Development of innovative and green adsorbents for in situ cleanup of fluoride-polluted groundwater: Mechanisms and field-scale studies.

In this study, the magnesium oxide (MgO)-based adsorbents [granulated MgO aggregates (GA-MgO) and surface-modified MgO powder (SM-MgO)] were developed to remediate a fluoride-contaminated groundwater site. Both GA-MgO and SM-MgO had porous, spherical, and crystalline structures. Diameters for GA-MgO and SM-MgO were 1-1.7 mm and 1-10 µm, respectively. The pseudo second-order dynamic adsorption and the Freundlich isotherm could be applied to express the chemical adsorption phenomena. The monolayer adsorption was the dominant mechanism at the initial adsorption period. During the latter part of fluoride adsorption, the multilayer adsorption became the dominant mechanism for fluoride removal from the water phase, which also resulted in the increased adsorption capacity. Higher hydroxide, phosphate, and carbonate concentrations caused a decreased fluoride removal efficiency due to the competition of sorption sites between fluoride and other anions with similar electronic properties. Fluoride removal mechanism using GA-MgO and SM-MgO as the adsorbents was mainly carried out by the chemical adsorption. Reaction paths contained two main processes: (1) formation of magnesium hydroxide after the reaction of MgO with water, and (2) the hydroxyl group of the magnesium hydroxide was replaced by fluoride ions to form magnesium fluoride precipitation. Results from column tests show that up to 61 and 73% of fluoride removal (initial fluoride concentration = 9.3 mg/L) could be obtained after 50 pore volumes of groundwater pumping with GA-MgO and SM-MgO injection, respectively. The GA-MgO system could be applied to contain and remediate fluoride-contaminated groundwater, and SM-MgO could be applied as an immediate fluoride removal alternative to achieve a rapid pollutant removal for emergency responses. Up to 71% of fluoride removal (fluoride concentration = 10.8 mg/L) could be obtained with GA-MgO injection after 30 days of operation. The developed GA-MgO system is a potential and green remediation alternative to contain the fluoride plume significantly.

Application of novel nanobubble-contained electrolyzed catalytic water to cleanup petroleum-hydrocarbon contaminated soils and groundwater: A pilot-scale and performance evaluation study.

Soil and groundwater contamination caused by petroleum hydrocarbons is a severe environmental problem. In this study, a novel electrolyzed catalytic system (ECS) was developed to produce nanobubble-contained electrolyzed catalytic (NEC) water for the remediation of petroleum-hydrocarbon-contaminated soils and groundwater. The developed ECS applied high voltage (220 V) with direct current, and titanium electrodes coated with iridium dioxide were used in the system. The developed ECS prototype contained 21 electrode pairs (with a current density of 20 mA/cm2), which were connected in series to significantly enhance the hydroxyl radical production rate. Iron-copper hybrid oxide catalysts were laid between each electrode pair to improve the radical generation efficiency. The electron paramagnetic resonance (EPR) and Rhodamine B (RhB) methods were applied for the generated radical species and concentration determination. During the operation of the ECS, high concentrations of nanobubbles (nanobubble density = 3.7 × 109 particles/mL) were produced due to the occurrence of the cavitation mechanism. Because of the negative zeta potential and nano-scale characteristics of nanobubbles (mean diameter = 28 nm), the repelling force would prevent the occurrence of bubble aggregations and extend their lifetime in NEC water. The radicals produced after the bursting of the nanobubbles would be beneficial for the increase of the radical concentration and subsequent petroleum hydrocarbon oxidation. The highly oxidized NEC water (oxidation-reduction potential = 887 mV) could be produced with a radical concentration of 9.5 × 10-9 M. In the pilot-scale study, the prototype system was applied to clean up petroleum-hydrocarbon polluted soils at a diesel-oil spill site via an on-site slurry-phase soil washing process. The total petroleum hydrocarbon (TPH)-contaminated soils were excavated and treated with the NEC water in a slurry-phase reactor. Results show that up to 74.4% of TPH (initial concentration = 2846 mg/kg) could be removed from soils after four rounds of NEC water treatment (soil and NEC water ratio for each batch = 10 kg: 40 L and reaction time = 10 min). Within the petroleum-hydrocarbon plume, one remediation well (RW) and two monitor wells (located 1 m and 3 m downgradient of the RW) were installed along the groundwater flow direction. The produced NEC water was injected into the RW and the TPH concentrations in groundwater (initial concentrations = 12.3-15.2 mg/L) were assessed in these three wells. Compared to the control well, TPH concentrations in RW and MW1 dropped to below 0.4 and 2.1 mg/L after 6 m3 of NEC water injection in RW, respectively. Results from the pilot-scale study indicate that the NEC water could effectively remediate TPH-contaminated soils and groundwater without secondary pollution production. The main treatment mechanisms included (1) in situ chemical oxidation via produced radicals, (2) desorption of petroleum hydrocarbons from soil particles due to the dispersion of nanobubbles into soil pores, and (3) enhanced TPH oxidation due to produced radicals and energy after nanobubble bursting.

