO•. The DTC degradation was less efficient than for OTC, with 99 % removal requiring twice the amount of ozone. OTC had almost no inhibition of Vibrio fischeri, however, the inhibition ratio was increased to 37 % (5-min) and 46 % (15-min) within 1 min of ozonation. Contrastly, DTC had toxic effects on V. fischeri (inhibition rate5min of 84 %) and sustained toxicity in samples treated for up to 40-min. The observed toxicities after treatment could be explained by the identified TPs (26 TPs for OTC and 23 for DTC, some identified for the first time) and their quantitative structure-activity relationship analysis data. Several TPs showed toxic or extremely toxic predicted effects on fish, daphnid, and green algae, corresponding with the V. fischeri inhibition results. Among the possible degradation pathways, aromatic ring hydroxylation and ring-opening pathways could lead to the formation of TPs less harmful to the environment.

Passive sampling and in vitro assays to monitor antiandrogens in a river affected by wastewater discharge.

Pharmaceuticals and personal care products, antibiotics, estrogens, and antiandrogens are found widely in aquatic environments. Monitoring studies by sampling surface water and effluents of wastewater treatment plants (WWTPs) have been conducted recently to monitor antiandrogens, which, along with estrogens, cause endocrine disruption. However, few studies have investigated antiandrogenic activity (AA) combined with a chemical analyses of emerging antiandrogens. Therefore, we analyzed the presence and persistence of 12 types of antiandrogens, atrazine, and carbamazepine using grab sampling and polar organic chemical integrative sampler (POCIS) along a river affected by WWTP discharges. Water and sediment samples were collected from the WWTP effluent (WW), as well as upstream (US) and downstream (DS) of the WWTP. We detected only tebuconazole, triclosan, propiconazole, and fluconazole during the two sampling campaigns in 2016 and 2017. Grab sampling of the site WW detected tebuconazole (7-77 ng/L), propiconazole (5-47 ng/L), and fluconazole (6-45 ng/L). However, the concentrations in the river water were below the detection limits. Nevertheless, fluconazole and triclosan were detected by POCIS in the site WW (45.7 and 26.8 ng/L, respectively) and all river samples ranges of 0.3-9.3 and 2.4-3.7, respectively. This detection was attributed to the limit of quantification of POCIS being lower than that of grab sampling. Nilutamide and triclosan were detected in the river sediment, suggesting that their concentrations in the water column were at least partly attenuated through sediment sorption. We also observed AA by analyzing POCIS extracts with the yeast androgen screen assay. The highest AA was found in the site WW and it was still observable several kilometers downstream of the point of discharge despite decreasing. Therefore, the WWTP effluent was most likely contributor to the persistent AA in the river.

Metal-organic framework MIL-100(Fe) for dye removal in aqueous solutions: Prediction by artificial neural network and response surface methodology modeling.

In this study, a metal organic framework MIL-100(Fe) was synthesized for rhodamine B (RB) removal from aqueous solutions. An experimental design was conducted using a central composite design (CCD) method to obtain the RB adsorption data (n = 30) from batch experiments. In the CCD approach, solution pH, adsorbent dose, and initial RB concentration were included as input variables, whereas RB removal rate was employed as an output variable. Response surface methodology (RSM) and artificial neural network (ANN) modeling were performed using the adsorption data. In RSM modeling, the cubic regression model was developed, which was adequate to describe the RB adsorption according to analysis of variance. Meanwhile, the ANN model with the topology of 3:8:1 (three input variables, eight neurons in one hidden layer, and one output variable) was developed. In order to further compare the performance between the RSM and ANN models, additional adsorption data (n = 8) were produced under experimental conditions, which were randomly selected in the range of the input variables employed in the CCD matrix. The analysis showed that the ANN model (R2 = 0.821) had better predictability than the RSM model (R2 = 0.733) for the RB removal rate. Based on the ANN model, the optimum RB removal rate (>99.9%) was predicted at pH 5.3, adsorbent dose 2.0 g L-1, and initial RB concentration 73 mg L-1. In addition, pH was determined to be the most important input variable affecting the RB removal rate. This study demonstrated that the ANN model could be successfully employed to model and optimize RB adsorption to the MIL-100(Fe).

