The Transit of 35SO4 2- and 3H2O Added In Situ to Soil in a Boreal Coniferous Forest

A solution containing ³⁵SO₄ ^2- and ³H₂O was applied to four plots (5 × 5 m) in a boreal coniferous forest in the Laflamme Lake watershed, Québec, under two contrasting conditions: in summer (plots 1 and 2), and on the snowpack before snowmelt (plots 3 and 4). The transit of both these tracers in the soil solution was then followed through a network of soil lysimeters located at different depths. Four months after the summer application, ³H₂O had infiltrated the whole soil profile at plot 1, while ³⁵SO₄ ^2- was only observed in the LFH and Bhf horizons. A ³⁵SO₄ ^2- budget calculated from mid-August to November indicated that 89 and 10.6% of the added ³⁵SO₄ ^2- was retained within the LFH and the Bhf layers, respectively. Fifteen months later, the added ³⁵SO₄ ^2- was distributed in the following proportions within the soil horizons: LFH (73.7%), Bhf (11.8%) and Bf (12.8%), for a total retention rate of 98.3%. The superficial penetration of ³H₂O at plot 2 was indicative of a major lateral water movement that prevented the calculation of a ³⁵SO₄ ^2- budget. This situation also was observed at plot 4 during snowmelt. At plot 3, ³H₂O moved freely through the soil profile and a significant fraction of the added ³⁵SO₄ ^2- reached the B horizons, where it was presumably adsorbed on aluminum (Al) and ferric (Fe) oxides. The ³⁵SO₄ ^2- budget for plot 3 from March to November indicated that 87% of the added ³⁵SO₄ ^2- was retained within the soil profile, with most being retained in the B horizons (LFH = 33.1%, Bhf = 33.1%, Bf = 20.8%). The contrasting retention patterns of ³⁵SO₄ ^2- within the soil profile following the summer addition and snowmelt likely was caused by the contrastingsoil temperatures and soil solution residence times within the differentsoil layers. The persistence of ³⁵SO₄ ^2- in the soil solution of the entire profile long after the initial tracer infiltration, and the relative temporal stability of specific activity of SO₄ ^2-, point to the establishment of an isotopic equilibrium between the added ³⁵SO₄ and the active S-containing reservoirs within a given soil horizon. Overall, the results clearly illustrate the very strong potential for ³⁵SO₄ ^2- retention and recycling in forest soils.     

Trends in Water Chemistry in a Maple Forest on a Steep Slope

Year-to-year variation in SO₄ ^2-,NO₃ ^-, Ca²⁺, K⁺, and Mg²⁺concentrations in forest floor and mineral soil percolatefrom a forested, podzolic soil at the Turkey Lakes Watershedon the Precambrian Shield was assessed for monotonic trendsbetween 1986 and 1995. Our objective was to examine howrapidly ion concentrations in soil percolate equilibratedafter stabilization of SO₄ ^2- concentrations inprecipitation. Significant negative trends were detected inmonthly Ca²⁺, and Mg²⁺ concentrations in forestfloor and SO₄ ^2-, Ca²⁺, and Mg²⁺ inmineral soil percolate during the 10-year-period. Thedecline in Ca²⁺ and Mg²⁺ was greater than annualdecreases in SO₄ ^2- and NO₃ ^- in forestfloor percolate and proportional to the reduction inSO₄ ^2- in mineral soil percolate. Response ofmineral soil percolate to a 15 mol_c L^-1SO₄ ^2- decrease in wet-only precipitation between1985 and 1986 was a gradual decline in SO₄ ^2-concentration through 1995. The five-year meanSO₄ ^2- concentration in bulk precipitation, forestfloor percolate, and mineral soil percolate decreased 8, 9and 18 mol_c L^-1 from 1986–90 to 1991–95.Microbial (mineralization of organic S) and sorption(release from and/or retention in the pool of insolubleSO₄ ^2-) processes in the soil were logicalexplanations for the observed changes in SO₄ ^2- inmineral soil percolate.     

