A robust self-regenerating graphene-based adsorbent for pharmaceutical removal in various water environments.

The presence of active pharmaceutical ingredients (APIs) in wastewater effluents and natural aquatic systems threatens ecological and human health. While activated carbon-based adsorbents, such as GAC and PAC, are widely used for API removal, they exhibit certain deficiencies, including reduced performance due to the presence of natural organic macromolecules (NOMs) and high regeneration costs. There is growing demand for a robust, stable, and self-regenerative adsorbent designed for API removal in various environments. In this study, we synthesized a self-generating metal oxide nano-composite (S-MGC) containing titanium dioxide (TiO2) and silicon dioxide (SiO2) combined with 3D graphene oxide (GO) to adsorb APIs and undergo regeneration via light illumination. We determined optimal TiO2:SiO2:GO compositions for the S-MGCs through experiments using a model contaminant, methylene blue. The physical and chemical properties of S-MGCs were characterized, and their adsorption and photodegradation capabilities were studied using five model APIs, including sulfamethoxazole, carbamazepine, ketoprofen, valsartan, and diclofenac, both in single-component and multi-component mixtures. In the absence of TiO2/SiO2, 3D graphene oxide (CGB) displayed better adsorption performance compared to GAC, and S-MGCs further improve CGB's adsorption capacity. This performance remained consistent in two complex water environments: aqueous solutions at varying NOM levels and artificial urine. TiO2 supported on the GO surface exhibits similar photocatalytic activity to suspended TiO2. In a continuous fixed-bed column test, S-MGCs demonstrated robust API adsorption performance that is maintained in the presence of NOM or urine, and can be regenerated through multiple cycles of adsorption and light illumination.

Comparison of two carbonaceous supported Fe-rich adsorbents for arsenate removal: A functionalisation and mechanistic study with applicability to groundwater treatment.

The presence of arsenic in groundwater, and through this in drinking water, has been shown to present a serious risk to public health in many regions of the world. In this study, two iron-rich carbonous adsorbents were compared for the removal of arsenate (As(V)) from groundwater. Biochars (FeO-biochar and FeO-pyrochar) derived from biomass waste were functionalised in two different ways with iron chloride for comparation. Batch and dynamic parameters were optimised to achieve >99% As(V) removal efficiency. Experimental data were best described by the pseudo-second order kinetic model, while multi-stage diffusion appeared to limit mass transfer of As(V). Among the isotherm models evaluated, the Freundlich model best described the experimental results with high correlation coefficients (R2 ≥ 0.94) for both adsorbents. Monolayer adsorption capacities were found to be 4.34 mg/g and 8.66 mg/g for FeO-biochar and FeO-pyrochar, respectively. Batch studies followed by instrumental characterisation of the materials indicated the removal mechanisms involved to be electrostatic interactions (outer-sphere), OH- ligand exchange (inner-sphere complexation) and hydrogen bonding with functional groups. Higher pHpzc (9.1), SBET (167.2 m2/g), and iron/elemental content for the FeO-pyrochar (compared with the FeO-biochar) suggested that both surface chemistry and porosity/surface area were important in adsorption. Dynamic studies showed FeO-pyrochar can be used to remove As(V) from groundwater even at low 'environmental' concentrations relevant to legislative limits (<10 µg/L), whereby 7 g of FeO-pyrochar was able to treat 5.4 L groundwater.

Architecture dependent transport behavior of iron (0) entrapped biodegradable polymeric particles for groundwater remediation.