Most suitable amino silane molecules for surface functionalization of graphene oxide toward hexavalent chromium adsorption.

Adsorption is a simple and effective method for the removal of hexavalent chromium (Cr(VI)) from contaminated water. Several amino silane-graphene oxide (GO) composites with different species of amino groups (pN-GO, psN-GO, and pssN-GO; p: primary, s: secondary, N: amine) were evaluated to investigate their adsorption capacity and the effects of primary and secondary amines on Cr(VI) adsorption. We conducted a quantitative analysis to reveal the difference between primary and secondary amines in terms of Cr(VI) removal efficiency. A synergic effect was observed between the neighboring secondary amines in pssN-GO. From the Langmuir model prediction, we found that the composite with pssN-GO exhibited the highest maximum adsorption capacity (260.74 mg/g), followed by those with psN-GO (208.22 mg/g) and pN-GO (189.47 mg/g). Monolayer adsorption was more dominant when using pssN-GO, with the pseudo-second-order model best fitting the kinetic experiment results, whereas multilayer adsorption was dominant when using psN-GO and pN-GO.

Oxidation of tetracycline and oxytetracycline for the photo-Fenton process: Their transformation products and toxicity assessment.

Advanced oxidation processes have gained significant attention for treating tetracycline (TC) and oxytetracycline (OTC), however, their oxidation using the photo-Fenton process has not been sufficiently studied. Although degradations of TC and OTC were enhanced by increasing H2O2 and Fe2+ within the ranges investigated (H2O2 = 20-50 mg/L and Fe = 1-10 mg/L) under UV irradiation, further experiments for the photo-Fenton process were conducted with 20 mg/L of H2O2 and 5 mg/L of Fe2+ to balance efficiency and cost. The photo-Fenton process (UV/H2O2/Fe2+) was shown to be more effective to remove TC and OTC than H2O2, ultraviolet (UV), and UV/H2O2 at the same doses of oxidants. Inorganic anions and cations were shown to inhibit the degradation of TC and OTC during the photo-Fenton process, in the following order: HPO42- > HCO3- â‰« SO42- > Cl- and Cu2+ ≫ Ca2+ > Na+. The TC and OTC degradation are generally improved by increasing pH, which is opposite to the kpCBA,obs values, caused by increasing the deprotonation degree of TC and OTC. Four and nine transformation products of TC and OTC, respectively, were detected over the treatment period. Among the transformation products, m/z 443.14 (C22H22N2O8) formed during TC degradation, and m/z 433.16 (C20H20N2O9) and m/z 415.15 (C20H18N2O8) formed during OTC degradation, were reported for the first time. Vibrio fischeri toxicity assessment indicated that the inhibition ratio was decreased with a decreasing TC concentration, while, OTC transformation lead to higher toxicity. The product (m/z 477.15b) was determined to be the compound causing toxicity during degradation of OTC by using the quantitative structure activity relationship (QSAR). This toxic transformation product caused higher inhibition ratios than its parental compound (OTC), but its further oxidization resulted in decreasing the inhibition ratios.

Investigating Microcystin-LR adsorption mechanisms on mesoporous carbon, mesoporous silica, and their amino-functionalized form: Surface chemistry, pore structures, and molecular characteristics.