Development of Stream Water Chemistry during Spring Melt in a Northern Hardwood Forest

The role of snowmelt and subsurface hydrology in determiningthe chemistry of a small headwater stream in the TurkeyLakes Watershed (TLW) was evaluated for the spring meltperiods 1992 to 1996. Spring runoff is the dominanthydrological event at the TLW each year. Processesoccurring within the snowpack during snowmelt wereprincipally responsible for the above-ground changes inchemical fluxes relative to bulk deposition (the effect ofwinter throughfall was minimal). Large changes in chemicalfluxes occurred below ground. Organic matter decomposition,weathering, nitrification, and element cycling are some ofthe more important below-ground processes that operateduring the snow accumulation and ablation season and controlthe composition of the water ultimately appearing in thestream. Maximum stream discharge was accompanied byelevated concentrations of H⁺, NO₃ ^-, K⁺,NH₄ ⁺, DOC, Al and Mn, but reduced levels ofCa²⁺, Mg²⁺, SO₄ ^2- and SiO₂. Theconcentration-discharge relationships were consistent withwater movement through and above the forest floor duringpeak discharge, a flowpath facilitated by rapid infiltrationof meltwater and the existence of a relatively impermeablelayer in the mineral soil creating a perched water table. Averaged over the five periods of snow accumulation andablation, it was estimated that pre-melt stream flow, andwater routed through the forest floor and through the uppermineral soil contributed 9, 28 and 63%, respectively, ofthe discharge measured at the outlet of the catchment. Theforest floor contribution would be greater at peak dischargeand at higher elevations. An end-member mixing modelestimated concentrations of SO₄ ^2-, NO₃ ^-,Cl^-, Ca²⁺, Mg²⁺, Na⁺ and Al that werecomparable to average values measured in the stream. Othervariables (NH₄ ⁺, H⁺, K⁺ and DOC) wereover-estimated implying retention mechanisms operatingoutside the model assumptions.     

Deposition Velocities of SO2 and O3 over Agricultural and Forest Ecosystems

The results of field studies that measured the flux anddeposition velocity of SO₂ and O₃ are reported. Three of the studies were over agricultural crops (pasture, corn, and soybean), and two were over forest (a deciduous forest and a mixed coniferous–deciduous forest). In all cases the deposition velocity for SO₂ was higher than that for O₃. Diurnal cycles of SO₂ deposition velocity were similar in shape, but not magnitude for all surfaces; however those for O₃ showed some difference between forest sites where the peak was in the morning, and the agricultural sites where the peak occurred at mid-day. Seasonal cycles of SO₂ were affected by deposition to surfaces when leaves were not active, yet surface conductance is significant, but not for O₃ where stomatal uptake is the primary pathway for deposition.(On assignment to the National Exposure Research Lab., US EPA) (e-mail:     

Immobilization of MSWI fly ash through geopolymerization: Effects of water-wash

The present research explored the role played by water-wash on geopolymerization for the immobilization and solidification of municipal solid waste incineration (MSWI) fly ash. The water-wash pretreatment substantially promoted the early strength of geopolymer and resulted in a higher ultimate strength compared to the counterpart without water-wash.XRD pattern of water-washed fly ash (WFA) revealed that NaCl and KCl were nearly eliminated in the WFA. Aside from geopolymer, ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O) was formed in MSWI fly ash-based geopolymer (Geo-FA). Meanwhile, calcium aluminate hydrate (Ca₂Al(OH)₇·3H₂O), not ettringite, appeared in geopolymer that was synthesized with water-washed fly ash (Geo-WFA). Leached Geo-WFA (Geo-WFA-L) did not exhibit any signs of deterioration, while there was visual cracking on the surface of leached Geo-FA (Geo-FA-L). The crack may be caused by the migration of K⁺, Na⁺, and Cl⁻ ions outside Geo-FA and the negative effect from crystallization of expansive compounds can not be excluded. Furthermore, transformation of calcium aluminate hydrate in Geo-WFA to ettringite in Geo-WFA-L allowed the reduction of the pore size of the specimen. IR spectrums suggested that Geo-WFA can supply more stable chemical encapsulation for heavy metals.Static monolithic leaching tests were conducted for geopolymers to estimate the immobilization efficiency. Heavy metal leaching was elucidated using the first-order reaction/diffusion model. Combined with the results from compressive strength and microstructure of samples, the effects of water-wash on immobilization were inferred in this study.     

