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.

Highly efficient capture of mercury from complex water matrices by AlZn alloy reduction-amalgamation and in situ layered double hydroxide.

Mercury pollution is a critical, worldwide problem and the efficient, cost-effective removal of mercury from complex, contaminated water matrices in a wide pH range from strongly acidic to alkaline has been a challenge. Here, AlZn and AlFe alloys are investigated and a new process of synergistic reduction-amalgamation and in situ layered double hydroxide (SRA-iLDH) for highly efficient capture of aqueous Hg(II) is developed using AlZn alloys. The parameters include the pH values of 1-12, the Hg(II) concentrations of 10-1000 mg L-1, and the alloy's Zn concentrations of 20%, 50% and 70% and Fe concentrations of 10%, 20% and 50%. The initial rate of Hg(II) uptake by AlZn alloys decreases with increasing Zn concentration while the overall rate is not affected. Specifically, AlZn50 alloy removes >99.5% Hg(II) from 10 mg L-1 solutions at pH 1-12 in 5 min at a rate constant of 0.055 g mg-1 min-1 and achieves a capacity of 5000 mg g-1, being the highest value reported so far. The super-performance of AlZn alloy is attributed to multiple functions of chemical reduction, dual amalgamation, in situ LDH's surface complexation and adsorption, isomorphous substitution and intercalation. This study provides a simple and highly efficient approach for removing Hg(II) from complex water matrices.

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.

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.

Physicochemical Characteristics of Biochar from Waste Cricket Chitin (Acheta domesticus).

The properties of biochar (BC) from crustacean chitin are relatively well understood, while there are few studies on BC from insect chitin. This study presents the characterization and phytotoxic assessment of BC produced from crickets and cricket chitin. Cricket powder (BCCR) and cricket chitin (BCCH) were pyrolyzed at 500 °C and 700 °C. Physicochemical characteristics, N ad-/desorption, FTIR, were examined. SEM images were also performed. Regardless of the pyrolysis temperature, biochars were characterized by a densely "packed" solid surface/monolithic type with a non-porous structure (0.05-0.22 m2/g) and high content of N (9.4-11.8%). BCCHs showed a higher pH (12.2-12.4) compared to BCCR (8.7-10.8). Based on the XRD analysis, BCs were characterized by an amorphous carbon turbostratic structure and a randomly oriented graphitic-like micro-crystallite structure. FTIR spectra of BCs confirmed the presence of various O2 and N-functional groups on the BC surface. BCCHs added to soil at rates from 0.5 to 1.5% significantly reduced the germination of Lepidium sativum. Stimulation of root elongation was also observed in the case of BCCR500 1.0% and BCCR700 1.5%. Thermal degradation of cricket powder and cricket chitin promotes the formation of organic N-containing heterocyclic rings, which lead to the production of N-doped carbons with potential uses in energy storage and the contaminations sorption.

Digestion of plastics using in vitro human gastrointestinal tract and their potential to adsorb emerging organic pollutants.

Excessive plastic use has inevitably led to its consumption by organisms, including humans. It is estimated that humans consume 20 kg of plastic during their lifetime. The presence of microplastics in the human body can carry serious health risks, such as biological reactions e.g. inflammation, genotoxicity, oxidative stress, apoptosis, as well toxic compounds leaching of unbound chemicals/monomers, free radicals or adsorbed organic pollutants, which mainly depend on the properties of the ingested plastic. Plastics are exposed to different substances (e.g., enzymes and acids) in the digestive system, which potentially affects their properties and structure. By stimulating the human digestive system and applying a set of advanced analytical tools, we showed that the surface of polystyrene and high-density polyethylene plastics frequently in contact with food undergoes fundamental changes during digestion. This results in the appearance of additional functional groups, and consequent increase in the plastic adsorption capacity for hydrophobic ionic compounds (such as triclosan and diclofenac) while reducing its adsorption capacity for hydrophobic non-ionic compounds (such as phenanthrene). Micro- and nanostructures that formed on the flat surface of the plastics after digestion were identified using scanning electron microscopy. These structures became defragmented and detached due to mechanical action, increasing micro- and nanoplastics in the environment. Due to their size, the release of plastic nanostructures after digestion can become an "accidental food source" for a wider group of aquatic organisms and ultimately for humans as the last link in the food chain. This, combined with improved adsorption capacity of digested plastics to hydrophobic ionic pollutants, can pose a serious threat to the environment including human health and safety.

The co-occurrence of Zn-and Cu-based engineered nanoparticles in soils: The metal extractability vs. toxicity to Folsomia candida.

The presence of engineered nanoparticles (ENPs) in soil gradually increases, among others due to the nano-agrochemicals application. So far, the co-existence of different ENPs in soil is poorly examined. Here, the metal extractability and toxicity of soils spiked (300 mg kg-1) singly and jointly with Zn- and Cu-based ENPs or metal salts were tested. The samples were aged for 1 and 90 days. The predicting available metal component of ENPs concentrations were determined by different methods including soil pore water collection and batch extractions with H2O, CaCl2 or DTPA. Survival and reproduction of Folsomia candida were also evaluated. The combined effect of ENPs on the extractability of metals was mainly found with DTPA characterized by the highest leaching capacity among the used extractants. In fresh soil, the mixtures of ENPs differentiated only DTPA-extractable Cu level, while aging resulted in changes in both Zn and Cu concentrations leached by CaCl2 or DTPA. However, the character of the combined effect was an ENPs- and soil type-dependent, whereas the mixtures of metal salts mostly provided higher Zn and Cu recovery than the individual compounds. The pattern of co-toxicity of metal-oxide ENPs was also time-dependent: the antagonistic and synergistic effect was observed in the samples after 1 and 90 days, respectively. However, the toxicity was weakly related with extractable concentrations in both single and joint treatment of metal compounds. The distinct joint effect patterns of ENPs imply the need for more in-depth investigation of mechanisms of activity of ENPs mixtures in soil.

