Effective sorption of perfluorooctane sulfonate (PFOS) on hexadecyltrimethylammonium bromide immobilized mesoporous SiO2 hollow sphere

The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L^?1. The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO₂ hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent.     

Comparison of biochar- and activated carbon-supported zerovalent iron for the removal of Se(IV) and Se(VI): influence of pH,ionic strength,and natural organic matter

Biochar (BC) and activated carbon (AC) were both produced from corn straw. Biochar-supported zerovalent iron (BC-ZVI) and activated carbon-supported zerovalent iron (AC-ZVI) were synthesized and applied for Se(IV)/Se(VI) removal. The sorption capacity of BC-ZVI for Se(IV) and Se(VI) was reported at 62.52 and 35.39 mg g^?1, higher than that of AC-ZVI (56.02 and 33.24 mg g^?1), respectively, due to its higher iron content and more positive charges. The spectroscopic analyses showed that Se(IV)/Se(VI) were reduced to Se(0)/Se(-II) of less toxicity and solubility. The effects of various factors such as pH, ionic strength, co-existing cations and anions, and natural organic matter (NOM) were also investigated. Ionic strength showed no significant effect on Se(IV)/Se(VI) removal, but pH was critical. The presence of NO₃^? and SO₄^2? did not cause obvious inhibition to the removal, while PO₄^3? inhibited the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI) significantly. Common cations (K⁺, Ca²⁺, and Mg²⁺) were found to slightly enhance the removal, while NOM significantly decreased the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI). Besides, NOM showed stronger inhibition effect on AC-ZVI than that on BC-ZVI. These results indicated that BC-ZVI, compared with AC-ZVI, could be a promising sorbent to remove Se(IV)/Se(VI) due to its low cost and high efficiency.

     

Value of biochars from Miscanthus x giganteus cultivated on contaminated soils to decrease the availability of metals in multicontaminated aqueous solutions

The objective of this study was to evaluate the sorption efficiency of eight biochars, made from Miscanthus x giganteus cultivated on contaminated agricultural soil, in aqueous solutions contaminated with metals alone or mixed with polycyclic aromatic hydrocarbons. These biochars were produced in different pyrolysis conditions (temperature, 400/600 °C; heating rate, 5/10 °C min⁻¹; duration, 45/90 min) and compared with an uncontaminated commercialized biochar made of wood. The physicochemical characterization of the Miscanthus biochars confirmed the impact of the pyrolysis on the biochar parameters with substantial differences between the biochars in terms of pH, cation exchange capacity, and specific surface area. The sorption experiment showed higher sorption efficiency of Cd, Pb, and Zn for the Miscanthus biochars produced at 600 °C compared with the biochars produced at 400 °C when the aqueous solutions were mono- or multicontaminated. Furthermore, the desorption study showed that the sorption process was largely irreversible. Therefore, the high sorption capacity of Miscanthus biochars and the low sorption reversibility confirmed that these biochars are a suitable sorbent for metals.

     

Preparation of various thiol-functionalized carbon-based materials for enhanced removal of mercury from aqueous solution

In this work, biochar (BC), activated carbon (AC), and graphene oxide (GO) were thiol-functionalized using 3-mercaptopropyltrimethoxysilane (3-MPTS) (named as BCS, ACS, and GOS, respectively). BCS, ACS, and GOS were synthesized mainly via the interaction between hydrolyzed 3-MPTS and surface oxygen-containing functional groups (e.g., –OH, O–C=O, and C=O) and π-π interaction. The materials before and after modification were characterized and tested for mercury removal, including sorption kinetics and isotherms, the effects of adsorbent dosage, initial pH, and ionic strength. Pseudo-second-order sorption kinetic model (R² = 0.992~1.000) and Langmuir sorption isotherm model (R² = 0.964~0.998) fitted well with the sorption data of mercury. GOS had the most –SH groups with the largest adsorption capacity for Hg²⁺ and CH₃Hg⁺ (449.6 and 127.5 mg/g), followed by ACS (235.7 and 86.7 mg/g) and BCS (175.6 and 30.3 mg/g), which were much larger than GO (96.7 and 4.9 mg/g), AC (81.1 and 24.6 mg/g), and BC (95.6 and 9.4 mg/g). GOS and ACS showed stable mercury adsorption properties at a wide pH range (2~9) and ionic strength (0.01~0.1 mol/L). Mercury maybe removed by ligand exchange, surface complexation, and electrostatic attraction.