Study of Bulk and Sub-Event Wet Deposition in Gebze,Turkey

This study presents the chemical composition of bulk deposition during the period of February 1996–May 1997 and the chemical composition of sub-event wet deposition on 13 August 1997 in Gebze. Samples were analyzed for SO₄ ^2-, NO₃ ^-, Cl^-,Ca²⁺, Mg²⁺, K⁺, Na⁺, and NH₄ ⁺ in addition to pH. The source of some ionic components in the bulk deposition such as K⁺ and Ca²⁺ were found to be the terrestrial regions, as expected. The (non-sea Cl^-)/Cl^- ratio of 0.05 suggests that the very large portion of Cl^- in the bulkdeposition was of marine origin. The ratio of (non-sea SO₄ ^2-)/SO₄ ^2- varied between 0.86 and 0.99,indicating that the main source of sulfate was not the sea. It is found that the sulfate and calcium concentrations were highest in summer and lowest in fall. The analysis of bulk deposition also indicated that nearly 24% of the events were acidic (pH < 5.6). During sub-event wet deposition collectedon the same site pH decreased continually, and during the passageof cold front concentrations of Cl^-, SO₄ ^2- and NO₃ ^- increased.     

Topographic Controls of Nitrogen,Sulfur, and Carbon Transport from a Tolerant Hardwood Hillslope

The lateral down-slope movement of water, NO₃ ^-, NH₄ ⁺, SO₄ ^2-, H⁺ and DOC through an ablation till was examined from 1987 to 1990 for a one hectaresoil catena on a steep hillslope with uniform forest cover at the Turkey Lakes Watershed (TLW), Ontario, Canada. Natural variation in the export of nutrients from the soil profile via soil water to Little Turkey Lake was assessed in relation to nutrient distribution in soil at different topographic positions.Subsurface throughflow exhibited dramatic differences in nutrientconcentrations and fluxes with slope position, largely reflectingthat of the soil horizons through which the water passed. GreaterNO₃ ^-, SO₄ ^2-, and DOC concentrations in subsurface water in the upper, well-drained hillslope were a reflection of enrichment by contact with more acidic, more developed podzols, and more favorable soil physical and biological conditions for NO₃ ^- retention in solution.Nutrient inputs to the lake were strongly influenced by increaseddown-slope transport of water, and increased SO₄ ^2-, N, and C retention in wetter, less-developed podzolic soils that characterize lower slope positions. An understanding of water movement and soil development variation withtopographic position was required to accurately estimate nutrient budgets for steep slopes at TLW.     

Photocatalytic Degradation of Poly(Vinyl Alcohol) on Pt/TiO<Subscript>2</Subscript> with Fenton Reagent

In this research Fenton reagent (Fe²⁺/H₂O₂) was investigated as oxidants to degrade poly (vinyl alcohol) (PVA). The role of nano-TiO₂ photocatalyst was discussed as an additive in Fenton reagent (Fe²⁺/H₂O₂). Pt/TiO₂ composites were also synthesized by photo-reaction to be used as additive in Fenton reagent. The rapid degradation of PVA was obtained when Pt/TiO₂ composites served as photocatalyst. The different photocatalytic efficiency of Pt/TiO₂- Fenton reagent (Fe²⁺/H₂O₂) was studied compared with TiO₂- Fenton reagent (Fe²⁺/H₂O₂) during the degradation of PVA.     

Acidification Trends and the Evolution of Neutralization Mechanisms through Time at the Bear Brook Watershed in Maine (BBWM), U.S.A.

