The modern industrial landscape is undergoing a profound transformation, driven by the principles of Green Chemistry. This paradigm shift moves beyond mere compliance, focusing on the intelligent design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances. This definitive guide explores the powerful, effective, and sustainable alternatives to traditional industrial solvents and cleaners, providing the expert knowledge needed to enhance safety, meet regulatory demands, and build a more sustainable operation.
Think-Do Chemicals Product Page
Coined by Paul Anastas and John Warner, the 12 Principles of Green Chemistry provide a framework for creating safer, more efficient, and more sustainable chemical processes. The shift to greener solvents and cleaners is directly guided by these principles, particularly:
By choosing solvents that align with these principles, industries can significantly reduce their environmental footprint and improve workplace safety.
For decades, industries relied on highly effective but hazardous solvents like Toluene, Xylene, and MEK. Today, a new generation of powerful, safer alternatives can often meet or exceed the performance of these legacy chemicals.
Derived from the peels of citrus fruits, d-Limonene is a highly effective, biodegradable solvent. It is a terpene, a naturally occurring organic compound, and an exceptional degreaser with a Kauri-butanol (KB) value comparable to many chlorinated solvents.
While flammable, Acetone is favored for its low toxicity and its exemption from many VOC (Volatile Organic Compound) regulations. It is a powerful solvent for resins and plastics, and it evaporates extremely quickly, leaving no residue.
Isopropyl Alcohol is a readily biodegradable solvent that is an excellent "middle-ground" choice. It's an effective cleaner and degreaser that is safe on most plastics and surfaces, unlike more aggressive solvents.
Choosing the best eco-friendly option requires balancing solvency power, evaporation rate, safety, and cost.
Solvent Solvency Power Evaporation Rate Primary Advantage Best For... d-Limonene High Slow Bio-based & Biodegradable Soak tank degreasing, adhesive removal where long contact time is beneficial. Acetone Very High Very Fast Low Toxicity & VOC Exempt Final wipe-down, resin/plastic cleanup, rapid surface prep. Isopropyl Alcohol (IPA) Moderate Fast Versatility & Material Safety Precision cleaning of electronics and sensitive surfaces. Ethyl Acetate High Fast Pleasant Odor & Effective Coatings, printing inks, and as a less harsh alternative to MEK.Industrial-strength vinegar, from 10% to 50% concentration, is a powerful, biodegradable cleaner and descaler. It is highly effective at removing mineral deposits (lime, calcium) from industrial equipment, cleaning concrete, and acting as an organic herbicide, replacing harsher mineral acids and synthetic herbicides.
Derived from citrus fruits, Citric Acid is an excellent, readily biodegradable cleaner. It is a powerful chelating agent, meaning it binds to and removes metal ions, making it exceptional for removing hard water stains, rust, and scale from stainless steel and other surfaces. It is a safe and effective replacement for phosphoric acid in many cleaning applications.
It is a critical misconception that eco-friendly or bio-based chemicals are completely safe to handle without precautions. All industrial chemicals require respect and proper handling.
Embracing Green Chemistry is a powerful business decision that enhances worker safety, ensures regulatory compliance, and meets the growing demand for sustainable practices. Alliance Chemical is your dedicated partner in this transition, providing a comprehensive portfolio of high-performance, eco-friendly solvents and cleaners backed by expert technical support.
Shop Eco-Friendly Solvents Consult Our Green Chemistry ExpertsThe physicochemical analysis of MSW compost is crucial for understanding its characteristics, which in turn affect metal pollution and the development of remediation plans. Table 2 provides an overview of the physicochemical properties and heavy metal levels in MSW compost. The pH was measured at 6.4, indicating a slightly acidic nature that can enhance the mobility and bioavailability of heavy metals53. Meanwhile, the EC value of 2.2 ds/m suggests low salinity levels. With a bulk density of 0.64 g/cm3 and relatively low organic content, these values indicate both organic matter and inert material/ash content on a dry weight basis. Composts with lower bulk density are preferred as they increase water retention when applied over extended periods54.
Organic material has the ability to bind with heavy metals, influencing their movement and availability. The metal levels in the original MSW compost sample show concentrations of 21.80, .51, 698.35, and .73 mg/kg (dry mass basis) for Cd, Cu, Pb, and Zn respectively. These levels surpass the environmental quality standard for compost (IS:)52, indicating unsuitability for agricultural use. This non-compliance could result in significant heavy metal contamination with adverse effects on the environment. The main reason behind elevated metal content in the initial MSW compost is the presence of Cd, Cu, Pb, and Zn commonly found in paints; electrical components; batteries; ceramics; fungicides; electroplating among others. These metals accumulate in municipal solid waste before being transferred to municipal solid waste compost through composting processes as they are inorganic and non-biodegradable42. More extensive findings for metal levels from microstructural examination are outlined in our earlier publication by Khare et al.12. The MSW compost has a particle size of ‘ < 4 mm’, leading to increased permeability, which may enhance the leaching of heavy metals and therefore potentially deteriorate the risk of groundwater contamination. The complex interplay between these conflicting interactions ultimately dictates the overall efficiency of removing heavy metals from municipal solid waste compost.