Polylactic acid based spherical particles with three architectural variations (Isotropic (P1), Semi porous (P2), and Janus (P3)) were employed to encapsulate zero valent iron nanoparticles (ZVINPs), and their performance was extensively evaluated in our previous studies. However, little was known about their transportability through saturated porous media of varying grain size kept under varying ionic strength. In this particular study, we aimed to investigate the architectural effect of polymeric particles (P1-P3) on their mobility through the sand column of varying grain size in presence of mono, di, and tri-valent ions of varying concentrations (25-200 mM (millimoles)). As per column breakthrough experiments (BTCs) using various types of sands, amphiphilic Janus type (P3) particles exhibited the maximum transportability among all the tested particles, irrespective of the nature of the sand. Owing to the narrower travel path, sands with lower porosity (31%) delayed the plateau by shifting it to a higher pore volume with a minimum retention of iron (C/Co: 0.94 for P3) in the column. The impact of mono (Na+, K+), di (Ca2+, Mg2+), and trivalent (Al3+) ions on their transportability was progressively increased from P3 to P1, especially at higher ionic concentrations (200 mM), with P3 being the most mobile particles (C/Co:0.54 for Al3+). Among all the ions, Al3+ exhibited maximum hindrance to their mobility through the sand column. This could be due to their strong charge screening effect coupled with cation bridging complex formation with moving particles. Experimental results obtained from BTCs were found to be well-fitted with a theoretical model based on advection-dispersion equation, showing minimum retention for P3 particles. Overall, it can be inferred that encapsulation of ZVINPs inside Janus particles (P3) with a right balance of amphiphilicity and highly negative surface charge would be required to achieve considerable transportability through sand aquifers to target contaminants in polluted groundwater existing under harsh conditions (high ionic concentrations).

Column study using modified banana pseudo stem as adsorbent for removal of Pb (II).

Eco-friendly adsorbents such as banana pseudo stem play a fundamental role in the removal of heavy metal elements from the wastewater. Key water resources and chemical industries have been encountering difficulties in removing heavy metal elements using existing conventional methods. The lead-removal process is currently a challenging task for environmental scientists and engineers in terms of cost, effluent disposal, and safety concerns. Hence, this work demonstrates the adsorption of Pb (II) onto modified banana pseudo stem (MBPS) powder as a potential adsorbent to treat different effluents. A characterization of modified banana pseudo-stem powder was performed using scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy which confirms the material. Experiments carried out using a column process for the removal of lead (II) from an aqueous solution at a fixed concentration of 50 ppm, pH 6 and contact time 120 min. The BET surface area of MBPS was found to be 7.27 m2/g. The results showed that the column studies explain better performance for the removal of Pb (II) and the maximum removal was found to be 49% at lower flow rate (5 mL/min) of fixed initial concentration of 50 ppm.

Alfalfa biochar supported Mg-Fe layered double hydroxide as filter media to remove trace metal(loid)s from stormwater.

Polluted stormwater (PSW) treatment is becoming increasingly important because of the existence of multiple pollutants from non-point pollution sources. Alfalfa biochar loaded with Mg/Fe layered double hydroxide (AF-LDH) was successfully synthesized to remove trace metal(loid)s from stormwater. The adsorption kinetics and isotherms of metal(loid)s in a mono-component system and the reusability of the composite materials was investigated in this study. The result showed that the maximum removal efficiency for Pb(II), Cu(II), Zn(II), Cd(II), As(V), and Cr(VI) were 98.98 %, 98.11 %, 97.88 %, 97.71 %, 98.81 %, and 50.89 %, respectively, when added calcined AF-LDH (AF-LDO) composite material to the multi-component solution. The AF-LDH and AF-LDO could efficiently remove trace pollutants (10-100 µg/L) from multi-component solution, especially for AF-LDO, which could completely remove the tested six trace metal(loid)s. Furthermore, Fourier transform infrared spectra and X-ray diffraction characterizations supported the Mg/Fe layered double hydroxide reconstruction. The main mechanisms of Pb(II), Cu(II), Zn(II), and Cd(II) (cationic metals) removal were ion exchange and surface precipitation, whereas As(V) and Cr(VI) (anionic metals) were mainly dislodged through the formation of surface complexation, electrostatic attraction, and interlayer anion exchange, concerning the -OH and -COOH of AF-LDH. Importantly, the results of the column experiment demonstrated that AF-LDO was superior to AF-LDH for anionic metal removal from stormwater. In this study, we synthesized AF-LDH and AF-LDO for trace metal(loid) removal and proposed a new and practical approach for stormwater purification.