The paired catchment study at the forested Bear Brook Watershed in Maine (BBWM) U.S.A. documents interactions among short- to long-term processes of acidification. In 1987–1989, runoff from the two catchments was nearly identical in quality and quantity. Ammonium sulfate has been added bi-monthly since 1989 to the West Bear catchment at 1800 eq ha^-1 a^-1; the East Bear reference catchment is responding to ambient conditions. Initially, the two catchments had nearly identical chemistry (e.g., Ca²⁺, Mg²⁺, SO₄ ^2-, and alkalinity ≈82, 32, 100, and 5 μeq L^-1, respectively). The manipulated catchment responded initially with increased export of base cations, lower pH and alkalinity, and increased dissolved Al,NO₃ ^- and SO₄ ^2-. Dissolved organic carbon and Si have remained relatively constant. After 7 yr of treatment, the chemical response of runoff switched to declining base cations, with the other analytes continuing their trends; the exports of dissolved and particulate Al, Fe, and P increased substantially as base cations declined. The reference catchment has slowly acidified under ambient conditions, caused by the base cation supply decreasing faster than the decrease of SO₄ ², as pollution abates. Export of Al, Fe and, P is mimicking that of the manipulated watershed, but is lower in magnitude and lags in time. Probable increasing SO₄ ^2- adsorption caused by acidification has moderated the longer-term trends of acidification of both watersheds. The trends of decreasing base cations were interrupted by the effects of several short-term events, including severe ice storm damage to the canopy, unusual snow pack conditions, snow melt and rain storms, and episodic input of marine aerosols. These episodic events alter alkalinity by5 to 15 μeq L^-1 and make it more difficult to determine recovery from pollution abatement.     

Formation and decomposition of tetrafluoroborate ions in the presence of aluminum

The formation and decomposition of tetrafluoroborate ions (BF₄⁻) in H₃BO₃-Al³⁺-F⁻ solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF₄⁻ increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF₄⁻ was stable under neutral and alkaline conditions. Fluoride in the form of BF₄⁻ was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF₄⁻ is proposed whereby fluoroaluminate ions formed by the reaction of BF₄⁻ with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.     

Mathematical model analysis of Fenton oxidation of landfill leachate

The treatment of concentrated landfill leachate rejected from reverse osmosis (RO) with Fenton process was studied, and the system model was developed through the examination of reaction kinetics. The leachate is typically non-biodegradable with low BOD₅/COD ratio 0.01. The oxidation reactions of Fenton process was found to be a two-stage process, where a fast initial reaction (H₂O₂/Fe²⁺) was followed by a much slower one (H₂O₂/Fe³⁺). A simple and more accurate mathematics model based on COD and TOC removals has been derived successfully to describe the two-stage reaction kinetics. The two corresponding parameters involved in this model have been identified as the initial reaction rate and the maximum oxidation removal efficiency, respectively. It was found to be very useful for evaluating the performance of Fenton system and/or for process design using the two parameters under different experimental conditions.     

Application of response surface methodology to the advanced treatment of biologically stabilized landfill leachate using Fenton’s reagent

A Fenton process that uses FeCl₂ as the alternative catalyst was employed to deal with the biologically treated landfill leachate. Data obtained revealed that this Fenton process can provide an equivalent pollutant removal as the Fenton process that uses FeSO₄ as catalyst. Central composite design (CCD) and response surface methodology (RSM) were applied to evaluate and optimize the four key factors, namely initial pH, Fe(II) dosage ([Fe²⁺]), H₂O₂/Fe(II) mole ratio ([H₂O₂]/[Fe²⁺] ratio) and reaction time, which affect the performance of the Fenton treatment. Chemical oxygen demand (COD) and color were selected as response variables. This approach provided statistically significant quadratic models, which were adequate to predict responses and to carry out optimization under the conditions studied. It was demonstrated that the interaction between initial pH and [H₂O₂]/[Fe²⁺] ratio has a significant effect on the COD removal, while the interaction between [H₂O₂]/[Fe²⁺] ratio and reaction time shows a large impact on color removal. The optimal conditions were found to be initial pH 5.9, [Fe²⁺] = 9.60 mmol/L, [H₂O₂]/[Fe²⁺] ratio = 2.38, reaction time = 5.52 h. Under this optimal scheme, the COD and color in the effluent were reduced to 159 mg/L and 25°, respectively, with an increase of BOD₅/COD ratio from 0.05 to 0.21.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Heterogeneous Sulfate Formation on Dust Surface and Its Dependence on Mineralogy: Balloon-Borne Observations from Balloon-Borne Measurements in The Surface Atmosphere of Beijing, China