Depending on the pH of the solution, GLDA molecules undergo dissociation. The phases of dissociation correspond to specific protonation constants. In strong acidic solutions (pH = 2), GLDA exists as a fully protonated molecule (H4GLDA). As pH increases, protons progressively detach from the oxygen atoms in the carboxyl groups, following successive logK values (stability constant) and leading to deprotonation in the liquid phase at equilibrium state28 (Eqs. (2)–(5)). Conversely48, under highly basic conditions, the last dissociation occurs with the proton from the amine nitrogen atom, resulting in a fully deprotonated form of GLDA4.
$$ {\text{H}}_{{4}} {\text{GLDA }} \leftrightarrow {\text{ H}}_{{3}} {\text{GLDA}}^{ - } + {\text{ H}}^{ + } $$ (2) $$ {\text{H}}_{{3}} {\text{GLDA}}^{ - } \leftrightarrow {\text{ H}}_{{2}} {\text{GLDA}}^{{{2} - }} + {\text{ H}}^{ + } $$ (3) $$ {\text{H}}_{{2}} {\text{GLDA}}^{{{2} - }} \leftrightarrow {\text{ H}}_{{3}} {\text{GLDA}}^{{{3} - }} + {\text{ H}}^{ + } $$ (4) $$ {\text{HGLDA}}^{{{3} - }} \leftrightarrow {\text{ GLDA}}^{{{4} - }} + {\text{ H}}^{ + } $$ (5)In this study, the recommended pH was 2.9 for GLDA, indicates that the compound exists48 in the form of H3GLDA-. Consequently, GLDA undergoes protonation or deprotonation as the pH decreases or increases. Protons obstruct the metal binding sites in MSW compost, causing metals initially fixed in the bimolecular layer of MSW compost colloid to be released into the liquid phase in their ionic form55. The balance of species in a metal–ligand system depends on the concentrations of all metals and ligands, as well as the stability constants of all complexes. When another metal–ligand complex or metal ion is introduced to the solution, a new equilibrium will be established. The coordination reactions between metal ions and ligands containing multiple bonding groups are often slowed down kinetically. Several variables can impact the stability of metal complexes, including the central metal ion's nature, ligand properties, chelating effect, macrocyclic effect, resonance effect, and steric hindrance56. The stability constant represents the increased stability of these complexes; higher values indicate greater stability47. According to research findings47,55, the observed values for the stability constants are as follows: Cu (13.03) > Pb (11.60) > Zn (11.52) > Cd (10.31). Interestingly, this research discovered a different trend in removal efficiency: Cd > Zn > Cu > Pb—contradicting the previously reported sequence. Pinto et al.28 proposed that this variation could be attributed to factors such as the disintegration rate of metal complexes and metal oxides on MSW compost surfaces.
Leaching effect on GLDA concentration: Chelator concentration is a crucial element that impacts the effectiveness of metal extraction by chelators in the process of leaching remediation for contaminated MSW compost43. Consequently, the impact of chelator concentration on metal extraction was investigated by combining MSW compost with different levels of GLDA ranging from 1 to 200 mM. Table S1 presents the leaching effect of GLDA concentration on the removal efficiencies of Cd, Cu, Pb and Zn from MSW compost. The highest removal percentages for Cd, Cu, Pb, and Zn were 81.7%, 40.6%, 48.6%, and 70.4% after leaching with GLDA. These findings were also aligned with a study carried out by Wu et al.57 which documented similar results. In the presence of GLDA, the study noted approximately 82% removal of Cd at pH 4.0. Meanwhile, removal of Zn remained persist. According to Suanon et al.15, the variations in results may be explained by changes in the heavy metal concentration within the waste and underlying circumstances in the environment, including toxic metals’ chemical composition and the existence of non-target elements. Figure 6a indicates that the removal efficiencies of Cd, Cu, Pb, and Zn exhibited a sharp increase with increasing GLDA concentrations up to 140 mM. The gains were gradual after 140 mM until 160 mM. This observation is in line with previous studies showing that higher chelator concentrations enhance the solubilization of heavy metals16,47. The increased availability of chelators for complexation with metal ions can be attributed to the increase in extraction efficiency, facilitating their mobilization from the MSW compost matrix58. An elevated concentration of chelating agent leads to increased binding of metal ions that are toxic which facilitates metal ion–ligand complexes formation, thus enhancing removal efficiency. This effect is attributed to the availability of more effective binding sites due to the higher concentration of the chelating agent16,55. Recent research discovered that GLDA exhibits stronger metal-binding capabilities at lower concentrations due to its higher number of functional groups and forms stable water-soluble complexes with metal ions59. However, the concurrent dissolution of target metals and other elements such as Fe, Mg, Al and Ca may reduce the overall removal efficiency, especially when the chelating agent concentration is low60.