New insights into the interactions between Pb(II) and fruit waste biosorbent.

Fruit waste is a sustainable biosorbent for heavy metal removal from wastewater. Elucidation of adsorption mechanism is imperative for the process control and development of effective adsorbents. In this study, watermelon rind (WR) exhibited selective and efficient Pb(II) adsorption with a maximum uptake of 230.5 mg/g at pH 5.0. The WR-packed bed column showed high Pb(II) uptake and robust durability over 10 adsorption-desorption cycles with long breakthrough time of 8-13 h (89-144 bed volume), and 95% of sequestered Pb(II) was rapidly desorbed in 1-2 h by 0.05 M HCl. Spectroscopic characterization by FTIR and XPS identified hydroxyl, carboxyl, amine, and ether groups as the binding sites for Pb(II) via the binding force of complexation. Physicochemical analysis showed that ion exchange with Mg2+ and Ca2+ accounted for 19% of Pb(II) adsorption by WR; electrostatic attraction and microprecipitation jointly contributed. Quantum chemistry simulation verified the interactions between Pb(II) and binding sites and revealed carboxyl was the preferential functional group. The findings corroborate the applicability of WR in scale-up Pb(II) removal/recovery from wastewater and elaborate the mechanisms of Pb(II) adsorption by the WR biosorbent. This also provides insights into the behavior of heavy metals in other liquid/solid interfaces.

Mesoporous carbon structure impregnated with 2D engineered zirconium: A sustainable adsorbent for the removal of dyes from the aqueous solution.

The key designing of new breeds of the adsorbents aimed to improve the physical, chemical and textural morphology along with surface functionalization, selectivity toward the contaminants, and regenerations efficiency. In this aspect, two adsorbents named wet oxidative and ultrasonicated zirconium impregnated composite, have been synthesized through two routes, i.e., wet oxidation and ultrasonication. In wet oxidation method, carbon-based materials are oxidized using an oxidant followed by impregnation, while in ultrasonication assisted route, the impregnation is carried out using acoustic phenomenon. The characterization study revealed that the wet oxidation process is more competent in impregnating zirconium and developing diverse porosity and functionalities. The maximum adsorption capacity of wet oxidative adsorbent was 812 mg/g for Reactive Blue 19 and 203.18 mg/g for Methylene Blue, that accentuated the efficiency of the adsorbent over raw activated carbon. The electrostatic interaction, hydrogen-bonding and ligand exchange phenomenon are the involved adsorption mechanism for dyes. The regeneration study finally asserts that the wet oxidative adsorbent shows an insignificant decrease in its capacity up to the 5th-cycle (i.e., 87.67% removal at 5th cycle) as compared to raw AC (46.71% removal at 5th cycle). Further, a continuous fixed-bed column study revealed a significant correlation between experimental breakthrough data and kinetic data. Thus, the developed adsorbent has a sedulous adsorption capacity to remove the most stubborn toxic dyes and can be used in industrial-scale applications.

Arsenite removal from drinking water by bark-based magnetic iron oxide particle (BMIOP): a column study.

The removal of arsenite [As(III)] from drinking water was investigated in a column at flow rates of 2.0 and 5.0 mL/min (up-flow direction) using bark-based magnetic iron oxide particles (BMIOP) prepared by coating (Fe(NO3)3.9H2O) over Tamarindus Indica bark. The BMIOP was compared with regenerated BMIOP, commercial activated carbon, commercial activated alumina (Al2O3). At 2.0 mL/min, empty bed contact time (EBCT), breakthrough time (BT), the volume of treated water and breakthrough capacity (BC) on fresh BMIOP were found to be 6.8 min, 33.15 h, 4.380 L and 0.742 mg/g, respectively, and at 5.0 mL/min, were found to be 4.1 min, 13 h, 3.675 L and 0.453 mg/g respectively. EBCT, BT and BC were increased by 65.85%, 155% and 63.79%, respectively, as the flow rate was reduced from 5.0 to 2.0 mL/min. After regeneration of BMIOP, EBCT, BT, saturated time, BC and saturation capacity (SC) were reduced by 21.95%, 15.38%, 55.15%, 16.78% and 29.71%, respectively. The BC of fresh BMIOP was increased by factors 4.15, 3.60 and 1.20 and SC by factors 9.51, 7.88 and 1.42 compared to commercial activated carbon, commercial activated Al2O3 and regenerated BMIOP, respectively. Logit model could be used for the design of the adsorption column. Thomas model and artificial neural network (ANN) were applied to predict the characteristic column parameters useful for process design. Quality of treated water meets BIS requirements. Toxicity Characteristic Leaching Procedure (TCLP) and semi-dynamic tests show that the exhausted BMIOP is safe for disposal in a secure landfill; hence, BMIOP has been proved to separate As(III) from water.