This study focuses on providing a direct insight into the process by which sulfate is formed on mineral dust surface in the actual atmosphere. Six sets of aerosol measurements were conducted in the outskirts of Beijing, China, in 2002–2003 using a tethered balloon. The mineralogy of individual dust particles, as well as its influence on the S (sulfur) loadings was investigated by SEM-EDX analysis of the directly collected particles. The mixed layer in the urban atmosphere was found to be quite low (500–600m), often appearing as a particle dense stagnant layer above the surface. It is suggested that mineral dust is a common and important fraction of the coarse particles in Beijing (35–68%), and that it is relatively enriched with Calcite (>28%). An exceptional amount of S was detected in the mineral particles, which can be explained neither by their original composition, nor by coagulation processes between the submicron sulfates and the dust. Heterogeneous uptake of gaseous SO₂, and its subsequent oxidation on dust was suggested as the main pathway that has actually taken place in the ambient environment. The mineral class found with the largest number of particles containing S was Calcite, followed by Dolomite, Clay, Amphibole etc., Feldspar, and Quartz. Among them, Calcite and Dolomite showed distinctly higher efficiency in collecting sulfate than the other types. A positive correlation was found with the number of S containing particles and the relative humidity. Calcite in particular, since almost all of its particles was found to contain S above 60% r.h. On the other hand, the active uptake of SO₂ by the carbonates was not suggested in the free troposphere downwind, and all the mineral classes exhibited similar S content. Relative humidity in the free troposphere was suggested as the key factor controlling the SO₂ uptake among the mineral types. In terms of sulfate loadings, the relationship was not linear, but rather increased exponentially as a function of relative humidity. The humidity-dependent uptake capacity of mineral types altogether showed an intermediate value of 0.07 gSO₄ ²⁻ g⁻¹ mineral at 30% r.h. and 0.40 gSO₄ ²⁻ g⁻¹ mineral at 80%, which is fairly consistent with laboratory experiments.     

Ammonium removal from landfill leachate by chemical precipitation

The landfill leachate in Hong Kong usually contains quite high NH₄⁺–N concentration, which is well known to inhibit nitrification in biological treatment processes. A common pre-treatment for reducing high strength of ammonium (NH₄⁺–N) is by an air-stripping process. However, there are some operational problems such as carbonate scaling in the process of stripping. For this reason, some technical alternatives for NH₄⁺–N removal from leachate need to be studied. In this study, a bench-scale experiment was initiated to investigate the feasibility of selectively precipitating NH₄⁺–N in the leachate collected from a local landfill in Hong Kong as magnesium ammonium phosphate (MAP). In the experiment, three combinations of chemicals, MgCl₂·6H₂O+Na₂HPO₄·12H₂O, MgO+85% H₃PO₄, and Ca(H₂PO₄)₂·H₂O+MgSO₄·7H₂O, were used with the different stoichiometric ratios to generate the MAP precipitate effectively. The results indicated that NH₄⁺–N contained in the leachate could be quickly reduced from 5618 to 112 mg/l within 15 min, when MgCl₂·6H₂O and Na₂HPO₄·12H₂O were applied with a Mg²⁺:NH₄⁺:PO₄³⁻ mol ratio of 1:1:1. The pH range of the minimum MAP solubility was discovered to be between 8.5 and 9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl₂·6H₂O and Na₂HPO₄·12H₂O, which may affect microbial activity in the following biological treatment processes. The other two combinations of chemicals [MgO+85% H₃PO₄ and Ca(H₂PO₄)2·H₂O+MgSO₄·7H₂O] could minimise salinity after precipitation, but they were less efficient for NH₄⁺–N removal, compared with MgCl₂·6H₂O and Na₂HPO₄·12H₂O. COD had no significant reduction during this precipitation. It was found that the sludge of MAP generated was easily settled within 10 min to reach its solids content up to 27%. The other characteristics including capillary suction time (CST) and dry density (DD) of the MAP sludge were also tested. The experimental results indicate that the settled sludge is quite solid and can be directly dumped at a landfill site even without any further dewatering treatment.     