On the other hand, at GLDA concentrations above 160 mM, there were no significant improvements in removing these metals. Higher concentrations of GLDA did not contribute towards enhanced removal of Cd, Cu, Pb, and Zn in MSW compost. This may be the result of reaching full capacity of metal-binding sites after rinsing with increased chelator concentrations. A previous study has also observed a comparable occurrence21,30. As a result, a range from 130 to 170 mM was chosen for additional statistical refinement in determining the optimal chelator concentration for GLDA-assisted leaching of metal-contaminated MSW compost.
Leaching effect on pH: The pH of the leaching solution plays a significant role in the effectiveness of chelators during the GLDA-assisted leaching of metal contaminated MSW compost. The pH level of the solution is believed to impact the solubility of heavy metals, as well as the structure and charge of chelators, and their interaction with metal ions28. As a result, contaminated MSW compost underwent treatment with GLDA solutions at different pH levels (ranging from 2 to 10) in order to study how the solution's pH affected the removal of Cd, Cu, Pb, and Zn with GLDA-assisted leaching. Table S2 provides leaching effect of pH on the removal efficiencies of Cd, Cu, Pb and Zn from MSW compost. The highest removal efficiencies were achieved at very low pH of 2, with 87.1%, 53.2%, 47.7%, and 58.6% for Cd, Cu, Pb, and Zn, respectively. Whereas at pH 4, the removal efficiencies were 73.3%, 29.2%, 32.5%, and 39.5% for Cd, Cu, Pb, and Zn, respectively (Fig. 6b). This observation is consistent with the fact that reduced pH levels promote metal dissolution and subsequent binding with chelating agents61. The acidic conditions facilitated the dissolution of metals bound to the MSW compost, causing them to readily dissolve in the lower pH environment50. The affinity of metals for a ligand plays a crucial role in forming metal–ligand complexes, where R–(COOH)m is an organic reagent (leaching solution) and Mn+ represents a metallic ion. The molecular structure of GLDA, with its four carboxyl groups (Fig. S1), explains this observation. According to Zaleckas et al.62, a greater capacity for metal extraction is exhibited by a molecule with more carboxyl groups compared to one with fewer carboxyl groups. Consequently, the removal efficiencies for toxic metals were higher at lower pH conditions. A decrease in the removal of Cd, Cu, Pb, and Zn was noted for GLDA as the pH of the solution increased from 3 to 10. The lowest efficiency in extracting metals was observed at pH 7. This pattern could be explained by increased competition from protons (H+) at lower pH levels and the formation of metal-hydroxide precipitates at higher pH levels, leading to a decrease in metal oxide solubility47. Complexation between heavy metals and chelators can be disrupted by these factors. The overall binding strength of the chelating agent may decrease as the pH increases. Consequently, the ideal pH for removing heavy metals seems to differ based on the particular chelator utilized45. Additionally, the leaching treatment at low pH can impact the fertility characteristics of MSW compost50. Therefore, it is advisable to allow saturated MSW compost after leaching to undergo open drying for 48 h in order to promote sufficient air circulation. This aeration process creates turbulence, leading to the release of aqueous CO2 (carbon dioxide), which reduces acidity and raises the pH level63,64. Furthermore, natural additives such as agricultural lime, crushed eggshells, bone meal, and calcium hydroxide can be utilized or bioaugmentation or cultivation could also be employed to slightly increase the pH level and enhance attributes of treated MSW compost. Moreover, a range of 2.5–3.5 for pH levels is further fine-tuned using statistical optimization through a RSM model.