Toxicity evaluation of a heavy-metal-polluted river: Pollution identification and bacterial community assessment.

The Salt River is an important urban river in Kaohsiung, Taiwan. In this study, the source identification and risk and toxicity assessment of the heavy-metal-contaminated sediments in the Salt River were investigated. The geo-accumulation index (Igeo), enrichment factor (EF), sediment quality guidelines (SQGs), potential ecological risk index (RI), pollution load index (PLI), and toxic units (TU) were applied to determine effects of heavy metals on microbial diversities and ecosystems. Results from the ecological and environmental risk assessment show that high concentrations of Zn, Cr, and Ni were detected in the midstream area and the sum of toxic units (ΣTUs) in the midstream (7.2-32.0) is higher than in the downstream (14.0-19.7) and upstream (9.2-17.1). It could be because of the continuous inputs of heavy-metal-contained wastewaters from adjacent industrial parks. Results also inferred that the detected heavy metals in the upstream residential and commercial areas were possibly caused by nearby vehicle emissions, non-point source pollution, and domestic wastewater discharges. Results of metagenomic assays show that the sediments contained significant microbial diversities. Metal-tolerant bacterial phyla (Proteobacteria: 24.4%-46.4%, Bacteroidetes: 1.3%-14.8%, and Actinobacteria: 2.3%-11.1%) and pathogenic bacterial phyla (Chlamydiae: 0.5%-37.6% and Chloroflexi: 5.8%-7.2%) with relatively high abundance were detected. Metal-tolerant bacteria would adsorb metals and cause the increased metal concentrations in sediments. Results indicate that the bacterial composition in sediment environments was affected by anthropogenic pollution and human activities and the heavy-metal-polluted ecosystem caused the variations in bacterial communities. PRACTITIONER POINTS: Microbial community in sediments is highly affected by heavy metal pollution. Wastewaters and vehicle traffic contribute to river sediments pollution by heavy metals. Proteobacteria, Bacteroidota, and Actinobacteria are dominant heavy-metal-tolerant bacterial phyla in sediments. Toxicity assessment is required to study risk levels of heavy-metal contained sediments.

Cleanup of Cr(VI)-polluted groundwater using immobilized bacterial consortia via bioreduction mechanisms.

Cr(VI) bioreduction has become a remedial alternative for Cr(VI)-polluted site cleanup. However, lack of appropriate Cr(VI)-bioreducing bacteria limit the field application of the in situ bioremediation process. In this study, two different immobilized Cr(VI)-bioreducing bacterial consortia using novel immobilization agents have been developed for Cr(VI)-polluted groundwater remediation: (1) granular activated carbon (GAC) + silica gel + Cr(VI)-bioreducing bacterial consortia (GSIB), and (2) GAC + sodium alginate (SA) + polyvinyl alcohol (PVA) + Cr(VI)-bioreducing bacterial consortia (GSPB). Moreover, two unique substrates [carbon-based agent (CBA) and emulsified polycolloid substrate (EPS)] were developed and used as the carbon sources for Cr(VI) bioreduction enhancement. The microbial diversity, dominant Cr-bioreducing bacteria, and changes of Cr(VI)-reducing genes (nsfA, yieF, and chrR) were analyzed to assess the effectiveness of Cr(VI) bioreduction. Approximately 99% of Cr(VI) could be bioreduced in microcosms with GSIB and CBA addition after 70 days of operation, which caused increased populations of total bacteria, nsfA, yieF, and chrR from 2.9 × 108 to 2.1 × 1012, 4.2 × 104 to 6.3 × 1011, 4.8 × 104 to 2 × 1011, and 6.9 × 104 to 3.7 × 107 gene copies/L. In microcosms with CBA and suspended bacteria addition (without bacterial immobilization), the Cr(VI) reduction efficiency dropped to 60.3%, indicating that immobilized Cr-bioreducing bacteria supplement could enhance Cr(VI) bioreduction. Supplement of GSPB led to a declined bacterial growth due to the cracking of the materials. The addition of GSIB and CBA could establish a reduced condition, which favored the growth of Cr(VI)-reducing bacteria. The Cr(VI) bioreduction efficiency could be significantly improved through adsorption and bioreduction mechanisms, and production of Cr(OH)3 precipitates confirmed the occurrence of Cr(VI) reduction. The main Cr-bioreducing bacteria included Trichococcus, Escherichia-Shigella, and Lactobacillus. Results suggest that the developed GSIB bioremedial system could be applied to cleanup Cr(VI)-polluted groundwater effectively.

