Hypermethylation of СpG islands in the promoter regions of several genes with basic protective function in blood leukocytes of individuals exposed to ionizing radiation long time ago (2–46 years), and differential effects of age and radiation exposure on hypermethylation was reported in our previous work. To validate these results, epigenetic modifications were assessed in an independent series of 49 nuclear industry workers from the “Mayak” facility (67–84 years old at sampling) with documented individual accumulated doses from the prolonged external γ-radiation exposure (95.9–409.5 cGy, end of work with radiation:0.3–39 years ago), and in 50 non-exposed persons matched by age. In addition to the genes analyzed before (RASSF1A, p16/INK4A, p14/ARF, GSTP1), four additional loci were analyzed: TP53, ATM, SOD3, ESR1. The frequency of individuals displaying promoter methylation of at least one of the 8 genes (71.4%) was significantly higher in exposed group as compared to the control group (40%), p = .002, OR = 3.75. A significantly elevated frequency of individuals with hypermethylated СpG islands in GSTP1, TP53, SOD3 promoters was revealed among exposed subjects as compared to the control group (p = .012, OR = 8.41; p = .041, OR = 4.02 and p = .009, OR = 3.42, respectively). A similar trend (p = .12, OR = 3.06) was observed for the p16/INK4A gene. As a whole, p16/INK4A and GSTP1 promoter hypermethylation in irradiated subjects from both previously and currently analyzed groups was pronounced. Thus, the direction of the effects was fully confirmed, suggesting the result reproducibility. No statistically significant correlation between promoter methylation and individual radiation dose was found. Further studies are required to create an array of blood epigenetic markers of radiation exposure associating with premature aging and age-related diseases and to accurately evaluate radiation-added effect across the range of doses.The results of studies of epigenetic changes in two independent samples of irradiated subjects indicated the significance of radiation factor in the induction of hypermethylation of CpG islands in gene promoters that is revealed in blood cells years and decades after exposure.

Ionizing γ-irradiation and solvent-assisted spiking are frequently applied to eliminate microbial activity and to induce hydrophobic organic compounds (HOCs) into soil, respectively, when studying the accumulation of chemicals in terrestrial organisms. However, the side-effects that may arise from these treatments on soil-HOC interaction and, subsequently, the kinetics and extents of bioaccumulation are not thoroughly understood. To this end, the accumulation of 1,1-dichloro-2,2-bis(p-chlorophenyl)etylene (p,p’-DDE) by Eisenia andrei was studied in sterilized or unsterilized and freshly spiked (FS) or historically contaminated (HC) soils in parallel with an analysis of aliphatic and hydrophilic soil organic matter (SOM) moieties using mid-infrared diffuse reflectance spectroscopy (DRIFT-S). Irradiation did not impart significant changes on spectral SOM descriptors. In contrast, earthworm inhabitation increased the relative presence of aliphatic moieties to a greater extent than hydrophilic ones, reaching or exceeding pre-treatment levels. Overall, effects on SOM chemistry can be ranked as earthworms > spiking > irradiation. Corresponding changes at the bioaccumulation level were observed for the FS soil (i.e., a 27% reduction in bioaccumulation upon sterilization) but not for the HC soil. This implies that in contrast to the interactions between aged p,p’-DDE and sterilized HC soil, the interactions established between freshly added p,p’-DDE and sterilized FS soil were altered by γ-irradiation-induced secondary effects alone or in combination with earthworm inhabitation. Thus, although the soil treatment processes studied here should not drastically impact compound bioaccumulation, they should be considered in mechanistic studies where the qualitative and quantitative aspects of compound-soil (organic matter)-earthworm interactions are at the centre of attention.

The generation of HONO and NO₂ by the photolysis of nitrates in the presence of humic acids (HA) was measured under various conditions. The photolysis experiments of HA, KNO₃ and KNO₃/HA under simulated sunlight was carried out by a flow tube reactor at ambient temperature and pressure. HONO and NO₂ were major products by the photolysis of KNO₃. By contrast, the photolysis of HA and KNO₃/HA mainly generated HONO. HA significantly enhanced the formation of HONO during the photolysis process of KNO₃. With increasing the KNO₃ mass, the HONO formation rate (RHONO) on KNO₃/HA increased while the photolysis rate normalized by the KNO₃ mass exhibited an opposite trend. RHONO on KNO₃/HA linearly increased with irradiation intensity (88–262 W/m²) and relative humidity (7–70%), whereas it linearly decreased with the pH (pH = 2–12). In addition, the reaction paths of the HONO formation by the photolysis of nitrates in the presence of HA were proposed according to experimental results. Finally, atmospheric implications of the enhanced HONO formation by the photolysis of nitrates in the presence of HA were discussed.