     

Effect of copper(II) on biodegradation of benzo[a]pyrene by Stenotrophomonas maltophilia

Benzo[a]pyrene (BaP) biodegradation by Stenotrophomonas maltophilia was studied under the influence of co-existed Cu(II) ions. About 45% degradation was achieved within 3 d when dealing with 1 mg L^?1 BaP under initial natural pH at 30 °C; degradation reached 48% in 2 d at 35 °C. Efficacy of BaP biodegradation reached the highest point at pH 4. In the presence of 10 mg L^?1 Cu(II) ions, the BaP removal ratio was 45% on 7th day, and maintained stable from 7 to 14 d at 30 °C under natural pH. The favorable temperature and pH for BaP removal was 25 °C and 6.0 respectively, when Cu(II) ions coexisted in the solutions. Experiments on cometabolism indicated that S. maltophilia performed best when sucrose was used as an additional carbon source. GC–MS analysis revealed that the five rings of BaP opened, producing compounds with one or two rings which were more bioavailable.     

Highly efficient biosorptive removal of lead from industrial effluent

This study has been focused on the efficient removal of Pb (II) from contaminated waters by biosorption using plant derived material. Accordingly an indigenous shrub, Tinospora cordifolia has been identified as the most suitable biosorbent. The plant biomass was subjected to optimization of various parameters such as the pH, equilibrium time, dosage, concentration, temperature and the applicable adsorption models. The optimum pH identified was 4.0 with a contact time of 60 min at room temperature (27 ± 2 °C). The experimental data fitted well to adsorption isotherms and the uptake capacity of Pb (II) was found to be 20.83 and 63.77 mg/g in batch mode and column mode, respectively. The high correlation factors obtained for Langmuir and Freundlich models indicated that both models were obeyed by the system. Kinetic study for adsorption of Pb (II) follow only pseudo second order rate of reaction. The accumulation of lead in biomass was confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. The FTIR analysis indicated the involvement of hydroxyl (−OH), alkenes (=CH) and carbonyl group (C = O) chelates in metal binding. The SEM and EDX analysis showed the structural changes and the filling of voids in the biomass thus, it indicated the metal-binding mechanism. In elution studies, the 0.1 M Na₂CO₃ was found to be the best with about 71% elution of the adsorbed metal. The biomass was then used for the removal of Pb (II) in synthetic and real wastewater samples from a lead-acid battery industry. It is also noteworthy that even at a very high concentration of 450 mg/L, the biomass was showing about 92% removal. The result is to establish the efficacy of T. cordifolia as a very good bioadsorbent for the Pb (II) removal from contaminated water.

     

Immobilization of mercury by pyrite (FeS2)

Elemental mercury (Hg⁰) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.     

Efficient removal of uranium(VI) from aqueous systems by heat-treated carbon microspheres

In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g^?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.     

A Box-Behnken design for determining the optimum experimental condition of the fungicide (Vapam) sorption onto soil modified with perlite

In the present study, response surface methodology (RSM) based on the Box-Behnken design (BBD) was employed to investigate the effects of the different operating conditions on the removal of the fungicide (Vapam) onto soil modified with perlite using sorption process. The process parameters such as pH of the fungicide solution (2, 5 and 8), temperature (15, 25 and 35°C), shaking time (2, 13 and 24 h) and the percentage of perlite in the modified soil (0, 2 and 4 %) were investigated using a four-factor-three-level Box-Behnken design at an initial fungicide concentration of C₀ = 1.6 mg/L as a fixed input parameter. A second-order quadratic model suggested the optimum conditions to be as follows: fungicide solution pH of 3.57, temperature of 15°C, shaking time of 3.5 h and 4% of perlite in the modified soil which resulted in the improvement of Vapam sorption. Under optimum conditions, the fungicide (Vapam) removal was predicted 12.88 μg/g by BBD. The confirmatory experiments were conducted and the results revealed that the fungicide removal was 13.14 μg/g which indicated that the predicted and the observed values of response (Vapam removal) were in close agreement. Therefore, the soil modified with perlite holds good potential for Vapam sorption. This is the first report on fungicide Vapam sorption onto soil modified with perlite using statistical experimental design employing response surface methodology.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.     

