Continuous-Flow System for Methylene Blue Removal Using a Green and Cost-Effective Starch Single-Rod Column.

A continuous-flow system based on a green and cost-effective monolithic starch cryogel column was successfully developed for removing methylene blue (MB). The proposed column exhibited high removal efficiency (up to 99.9%) and adsorption capacity (25.4 mg·g-1) for synthetic and real samples with an adsorbent cost of USD 0.02. The influence of various operation parameters, including the flow rate, initial concentration, column height, and temperature, on the MB removal efficiency was examined and reported. The MB removal efficiency remained >99% in the presence of potential interferences, highlighting the good performance of the cryogel column. The Yoon-Nelson dynamic model explained the MB adsorption better than the Bohart-Adams model, as indicated by the higher R2 values (R2 = 0.9890-0.9999) exhibited by the former and current trends of its parameters. The MB removal efficiency of the cryogel column remained at 62.7% after three reuse cycles. The wastewater containing MB collected from a local batik-production community enterprise in Phuket, Thailand was applied to the proposed continuous-flow system under optimum conditions, and results indicated that 99.7% of the MB present in 2.4 L of wastewater was removed. These results validate the excellent application potential of the cryogel column for the continuous-flow adsorption of MB. This study will facilitate future industrial applications and process designs of the continuous-flow system.

Continuous Phosphate Removal and Recovery Using a Calcium Silicate Hydrate Composite Monolithic Cryogel Column.

Toward the development of a practical and green approach for removing phosphate from water, a monolithic cryogel based on starch and calcium silicate hydrate (Cry-CSH) was employed as a phosphate adsorbent in a continuous flow system for the first time. The influence of flow rate, initial phosphate concentration, and adsorbent height on the adsorption efficiency was investigated. As the rate of flow and the initial concentration of phosphate increased, the total quantity of adsorbed phosphate dropped; however, the performance of the column was greatly enhanced by an increase in adsorbent height. The experimental data fit the Adams-Bohart model better than the Thomas and Yoon-Nelson models at the beginning of the adsorption process. To evaluate its applicability, the continuous flow system based on the monolithic Cry-CSH column was applied for the removal of phosphate from the discharge effluent of the Patong Municipality Wastewater Treatment Plant (Phuket, Thailand), achieving an excellent total adsorption of 94.61%.

Recovering Phosphate from Complex Wastewater Using Macroporous Cryogel Composited Calcium Silicate Hydrate Nanoparticles.

Since currently used natural, nonrenewable phosphorus resources are estimated to be depleted in the next 30-200 years, phosphorus recovery from any phosphorus-rich residues has attracted great interest. In this study, phosphorus recovery from complex wastewater samples was investigated using continuous adsorption on cryogel column composited calcium silicate hydrate nanoparticles (CSH columns). The results showed that 99.99% of phosphate was recovered from a synthetic water sample (50 mg L-1) using a 5 cm CSH column with a 5 mL min-1 influent flow rate for 6 h while 82.82% and 97.58% of phosphate were recovered from household laundry wastewater (1.84 mg L-1) and reverse osmosis concentrate (26.46 mg L-1), respectively. The adsorption capacity decreased with an increasing flow rate but increased with increasing initial concentration and column height, and the obtained experimental data were better fitted to the Yoon-Nelson model (R2 = 0.7723-0.9643) than to the Adams-Bohart model (R2 = 0.6320-0.8899). The adsorption performance of phosphate was decreased 3.65 times in the presence of carbonate ions at a similar concentration, whereas no effect was obtained from nitrate and sulfate. The results demonstrate the potential of continuous-flow phosphate adsorption on the CSH column for the recovery of phosphate from complex wastewater samples.

Starch Biocryogel for Removal of Methylene Blue by Batch Adsorption.

A green monolithic starch cryogel was prepared and applied for the removal of methylene blue (MB) using a batch system. The influence of various experimental parameters on MB adsorption was investigated. High removal efficiency (81.58 ± 0.59%) and adsorption capacity (34.84 mg g-1) were achieved. The Langmuir model better fitted the experimental data (determination coefficient (R2) = 0.9838) than the Freundlich one (R2 = 0.8542), while the kinetics of MB adsorption on the cryogel followed a pseudo-second-order model. The adsorption process was spontaneous and endothermic with an activation energy of 37.8 kJ mol-1 that indicated physical adsorption. The starch cryogel was used for MB removal from a wastewater sample collected from a local Batik production community enterprise in Phuket, Thailand, and a removal efficiency of 75.6% was achieved, indicating that it has a high potential as a green adsorbent for MB removal.

Portable Colorimetric Hydrogel Test Kits and On-Mobile Digital Image Colorimetry for On-Site Determination of Nutrients in Water.

