# Microplastic mineralization rate in Fenton reactions depends on polymer type

## TL;DR

Fenton reactions can break down microplastics, but the speed depends on plastic type and hydrogen peroxide concentration, with polyester being most susceptible and polystyrene least.

## Contribution

The study reveals that polymer structure and radical dynamics significantly influence Fenton-based microplastic mineralization rates.

## Key findings

- PES showed the highest mineralization rate, followed by PP, while PS and LDPE had the lowest.
- High H2O2 concentrations increased CO2 release for PES and PP but not for PS and LDPE.
- Structural factors, like aromaticity in PS, may explain slower mineralization compared to aliphatic polymers like PP.

## Abstract

Despite microplastics (MPs) being highly inert pollutants, Fenton‐type reactions—using hydrogen peroxide (H2O2) and iron(II) ions (Fe2+)—may effectively initiate chain cleavage and induce mineralization. However, mineralization rates and mechanisms for different MP types at varying Fenton reagent concentrations remain unclear. This study examined the mineralization of four MPs— low‐density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), and polyester (PES)—by measuring CO2 release across varying H2O2 concentrations. Mineralization rates depended on both polymer type and H2O2 concentration. PES showed the highest degree of mineralization, followed by PP, while LDPE and PS exhibited the lowest rates. Increased H2O2 concentrations enhanced CO2 release and accelerated reaction saturation, especially for PES and PP, suggesting efficient mineralization due to elevated hydroxyl radical (OH˙) production. In contrast, PS and LDPE showed no significant increase in mineralization above certain H2O2 levels. Despite visible Fe‐oxide precipitates, scanning electron microscopy did not provide evidence of surface changes associated with mineralization. Contrary to expectations, aromatic PS was less susceptible to Fenton mineralization than aliphatic PP, possibly due to structural factors. The study also emphasizes the importance of radical recombination and scavenging at high OH˙ concentrations, which can lower mineralization efficiency. Non‐integer reaction orders suggest a multi‐step mineralization process influenced by both polymer structure and radical dynamics. These findings underscore the high environmental persistence of MPs, as natural mineralization, such as by fungi utilizing Fenton‐like mechanisms, occurs at even slower rates than those observed under controlled lab conditions.

Fenton reactions can mineralize microplastics, but efficiency strongly depends on plastic type and hydrogen peroxide concentration.Polyester (PES) is most susceptible, followed by polypropylene (PP), while polystyrene (PS) and low‐density polyethylene (LDPE) show high resistance.The structure of plastics significantly influences their mineralization, and unexpectedly, polystyrene (aromatic) mineralizes more slowly than polypropylene (aliphatic).Excess reactive radicals reduce efficiency through recombination and scavenging, limiting overall mineralization.Environmental persistence remains high, since natural processes like fungal Fenton reactions are slower than lab‐based mineralization.

Fenton reactions can mineralize microplastics, but efficiency strongly depends on plastic type and hydrogen peroxide concentration.

Polyester (PES) is most susceptible, followed by polypropylene (PP), while polystyrene (PS) and low‐density polyethylene (LDPE) show high resistance.

The structure of plastics significantly influences their mineralization, and unexpectedly, polystyrene (aromatic) mineralizes more slowly than polypropylene (aliphatic).

Excess reactive radicals reduce efficiency through recombination and scavenging, limiting overall mineralization.

Environmental persistence remains high, since natural processes like fungal Fenton reactions are slower than lab‐based mineralization.

Microplastics are very resistant to natural breakdown, but chemical reactions using hydrogen peroxide and iron (Fenton reactions) can help mineralize them. We tested four common plastics—polyester (PES), polypropylene (PP), polystyrene (PS), and low‐density polyethylene (LDPE)—at different hydrogen peroxide levels, measuring breakdown by carbon dioxide release. PES mineralized the fastest, followed by PP, while PS and LDPE showed little change beyond certain conditions. Higher hydrogen peroxide sped up reactions for PES and PP, but too many reactive molecules sometimes reduced efficiency. Surprisingly, PS was less reactive than PP, likely due to structural differences. Although iron deposits formed, microscope images did not show clear surface damage. Overall, results highlight that microplastics are highly persistent, and natural processes like fungal degradation would be even slower than what we observed in the lab.