Effect of chemical aging on phosphate adsorption and ecotoxicological properties of magnesium-modified biochar.

Using magnesium-biochar composites (Mg-BC) in adsorption allows for the efficient and economically relevant removal of phosphate (PO43-) from water and wastewater. Applying Mg-BC for pollutant removal requires evaluating the adsorption capacity of composites and their ecotoxicological properties. Investigating the composite aging during the application of these composites into the soil is also essential. In the present study, nonaged and aged (at 60 or 90 °C) Mg-BC composites were investigated in the context of pyrolysis temperature (500 or 700 °C). All analyzed biochars were examined by Fourier transform infrared spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and surface area. The content of polycyclic aromatic hydrocarbons (PAHs) (bioavailable Cfree and organic solvent-extractable Ctot), heavy metals (HMs), and environmentally persistent free radicals (EPFRs) were determined. Ecotoxicity was evaluated using tests with Folsomia candida and Allivibrio fischeri. The dependence of adsorption on pyrolysis temperature and composite aging time was observed. Changes in physicochemical properties occurring as a result of aging reduced the adsorption of PO43- on Mg-BC composites. It was found that nonaged Mg-BC700 was more effective (9.55 mg g -1) in the adsorption of PO43- than Mg-BC500 (5.75 mg g-1). The adsorption capacities of aged composites were from 21 to 61% lower than those of the nonaged composites. Due to aging, the content of Cfree PAHs increased by 3-5 times depending on the pyrolysis temperature. However, aging reduced the Ctot PAHs in all composites from 24 to 35% depending on the pyrolysis temperature. Ecotoxicological evaluation of Mg-BC composites showed increased toxicity after aging to both organisms. The use of aged BC potentially increases the contaminant content and toxicity of Mg-BC composites.

Effect of zinc-biochar composite aging on its physicochemical and ecotoxicological properties.

The stability of Zn-biochar composites is determined by environmental factors, including the aging processes. This paper focused on the ecotoxicological evaluation of Zn-biochar (Zn-BC) composites subjected to chemical aging. Pristine biochars and composites produced at 500 or 700 °C were incubated at 60 and 90 °C for six months. All biochars were characterized in terms of their physicochemical (elemental composition, Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and porous structure), ecotoxicological properties (tested with Folsomia candida and Aliivibrio fischeri) and contaminant content (polycyclic aromatic hydrocarbons (PAH), heavy metals (HM) and environmentally persistent free radicals (EPFR)). An increase in the number of surface oxygen functional groups and increased hydrophilicity and polarity of all Zn-BC composites were observed due to oxidation during aging. It was also found that Zn-BC aging at 90 °C resulted in a 28-30% decrease in solvent-extractable PAHs (Æ©16 Ctot PAHs) compared to nonaged composites. The aging process at both temperatures also caused a 104 fold reduction in EPFRs in Zn-BC composites produced at 500 °C. The changes in the physicochemical properties of Zn-BC composites after chemical aging at 90 °C (such as pH and HM content) caused an increase in the toxicity of the composites to Folsomia candida (reproduction inhibition from 19 to 24%) and Aliivibrio fischeri (luminescence inhibition from 96 to 99%). The aging of composites for a long time may increase the adverse environmental impact of BC-Zn composites due to changes in physicochemical properties (itself and its interactions with pollutants) and the release of Zn from the composite.

Ecotoxicological characterization of engineered biochars produced from different feedstock and temperatures.