Leaching effect on retention time: Retention time plays a crucial role in the chelator-assisted removal of heavy metals from contaminated MSW compost. It directly affects the duration of interaction between the MSW compost and the chelator solution43. To understand its impact, the extraction of Cd, Cu, Pb, and Zn using GLDA was studied at different retention times (0, 10, 20, 30,40, 50, 60, 90, 120, 240, 360, 480 min) while maintaining constant pH. Table S3 shows leaching effect of retention time on the removal efficiencies of Cd, Cu, Pb and Zn from MSW compost. In this study, the removal efficiencies of Cd, Cu, Pb, and Zn showed a significant increase within the first 60 min of leaching, with values of 67.6%, 45.1%, 51.7%, and 64.1% respectively (p < 0.05). Subsequently, the removal efficiencies continued to rise at a slower rate, reaching equilibrium at around 120 min with removal efficiencies of 83.0%, 81.3%, 86.0%, and 79.5% for Cd, Cu, Pb, and Zn, respectively (Fig. 6c). A prominent linear relation (p < 0.05) was established between removal efficiencies and retention time. As the leaching process extended beyond 120 min, the removal efficiencies remained relatively constant, even up to a retention time of 480 min. The findings indicate that the leaching of Cd, Cu, Pb, and Zn from MSW compost using GLDA involves a two-phase kinetic process. The first phase, which occurs swiftly within the initial 60 min, is succeeded by a steady extraction process over the resulting hours.
This pattern aligns with previous research examining the soil washing time65. The phenomenon can be attributed to the movement of metals that are weakly attached can easily form complexes with GLDA and are rapidly released, leading to a sharp increase in metal removal efficiencies31. As the contact period increases, GLDA forms complexes with stable metal species, progressively improving the metal removal efficiency at a slower rate. Therefore, for achieving optimal conditions a range from 120 to 180 min of retention time was selected for statistical analysis.
In this research, the kinetic parameters were also evaluated using the pseudo-first and second order rate equations (Equations S1 and S2, respectively). The fitting of these two kinetic models to the equilibrium data of toxic metals is presented in Fig. S3. The pseudo-second-order kinetic model provides the best fit for describing the leaching kinetics of toxic metals in MSW compost. This model exhibited higher values of the linear regression coefficient (R2 > 0.99, in all cases) compared to the pseudo-first-order model. These findings suggest that when biodegradable chelator is used for remediation of Cd, Pb, and Zn polluted soil, the chemisorption-controlled mechanism is involved during desorption process65, which entails valence forces resulting from electron transfer between the functional groups in the washing solutions and the heavy metal ions. This observation confirms that metal ions can bond with the functional groups in the washing solutions. The results of this study align with those of previous research, such as the works of31, where the pseudo-second-order model was utilized to remediate soil contaminated with Cd, Pb, and Zn.
Want more information on Environmentally Friendly Chelating Chemical Solutions? Feel free to contact us.
Furthermore, the higher k2 value, indicating stronger mobility, was found for Pb > Cd > Cu > Zn in MSW compost, influencing the metal removal efficiency. These findings align with a previous investigation consistent with study conducted by Kulikowska et al.53, which displays a higher removal of Cd compared to Pb due to the presence of humic compounds. The presence of humic compound in MSW compost can both enhance and hinder metal chelation66,67. It enhances chelation through complexation and the production of organic ligands as it contains diverse functional groups such as carboxyl, hydroxyl, and phenolic groups that can form stable metal-complexes and increases metal solubility. Additionally, organic matter can produce natural chelating agents like fulvic and humic acids which bind strongly with metal ions, preventing their precipitation and facilitating their transport within the compost68. However, it hinders chelation by strong sorption to stable organic fractions of organic matter, particularly in humus-rich regions of the compost, formation of insoluble complexes, and competitive binding sites due to high level of organic matter content, reducing metal availability for biological uptake68,69. The results were also aligned with previous research investigating the process of kinetic equilibrium31. According to Tang et al.70, the extraction process taking retention time into account, can be elucidated through two mechanisms: a gradual phase involving external diffusion, robust dissolution, and thorough scrubbing, resulting in peak extraction efficiency. Equilibrium concentration was reached within 120 min of extraction for all metals. The observation is aligned to the fact that k2 values are primarily influenced within the initial minutes of the leaching process, as noted by Kulikowska et al.53. Hence, to achieve equilibrium conditions retention time may have greater importance than k2 value.
When managing MSW compost contaminated with heavy metals using GLDA-assisted leaching, the chelation process encompasses multiple stages such as protonation/deprotonation equilibria, interactions between metal ions and ligands, and reactions occurring at the interface of solid and liquid phases. The specific mechanism derived from these findings is provided below:
The initial stage of utilizing MSW compost to eliminate heavy metals begins with the liberation of unbound H + ions from GLDA, a polydentate chelating agent. This facilitates the breakdown of alkaline oxides and enhances the solubilization of metals. The equilibrium reactions28,47 for different forms of GLDA are illustrated in Eqs. (2)–(5). Upon decreasing or increasing the pH, the GLDA could be either protonated or deprotonated46. The existence of protons disturbs the binding sites of heavy metals in MSW compost, leading to the release of heavy metals that were originally trapped in the biolayer of compost colloids into the liquid phase in an ionic state55.