A zero-valent iron and zeolite filter for nitrate recycling from agricultural drainage water.

Nitrate reduction to ammonium followed by ammonium capture and reuse, represent a new pathway to recycle nitrogen, prevent eutrophication, and to save energy used for industrial ammonium production. The present study investigates the principle of nitrogen recycling to agricultural drainage water using a coupled zero-valent iron (ZVI) and zeolite-based filter column system tested in laboratory and field continuous-flow experiments. A 40-day laboratory test showed 82% nitrate removal, of which 70% was converted to ammonium. In the following pilot scale field test, a total of 59.2 m3 (1700 pore volumes) drainage water with a nitrate concentration of 2-8 mg L-1 NO3--N was filtrated. An oxidizing unit inserted after the ZVI unit removed iron(II) and optimized ammonium retention in the zeolite unit. Nitrate removal efficiency was 94% for the entire 56-day period with a slight pH increase (pH 8.9). All ammonium produced was retained by the zeolite unit. Formation of green rust carbonate (layered FeII-FeIII-hydroxide) was observed on ZVI particle surfaces, which may increase the redox capacity of the filter system by up to 50% and contribute to its cost-efficiency. Moreover, all phosphate in the influent waters with concentrations between 0.1 and 0.5 mg L-1 was retained due to sorption by iron oxides in the system. Corrosion products formed cause partial filter clogging and should be removed by regular cleaning and backflushing. In conclusion, the ZVI - zeolite coupled filter system serves as a promising and cost-effective technology for nutrient removal and ammonium retention from agricultural drainage water.

Modified Grape Seeds: A Promising Alternative for Nitrate Removal from Water.

The aim of this work was to investigate grape seeds as a potential adsorbent for nitrate removal from water. Grape seeds were modified by quaternization and the applicability of the modified grape seeds (MGS) was evaluated in batch adsorption experiments. Fixed bed adsorption and regeneration studies were carried out to determine the regeneration capacity of MGS. The maximum adsorption capacity of 25.626 mg g-1 at native pH (6.3) for nitrate removal by MSG was comparable to that of the commercial anion exchange resin Relite A490 under similar conditions. The percent removal of nitrate from model nitrate solution was 86.47% and 93.25% for MGS, and Relite A490, respectively, and in synthetic wastewater 57.54% and 78.37%. Analysis of the batch adsorption data using isotherm models revealed that the Freundlich model provided a better fit to the data obtained than the Langmuir model, indicating multilayer adsorption. In kinetic terms, the results showed that the adsorption followed the pseudo-first order model. By investigating the adsorption mechanism, the results suggest that the intraparticle diffusion model was not the only process controlling the adsorption of nitrate on MGS. In column experiments (adsorption/desorption studies), three adsorption cycles were tested with minimal decrease in adsorption capacities, implying that this alternative adsorbent can be successfully regenerated and reused.

Biochar application in organics and ultra-violet quenching substances removal from sludge dewatering leachate for algae production.