Sustainable biochar-based soil fertilizers and amendments as a new trend in biochar research.

Today's world is struggling with many environmental problems. Due to the ever-growing size of the population, it is necessary to produce more and more food. The consequence of such a large demand for food is excessive fertilization of soils, often in an uncontrolled manner. The paper presents an overview of the different types of biochar (BC) fertilizers obtained by: coating BCs with a protective layer, coating commercial fertilizers with a layer of BCs, or mixing BCs with commercial fertilizers. Although the use of these new types of fertilizers has a positive effect on soil properties and crop yields, the production and use of "simple" inorganic fertilizers are dominant. The solution to starting the change of this trend may be the use of BC-compost systems as an effective soil amendment, due to the fact that composts are still the most frequently used products by farmers. The review summarized two types of BC-compost soil amendments: BC mixed with ready-made compost and BC co-composted with compost raw material. These types of soil amendments contribute to a significant reduction in the consumption of commercial inorganic fertilizers, and thus less pollution of the natural environment, while allowing for a high yield of safe food.

Adsorption and desorption of antiviral drugs (ritonavir and lopinavir) on sewage sludges as a potential environmental risk.

The aim of this work was to evaluate the adsorption capacity and mechanism of two antiviral drugs AVDs (lopinavir (LOP) and ritonavir (RIT)) on three various sewage sludges (SSLs). The results showed that SSLs differed in the structure and chemical composition and LOP and RIT had a high affinity to the studied SSLs (Kd in ranges 2076-3449 L/kg). The adsorption capacities differed between SSLs and ranged 7.55-8.71 mg/g (RIT) and 8.10-8.64 mg/g (LOP). The Freundlich model provided a best fitting of adsorption isotherms of all AVDs-SSLs. The adsorption kinetics were best described by pseudo-second order kinetic model. The adsorption of LOP and RIT on SSLs was exothermic, spontaneous, and thermodynamically feasible. The sorption of LOP and RIT to SSLs was complex due to the diverse chemical composition of SSLs and the differences in the chemical structure of AVDs. Analysis of binary solution of both AVDs showed the competition effect between AVDs and a decrease in adsorption efficiency (3-17%) compared to single solutions. The amount of desorbed AVDs from all SSLs was low (less than 15%). The findings of the present work are significant in the prediction of fate and persistence of AVDs on SSLs in the context of their further transmission and possible environmental contamination.

Vapour-phase method in the synthesis of polymer-ibuprofen sodium-silica gel composites.

The study discusses the synthesis of polymer-silica composites comprising water soluble drug (ibuprofen sodium, IBS). The polymers selected for this study were poly(TRIM) and poly(HEMA-co-TRIM) produced in the form of permanently porous beads via the suspension-emulsion polymerization method. The acid and base set ternary composites were prepared by the saturation of the solid dispersions of drug (poly(TRIM)-IBS and/or poly(HEMA-co-TRIM)-IBS) with TEOS, and followed by their exposition to the vapour mixture of water and ammonia, or water and hydrochloric acid, at autogenous pressure. The conducted analyses reveal that the internal structure and total porosity of the resulting composites strongly depend on the catalyst which was used for silica precursor gelation. The parameters characterizing the porosity of both of the acid set composites are much lower than the parameters of the base set composites. Moreover, the basic catalyst supplied in the vapour phase does not affect the ibuprofen sodium molecules, whereas the acid one causes transformation of the ibuprofen sodium into the sodium chloride and a derivative of propanoic acid, which is poorly water soluble. The release profiles of ibuprofen sodium from composites demonstrate that there are differences in the rate and efficiency of drug desorption from them. They are mainly affected by the chemical character of the polymeric carrier but are also associated with the restricted swelling of the composites in the buffer solution after precipitation of silica gel.

Encapsulation of diclofenac sodium within polymer beads by silica species via vapour-phase synthesis.

The present study concerns the preparation of ternary composites via the in situ encapsulation of solid dispersion of diclofenac sodium within the acrylic polymer beads. The encapsulating species were produced through the hydrolysis and condensation of the silica precursors (tetraethoxysilane or ethyltriethoxysilane) introduced into the solid dispersion. The transformation of precursors occurred in the vapor phase of ammonia. A great advantage of the presented vapor-phase method is preventing the desorption of the highly soluble drug during gelation of silica precursors, which stands in contrast to the conventional sol-gel processes occurring in the solution. The conducted studies, involving the low temperature N2 sorption together with spectroscopic techniques, provide insight into the structural differences of drug loaded particles. They reveal that the formation of silica gel accompanies the conversion of the drug into its amorphous form. Finally, the desorption profiles of diclofenac sodium demonstrate that the deposition of silica gel successfully diminishes the degree of the initial drug desorption while significantly modifying its release rate.