Multiple copper adsorption and regeneration by zeolite 4A synthesized from bauxite tailings

Copper ions were first adsorbed by zeolite 4A synthesized from bauxite tailings, the desorption of Cu(II) using Na₂EDTA solutions was performed, and the recycling of zeolite 4A in adsorption and desorption was systematically investigated. It was observed that the Cu(II) removal efficiency was directly dependent on the initial pH value. The maximum removal efficiency of Cu(II) was 96.2% with zeolite 4A when the initial pH value was 5.0. Cu(II) was completely absorbed in the first 30 min. It was also observed that the desorption efficiency and zeolite recovery were highly dependent on the initial pH and concentration of Na₂EDTA in the solution. The desorption efficiency and percent of zeolite recovered were 73.6 and 85.9%, respectively, when the Na₂EDTA solution concentration was 0.05 mol L^?1 and the pH value was 8. The recovered zeolites were pure single phase and highly crystalline. After 3 cycles, the removal efficiency of Cu(II) was as high as 78.9%, and the zeolite recovery was 46.9%, indicating that the recovered zeolites have good adsorption capacity and can repeatedly absorb Cu(II).

     

Hydrous ferric oxide nanoparticles hosted porous polyethersulfone adsorptive membrane: chromium (VI) adsorptive studies and its applicability for water/wastewater treatment

In this present study, adsorptive membranes for Cr(VI) ion removal were prepared by blending polyethersulfone (PES) with hydrous ferric oxide (HFO) nanoparticles (NPs). The effects of HFO NPs to PES weight ratio (0–1.5) on the physicochemical properties of the resultant HFO/PES adsorptive membranes were investigated with respect to the surface chemistry and roughness as well as structural morphologies using different analytical instruments. The adsorptive performance of the HFO NPs/PES membranes was studied via batch adsorption experiments under various conditions by varying solution pH, initial concentration of Cr(VI), and contact time. The results showed that the membrane made of HFO/PES at a weight ratio of 1.0 exhibited the highest adsorption capacity which is 13.5 mg/g. Isotherm and kinetic studies revealed that the mechanism is best fitted to the Langmuir model and pseudo-second-order model. For filtration of Cr(VI), the best promising membranes showed improved water flux (629.3 L/m² h) with Cr(VI) ion removal of 75%. More importantly, the newly developed membrane maintained the Cr(VI) concentration below the maximum contamination level (MCL) for up to 9 h.

     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Characterization and Cu sorption properties of humic acid from the decomposition of rice straw

Humic acid (HA) derived from rice straw decomposed for 1 (HA-1), 3 (HA-3), 6 (HA-6) and 12 (HA-12) months was characterized by potentiometric titration and solid-state cross-polarization magic-angle spinning ¹³C nuclear magnetic resonance spectroscopy (CPMAS ¹³C NMR). The sorption of Cu on examined HA was investigated using a combination of batch sorption, isothermal titration calorimetry (ITC) and sequential desorption. Results showed that the functional group content and the humification degree of HA tended to increase with increasing decomposition time especially in the latter stage of examined decomposition period. Cu sorption on HA was a rapid process that occurred within the first 1 h and the sorption capacity increased from 245.4 mmol kg⁻¹ on HA-1 to 294.6 mmol kg⁻¹ on HA-12. The sorption of Cu was endothermic, spontaneous and the randomness was increased during Cu sorption. Sorbed Cu on examined HA can be hardly released by NH₄Ac but nearly fully released by EDTA. Forming inner-sphere complexes was the main mechanism of Cu sorption on examined HA. This study could provide valuable information for a better understanding on the environmental impacts of the decomposition of organic waste.

