Microorganisms and their metabolites affect the content of polycyclic aromatic hydrocarbons and their derivatives in pyrolyzed material.

Toxic polycyclic aromatic hydrocarbons (PAHs) and more toxic N- and O-containing derivatives can be determined in biochar. However, their fate in the environment and bioavailability depends on many parameters and was not studied yet. In the presented studies a set of biochars obtained from various feedstock at the same pyrolysis temperature (600 °C) subjected to environmental pressure e.g. soil microorganisms and enzymes was described. Presented study aimed to determine the effect of biological agents on the physicochemical characteristic and the content of PAHs and their derivatives in biochars after long-term treatment (6 months). The results indicated that enzymatic aging usually lowered (up to 94 %) the content of PAHs and their derivatives in biochar. Simultaneously, biological aging reduced the bioavailability of tested compounds. Considering the total fraction of PAHs and their derivatives, biochars treated with nutrients and microbial inoculum were characterized by the lowest content of analytes (even in comparison to biochars treated with nutrients alone). To complement the obtained results, the content of C, H, N, O, and ash as well as specific surface area, aromaticity, polarity, and hydrophilicity in biochar before and after modifications were determined. In general, enzymatic aging increased, and biological aging decreased the content of C% and H% in biochar. Both aging processes lowered the H/C ratio which indicated the decrease of the aromatization degree for artificially altered biochar.

Radially aligned hierarchical N-doped porous carbon beads derived from oil-sand asphaltene for long-life water filtration and wastewater treatment.

The application of waste-derived highly efficient adsorbent for organic pollutants removal from water and wastewater is presented. Highly porous carbon beads with radially aligned macrochannels were prepared from asphaltene. Well-ordered inwardly aligned macrovoids favored solute diffusion and maximized the liquid accommodation capacity. A further N-doping could modulate the sorbent hydrophilicity leading to an outstanding absorption performance for a range of organic solvents and oily chemicals. N-doped carbon beads were effective sorbents of lopinavir (LNV) and ritonavir (RNV) from water and wastewater. The process of sorption was fast, and the highest removal was noted for RNV than LPV. N-doping favored LNV and RNV adsorption due to the increased porous structure of N-doped asphaltene beads. The chemisorption of both LPV and RTV was a rate-limiting step. The presence of co-pollutants in treated wastewater enhanced LPV and RNV removal and an up to 470 % increase was noted. The presence of LPV or RTV in distilled water was not toxic to Aliivibrio fischeri or even can stimulate their growth. However, after the adsorption process, the solution of RTV reduced its toxicity significantly and the final solution was not toxic. The opposite effect was noted for LPV. Given the repeatability, high removal performance, and cost-effectiveness of the asphaltene-based carbon microtubes when compared to other well-known sorbents such as carbon nanotubes, they demonstrated great potential as a low-cost and effective agent for long-life water filtration and wastewater treatment.

Validated QuEChERS-based UHPLC-ESI-MS/MS method for the postharvest control of patulin (mycotoxin) contamination in red-pigmented fruits.

The paper outlines a procedure based on ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry and QuEChERS pretreatment for the determination of patulin in selected berries and stone fruits. The mycotoxin was determined in the positive electrospray ionization mode utilizing the formation of its methanol adduct. The method was validated for 4 fruit matrices: strawberry (Rosaceae, Fragaria), raspberry (Rosaceae, Rubus), redcurrant (Rosaceae, Prunus) and sour cherry (Grossulariaceae, Ribes). The fruits were characterized by total phenolics, flavonoids, and anthocyanin contents and obtained results were within the ranges of 2.65-11.22 mg GAE/g, 1.06-4.67 mg CE/g, 0.05-1.44 mg cyd-3-glu/g, respectively. The limits of quantification ranged from 0.65 µg/kg to 3.01 µg/kg depending on the fruit type. The method was applied to 71 fruit samples collected in Poland. Analysis of moldy fruit samples has shown a high incidence of patulin contamination.

Determination of fluoride content in teas and herbal products popular in Poland.