Bioremediation of hexavalent-chromium contaminated groundwater: Microcosm, column, and microbial diversity studies.

Sulfate reducing bacteria (SRB) have the capability of bioreducing hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] under sulfate-reducing conditions for toxicity reduction. However, a high amount of sulfate addition would cause elevated sulfide production, which could inhibit the growth of SRB and result in reduced Cr(VI) bioreduction efficiency. A slow release reagent, viscous carbon and sulfate-releasing colloidal substrates (VCSRCS), was prepared for a long-lasting carbon and sulfate supplement. In the column study, VCSRCS was injected into the column system to form a VCSRCS biobarrier for Cr(VI) containment and bioreduction. A complete Cr(VI) removal was observed via the adsorption and bioreduction mechanisms in the column with VCSRCS addition. Results from X-ray diffractometer analyses indicate that Cr(OH)3(s) and Cr2O3(s) were detected in precipitates, indicating the occurrence of Cr(VI) reduction followed by Cr(III) precipitation. Results from the Fourier-transform infrared spectroscopy analyses show that cell deposits carried functional groups, which could adsorb Cr. Addition of VCSRCS caused increased populations of total bacteria and dsrA, which also enhanced Cr(VI) reduction. Microbial diversity results indicate that VCSRCS addition resulted in the growth of Cr(VI)-reducing bacteria including Exiguobacterium, Citrobacter, Aerococcus, and SRB. Results of this study will be helpful in developing an effective and green VCSRCS biobarrier for the bioremediation of Cr(VI)-polluted groundwater.

Bioremediation of trichloroethylene-polluted groundwater using emulsified castor oil for slow carbon release and acidification control.

In this study, the emulsified castor oil (ECO) substrate was developed for a long-term supplement of biodegradable carbon with pH buffering capacity to anaerobically bioremediate trichloroethylene (TCE)-polluted groundwater. The ECO was produced by mixing castor oil, surfactants (sapindales and soya lecithin [SL]), vitamin complex, and a citrate/sodium phosphate dibasic buffer system together for slow carbon release. Results of the emulsification experiments and microcosm tests indicate that ECO emulsion had uniform small droplets (diameter = 539 nm) with stable oil-in-water characteristics. ECO had a long-lasting, dispersive, negative zeta potential (-13 mv), and biodegradable properties (viscosity = 357 cp). Approximately 97% of TCE could be removed with ECO supplement after a 95-day operational period without the accumulation of TCE dechlorination byproducts (dichloroethylene and vinyl chloride). The buffer system could neutralize acidified groundwater, and citrate could be served as a primary substrate. ECO addition caused an abrupt TCE adsorption at the initial stage and the subsequent removal of adsorbed TCE. Results from the next generation sequences and real-time polymerase chain reaction (PCR) indicate that the increased microbial communities and TCE-degrading bacterial consortia were observed after ECO addition. ECO could be used as a pH-control and carbon substrate to enhance anaerobic TCE biodegradation effectively. PRACTITIONER POINTS: Emulsified castor oil (ECO) contains castor oil, surfactants, and buffer for a slow carbon release and pH control. ECO can be a long-term carbon source for trichloroethylene (TCE) dechlorination without causing acidification. TCE removal after ECO addition is due to adsorption and reductive dechlorination mechanisms.

Application of zeolitic imidazolate framework for hexavalent chromium removal: A feasibility and mechanism study.

The mechanisms and effectiveness of using zeolitic imidazolate framework (ZIF-8) [a sub-family of metal-organic framework (MOF)] particles on hexavalent chromium [Cr(VI)] removal were evaluated. The ultrasonic mixing method was applied for the preparation of ZIF-8, and chemicals used for ZIF-8 synthesis included ammonium hydroxide, zinc nitrate hexahydrate, and 2-methylimidazole. ZIF-8 particle had a clear rhombic dodecahedron morphology shape and a strong peak intensity with high crystallinity. The adsorption capacity (AC) of ZIF-8 was 30.3 mg of Cr(VI)/g of ZIF-8 [Cr(VI) = 50 mg/L]. The AC of Cr(VI) raised to 34.3 mg/g under acidic conditions (pH = 5), and the AC dropped to below 13.7 mg/g with a pH range from 7 to 11. It could be because of the competitive effects between CrO4 2- and hydroxide ions for adsorption locations of ZIF-8. Cr(VI) removal relied on the amount of Cr(VI) adsorbed on the particles of ZIF-8, and the mechanisms of Cr(VI) adsorption by ZIF-8 included chemical/physical processes and the rate-limiting step was the chemical adsorption. A fraction of sorbed Cr(VI) was reduced to Cr(III), and thus, ZIF-8 could serve as a reducing agent during Cr(VI) reduction. Cr(VI) was removed effectively from the water phase by ZIF-8 via adsorption and reduction mechanisms. PRACTITIONER POINTS: ZIF-8 particles had an adsorption capacity of 30.33 mg of Cr(VI)/g of ZIF-8. Cr(VI) sorption by ZIF-8 has chemical (rate-limiting step) and physical processes. ZIF-8 can serve as a reducing agent for Cr(VI) reduction. Cr(VI) can be removed by ZIF-8 via the adsorption and reduction mechanisms.