Moreover, a comprehensive understanding of GLDA's capacity for heavy metal removal involves considering the interaction between metal ions and complexation. The interaction of GLDA (L-) and heavy metal ions (M2+) leads to the formation of reversible metal–ligand complexes at a 1:1 ratio47,57. These interactions are described by reactions Eqs. (6)–(9):
$$ {\text{M}}^{{{2} + }} + {\text{ H}}_{{3}} \left( {\text{L}} \right)^{ - } \leftrightarrow \, \left[ {{\text{MH}}_{{3}} \left( {\text{L}} \right)} \right]^{ + } $$ (6) $$ {\text{M}}^{{{2} + }} + {\text{ H}}_{{2}} \left( {\text{L}} \right)^{{{2} - }} \leftrightarrow \, \left[ {{\text{MH}}_{{2}} \left( {\text{L}} \right)} \right] $$ (7) $$ {\text{M}}^{{{2} + }} + {\text{ H}}\left( {\text{L}} \right)^{{{3} - }} \leftrightarrow \, \left[ {{\text{MH}}\left( {\text{L}} \right)} \right]^{ - } $$ (8) $$ {\text{M}}^{{{2} + }} + \, \left( {\text{L}} \right)^{{{4} - }} \leftrightarrow \, \left[ {{\text{M}}\left( {\text{L}} \right)} \right]^{{{2} - }} $$ (9)Due to the formation of metal–ligand complexes (M–L), the stability constant (log K) of the complex is defined to represent its thermodynamic stability, with higher log K values indicating greater stability. However, in our study, we noted the log K values (in ascending sequence) for Cu, Pb, Zn, and Cd as 13.03, 11.60, 11.52, and 10.31 correspondingly47,55. Whereas we found a different pattern of removal efficiency: Cd > Zn > Cu > Pb. This contradicts the previously suggested sequence. According to Pinto et al.28 the differences in variation might result from factors like the breakdown rate of metal complexes and metal oxides on the surface of MSW compost.
The GLDA-assisted leaching can be categorized into two stages, depending on the target heavy metals (Mim+) and other constituents found in the MSW compost matrix. The initial stage involves the interplay between the metal and GLDA (Ln−, n = 0, 1, 2, 3, 4) present in the solution at the interface of solid–liquid phases. The interaction between GLDA and heavy metals involved incorporating metal ions into the heterocyclic structures of GLDA, replacing monodentate ligands with multidentate ligands to form M–L complexes Ferraro et al.55. The substitution processes show that the GLDA replaces other components (e.g., OH− ions) in the MSW compost (Compost) matrix to form metal-GLDA complexes. Formation of these complexes aids in extracting metals from solid matrix into liquid phase. This includes reactions Eqs. (10)–(12) such as:
$$ \left( {{\text{Compost }}{-}{\text{ O}}} \right) \, {-}{\text{ M}}_{{\text{i}}}^{{{\text{m}} + }} + {\text{ L}}^{{{\text{n}} - }} + {\text{ H}}_{{2}} {\text{O }} \leftrightarrow \, \left( {{\text{Compost}}} \right) \, {-}{\text{ OH }} + {\text{ M}}_{{\text{i}}} {-}{\text{ L}}^{{{\text{m}} + \left( {{\text{n}} - {1}} \right) - }} + {\text{ OH}}^{ - } $$ (10) $$ \left( {{\text{OH}}} \right)_{{\text{m}}} {\text{M}}_{{\text{i}}} + {\text{ L}}^{{{\text{n}} - }} \leftrightarrow {\text{ M}}_{{\text{i}}} {-}{\text{ L}}^{{{\text{m}} + {\text{n}} - }} + {\text{ mOH}}^{ - } $$ (11) $$ {\text{M}}_{{\text{i}}} {\text{O }}\left( {{\text{M}}_{{\text{i}}} {\text{O}}} \right)^{{{\text{m}} + {2} - }} + {\text{ L}}^{{{\text{n}} - }} + {\text{ H}}_{{2}} {\text{O }} \leftrightarrow {\text{ M}}_{{\text{i}}} {-}{\text{ L}}^{{{\text{m}} + {\text{n}} - }} + {\text{ 2OH}}^{ - } $$ (12)In the second stage, two primary processes occur: surface complexation (Eq. 13) or ion-exchange of metals with other cationic species (Mjmj+) in solution like K+ and Ca2+ ions (Eqs. 14, 15); and the second process suggests that some metals may not form complexes or undergo adsorption but remain in a free state in the liquid phase (Eq. 16).