Purpose: Fluoride level, due to its narrow therapeutical range, must be constantly monitored in beverages, especially in daily-consumed plant infusions. Fluoride is important for prevention of tooth decay and osteoporosis, but its excess leads to fluorosis. Since tea can selectively absorb fluorides from soils, the question arises if a long-term consumption can pose an adverse effect on human health. Methods: Infusions of 33 popular teas (black, green, white, earl grey, pu-erh), tea-like products (rooibos, yerba mate) and herbs (chamomile, mint, nettle, purges, yarrow) available in the Polish market were analyzed with respect to a fluoride level by means of a validated ion-selective electrode method, which is proven to be fast and reliable. Results: Significantly different fluoride concentrations in infusions were observed, with black tea on top, where extraction of fluoride is the highest (average 2.65 mg F-/L, range 0.718-6.029 mg/L). Two-fold higher fluoride contents were measured in infusions made from black tea bags than from leaves (average 3.398 mg/L and 1.529 mg/L, respectively). Green teas released comparable amounts of fluoride as black teas, while in herbal extracts the fluoride content was negligible. Conclusions: The rank with respect to the fluoride concentration in an infusion is as follows: black tea > green tea > earl grey > pu-erh > white tea>>>rooibos, yerba mate, herbal products. Increasing of brewing time results in an increased fluoride content, but the overall content of fluoride in the analyzed infusions of teas and herbs was not high enough to cause a risk of fluorosis, even if left to brew up to 15 min.

Long-term physical and chemical aging of biochar affected the amount and bioavailability of PAHs and their derivatives.

Biochar applied into the soil is recommended as an effective tool for increasing its properties and crop productivity. However, biochar can contain some potentially toxic compounds such as polycyclic aromatic hydrocarbons (PAHs). Moreover, during biochar production or environmental application (e.g. as soil fertilizer), more toxic PAHs derivatives containing nitrogen, oxygen or sulfur can be formed. There is a lack of information on how the environmental factors affect the bioavailability of such compounds during the long-term application of BC into the soil. In the presented studies the effects of physical (freeze-thaw cycles) and chemical aging (temperatures 60 °C and 90 °C) on the total and bioavailable content of PAHs and their derivatives were estimated. The results indicate that long-term (6 months) aging affected the physicochemical characteristic of biochars promoting the formation of new C and O-containing species on the BC surface increasing their polarity and hydrophilicity. Physical and chemical aging promoted the formation of compounds with higher molecular weight and a significant (up to 550 %) increase in the bioavailability of PAHs and their derivatives. The results of this study highlight the importance of the bioavailable fraction of PAHs and their derivatives for evaluation of the toxicity of aged biochar.

Low bioavailability of derivatives of polycyclic aromatic hydrocarbons in biochar obtained from different feedstock.

In the last years, there is great progress in the field of studies on the thermal transformation of wastes into valuable materials such as biochar. High-temperature processes, however, are connected with the formation of polycyclic aromatic hydrocarbons (PAHs) with confirmed toxicity. However, during pyrolysis, some derivatives containing oxygen, nitrogen, or sulfur can also be formed. Their toxicity is expected to be higher than parent PAHs. However, the key parameter in the agricultural application of carbonaceous materials is PAHs' bioavailability. The aim of the presented studies was the determination of the effect of various feedstock (wheat straw (Triticum L.), willow (Salix viminalis), sunflower, residues from softwood and hardwood, sewage sludges, and residues from biogas production) on the formation of PAHs and their derivatives (O-, N-PAHs) in biochar and their bioavailability. The results indicated that the content of total and bioavailable PAHs in obtained biochar was rather low. The concentration of total PAHs in plant-derived biochar reached 57 ± 3 ng g-1 - 181 ± 8 ng g-1, whereas sewage sludge-derived biochar contained from 121 ± 6 ng g-1 to 188 ± 9 ng g-1 of PAHs. The highest concentration of PAHs was noted in biochar obtained from residues from biochar production - up to 202 ± 9 ng g-1. The total concentration of bioavailable PAHs was lower and reached 2-4.45 ng L-1 for plant-derived biochar, 3-40 ng L-1 for sewage sludge-derived biochar. The highest content of bioavailable PAHs was noted in biochar obtained from residues from biogas production: 9-42 ng L-1 indicating that increased attention should be paid to using this type of biochar. Among PAHs derivatives, nitronaphthalene, 1-methyl-5-nitronaphthalene, 1-methyl-6-nitronaphthalene, 9,10-anthracenedione, 4H-cyclopenta(def)phenanthrene, nitropyrene were determined at various levels and their concentrations were from below the limit of detection (LOD) to 28 ng L-1 for plant-derived biochar, 3-16 ng L-1 for biochar obtained from residues from biogas production, and 5-45 ng L-1 for sewage sludge-derived biochar. The content of bioavailable PAHs derivatives was, generally, one order of magnitude lower than parent PAHs derivatives, and reached from below LOD up to almost 1 ng L-1 for plant-derived biochar, from 0.5 to 2 ng L-1 for biochar obtained from residues from biogas production, and from 0.2 to almost 5 ng L-1 for sewage sludge-derived biochar confirming the safety of agricultural usage of biochar.

Revealing the toxicity of lopinavir- and ritonavir-containing water and wastewater treated by photo-induced processes to Danio rerio and Allivibrio fischeri.