     

Sorption of perfluorooctane sulfonate to carbon nanotubes in aquatic sediments

To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4% multiwalled carbon nanotubes (MWCNTs), as a function of factors affecting PFOS sorption; aqueous concentration, pH and Ca²⁺ concentration. Sorption to MWCNT in the sediment–MWCNT mixtures was assessed by subtracting the contribution of PFOS sorption to sediment-only from PFOS sorption to the total sediment–MWCNT mixture. PFOS Log K_D values ranged 0.52–1.62 L kg^?1 for sediment and 1.91–2.90 L kg^?1 for MWCNT present in the sediment. The latter values are relatively low, which is attributed to fouling of MWCNT by sediment organic matter. PFOS sorption was near-linear for sediment (Freundlich exponent of 0.92 ± 0.063) but non-linear for MWCNT (Freundlich exponent of 0.66 ± 0.03). Consequently, the impact of MWCNT on sorption in the mixture was larger at low PFOS aqueous concentration. Effects of pH and Ca²⁺ on PFOS sorption to MWCNT were statistically significant. We conclude that MWCNT fouling and PFOS concentration dependency are important factors affecting PFOS–MWCNT interactions in sediments.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Effectiveness and mechanisms of hydrogen sulfide adsorption by camphor-derived biochar

The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on a biochar through pyrolysis at various temperatures (100 to 500°C) were investigated. The biochar used in the current study was derived from the camphor tree (Cinnamomum camphora). The samples were ground and sieved to produce particle sizes of 0.4 mm to 1.25 mm, 0.3 mm to 0.4 mm, and <0.3 mm. The H₂S breakthrough capacity was measured using a laboratory-designed test. The surface properties of the biochar were characterized using pH and Fourier-transform infrared spectroscopy (FTIR) analysis. The results obtained demonstrate that all camphor-derived biochars were effective in H₂S sorption. Certain threshold ranges of the pyrolysis temperature and surface pH were observed, which, when exceeded, have dramatic effects on the H₂S adsorption capacity. The sorption capacity ranged from 1.2 mg/g to 121.4 mg/g. The biochar with 0.3 mm to 0.4 mm particle size possesses a maximum sorption capacity at 400°C. The pH and FTIR analysis results showed that carboxylic and hydroxide radical groups were responsible for H₂S sorption. These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S.

Implications: This paper studies the potential of biochar derived by camphor to adsorb hydrogen sulfide at environmentally sustainable temperatures. The different sizes of the biochars and the different temperatures of pyrolysis for the camphor particle have a great impact on adsorption of hydrogen sulfide.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Enhanced effect of HAH on citric acid-chelated Fe(II)-catalyzed percarbonate for trichloroethene degradation

This work demonstrates the impact of hydroxylamine hydrochloride (HAH) addition on enhancing the degradation of trichloroethene (TCE) by the citric acid (CA)-chelated Fe(II)-catalyzed percarbonate (SPC) system. The results of a series of batch-reactor experiments show that TCE removal with HAH addition was increased from approximately 57 to 79% for a CA concentration of 0.1 mM and from 89 to 99.6% for a 0.5 mM concentration. Free-radical probe tests elucidated the existence of hydroxyl radical (HO^•) and superoxide anion radical (O₂ ^•-) in both CA/Fe(II)/SPC and HAH/CA/Fe(II)/SPC systems. However, higher removal rates of radical probe compounds were observed in the HAH/CA/Fe(II)/SPC system, indicating that HAH addition enhanced the generation of both free radicals. In addition, increased contribution of O₂ ^•- in the HAH/CA/Fe(II)/SPC system compared to the CA/Fe(II)/SPC system was verified by free-radical scavengers tests. Complete TCE dechlorination was confirmed based on the total mass balance of the released Cl⁻ species. Lower concentrations of formic acid were produced in the later stages of the reaction for the HAH/CA/Fe(II)/SPC system, suggesting that HAH addition favors complete TCE mineralization. Studies of the impact of selected groundwater matrix constituents indicate that TCE removal in the HAH/CA/Fe(II)/SPC system is slightly affected by initial solution pH, with higher removal rates under acidic and near neutral conditions. Although HCO₃ ⁻ was observed to have an adverse impact on TCE removal for the HAH/CA/Fe(II)/SPC system, the addition of HAH reduced its inhibitory effect compared to the CA/Fe(II)/SPC system. Finally, TCE removal in actual groundwater was much significant with the addition of HAH to the CA/Fe(II)/SPC system. The study results indicate that HAH amendment has potential to enhance effective remediation of TCE-contaminated groundwater.