$$ \left( {\text{Compost}} \right) \, {-}{\text{OH}} +{\text{M}}_{\text{i}}^{\text{m}+} {-}{\text{L}}^{{\text{n}} - }\leftrightarrow \, \left( {\text{Compost}} \right) \,{-}{\text{L}}^{{\left( {{\text{n}} - {1}} \right) - }} {-}{\text{M}}_{\text{j}}^{\text{m}+} +{\text{OH}}^{-} $$ (13) $$ \left( {\text{Compost }} \right) \, {-}{\text{ L}}^{{{\text{n}} - }} {-}{\text{ M}}_{{\text{i}}}^{{{\text{mi}} + }} + \, \left( {{\text{Compost}}} \right) \, {-}{\text{ O }}{-}{\text{ M}}_{{\text{j}}}^{{{\text{mj}} + }} + {\text{ H}}^{ + } \leftrightarrow \, \left( {{\text{Compost}}} \right) \, {-}{\text{ L}}^{{{\text{n}} - }} {-}{\text{ M}}_{{\text{j}}}^{{{\text{mi}} + }} + \, \left( {{\text{Compost}}} \right) \, {-}{\text{ OH}}^{ + } + {\text{ M}}_{{\text{i}}}^{{{\text{mj}} + }} $$ (14) $$ \left( {{\text{Compost}}} \right) \, {-}{\text{ L}}^{{{\text{n}} - }} {-}{\text{ M}}_{{\text{j}}}^{{{\text{mi}} + }} + {\text{ OH}}^{ + } \leftrightarrow \, \left( {{\text{Compost}}} \right) \, {-}{\text{ OH}}^{ + } + {\text{ M}}_{{\text{j}}}^{{}} {-}{\text{ L}}^{{{\text{m}} + \left( {{\text{n}} - {1}} \right) - }} $$ (15) $$ \left( {{\text{Compost}}} \right) \, {-}{\text{ OH }} + {\text{ M}}_{{\text{i}}}^{{{\text{m}} + }} \leftrightarrow \, \{ \left( {{\text{Compost}}} \right) \, {-}{\text{ O}}]{\text{ M}}_{{\text{i}}}^{{{\text{m}} + {1} - }} + {\text{ H}}^{ + } $$ (16)Based on these mechanisms, it is implied that several processes are involved in the elimination of heavy metals through GLDA-assisted leaching:
Solubilization Effect: Metal oxides can solubilize, releasing metals into the solution.
Stable Metal-GLDA Complexes: formation of stable M–L complexes by sorption with compost organic matter function groups and linked to form organic matter/metal hydroxides
Ion exchange: Heavy metals undergo surface binfding, with K+ by electrostatic outer–sphere complexation and exchange with Ca2+ by inner-sphere complexation and co-precipitation
Surface complexation: Heavy metals engage in surface binding with available complexing sites on GLDA.
Overall, these processes help in effectively eliminating heavy metals from MSW compost, suggesting that GLDA-assisted leaching could be a powerful technique for addressing contaminated MSW compost. It is also important to note that, to manage chelated leachates with heavy metals and prevent secondary pollution after biodegradation, leachates are treated using methods like chemical precipitation, ion exchange, adsorption, or membrane filtration. Additionally, biological treatments such as bioremediation with microorganisms or phytoremediation with plants can be employed. Of course, regular monitoring of treated leachates ensures that metal concentrations meet environmental safety standards and that no harmful byproducts are present. Table S4 outlines effective techniques for converting chelated metal-complex solutions into useful resources, offering valuable support for both environmental decontamination and addressing scarcity of resources.
