Apart from the conventional polyethylene and the bio-based or mainly bio-based biodegradable in soil mulching films, polyethylene mulching films of controlled degradation in soil are already used in agriculture. The use of special pro-oxidants as additives is expected to accelerate the abiotic oxidation and the subsequent chain scission of the polymer under specific UV radiation or thermal degradation conditions, according to the literature. The role of pro-oxidants in the possible biodegradation of polyethylene has been theoretically supported through the use of controlled laboratory conditions. However, results obtained in real soil conditions, but also several laboratory test results, are not supporting these claims and the issue remains disputed. Mulching films made of linear low-density polyethylene (LLDPE) with pro-oxidants, after being used for one cultivation period in an experimental field with watermelon cultivation, were buried in the soil under real field conditions. This work presents the analysis of the degradation of the mulching films during the cultivation period as compared to the corresponding changes after a long soil burial period of 8.5 years. The combined effects of critical factors on the photochemical degradation of the degradable mulching LLDPE films with pro-oxidants under the cultivation conditions and their subsequent further degradation behaviour in the soil are analysed by testing their mechanical properties and through spectroscopic and thermal analysis.
Bio-based, biodegradable in soil, as well as degradable polyethylene mulching films with pro-oxidants, have been introduced in the market in an effort to deal with the serious problem of managing plastic waste streams generated from conventional mulching films. In a previous experimental investigation, a series of naturally degraded under water melon cultivation conditions linear low density polyethylene (LLDPE) mulching films with pro-oxidants, buried in the field for 8.5 years, were recovered intact even though undergoing a continuous slow abiotic degradation in soil. The aim of the present article was to simulate the behavior of the LLDPE mulching films with pro-oxidants under a much longer time-scale (e.g. some decades). Toward this purpose, samples of LLDPE with pro-oxidants film were artificially degraded to simulate severe degradation/fragmentation of these films while been buried in the soil for many years, following the end of the cultivation season. Further degradation of these severely degraded samples was investigated by burying them in the soil over a period of seven years. During this burial period, all degradation parameters and their evolution with time were measured. The artificially degraded LLDPE film samples with pro-oxidants, in contrast to the naturally degraded film that remained intact for 8.5 years, were gradually transformed into tiny micro-fragments in the soil. These fragments, through a continuing abiotic degradation process under natural soil conditions are eventually transformed into invisible micro-fragments. The fate of these micro-fragments and their long-term impact to the environment and human health is unpredictable.
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