Algae production in nutrient rich sludge dewatering leachate after biogas production is a promising option for wastewater treatment plants. However, the ultra-violet (UV) absorbing characteristic of UV-quenching substances (UVQS) existing in these waters can notably reduce the light transmission within the liquid body. The present work demonstrates a comparative adsorptive removal of UVQS, and other organic substances (expressed as COD and TOC) onto the "acid catalyst" functionalised adsorbent (PPhA) and commercial activated carbon (CAC) from leachate originating from leftover sludge dewatering after biogas production. Laboratory scale column studies were performed to investigate the adsorption performance of selected parameters. The PPhA increased the UV transmittance of leachate more than 4 times and outperformed CAC. Bed Depth Service Time and Yan models were used on the experimental data in order to estimate the maximum adsorption capacity and evaluate the characteristics of the fixed-bed. The PPhA equilibrium uptake of COD and TOC amounted to 5.7 mg/g and 0.9 mg/g, respectively. The postulated removal mechanism in environmentally relevant conditions (e.g., pH neutral) suggested a complex interaction between the biochar and organic macromolecules. Diluted phosphoric acid solution (0.01 mol/L) was successfully used for the column regeneration. Beside the UVQS, PPhA showed affinity towards toxic heavy metals (e.g., Pb, Ni, Co) pointing out the rich surface chemistry of the PPhA. Based on the obtained results and successfully implemented scale-up methodology, the low-cost PPhA adsorbent might effectively compete with the CAC as a highly efficient platform in wastewaters leachate processing.

Accumulation of heavy metals in stormwater biofiltration systems augmented with zeolite and fly ash.

The discharge of high levels of heavy metals into the environment is of concern due to its toxicity to aquatic life and potential human health impacts. Biofiltration systems have been used in urban environments to address nutrient contamination, but there is also evidence that such systems can be effective in reducing heavy metals concentration in stormwater. However, the accumulation pattern of heavy metals and lifespan of such systems, which are important in engineering design, have not been thoroughly explored. This study investigated the accumulation patterns of lead (Pb), copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe), which are common in urban runoff, in non-vegetated filtration columns using three different types of filter media, namely sand (S), and mixtures of sand with fly ash (sand-fly ash mix, SF), and with zeolite (sand-zeolite mix, SZ). The columns were assessed in terms of infiltration rate, the mass of heavy metals accumulation at different depths, and formation of crust layer (schmutzdecke) at the surface. The results show that most of the heavy metals accumulated at the top 5-10 cm of the filter media. However, Zn was found adsorbed to a depth of 15 cm in S and SZ columns, while Mn and Fe were present in column S throughout the entire 30 cm depth of the filter media. The presence especially of Zn, Mn, and Fe in the deeper portions of the filter media before the top 5 cm layer reached its maximum adsorption capacity, hints that transport to the deeper layers is not necessarily dependent on saturation of the upper layers for these heavy metals. SF accumulated heavy metals most at the top 5 cm of the filter media layer, and retained twice the mass of heavy metals in the crust layer, compared to S and SZ columns. SF also yielded the lowest value of infiltration rate of 31 mm/h. Considering both metals accumulation and clogging potential of the filter media, the periodic maintenance of these systems is suggested to be approximately between 1.5 and 3 years.

Removal of arsenic from aqueous solution by novel iron and iron-zirconium modified activated carbon derived from chemical carbonization of Tectona grandis sawdust: Isotherm, kinetic, thermodynamic and breakthrough curve modelling.