The process conditions for GLDA-assisted leaching of heavy metals from MSW compost were optimized using a three-level, three-factor Box-Behnken design (BBD) in RSM. BBD experimental range and level of independent variables are provided in Table 3. The design of experiment proposed by BBD and the results are presented in Table S5. A polynomial model was utilized to analyze the data displayed in Table S6, which relates to the efficiency of metal removal. The impact of each factor on the model's response was investigated using analysis of variance. The experimental data was analyzed through multiple regression to fit the results of the BBD to a modified quadratic polynomial equation. The final models in terms of coded factors for the leaching rates of Cd, Cu, Pb, and Zn are provided in Eqs. (17)–(20), respectively. These equations represent k1, k2, k3 as GLDA concentration, pH, retention time; while interaction factors are represented by k1k2, k1k3, and k2k3 are the interaction factors.
$${R}_{Cd}=87.22+2.21{k}_{1}-1.59{k}_{2}-0.30{k}_{3}+0.52{k}_{1}{k}_{2}-0.89{k}_{1}{k}_{3}-0.40{k}_{2}{k}_{3}-0.65{k}_{1}^{2}-0.14{k}_{2}^{2}+0.25{k}_{3}^{2}$$ (17) $${R}_{Cu}=36.50+1.58{k}_{1}-1.95{k}_{2}-17.97{k}_{3}+1.58{k}_{1}{k}_{2}-0.33{k}_{1}{k}_{3}-2.92{k}_{2}{k}_{3}+1.80{k}_{1}^{2}+2.29{k}_{2}^{2}+17.13{k}_{3}^{2}$$ (18) $${R}_{Pb}=42.53+1.65{k}_{1}-1.30{k}_{2}-18.02{k}_{3}+2.41{k}_{1}{k}_{2}+0.12{k}_{1}{k}_{3}-1.55{k}_{2}{k}_{3}+0.95{k}_{1}^{2}-1.18{k}_{2}^{2}+18.04{k}_{3}^{2}$$ (19) $${R}_{Cd}=56.67+4.61{k}_{1}-0.75{k}_{2}-10.23{k}_{3}+1.61{k}_{1}{k}_{2}+3.22{k}_{1}{k}_{3}+0.88{k}_{2}{k}_{3}-1.14{k}_{1}^{2}+0.27{k}_{2}^{2}+10.18{k}_{3}^{2}$$ (20)According to Table S6, models with F-values of 24.56, 128.08, 389.8, and 41.78 (p < 0.05) demonstrate significant statistical relevance. Moreover, the conformity between projected and experimental values for MSW compost is apparent from the high R2 and R2 adj. values close to 1.0, indicating substantial explanatory power in the models. The experiments were also highly reliable and precise with a coefficient of variation of p < 0.05 for all metals71. The study additionally evaluated the model's precision (adequate precision) using signal-to-noise ratio31. The precision values of 18.09, 28.61, 51.29, and 19.45 indicate that all four models were satisfactory. The linear effects of GLDA concentration, pH, and retention time exhibited statistical significance based on results obtained from significance tests.
The experimental data illustrated in Fig. S4 demonstrate adherence to a normal distribution, indicating that the data maintained their regularity without any alteration of responses. The effectiveness of the constructed models was confirmed through ANOVA and diagnostic plots, with statistical significance (p < 0.05) and non-symmetrical scattering in residual versus projected value plots (Fig. S5 b, d, f, h). Additionally, it was found that quadratic models effectively controlled heavy metal removal based on similar distributions of projected removal efficiencies for Cd, Cu, Pb, and Zn from both models and observed experimental data along the 45° line (Fig. S5 a, c, e, g). These results indicate that the BBD model accurately optimizes toxic metal removal.
RSM was employed to analyze the interaction effects of two independent factors on the leaching of Cd, Cu, Pb, and Zn. Contour plots were generated based on the fitted model equations to illustrate these effects. Figure 6 presents contour plots depicting the impact of variables on the leaching percentage of Cd (Fig. 7a, b, c), Cu (Fig. 7d, e, f), Pb (Fig. 7 g, h, i, and Zn (Fig. 7j, k, l). The contour lines directly indicate the degree of interaction between two factors; a circle signifies that there is no significant interaction whereas an ellipse indicates a significant interaction65. Moreover, Tindanzor et al.72 highlighted that the center of an elliptical representation represents optimum conditions. In terms of single variable impact, GLDA concentration, pH, and retention time exhibited distinct influences on leaching rates of target metals.
As GLDA concentration climbed from 130 to 150 mM, the removal efficiencies of Cd, Cu, Pb, and Zn in MSW compost increased continuously. However, at lower pH conditions the impact was more significant. This observation aligns with the results reported in previous research50,57. The metal removal efficiency gradually decreased to 120 min of retention time, then exhibited an upward trend in response to greater concentrations of GLDA. The highest metal removal efficiencies were obtained on using a concentration of 170 mM GLDA and a retention time of 120 min, with the exception of Zn, which required a concentration of 150 mM GLDA and the same retention time. An increase in the heating agent's concentration and retention time duration may facilitate the disruption of the metals' chemical bonds in MSW compost, leading to more effective metal removal60. The elimination of Cd, Cu, Pb, and Zn was also affected by the relation between pH and retention time, as shown by the curved surface variation. The removal efficiencies of heavy metals would improve at lower pH and shorter retention time, indicating that an increase in hydrogen ions (H+) causes a significant release of metals in MSW compost via ion exchange, which increases protonation of the surface colloids31. The results of the three-factor design method agreed with this finding.