Microcystin-LR (MC-LR) is the most common cyanotoxin released from algal-blooms. The study investigated the MC-LR adsorption mechanisms by comparing adsorption performance of protonated mesoporous carbon/silica (MC-H, MS-H) and their amino-functionalized forms (MC-NH2 and MS-NH2) considering surface chemistry and pore characteristics. The maximum MC-LR adsorption capacity (Langmuir model) of MC-H (37.87 mg/g) was the highest followed by MC-NH2 (29.25 mg/g) and MS-NH2 (23.03 mg/g), because pore structure is partly damaged during amino-functionalization. However, MC-NH2 (k2 = 0.042 g/mg/min) reacted faster with MC-LR than MC-H during early-stage adsorption due to enhancing electrostatic interactions. Intra-particle diffusion model fit indicated Kp,1 of MC-H (2.11 mg/g/min1/2) was greater than MC-NH2 due to its greater surface area and pore volume. Also, large mesopore diameters are favorable to MC-LR adsorption by pore diffusion. The effect of adsorbate molecular size on adsorption trend against MC-H, MC-NH2 and MS-NH2 was determined by kinetic experiments using two dyes, reactive blue and acid orange: MS-NH2 achieved the highest adsorption for both dyes due to the large number of amino groups on its surface (41.2 NH2/nm2). Overall, it was demonstrated that adsorption of MC-LR on mesoporous materials is governed by (meso-)pore diffusion and π - π (and hydrophobic) interactions induced by carbon materials; in addition, positively-charged grafted amino groups enhance initial MC-LR adsorption rate.

Quaternized Amphiphilic Block Copolymers/Graphene Oxide and a Poly(vinyl alcohol) Coating Layer on Graphene Oxide/Poly(vinylidene fluoride) Electrospun Nanofibers for Superhydrophilic and Antibacterial Properties.

Poly(vinylidene fluoride) (PVDF) is common polymer for electrospinning, however, its high hydrophobicity is a major drawback, which cause fouling. To introduce hydrophilicity and antibacterial activity, quaternary ammonium-functionalized amphiphilic diblock copolymers were synthesized and blended with a PVDF/graphene oxide (GO) solution, then, electrospun and coated with a hydrophilic polymer, poly(vinyl alcohol) (PVA). The amphiphilic block copolymer, consisting of a hydrophobic poly(methyl methacrylate) block and a hydrophilic poly[N,N-2-(dimethylamino)-ethyl methacrylate) block (PMMA-b-PDMAEMA), was synthesized. Polymeric quaternary ammonium with three different alkyl chain lengths (C2, C4, and C8) were successfully introduced to obtain as q-PMMA-b-PDMAEMA. The q-PMMA-b-PDMAEMA in the nanofiber matrix was confirmed by C=O bands (1734 cm-1) in the Fourier transform infrared spectra. Nano-sized spherical protuberances were distributed on the surface as revealed by field emission scanning and transmission electron microscopies. The PVDF/GO/q-PMMA-b-PDMAEMA@PVA nanofibers has superhydrophilic properties (water contact angle = 0-20°) and the pure water flux was generally improved by increasing the alkyl chain length. When introducing the longest alkyl chain (C8,OBC), the total fouling ratio was the lowest (49.99%) and the bacteria removal capacities after 60 min were the highest for both Escherichia coli (4.2 × 105 CFU/mg) and Staphylococcus aureus (6.1 × 105 CFU/mg) via growth inhibition and cytoplasmic membrane damage.

Investigation of the mechanism of chromium removal in (3-aminopropyl)trimethoxysilane functionalized mesoporous silica.

We are proposed that a possible mechanism for Cr(VI) removal by functionalized mesoporous silica. Mesoporous silica was functionalized with (3-aminopropyl)trimethoxysilane (APTMS) using the post-synthesis grafting method. The synthesized materials were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), N2 adsorption-desorption analysis, Fourier-transform infrared (FT-IR), thermogravimetric analyses (TGA), and X-ray photoelectron spectroscopy (XPS) to confirm the pore structure and functionalization of amine groups, and were subsequently used as adsorbents for the removal of Cr(VI) from aqueous solution. As the concentration of APTMS increases from 0.01 M to 0.25 M, the surface area of mesoporous silica decreases from 857.9 m2/g to 402.6 m2/g. In contrast, Cr(VI) uptake increases from 36.95 mg/g to 83.50 mg/g. This indicates that the enhanced Cr(VI) removal was primarily due to the activity of functional groups. It is thought that the optimum concentration of APTMS for functionalization is approximately 0.05 M. According to XPS data, NH3+ and protonated NH2 from APTMS adsorbed anionic Cr(VI) by electrostatic interaction and changed the solution pH. Equilibrium data are well fitted by Temkin and Sips isotherms. This research shows promising results for the application of amino functionalized mesoporous silica as an adsorbent to removal Cr(VI) from aqueous solution.