The aim of the present study was: development of activated carbon modified with iron (Fe@AC) and modified with iron and zirconium (Fe-Zr@AC) from the Tectona grandis sawdust (TGS) waste biomass and its potential applicability for the removal of As (III) from contaminated water by batch and column mode. The biomass waste was pre-treated with ferric chloride (FeCl3) and the mixture of FeCl3 and zirconium oxide (ZrO2) and then pyrolyzed at 500 °C for 2 h. The properties of both bioadsorbents were comprehensively characterized by using Scanning electron microscopy (SEM), Energy dispersive X-ray (EDX), Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), Particle Size analysis (PSA), point of zero charge (pHZPC), Brunauer-Emmett-Teller (BET) to prove successful impregnation of the Fe and Zr on the surface of AC of TGS. FTIR analysis clearly indicates the Fe and Fe-Zr complexation on biosorbents surface and biosorption of As (III). The results revealed that maximum As (III) removal was achieved 86.35% by Fe-Zr@AC (3 g/L dose, pH-7.0, temperature-25 °C and concentration 0.5 mg/L). However, maximum removal of As (III) was attained ~75% by Fe@AC (with dose-4g/L, pH-7.0, temperature-25 °C and concentration 0.5 mg/L) at the initial concentration of 0.5 mg/L of As (III). Fe-Zr@AC exhibits higher efficiency with qmax value 1.206 mg/g than Fe@AC with the qmax value 0.679 mg/g for the removal of As(III). While in the column study, Fe-Zr@AC exhibited 98.8% removal at flow rate of 5 mL/min and bed height of 5 cm. Biosorption Isotherm and Kinetics were fitted good with Langmuir isotherm (R2 ≥ 0.99) and followed pseudo-second-order (R2 ≥ 0.99). The regeneration study indicates that the prepared biosorbents efficiently recycled up to five cycles. Therefore, Fe@AC and Fe-Zr@AC derived from TGS has been showed to be novel, effective, and economical biosorbent. The collective benefits of easy development, good affinity towards As (III), good separability, reusability, and inexpensive of magnetized Fe@AC and Fe-Zr@AC make it a novel biosorbent. The application of Fe-Zr@AC for the removal of As (III) from the water was very efficient its concentration in the solution after treatment was found below the 10 µg/L as per the guideline WHO.

A novel optical biosensor for in situ and small-scale monitoring of bacterial transport in saturated columns.

In situ monitoring techniques can provide new insight into bacterial transport after inoculating exogenous bacteria into contaminated soils for bioremediation. A real-time and non-destructive optical sensor (the optrode) was employed to monitor in situ transport of two fluorescently labelled bacteria - Green Fluorescent Protein (Gfp)-labelled, hydrophilic Pseudomonas putida and Tomato Fluorescent Protein (td)-labelled, hydrophobic Rhodococcus erythropolis, in a saturated sand column with and without rhamnolipid surfactant. In situ measurements were made at three sampling ports in the column with the optrode in two sets of column experiments. In Experiment 1, liquid samples were extracted for ex situ analyses (plate counts and fluorescence), while in Experiment 2 no liquid samples were extracted. Extracting liquid samples for ex situ analyses in Experiment 1 disturbed in situ measurements; in situ measured bacterial concentrations were lower, or a significant lag in breakthrough occurred relative to ex situ measurements. In Experiment 2, the optrode worked well in monitoring bacterial transport, which gave consistent transport parameters at each sampling port. Moreover, the optrode enabled the impact of bacterial hydrophobicity and rhamnolipid surfactant on bacterial transport to be observed. Specifically, hydrophilic P. putida was transported faster through the column than hydrophobic R. erythropolis; we infer from this result that fewer P. putida cells adsorb to sand particles than do R. erythropolis cells. The rhamnolipid surfactant enhanced the transport of both hydrophilic and hydrophobic bacteria. These two observations are consistent with Lifshitz-van der Waals forces and acid-base interactions between bacteria and sand.

Simultaneous removal of harmful anions from geothermal waters using OH- intercalated Mg-Fe-LDH: batch and field column studies.