The optimization of parameters using RSM indicates that GLDA-assisted leaching of MSW compost is observed at GLDA concentration of 150 mM, pH value of 2.9, and a retention time of 120 min. At these optimal conditions, the anticipated removal efficiencies for Cd-90.32%, Cu-81.96%, Pb-91.62%, and Zn-80.34%. The validation test results show values of 90.07% for Cd, 80.44% for Cu, 92.28% for Pb, and 81.95% for Zn at 95% confidence and prediction intervals. So, the models are well fitted and highly significant. Thus, the findings suggest that BBD is a valuable method for enhancing the toxic metal removal efficiency.
A comparison experiment was performed to assess Cd, Cu, Pb, and Zn removal effectiveness using GLDA and conventional chelating agent EDTA under optimal operational conditions (150 mM GLDA concentration, 2.9 pH, and 120 min retention time). GLDA-assisted leaching obtained the removal efficiency of Cd as 90.07%, Cu as 80.44%, Pb as 92.28%, Zn as 81.95%. The findings indicated that EDTA demonstrated excellent extraction efficiency for Cd (94.08%), Cu (82.36%), Pb (93.16%) and Zn (85.74%) in comparison to GLDA, as outlined in Table 2. This superior performance of EDTA is because of the presence of carboxylic acid groups in high concentration and also results in more stable metal complexes, as discussed by Begum et al.46. However, it is worth noting that GLDA also demonstrated substantial removal of Cd, Cu, Pb, and Zn, although not as efficient as EDTA. Despite the effective extraction capabilities of EDTA, its use poses environmental risks due to its non-biodegradability and potential adverse effects on ecosystems, such as promoting eutrophication, as mentioned in prior research32. As highlighted in a study21, GLDA is biodegradable and non-toxic to the ecosphere. Therefore, GLDA is a practical and eco-friendly chelating agent for addressing severe metal contamination in MSW compost. By employing GLDA technology, not only environmental impact of heavy metal pollution is minimized but it also promotes the reuse and recycling of resources, contributing towards the circular economy. The quality and classification of the GLDA-treated MSW compost can be determined using the criteria outlined by Saha et al.54, which includes marketable classes (A, B, C, D) or restricted use classes. This classification will define the specific purpose and application of the compost accordingly. Regarding the potential reuse of GLDA-treated MSW, a thorough research by Saha et al.54 proposes a scheme for categorizing composts into different marketable classes (A, B, C, and D) and restricted use classes (RU-1, RU-2, and RU-3) based on their fertilizing potential and potential for contaminating the soil and food chain, which is beneficial for relevant stakeholders (Table S7).
The geochemical distribution of metals in various fractions within MSW compost is essential for comprehending the affinity between metal pollutants, their mobility, bioavailability, and detailed information regarding pollutant toxicity. Therefore, a sequential extraction was carried out on pre- and post-treated MSW compost to examine the geochemical distribution of Cd, Cu, Pb, and Zn across different phases as discussed in Section "Sequential Extraction Experiment". Table S8 presents the average concentrations of metal fractions in the MSW compost sample with varying distributions for each metal fraction. From Fig. 8, certain general trends were observed.
The distribution of Cd, Cu, and Pb indicates the highest proportions of 33.84%, 70.87%, and 45.41%, while Zn has the second-highest proportion at 27.14% in the exchangeable fraction (F2) in the original sample. Metals in this fraction are held on the solid surface by weak electrostatic forces and could be released through ion-exchange processes. Factors such as changes in pH or ionic composition may affect remobilization from this fraction53. However, Zn showed a higher fraction in F6 (40.51%), suggesting that it is closely integrated with the crystalline lattice of MSW compost matrix, making it less easily extractable even with chemical treatment enhancements73. Table S8 indicates that a significant percentage of Cd (51.91%), Cu (87.30%), and Pb (66.86%) is weakly associated with F1, F2, and F3 fractions at levels exceeding 50% of the total. This finding supports previous research suggesting that these metals can be effectively removed using chelating agents21,46. The instability and susceptibility to environmental conditions of fractions F1, F2, and F3 make them prone to leaching into the environment. Several studies have highlighted that these fractions may accumulate in plants and pose risks to the food chain21,32.
Contact us to discuss your requirements of pasp na. Our experienced sales team can help you identify the options that best suit your needs.