Application of iron/aluminum bimetallic nanoparticle system for chromium-contaminated groundwater remediation.

When the nanoscale zero valent iron (nZVI) is used for the reduction of hexavalent chromium (Cr6+) to trivalent chromium (Cr3+) in groundwater, the reduction efficiency is decreased due to the passivation of reactive sites by precipitation. The bimetallic nanoparticle (BNP) can be created with the addition of the second metal to achieve a higher activity and reduce the occurrence of the ferrous/ferric hydroxide precipitation. In this study, the iron-coated aluminum (Fe/Al) BNP and aluminum-coated iron (Al/Fe) BNP systems were designed for remediating Cr6+-contaminated groundwater. The chemical liquid-phase deposition and co-reduction method was applied to produce BNPs. Cr6+ removal rate by Fe/Al BNPs was directly proportional to the saturation concentration and reactive sites, which caused a higher Cr6+ removal rate. The pseudo-first-order kinetic model could be used to describe the Cr6+ adsorption mechanism by Fe/Al BNPs. Results show that Fe/Al BNPs and Al/Fe BNPs could reduce Cr6+ to Cr3+, and the removal efficiencies for Cr6+ were 1.47 g/g BNP and 0.07 g/g BNP, respectively. Detection of Cr3+ in the aqueous phase was observed during the Cr6+ removal process. Results from X-ray diffraction (XRD) analysis confirmed that Cr(OH)3 was present on the surface of BNPs. Main mechanisms caused Cr6+ removal included reduction, precipitation, and adsorption. The reduction of Cr6+ produced OH-, which created alkaline environment and facilitated the formation of chromium hydroxide precipitates [Cr(OH)3]. Thus, the migration of Cr3+ was prevented and the environmental risk was reduced. BNP had a higher activity and stability, and it was applicable for Cr6+-contaminated site remediation.

Remediation of TCE-contaminated groundwater using KMnO4 oxidation: laboratory and field-scale studies.

The objectives of this study were to (1) conduct laboratory bench and column experiments to determine the oxidation kinetics and optimal operational parameters for trichloroethene (TCE)-contaminated groundwater remediation using potassium permanganate (KMnO4) as oxidant and (2) to conduct a pilot-scale study to assess the efficiency of TCE remediation by KMnO4 oxidation. The controlling factors in laboratory studies included soil oxidant demand (SOD), molar ratios of KMnO4 to TCE, KMnO4 decay rate, and molar ratios of Na2HPO4 to KMnO4 for manganese dioxide (MnO2) production control. Results show that a significant amount of KMnO4 was depleted when it was added in a soil/water system due to the existence of natural soil organic matters. The presence of natural organic material in soils can exert a significant oxidant demand thereby reducing the amount of KMnO4 available for the destruction of TCE as well as the overall oxidation rate of TCE. Supplement of higher concentrations of KMnO4 is required in the soil systems with high SOD values. Higher KMnO4 application resulted in more significant H+ and subsequent pH drop. The addition of Na2HPO4 could minimize the amount of produced MnO2 particles and prevent the clogging of soil pores, and TCE oxidation efficiency would not be affected by Na2HPO4. To obtain a complete TCE removal, the amount of KMnO4 used to oxidize TCE needs to be higher than the theoretical molar ratio of KMnO4 to TCE based on the stoichiometry equation. Relatively lower oxidation rates are obtained with lower initial TCE concentrations. The half-life of TCE decreased with increased KMnO4 concentrations. Results from the pilot-scale study indicate that a significant KMnO4 decay occurs after the injection due to the reaction of KMnO4 with soil organic matters, and thus, the amount of KMnO4, which could be transported from the injection point to the downgradient area, would be low. The effective influence zone of the KMnO4 oxidation was limited to the KMnO4 injection area (within a 3-m radius zone). Migration of KMnO4 to farther downgradient area was limited due to the reaction of KMnO4 to natural organic matters. To retain a higher TCE removal efficiency, continuous supplement of high concentrations of KMnO4 is required. The findings would be useful in designing an in situ field-scale ISCO system for TCE-contaminated groundwater remediation using KMnO4 as the oxidant.