Unlike collectively treatable industrial wastewaters where only one or a few pollutants have concentrations much higher than the relevant standards, geothermal waters, in which multiple harmful constituents coexist, are usually discharged dispersedly, provoking a big challenge for their effective treatment. Here, a Mg/Fe layered double hydroxide with OH- intercalated (Mg-Fe-OH-LDH) was synthesized in a mechanochemical way and then applied in the treatment of various types of high-temperature geothermal waters in western Yunnan (China) containing a variety of harmful anions (As, Sb, W, and F) and inducing local environmental pollution. Due to the endothermic nature of removal of aqueous As, Sb, W, and F by Mg-Fe-OH-LDH, the original high temperatures of the geothermal waters could promote their sorption effectively. Batch sorption experiments demonstrated that over 94% and 80% of the As and W removal amounts could be reached within the first 10 and 20 min, respectively. On-site column experiments confirmed that the sorbent could remove the targeted harmful constituents from the investigated geothermal waters efficiently. In fact, the performance of the sorbent in the column studies was even better than that in the batch experiments, which can be ascribed to the continuous impetus for sorption caused by the concentration gradient in the flowing sorption system. Specifically, Mg-Fe-OH-LDH displayed the best sorption performance for As(V) among various harmful constituents, and the sorption of As along with W and F was little affected by the coexisting common anions in the geothermal waters, including Cl-, SO42-, and HCO3-/CO32-. In contrast, the removal of Sb(V) from geothermal waters may be impeded to a certain extent by SO42- and CO32-, which possessed stronger electronegativity or smaller ionic radii. This study is the first attempt to apply Mg-Fe-LDH in treatment of geothermal waters with multiple harmful constituents and sheds a light on providing a practical approach for field treatment of geothermal water-derived pollution.

Evaluation of engineered sorbents for the sorption of mercury from contaminated bank soils: a column study.

As a global environmental pollutant, mercury (Hg) threatens our water resources and presents a substantial risk to human health. The rate and extent of immobilization of Hg2+ (hereafter, Hg) on engineered sorbents (Thiol-SAMMS®, pine biochar, SediMite™, Organoclay™ PM-199, and quartz sand as a control) was evaluated using flow-through column experiments. The effectiveness of the sorbents was based on (1) the percentage of Hg removed in relation to the total amount of Hg passing the sorbent column, and (2) the rate of Hg uptake compared to the nonreactive tracer bromide (Br-). All sorbents removed Hg to a certain extent, but none of the sorbents removed all the Hg introduced to the columns. Thiol-SAMMS showed the highest mean percentage of Hg removed (87% ± 2.9%), followed by Organoclay PM-199 (71% ± 0.4%), pine biochar (57% ± 22.3%), SediMite (61% ± 0.8%), and the control quartz sand (11% ± 5.6%). Thiol-SAMMS was the only sorbent to exhibit retardation of Hg in comparison to the conservative tracer Br-. For the remaining sorbents, Br- along with low concentrations of Hg were eluted within the first 3 pore volumes, indicating limited retardation of Hg. Overall, removal of Hg by sorbents was substantial, suggesting that sorbents might be suitable for deployment in contaminated environments. High concentrations of DOM leaching from the soil columns likely influenced the speciation of Hg and inhibited sorption to the sorbents. Incomplete removal of Hg by any sorbent suggests that additional optimization is needed to increase efficiency.

Balancing Hydraulic Control and Phosphorus Removal in Bioretention Media Amended with Drinking Water Treatment Residuals.

Green stormwater infrastructure like bioretention can reduce stormwater runoff volumes and trap sediments and pollutants. However, bioretention soil media can be both a sink and source of phosphorus (P). We investigated the potential tradeoff between hydraulic conductivity and P sorption capacity in drinking water treatment residuals (DWTRs), with implications for bioretention media design. Batch isotherm and flow-through column experiments were used to quantify the maximum P sorption capacity (Smax) and rate of P sorption for three DWTR sources. Smax values varied greatly among DWTR sources and methodologies, which has implications for regulatory standards. We also conducted a large column experiment to determine the hydraulic and P removal effects of amending bioretention media with solid and mixed layers of DWTRs. When applied to bioretention media, the impact of DWTRs on hydraulic conductivity and P removal depended on layering strategy. Although DWTR addition in solid and mixed layer designs improved P removal, the solid layer restricted water flow and exhibited incomplete P removal, while the mixed layer had no effect on flow and removed ~100% of P inputs. We recommend that DWTRs be mixed with sand in bioretention media to simultaneously achieve stormwater drainage and P reduction goals in green stormwater infrastructure.

Locally available agroresidues as potential sorbents: modelling, column studies and scale-up.