Biochar (BC) engineering, which has recently gained a lot of interest, allows designing the functional materials. BC modification improves the properties of pristine biochar, especially in terms of adsorption parameters. An interesting type of modification is the introduction of metals into the BC's structure. There is a knowledge gap regarding the effects of modified BC (e.g., BC-Mg, BC-Zn) on organisms. The aim of this study was the ecotoxicological evaluation of BC-Mg and BC-Zn composites, received under diverse conditions from willow or sewage sludge at 500 or 700 °C. The ecotoxicological tests with bacteria Vibrio fischeri (V. fischeri) and invertebrates Folsomia candida (F. candida) were applied to determine the toxicity of BC. The content of toxic substances (e.g., polycyclic aromatic hydrocarbons (PAHs), heavy metals (HMs), environmentally persistent free radicals (EPFRs)) in BC were also determined and compared with ecotoxicological parameters. The ecotoxicity of studied BCs depends on many variables: feedstock type, pyrolysis temperature and the modification type. The Zn and Mg modification reduced (from 28 to 63 %) the total Æ©16 PAHs content in willow-derived BCs while in SL-derived BCs the total Æ©16 PAHs content was even 1.5-3 times higher compared to pristine BCs. The Zn modified willow-derived BCs affected positively on F. candida reproduction but showed inhibition of luminescence V. fischeri. BC-Mg exhibited harmful effect to F. candida. The ecotoxicological assessment carried out sheds light on the potential toxicity of BC-Zn and BC-Mg composites, which are widely used in the removal of heavy metals, pharmaceuticals, dyes from waters and soils.

Ecotoxicological characteristics and properties of zinc-modified biochar produced by different methods.

Despite the dynamic progress of BC engineering, there is a lack of knowledge on the toxicity and environmental impact of modified BC. The aim of this study was the ecotoxicological evaluation of BC modified with zinc (Zn) using different methods: impregnation of feedstock with Zn before pyrolysis (PR), impregnation with Zn after pyrolysis (PS) and impregnation with Zn after pyrolysis with an additional calcination step (PST). The ecotoxicological assessment was based on tests with invertebrates (Folsomia candida, Daphnia magna) and bacteria (Aliivibrio fischeri). The post-treated and calcined composites had a higher content of total (Ctot) PAHs (144-276 µg kg-1) than pre-treated BC-Zn (68-157 µg kg-1). All BC-Zn treatments stimulated the reproduction of F. candida at the lowest BC dose (0.5%) by 4-24%. Increasing the biochar dose to 1% and 3% retained the stimulating effect of the pre-modified biochars (from 19 to 41%). Pre-modified BC-Zn reduced the luminescence of A. fischeri from 40% to 80%. Post-treated BCs reduced bacterial luminescence by 99%, but the calcination step limited the toxic effects to the level observed for the control. Post-treated BCs had a toxic effect on D. magna, with EC50 values ranging from 433 to 783 mg L-1. The ecotoxicity of composites depends on modification methods, BC dose and pyrolysis temperature. The application of limiting conditions for HM leaching (i.e., pre-modification, calcination) increased the safety of using Zn-biochar composites.

From waste to fertilizer: Nutrient recovery from wastewater by pristine and engineered biochars.

Biochar application for the recovery of nutrients from wastewater is a sustainable method based on a circular economy. Wastewater, food wastewater, and stormwater are valuable sources of nutrients (i.e., PO43-, NO3-, and NH4+). The unique properties of biochar, such as its large specific surface area, pH buffering capacity, and ion-exchange ability, make it a cost-effective and environmentally friendly adsorbent. Biochar engineering improves biochar properties and provide targeted adsorbents. The biochar-based fertilizers can be a sustainable alternative to traditional fertilization. The aim of the study was to compare the potential of pristine and engineered biochars to recover nutrients from wastewater and to determine the factors which may affect this process. Engineered biochar can be used as a selective adsorbent from multicomponent solutions. Adsorption on engineered biochar can be also regulated by additional mechanisms: surface precipitation and ligand/ion exchange. Metal modification (e.g. Mg, Fe) enhances PO43- and NO3- adsorption capacity, and thus may provide the extra plant macro-/micronutrients. The desorption mechanism, which is the basis for nutrient release are strongly pH depended. The use of biochar-based fertilizer can have economic and agricultural benefits when using waste materials and reducing pyrolysis energy costs.