In coronavirus disease 2019 (COVID-19), among many protocols, lopinavir and ritonavir in individual or combined forms with other drugs have been used, causing an increase in the concentration of antiviral drugs in the wastewater and hospital effluents. In conventional wastewater treatment plants, the removal efficiency of various antiviral drugs is estimated to be low (<20%). The high values of predicted no-effect concentration (PNEC) for lopinavir and ritonavir (in ng∙L-1) reveal their high chronic toxicity to aquatic organisms. This indicates that lopinavir and ritonavir are current priority antiviral drugs that need to be thoroughly monitored and effectively removed from any water and wastewater samples. In this study, we attempt to explore the impacts of two photo-induced processes (photolysis and photocatalysis) on the toxicity of treated water and wastewater samples containing lopinavir and ritonavir to zebrafish (Danio rerio) and marine bacteria (Allivibrio fischeri). The obtained results reveal that traces of lopinavir in water under photo-induced processes may cause severe problems for Danio rerio, including pericardial edema and shortening of the tail, affecting its behavior, and for Allivibrio fischeri as a result of the oxygen-depleted environment, inflammation, and oxidative stress. Hence, lopinavir must be removed from water and wastewater before being in contact with light. In contrast, the photo-induced processes of ritonavir-containing water and wastewater reduce the toxicity significantly. This shows that even if the physicochemical parameters of water and wastewater are within the standard requirements/limits, the presence of traces of antiviral drugs and their intermediates can affect the survival and behavior of Danio rerio and Allivibrio fischeri. Therefore, the photo-induced processes and additional treatment of water and wastewater containing ritonavir can minimize its toxic effect.

The antioxidant defense responses of Hordeum vulgare L. to polycyclic aromatic hydrocarbons and their derivatives in biochar-amended soil.

The recent studies indicated that the biochar (BC) may be a source of polycyclic aromatic hydrocarbons (PAHs) as well as their oxygen, nitrogen, or sulfur-containing derivatives that are considered as more toxic pollutants than their parent compounds. Here, the assessment of the impact of various biochars addition (1% wt.) to soil on barley Hordeum vulgare L. growth was presented. The concentrations of bioavailable PAHs and their derivatives in biochar were determined. PAHs increased reactive oxygen species generation resulting in oxidative stress in organisms. In this study, the response of soil-grown plants was examined in terms of the activity of the antioxidative enzymes (superoxide dismutase, catalase, peroxidase), lipid peroxidation, and the expression of genes related to oxidative stress. The results indicate that despite low content of a bioavailable fraction of parent compounds and their derivatives (up to 4.45 ± 0.24 ng gbiochar-1 and 0.83 ± 0.03 ng L-1, respectively) the biochemical response of plant was present, the activity of superoxide dismutase increased up to 2 times, but the activity of the other enzymes was lowered. The transcript level values support the studies on enzymatic activity. The presence of PAHs and their derivatives induced oxidative stress slightly but the plant was able to mitigate it.

Occurrence and toxicity of polycyclic aromatic hydrocarbons derivatives in environmental matrices.

In the last years, there is great attention paid to the determination of polycyclic aromatic hydrocarbons (PAHs) in different environmental matrices. Extensive reviews on PAHs presence and toxicity were published recently. However, PAHs formation and transformation in the environment lead to the production of PAHs derivatives containing oxygen (O-PAHs), nitrogen (N-PAHs and aazarenes AZA) or sulfur (PASHs) in the aromatic ring. The development of new analytical methods enabled the determination of these novel contaminants. The presence of oxygen, nitrogen, or sulfur in PAHs aromatic rings increased their toxicity. The most common primary sources of PAHs derivatives are biological processes such as microbial activity (in soil, water, and wastewater treatment plants (O-PAHs)) and all processes involving combustion of fuel, coal, and biomass (O-PAHs, N-PAHs, AZA, PASHs). The secondary resources involved i) photochemical (UV light), ii) radical-mediated (OH, NO3), and iii) reactions with oxidants (O3, NOx) (O-PAHs, N-PAHs, AZA). Furthermore, N-PAHs were able to transform to their corresponding O-PAHs, while other derivatives were not. It indicated that N-PAHs are more vulnerable to photooxidation in the environment. 85% of O- and N-PAHs were detected with particle matter below 2.5 µm suggesting their easier bioaccessibility. More than 90% of compounds with four and more aromatic cycles were present in the particle phase in the air. Although the concentrations of N-PAHs or O-PAHs may be similar to PAHs concentration or even 1000 times lower than parent PAHs, PAHs derivatives accounted for a significant portion of the total mutagenicity. The present review is describing the results of the studies on the determination of PAHs derivatives in different environmental matrices including airborne particles, sediments, soil, and organisms. The mechanisms of their formation and toxicity were assessed.