Sawdust, cotton stalk and groundnut shell were used for removal of methylene blue from aqueous solution using batch sorption. Effect of initial dye concentration, temperature, and particle size of sorbents on methylene blue removal was investigated. Sorption capacity increases with rise in initial dye concentration and temperature. Impact of particle size on sorption of methylene blue was investigated and indicated that removal of dye increases with decrease in particle size of sorbents. Maximum sorption for sawdust, cotton stalks and groundnut shell were 9.22 mg g-1, 8.37 mg g-1 and 8.20 mg g-1 respectively; at 60 °C and 100 ppm initial dye concentration. Sorption isotherms were analyzed using fundamental Freundlich isotherm. Subsequently, sips isotherm model was employed for better fitting. Kinetic study shows that, biosorption process is pseudo-second-order in nature. During the course of this study, adsorption dynamics revealed that film diffusion was key step for biosorption. In addition, thermodynamics of sorption was studied; and it was found that Gibbs free energy (∆G°) decreases with increase in temperature. Sawdust was found to be best among all the sorbents. Therefore, column studies and breakthrough curve modelling were performed using sawdust. Furthermore, it was estimated that a scaled-up column using sawdust can treat 6672 L of wastewater in 24 h with 80% efficiency.

Risks of graphene nanomaterial contamination in the soil: evaluation of major ions.

Soils are facing new environmental contaminants, such as nanomaterials. While these emerging contaminants are increasingly being released into soil, their potential impact on this medium and their effect on soil's major chemical components (e.g., sulfate, nitrate, ammonia, and phosphate) have yet to be examined, as well as their relation with microbial toxicity. Herein, column experiments were conducted to investigate the behavior of major ions under 10 and 200 mg/L multiple contaminations of graphene nanomaterials in agricultural and undisturbed soils, as well as the retention of the graphene nanomaterials in the soil and their effect on soil zeta potentials throughout the column. Moreover, to evaluate the impact of the risks of graphene nanomaterial contamination on soil major ions, the present study also examines the bacterial toxicity. The results showed that graphene retention was influenced the soil zeta potentials. Graphene also influenced the concentrations of the major ions in soil and the order of the influence degree was sulfate > phosphate > ammonia > nitrate. The changes of the major ions in soil by the exposure of graphene nanomaterials have also affected the response of selected bacteria.

Surface functionalization of recycled polyacrylonitrile fibers with ethylenediamine for highly effective adsorption of Hg(II) from contaminated waters.

In this research, recycled polyacrylonitrile fibers (PANFs) acquired from the textile recycling process were amino-functionalized in one simple step by means of ethylenediamine (EDA). The amino-functionalized polyacrylonitrile fibers (AF-PANFs) were utilized for adsorption of Hg(II) ions from aquatic media. Temperature and contact time during the synthesis were optimized by the Central Composite Design (CCD) method. FE-SEM, EDS, BET, and FT-IR analysis, and pHZPC measurement were conducted to characterize the features of the AF-PANFs. The average diameter of raw fiber was 20 µm, which increased 20 percent after functionalizing. The impact of independent parameters on the adsorption process was investigated using the Box-Behnken Design (BBD) method during the batch experiments. The column tests were conducted in a semi-continuous system with the removal efficiency of over 99% for various initial concentrations after specific cycles. Freundlich, Langmuir, UT, Redlich-Peterson, and Temkin isotherm models were employed to analyze the relation between the final concentration of Hg(II) (Co) and the equilibrium adsorption capacity (qe) of the AF-PANFs. According to the isotherm models and experimental results, the maximum qe of the AF-PANFs was 1116 mg g-1 at initial Hg(II) concentration of 850 mg L-1, contact time of 120 min, solution pH of 6, and at 40 °C. Kinetic and thermodynamic studies illustrated the approximate equilibrium time and endothermicity or exothermicity of the process. Regeneration of the AF-PANFs was accomplished for seven times without efficiency drop. The superb performance of the AF-PANFs in the presence of co-existing ions did not decline.