Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.
The term "Total petroleum hydrocarbons" (TPH) is used to describe a complex mixture of petroleum-based hydrocarbons primarily derived from crude oil. Those compounds are considered as persistent organic pollutants in the terrestrial environment. A wide array of organic amendments is increasingly used for the remediation of TPH-contaminated soils. Organic amendments not only supply a source of carbon and nutrients but also add exogenous beneficial microorganisms to enhance the TPH degradation rate, thereby improving the soil health. Two fundamental approaches can be contemplated within the context of remediation of TPH-contaminated soils using organic amendments: (i) enhanced TPH sorption to the exogenous organic matter (immobilization) as it reduces the bioavailability of the contaminants, and (ii) increasing the solubility of the contaminants by supplying desorbing agents (mobilization) for enhancing the subsequent biodegradation. Net immobilization and mobilization of TPH have both been observed following the application of organic amendments to contaminated soils. This review examines the mechanisms for the enhanced remediation of TPH-contaminated soils by organic amendments and discusses the influencing factors in relation to sequestration, bioavailability, and subsequent biodegradation of TPH in soils. The uncertainty of mechanisms for various organic amendments in TPH remediation processes remains a critical area of future research.
The harmful effects of microplastics (MPs) pollution in the soil ecosystem have drawn global attention in recent years. This paper critically reviews the effects of MPs on soil microbial diversity and functions in relation to nutrients and carbon cycling. Reports suggested that both plastisphere (MP-microbe consortium) and MP-contaminated soils had distinct and lower microbial diversity than that of non-contaminated soils. Alteration in soil physicochemical properties and microbial interactions within the plastisphere facilitated the enrichment of plastic-degrading microorganisms, including those involved in carbon (C) and nutrient cycling. MPs conferred a significant increase in the relative abundance of soil nitrogen (N)-fixing and phosphorus (P)-solubilizing bacteria, while decreased the abundance of soil nitrifiers and ammonia oxidisers. Depending on soil types, MPs increased bioavailable N and P contents and nitrous oxide emission in some instances. Furthermore, MPs regulated soil microbial functional activities owing to the combined toxicity of organic and inorganic contaminants derived from MPs and contaminants frequently encountered in the soil environment. However, a thorough understanding of the interactions among soil microorganisms, MPs and other contaminants still needs to develop. Since currently available reports are mostly based on short-term laboratory experiments, field investigations are needed to assess the long-term impact of MPs (at environmentally relevant concentration) on soil microorganisms and their functions under different soil types and agro-climatic conditions.