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Ionizing radiation causes a variety of effects, including DNA damage associated to cancers. However, the effects in progeny from irradiated parents is not well documented. Using zebrafish as a model, we previously found that parental exposure to ionizing radiation is associated with effects in offspring, such as increased hatching rates, deformities, increased DNA damage and reactive oxygen species. Here, we assessed short (one month) and long term effects (one year) on gene expression in embryonic offspring (5.5 h post fertilization) from zebrafish exposed during gametogenesis to gamma radiation (8.7 or 53 mGy/h for 27 days, total dose 5.2 or 31 Gy) using mRNA sequencing. One month after exposure, a global change in gene expression was observed in offspring from the 53 mGy/h group, followed by embryonic death at late gastrula, whereas offspring from the 8.7 mGy/h group was unaffected. Interestingly, one year after exposure newly derived embryos from the 8.7 mGy/h group exhibited 2390 (67.7% downregulated) differentially expressed genes. Overlaps in differentially expressed genes and enriched biological pathways were evident between the 53 mGy/h group one month and 8.7 mGy/h one year after exposure, but were oppositely regulated. Pathways could be linked to effects in adults and offspring, such as DNA damage (via Atm signaling) and reproduction (via Gnrh signaling). Comparison with gene expression analysis in directly exposed embryos indicate transferrin a and cytochrome P450 2x6 as possible biomarkers for radiation response in zebrafish. Our results indicate latent effects following ionizing radiation exposure from the lower dose in parents that can be transmitted to offspring and warrants monitoring effects over subsequent generations.

Recent advances in research on algae inhibition by using low-cost straw proposed a possible mechanism that reactive oxygen species (ROS) generated by the solar irradiation of straw-derived dissolved organic matter (DOM) might contribute to cyanobacteria inhibition. However, this process is not clearly understood. Here, DOM from three types of straw (barley, rice, and wheat) and natural organic matter (NOM) isolates were investigated in terms of their photochemical properties and ROS generating abilities. Results demonstrated that the DOM derived from the aeration decomposition of barley straw (A-DOMbs) yielded the best formation efficiencies of hydrogen peroxide (H₂O₂) and hydroxyl radicals (•OH) under solar-simulated irradiation in all organic matter samples. Correlation analysis implies that optical parameters and phenolic hydroxyl group contents can signify ROS generating abilities of different DOM solutions. Bioassay results show that A-DOMbs possesses the highest inhibition performance for M. aeruginosa in all DOM samples, much higher than those of NOM isolates. The addition of catalase greatly relieves the inhibition performance, making the loss of chlorophyll a content decreased from 37.14% to 7.83% in 2 h for A-DOMbs, which implies that for cyanobacteria growth inhibition, photochemically-produced H₂O₂ from SOM is far more important than singlet oxygen (¹O₂), •OH, and even SOM itself. Our results show that H₂O₂ photochemically generated from straw-derived DOM is able to result in rapid inhibition of M. aeruginosa in a relatively short period, furthering the understanding of complicated mechanisms of cyanobacteria inhibition by using low-cost straw in eutrophic waters.

Genetic and epigenetic changes were investigated in chronically irradiated Scots pine (Pinus sylvestris L.) populations from territories that were heavily contaminated by radionuclides as result of the Chernobyl Nuclear Power Plant accident. In comparison to the reference site, the genetic diversity revealed by electrophoretic mobility of AFLPs was found to be significantly higher at the radioactively contaminated areas. In addition, the genome of pine trees was significantly hypermethylated at 4 of the 7 affected sites.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

In this study, degradation affinities of 14 antibiotics and one metabolite were determined in batch experiments. A modelling framework was applied to decrypt potential ranges of abiotic, biotic and photolytic degradation coefficients. In detail, we performed batch experiments with three different sewages in the dark at 7 °C and 22 °C. Additionally, we conducted further batch experiments with artificial irradiation and different dilutions of the sewage at 30 °C – de novo three different sewages were used. The batch experiments were initially spiked with a stock solution with 14 antibiotics and one metabolite to increase background concentrations by 1 μg L−1 for each compound. The final antibiotic concentrations were sub-inhibitory with regard to sewage bacteria. The here presented modelling framework based on the Activated Sludge Model No. 3 in combination with adsorption and desorption processes. The model was calibrated with monitored standard sewage compounds before antibiotic degradation rates were quantified. The model decrypted ranges of abiotic, biotic and photolytic degradation coefficients. In detail, six antibiotics were not abiotic degradable at 7 °C, five antibiotics not at 22 °C and only 2 antibiotics at 30 °C. Finally, nine antibiotics were not significantly biodegradable at 7 °C and 22 °C. The model determined the link between adsorption characteristics and biodegradation rates. In detail, the rate was significantly affected by the bio-solid partition coefficient and the duration until adsorption was balanced. All antibiotics and the metabolite were photolytic degradable. In general, photolytic degradation was the most efficient elimination pathway of presented antibiotics except for the given metabolite and penicillin antibiotics.