Mesoporous carbon for efficient removal of microcystin-LR in drinking water sources, Nak-Dong River, South Korea: Application to a field-scale drinking water treatment plant.

Microcystin-LR (MC-LR) is a growing issue as it is toxic and difficult to remove in drinking water treatment plants (DWTPs). Mesoporous carbon (MC) is evaluated as an alternative adsorbent for MC-LR removal and compared with three widely-used powdered activated carbons (PACs). MC was more favorable for MC-LR removal than PACs. MC-LR adsorption on MC was a rapid process (k2 = 1.02  ×  10-4 g/µg/min) that completed within 15 min, while adsorption on PACs took 60 min. The maximum adsorption capacity of MC-LR was 18,008 µg/g (MC), which was higher than that of the PACs. Two mechanisms were associated with adsorption: the small hydro-dynamic diameter of MC in an aqueous solution increased the instantaneous attraction of MC-LR to its surface, and the numerous mesopores enhanced pore diffusion. The MC could remove MC-LR to meet the drinking water guidance level (1 µg/L) from an the MC-LR concentration range of 5-20 µg/L in drinking water sources, and 10 min of treatment was sufficient to meet this level (MC dose = 20 mg/L). The field-scale DWTP was operated by adding 1 or 5 mg/L MC to the mixing basin, and 49.49% and 74.50% of MC-LR was removed, respectively. Geosmin and 2-methylisoborneol were slightly reduced when 5 mg/L of MC was applied.

Blend-electrospun graphene oxide/Poly(vinylidene fluoride) nanofibrous membranes with high flux, tetracycline removal and anti-fouling properties.

Graphene oxide (GO)/poly(vinylidene fluoride) (PVDF) electrospun nanofibrous membranes (ENMs) have been fabricated to remove tetracycline (TC) from water via adsorptive-filtration. The pure water permeation flux of GO/PVDF ENMs (27,407-29,337 LMH/bar) was increased compared with that of PVDF ENMs. The flow pore diameter was steadily reduced by increasing the GO content from 0 to 1.5 wt% in the GO/PVDF ENMs. The maximum TC adsorption capacity of GO is 720.26 mg/g (Langmuir model) and GO retained its TC adsorption property after incorporation into GO/PVDF ENMs during water filtration (transmembrane pressure = 0.91 bar). The maximum experimental TC removal capacity (qa,exp) was 17.92 mg/g with 1.5 wt% of GO (GO1.5/PVDF) ENMs, which was similar to the modified dose-response model value of 18.03 mg/g. In the presence of natural organic matter, TC adsorption was enhanced, because hydrophobic organic carbon improved hydrophobic and π-π interactions. The presence of Cu(II) further improved the TC adsorption capacity of GO1.5/PVDF ENMs through cation bridging. However, the presence of Ca(II) hindered TC adsorption by an electron shielding effect. For examining anti-fouling activity of GO1.5/PVDF ENMs, the log removal values of both bacteria, Escherichia coli and Staphylococcus aureus, were maintained at over 5 during water filtration. In addition, incorporation of GO in PVDF ENMs prevents bovine serum albumin (BSA) adsorption by both increasing the hydrophilicity of the ENMs forming hydration layer on the surface and electrostatic repulsion between both negatively charged BSA and GO in GO1.5/PVDF ENMs (zeta potential = - 14.14 mV, deionized water at pH 6).

Chromium removal from aqueous solution by a PEI-silica nanocomposite.

