Soil pollution with heavy metals is a serious threat to the environment. However, soils polluted with heavy metals are considered good sources of native metal-resistant Trichoderma strains. Trichoderma spp. are free-living fungi commonly isolated from different ecosystems, establishing endophytic associations with plants. They have important ecological and biotechnological roles due to their production of a wide range of secondary metabolites, thus regulating plant growth and development or inducing resistance to plant pathogens. In this work we used indigenous Trichoderma strains that were previously isolated from different soil types to determine their tolerance to increased copper and nickel concentrations as well as mechanisms of metal removal. The concentrations of bioavailable metal concentrations were determined after extraction with diethylene-triamine pentaacetate (DTPA)-extractable metals (Cd, Cr, Co, Cu, Pb, Mn, Ni, and Zn) from the soil samples by inductively coupled plasma-optical emission spectrometry (ICP-OES). Two indigenous T. harzianum strains were selected for copper tolerance, and three indigenous T. longibrachiatum strains were selected for nickel tolerance tests. Strains were isolated from the soils with the highest and among the lowest DTPA-extractable metal concentrations to determine whether the adaptation to different concentrations of metals affects the mechanisms of remediation. Mechanisms of metal removal were determined using Fourier-transform infrared spectroscopy (FTIR) and X-ray fluorescence spectroscopy (XRF), non-destructive methods characterized by high measurement speed with little or no need for sample preparation and very low costs. Increased DTPA-extractable metal content for nickel and copper was detected in the soil samples above the target value (TV), and for nickel above the soil remediation intervention values (SRIVs), for total metal concentrations which were previously determined. The SRIV is a threshold of metal concentrations indicating a serious soil contamination, thus confirming the need for soil remediation. The use of FTIR and XRF methods revealed that the presence of both biosorption and accumulation of metals in the Trichoderma cells, providing good bioremediation potential for Ni and Cu.

Microplastics (MPs), chlorinated phenols (CPs), polycyclic aromatic hydrocarbons (PAHs) and halogenated benzenes (HBs) are pollutants that are widely present in freshwater systems. As alternatives to conventional plastics, bioplastics are receiving a lot of attention, but there are limited data on their impact on pollutant behavior. This work therefore investigated the impact of pH on the sorption of CPs, PAHs and HBs, as some of the toxic and highly persistent pollutants, on seven different plastics using kinetic and isotherm studies. The pH of the water matrix impacted the adsorption behavior of CPs on all selected MPs, with the highest degree of adsorption occurring at pH 7 for the majority of the selected CPs. The highest adsorption affinity of CPs on the MPs, at pH 7, was obtained for 4-chlorophenol and 2,4-dichlorophenol on powdered polyethylene standard (q_t = 221 μg/g), while the lowest was obtained for the adsorption of pentachlorophenol on polyethylene terephthalate (q_t = 25 μg/g). On the other hand, the pH value of the water matrix did not affect the adsorption of halogenated benzenes and PAHs on MPs. The pseudo-second-order rate model fit the adsorption kinetics data of all experiments. The results obtained for the adsorption of CPs on MPs indicated a lower sorption affinity of CPs with MPs at pH 4 and pH 10 compared to pH 7. The Langmuir isotherm, at pH 7, implied that 4-chlorophenol’s adsorption affinity was not significantly influenced by the type of MPs. On the other hand, at pH 7, the adsorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol varied greatly, with powdered MP types showing the highest affinity for CP adsorption. Furthermore, the obtained adsorption isotherm results imply that electrostatic attraction, hydrogen bonds, π-π interactions and van der Waals interactions, are an integral part of adsorption mechanisms of the CPs on the MPs.