Influence of H2SO4 and ferric iron on Cd bioleaching from spent Ni–Cd batteries

The paper is concerned with biohydrometallurgical methods of cadmium recovery from spent Ni–Cd batteries. Cd leaching efficiency from electrode material in different media (H₂SO₄ and Fe₂(SO₄)₃ solutions), at different Fe(III) concentrations and using the bacteria Acidithiobacillus ferrooxidans were investigated. The main aim of this study was to understand which from the bioleaching products (sulphuric acid or ferric sulphate) play a main role in the bioleaching process of Cd recovery. The influence of Fe ions on Cd leachability was confirmed. The best leaching efficiency of Cd (100%) was reached by bioleaching and also by leaching in Fe₂(SO₄)₃ solution. The results of X-ray diffraction confirmed that no cadmium was present in solid residuum obtained after the Cd bioleaching as well as Cd leaching using solely ferric iron. The use of H₂SO₄ solution resulted in the lowest efficiency of Cd leachability, the presence of hydroxides in electrode materials caused neutralization of the leaching solution and inhibition of Cd leaching.     

Laboratory studies on the remediation of mercury contaminated soils

Mercury, in contrast to other toxic metals, cycles between the atmosphere, land, and water. During this cycle, it undergoes a series of complex chemical and physical transformations. Because of these transformations, it is found in the environment not only as simple inorganic and organic compounds, but also as complex compounds. As a result, it is difficult to remediate mercury contaminated materials. Laboratory studies were conducted with a mercury contaminated complex waste from an industrial site to evaluate the ability of extractants such as H₂O₂, H₂SO₄ and Na₂S₂O₃ to decontaminate the waste. Up to 87 percent of the total mercury present in the waste was extracted. Mercury was recovered as insoluble mercury sulfide by adding Na₂S solution to the combined filtrates from the H₂O₂ + H₂SO₄ and Na₂S₂O₃ treatment steps. The technique described in this article is capable of recovering mercury in a usable form and can be used as a pretreatment to remediate mercury contaminated waste before laud disposal.     

Recent Recovery of Lake Water Quality in Southern Québec Following Reductions in Sulfur Emissions

Since 1985, monitoring activities have been conducted in a networkof 43 lakes comprising the Québec portion of the Long-Range Transport of Airborne Pollutants (LRTAP) program. The results to date indicate that Québec lakes generally are responding positively to the generalized decline in precipitation sulfate (SO₄ ^2-), with 40 of the 43 lakes now showing steep declines in SO₄ ^2- concentrations. The drop in SO₄ ^2- was associated with a significant decrease in Ca²⁺ concentrations in 77% of the lakes (67% for Mg²⁺ concentrations). Overall, the acid-neutralizing capacity was increasing in 19 lakes and decreasing only in three, while 21 lakes showed no temporal trends. Compared with previous trend studies of the LRTAP-Québec network for the period of 1985–1993, the longer period (1985–1999) shows a clear improvement, with the proportion of lakes that were acidifying changing from 24 to 7% and with the proportion of lakes that were recovering changing from 16 to 35%. These observations suggest that the recent drop in SO₄ ^2- deposition in the northeastern U.S. and eastern Canada was significant enough to allow chemical recovery for a significant proportion of Québec lakes.     

Adsorption of Pb2+ and Cd2+ on the l-cysteine-functionalized graphene oxide/chitosan/polyvinyl alcohol hydrogel: Kinetic,isotherm, and thermodynamic study

In this study, polyvinyl alcohol-chitosan-cysteine-functionalized graphene oxide (PCCFG) hydrogel was synthesized from l -cysteine-functionalized graphene oxide (CFG), chitosan (CS), and polyvinyl alcohol (PVA). The hydrogel was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy and employed for removing lead ion (Pb²⁺) and cadmium ion (Cd²⁺) from aqueous solution. The effects of initial metal ion concentration, hydrogel dose, pH, time, and temperature were studied. The experimental data were well described by a pseudo-second-order kinetic model and Langmuir isotherm with maximum adsorption capacities of 250 and 192 mg g⁻¹ at 25°C for Pb²⁺ and Cd²⁺, respectively. The adsorption capacity of the PCCFG hydrogel increased with an increase in temperature. The value of ∆G° was negative, which shows the spontaneity of the reaction (electron exchange or ion exchange) between the metal ion and electron-rich atoms (–N, –S, –O). The positive ∆H° shows that the adsorption reaction consumes energy and the positive ∆S° shows the strong affinity of PCCFG toward the Pb²⁺ and Cd²⁺ ions. Pb²⁺ had better affinity and less spontaneity than Cd²⁺. The results show that the coexistence of Pb²⁺, Cd²⁺, and Cu²⁺ in the solution inhibits the adsorption capacity of PCCFG.