It is essential and important to determine the adsorption mechanism as well as removal efficiency when using an adsorption technique to remove toxic heavy metals from wastewater. In this research, the removal efficiency and mechanism of chromium removal by a silica-based nanoparticle were investigated. A PEI-silica nanoparticle was synthesized by a one-pot technique and exhibited uniformly well-dispersed PEI polymers in silica particles. The adsorption capacity of chromium ions was determined by a batch adsorption test, with the PEI-silica nanoparticle having a value of 183.7 mg/g and monolayer sorption. Adsorption of chromium ions was affected by the solution pH and altered the nanoparticle surface chemically. First principles calculations of the adsorption energies for the relevant adsorption configurations and XPS peaks of Cr and N showed that Cr(VI), [HCrO4]- is reduced to two species, Cr(III), CrOH2+ and Cr3+, by an amine group and that Cr(III) and Cr(VI) ions are adsorbed on different functional groups, oxidized N and NH3+.

Ultrasonic spray pyrolysis synthesis of reduced graphene oxide/anatase TiO2 composite and its application in the photocatalytic degradation of methylene blue in water.

Reduced graphene oxide (RGO)/anatase TiO2 composite was prepared using a simple one-step technique-ultrasonic spray pyrolysis-in order to inhibit the aggregation of TiO2 nanoparticles and to improve the photocatalytic performance for degradation of methylene blue (MB). Different proportions (0-5 wt%) of RGO/TiO2 composites were characterized by scanning electronic microscopy (SEM), dispersive X-ray spectrometry (EDS), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), Raman spectroscopy, UV-vis spectroscopy, and electrochemical impedance spectroscopy (EIS) to verify mechanism. From these analysis, TiO2 nanoparticles are distributed uniformly on the RGO sheets with crumpled shape during ultrasonic spray pyrolysis and surface area is increasing by increasing portion of RGO. Band gap of RGO5/TiO2 (5 wt% of RGO) composite is 2.72 eV and band gap was reduced by increasing portion of RGO in RGO/TiO2 composites. The RGO5/TiO2 composite was superior to other lower content of RGO/TiO2 composites with a rapid transport of charge carriers and an effective charge separation. The highest removal efficiency of MB was obtained at the RGO5/TiO2 composite under UVC irradiation, which coincided with the EIS, and the optimal dose of the composite was determined to be 0.5 g/L. The RGO5/TiO2 composite improve the photocatalytic degradation rate of MB over the TiO2 due to a retardation of electron-hole recombination. The MB adsorption capacity and photocatalytic degradation efficiency were greatly affected by pH changes and increased with increasing pH due to electrostatic interactions and generation of more hydroxyl radicals. The reusability of RGO5/TiO2 composite was examined during 3 cycles.

Adsorption of microcystin-LR on mesoporous carbons and its potential use in drinking water source.

Microcystin-LR (MC-LR) is a common toxin derived from cyanobacterial blooms an effective, rapid and non-toxic method needs to be developed for its removal from drinking water treatment plants (DWTP). For an adsorption-based method, mesoporous carbon can be a promising supplemental adsorbent. The effect of mesoporous carbon (MC1, MC2, and MC3) properties and water quality parameters on the adsorption of MC-LR were investigated and the results were analyzed by kinetic, isotherm, thermodynamic, Derjaguin-Landau-Verwey-Overbeek (DLVO), and intraparticle diffusion models. MC1 was the most appropriate type for the removal of MC-LR with a maximum adsorption capacity of 35,670.49 µg/g. Adsorption of MC-LR is a spontaneous reaction dominated by van der Waals interactions. Pore sizes of 8.5-14 nm enhance the pore diffusion of MC-LR from the surface to the mesopores of MC1. The adsorption capacity was not sensitive to changes in the pH (3.2-8.0) and the existence of organic matter (2-5 mg/L). Furthermore, the final concentration of MC-LR was below the WHO guideline level after a 10-min reaction with 20 mg/L of MC1 in the Nak-Dong River, a drinking water source. The MC-LR adsorption mainly competed with humic substances (500-1000 g/mole); however, they did not have a great effect on adsorption.