Portable colorimetric hydrogel test kits are newly developed for the on-site detection of nitrite, nitrate, and phosphate in water. Griess-doped hydrogel was prepared at the bottom of a 1.5 mL plastic tube for nitrite detection, a nitrate reduction film based on zinc powder was placed on the inner lid of a second 1.5 mL plastic tube for use in conjunction with the Griess-doped hydrogel for nitrate detection, and a molybdenum blue-based reagent was entrapped within a poly(vinyl alcohol) hydrogel matrix placed at the bottom of a third 1.5 mL plastic tube to detect phosphate. These test kits are usable with on-mobile digital image colorimetry (DIC) for the on-site determination of nutrients with good analytical performance. The detection limits were 0.02, 0.04, and 0.14 mg L−1 for nitrite, nitrate, and phosphate, respectively, with good accuracy (<4.8% relative error) and precision (<1.85% relative standard deviation). These test kits and on-mobile DIC were used for the on-site determination of nutrients in the Pak Bang and Bang Yai canals, the main canals in Phuket, Thailand. The concentrations of nitrite, nitrate, and phosphate were undetectable to 0.60 mg L−1, undetectable to 2.98 mg L−1, and undetectable to 0.52 mg L−1, respectively.

Griess-doped polyvinyl alcohol thin film for on-site simultaneous sample preparation and nitrite determination of processed meat products.

To facilitate on-site nitrite determination for processed meat products, Griess-doped polyvinyl alcohol film was synthesized in the bottom of a plastic tube for in-tube determination. The tube's aperture was used to control the sample dimensions. Each sample, cut into eight sectors, was subjected to nitrite extraction by water. Use of tap water or commercial drinking water vs. ultrapure water was associated with < 2% differences in nitrite levels. The use of film and digital image colorimetry showed a low limit of detection (12.6 ± 0.5 µg L-1), good precision (1.0%RSD, n = 5 days), and good accuracy (93.2 ± 3.5 to 108.5 ± 1.8%recovery). Using these methods, sodium nitrite concentrations in 700 processed meat products for sale in Phuket, Thailand, were found to range from 6.8 ± 0.2 to 113.6 ± 1.3 mg kg-1. These results showed no significant differences with the HPLC standard method (p > 0.05, n = 45).

Removal and recovery of phosphate using a novel calcium silicate hydrate composite starch cryogel.

Phosphate is a major pollutant that deteriorates water quality and causes eutrophication, a novel calcium silicate hydrate composite cryogel (Cry-CSH) was thus successfully prepared for phosphate removal and recovery in this work. Calcium silicate hydrate (C-S-H) was mixed with the gel precursor (7.5% w/w) prepared from native starch and limewater (saturated calcium hydroxide solution as the cross-linker). The mixture was frozen and thawed for 3 cycles giving an interconnected macroporous composite. This had C-S-H nanoparticles (75 mg) immobilized on a monolithic floatable cryogel network (2.5 cm diameter × 1.0 cm height) enabling an easier recovery and without the losses that occur when using C-S-H nanoparticles. The phosphate adsorption reaches equilibrium at 120 min with adsorption capacity of 2.50 mgPO43-/gCry-CSH (65.42 mgPO43-/gC-S-H) under optimum conditions. Adsorption equilibrium data were well fit by the Freundlich isotherm model, while kinetic results were well fit by the pseudo second-order model. The calculated activation energy (Ea) of 43.9 kJ/mol indicates chemical adsorption, while a positive change in enthalpy (ΔH0, 19.3 kJ/mol) indicates the endothermic nature of phosphate adsorption. Cry-CSH can remove phosphate from wastewater and effluent samples with excellent removal efficiency (>98%). It can float on water surface for at least 105 days without damage, while its phosphate adsorbed form can be biodegraded within 10 days under soil buried conditions. Thus, this work demonstrated the significant potential of Cry-CSH for practical and environmentally friendly phosphate removal and recovery.

Preparation and Characterization of Calcium Cross-Linked Starch Monolithic Cryogels and Their Application as Cost-Effective Green Filters.

Monolithic cryogels from starch were successfully synthesized and applied as alternative biodegradable filters for the first time. Rice flour was cross-linked with Ca2+ from limewater during gelatinization before being frozen and then thawed for three cycles. The resultant material was then soaked in ethanol for 3 h before incubation at 80 °C for 1 h, yielding monolithic material with interconnected pores in sizes of 51 ± 18 to 52 ± 15 µm without any need of freeze-drying. The cryogels possessed macroporous structure with specific surface areas from 1.1 to 4.3 m2g-1, they could adsorb water from 599 ± 27 to 635 ± 59% of their dry weight with low swelling ratios of 6.0 ± 0.3 to 6.4 ± 0.6 gwater/gcryogel, and could be applied as biofilters to remove suspended particles and reduce the light absorption of water sample from 25 ± 3 to 96 ± 5%. The prepared biofilters can be re-used up to three times, although they cost only USD 0.0004/piece. Complete weight loss resulted from burial in soil for 30 days, indicating environmentally friendly biodegradation and potential for environmental applications.

Greener Monolithic Solid Phase Extraction Biosorbent Based on Calcium Cross-Linked Starch Cryogel Composite Graphene Oxide Nanoparticles for Benzo(a)pyrene Analysis.

Benzo(a)pyrene (BaP) has been recognized as a marker for the detection of carcinogenic polycyclic aromatic hydrocarbons. In this work, a novel monolithic solid-phase extraction (SPE) sorbent based on graphene oxide nanoparticles (GO) in starch-based cryogel composite (GO-Cry) was successfully prepared for BaP analysis. Rice flour and tapioca starch (gel precursors) were gelatinized in limewater (cross-linker) under alkaline conditions before addition of GO (filler) that can increase the ability to extract BaP up to 2.6-fold. BaP analysis had a linear range of 10 to 1000 µgL-1 with good linearity (R2 = 0.9971) and high sensitivity (4.1 ± 0.1 a.u./(µgL-1)). The limit of detection and limit of quantification were 4.21 ± 0.06 and 14.04 ± 0.19 µgL-1, respectively, with excellent precision (0.17 to 2.45%RSD). The accuracy in terms of recovery from spiked samples was in the range of 84 to 110% with no significant difference to a C18 cartridge. GO-Cry can be reproducibly prepared with 2.8%RSD from 4 lots and can be reused at least 10 times, which not only helps reduce the analysis costs (~0.41USD per analysis), but also reduces the resultant waste to the environment.

A novel colorimetric sensor based on modified mesoporous silica nanoparticles for rapid on-site detection of nitrite.

A novel colorimetric sheet based on Griess reagent-doped mesoporous silica nanoparticles was developed for nitrite detection. Griess reagent was adsorbed on long-range ordered hexagonal mesoporous silica nanoparticles and developed ink-bottle pores with some disorder. When the modified nanoparticles were bound using starch to fabricate a thin (~ 313 µm) colorimetric sheet, spherical particles with a rougher surface and some distortion of their mesoporosity were observed. The sheet was used in conjunction with digital image colorimetry (DIC) and provides a wide linear range of 0.05 to 2.50 mg L-1 with a low detection limit (15.0 µg L-1-NO2-, equal to 4.5 µg L-1 NO2--N), good inter-day precision (1.93%RSD), and excellent precision (2.67% relative error). The colorimetric sensors produced from the sheet costs only 0.04 USD each, while the DIC uses a standard smartphone for photographic detection. The method developed offers an easier and cheaper means of conducting rapid on-site determination of nitrite in water with reliable quantitative results. Graphical abstract.

Convenient environmentally friendly on-site quantitative analysis of nitrite and nitrate in seawater based on polymeric test kits and smartphone application.

Nowadays, nitrate (NO3-) and nitrite (NO2-) in aquatic ecosystems have increased due to various anthropogenic activities leading to deterioration of the ecosystem and can accelerate eutrophication. A Griess reagent-doped hydrogel test kit and a zinc powder-doped starch film were thus developed for on-site quantitative analysis of nitrate and nitrite. A clear colorless hydrogel tablet (diameter 1.5 cm 2 mm thickness) turned pink-violet after reacting with a standard solution of nitrite while the gray zinc-doped starch film (8.36 µm thickness) fabricated on the inner lid of small plastic tube was used for the in-tube reduction of nitrate to be nitrite. The use of this film followed by nitrite testing using the hydrogel tablet was used as a nitrate test. Both the materials developed were used in conjunction with digital image colorimetry (DIC) using smartphone application for on-site quantitative analysis of nitrite and nitrate. Good linearity (R2 > 0.99) ranges of 0.05 to 5 mg L-1 for nitrite and 1 to 50 mg L-1 for nitrate were obtained and detection limits of 50 µg L-1 for nitrite and 0.32 mg L-1 for nitrate were achieved. Good accuracy was obtained in terms of a relative error in a range of 0.75 to 2.68% with inter-day precision in a range of 0.20 to 0.50%RSD (n = 3). Quantitative analysis of nitrate and nitrite in 10 seawater samples taken in Phuket was in good agreement with the standard method (95% confidence level). Since the method developed employs test kits synthesized using biodegradable polymers and DIC using a smartphone application, it will allow the rapid on-site quantitative detection of nitrate and nitrite in a more convenient and environmentally friendly system.

Difluoroboron-Curcumin Doped Starch Film and Digital Image Colorimetry for Semi-Quantitative Analysis of Arsenic.

This work presents a novel, simple, rapid, and cost effective method for semi-quantitative analysis of arsenic(III) in water sample. The method was based on the digital image colorimetry (DIC) of difluoroboron-curcumin doped starch film (BF2-cur-film) and arsenic ion in water. A red BF2-cur-film (9.4 µm) was fabricated by entrapped difluoroboron-curcumin (BF2-curcumin, particle size of 60 - 113 nm) in tapioca starch film. When the standard solution of arsenic (1 mL) was added into small plastic tube containing BF2-cur-film on its inner lid, blue solution (λmax at 610 nm) was observed instead of orange color in blank solution (λmax at 495 nm). When BF2-cur-film was used in conjunction with DIC, a wide linear range of 0 - 10 mg L-1 with good linearity (R2 > 0.99) was obtained from green channel with low detection limit of 0.04 mg L-1. Moreover, good precision (0.9 - 1.2%RSD, n = 4 days) and accuracy (0.03% relative error) were also achieved.