The impact of global climate changes on trace and rare earth elements mobilization in emerging periglacial terrains: Insights from western shore of Admiralty Bay (King George Island, Antarctic).

In the rapidly changing climate, the biogeochemical behaviours of trace elements and Rare Earth Elements (REEs) in emerging periglacial environments assumes profound importance. This study provides pivotal insights into this dynamic by investigating the Antarctic's response to global climate change. The bedrock of King George Island is rich in REEs, with the presence of trace metals (TEs), with the highest concentrations of metals found in ornithogenic soil (∑REE 84.01-85.53 mg∙kg-1 dry weight). REEs in the studied soil, found mainly in igneous rocks, as is indicated by the positive correlation of these elements with sodium and calcium. The TEs released as a result of weathering are leached by water flowing down local watercourses to Admiralty Bay, as indicated by the decreasing results of ∑REE = 11.59 µg∙dm-3 in watercourse water, ∑REE = 1.62 µg∙dm-3 in watercourse pools and ∑REE = 0.66 µg∙dm-3 in the water of Admiralty Bay at the outlet of the watercourse. Water originating from the melting of snow on the glacier also carried REEs (∑REE = 0.14 µg∙dm-3), a fact which suggest the further influx of these elements from atmospheric deposition. The Prasiola crispa turned out to be the most susceptible to the accumulation of REEs (∑ 80.73 ± 5.05 µg g-1) and TEs, with the exception of chromium and zinc, whose concentrations were found to be at their highest in Deschampsia antarctica. In Usnea antarctica, Xanthoria candelaria, and Ceratodon purpureus and Politrichastrum alpinum, a dominant role in the accumulation of REEs was played by HREEs. The determined enrichment factor (EF) indicates that the soil cover is a source of REEs (EFAlgae for ∑REE = 5.07; EFLichen for ∑REE = 6.65; EFBryophyta for ∑REE = 5.04; EFVascular for ∑REE = 4.38), while Ni, As and Pb accumulated in plants may originate from other sources than the soil.

Studies on the Efficiency of Iron Release from Fe(III)-EDTA and Fe(III)-Cit and the Suitability of These Compounds for Tetracycline Degradation.

Iron ions can be used to degrade tetracycline dispersed in nature. Studies of absorption and fluorescence spectra and quantum chemistry calculations showed that iron is more readily released from Fe(III)-citrate than from Fe(III)-EDTA, so Fe(III)-citrate (Fe(III)-Cit) is more suitable for tetracycline (TC) degradation. At 30 °C, a severe degradation of TC by Fe(III)-Cit occurred as early as after 3 days of incubation in the light, and after 5 days in the dark. In contrast, the degradation of TC by Fe(III)-EDTA proceeded very slowly in the dark. By the fifth day of incubation of TC with Fe(III)-Cit in darkness, the concentrations of the former compound dropped by 55% and 75%, at 20 °C and 30 °C, respectively. The decrease in tetracycline concentrations caused by Fe(III)-EDTA in darkness at the same temperatures was only 2% and 6%, respectively. Light increased the degradation rates of TC by Fe(III)-EDTA to 20% and 56% at 20 °C and 30 °C, respectively. The key role of the light in the degradation of tetracycline by Fe(III)-EDTA was thus demonstrated. The TC degradation reaction showed a second-order kinetics. The rate constants of Fe(III)-Cit-induced TC degradation at 20 °C and 30 °C in darkness were k = 4238 M-1day-1 and k = 11,330 M-1day-1, respectively, while for Fe(III)-EDTA were 55 M-1day-1 and 226 M-1day-1. In light, these constants were k = 15,440 M-1day-1 and k = 40,270 M-1day-1 for Fe(III)-Cit and k = 1012 M-1day-1 and 2050 M-1day-1 at 20 °C and 30 °C; respectively. A possible reason for the higher TC degradation rate caused by Fe(III)-Cit can be the result of its lower thermodynamical stability compared with Fe(III)-EDTA, which we confirmed with our quantum chemistry calculations. Two quantum chemistry calculations showed that the iron complex with EDTA is more stable (the free energy of the ensemble is 15.8 kcal/mol lower) than the iron complex with Cit; hence, Fe release from Fe(III)-EDTA is less effective.

Physiological and Biochemical Parameters of Common Duckweed Lemna minor after the Exposure to Tetracycline and the Recovery from This Stress.

In this study, the ability of Lemna minor L. to recover to normal growth, after being degraded in a tetracycline-containing medium, was extensively investigated. The plants were exposed to tetracycline (TC) at concentrations of 1, 2.5, and 10 mM. Subsequently, their physiological status was analysed against the following criteria: rate of plant growth; free radical accumulation; antioxidant enzyme activity; chlorophyll content; HSP70 protein content; cell membrane permeability, and mitochondrial activity. The study showed that duckweed can considerably recover from the damage caused by antibiotics, within a week of cessation of stress. Of the plant properties analysed, mitochondrial activity was the most sensitive to antibiotic-induced disturbances. After transferring the plants to a tetracycline-free medium, all plant parameters improved significantly, except for the mitochondrial activity in the plants grown on the medium containing the highest dose of tetracycline. In the plants treated with this antibiotic at the concentration of 10 mM, the proportion of dead mitochondria increased and was as high as 93% after one week from the beginning of the recovery phase, even after the transfer to the tetracycline-free medium.

Effect of Dimer Structure and Inhomogeneous Broadening of Energy Levels on the Action of Flavomononucleotide in Rigid Polyvinyl Alcohol Films.

The results of time-resolved fluorescence measurements of flavin mononucleotide (FMN) in rigid polyvinyl alcohol films (PVA) demonstrate that fluorescence intensity decays are strongly accelerated in the presence of fluorescent dimers and nonradiative energy transfer processes. The fluorescence decay originating both from H and J dimer states of FMN was experimentally observed for the first time. The mean fluorescence lifetimes for FMN dimers were obtained: τfl = 2.66 ns (at λexc = 445 nm) and τfl = 2.02 (at λexc = 487 nm) at λobs = 600 nm and T = 253 K from H and J state of dimers, respectively. We show that inhomogeneous orientational broadening of energy levels (IOBEL) affects the shape of the fluorescence decay and leads to the dependence of the average monomer fluorescence lifetime on excitation wavelength. IOBEL affected the nonradiative energy transfer and indicated that different flavin positioning in the protein pocket could (1) change the spectroscopic properties of flavins due to the existence of "blue" and "red" fluorescence centers, and (2) diminish the effectiveness of energy transfer between FMN molecules.

Spectroscopic and theoretical studies of fluorescence effects induced by the ESIPT process in a new derivative 2-Hydroxy-N-(2-phenylethyl)benzamide - Study on the effects of pH and medium polarity changes.

The paper presents the results of studies conducted with the use of stationary and time-resolved fluorescence spectroscopy for the new derivative 2-Hydroxy-N-(2-phenylethyl)benzamide (SAL-3) in aqueous solutions with various concentrations of hydrogen ions as well as in solvent mixtures (i.e. media with changing polarity/polarizability). For the compound selected for the study placed in aqueous solutions with varying concentrations of hydrogen ions, the fluorescence emission spectra revealed a single emission band within most of the pH range, however, at low pH (pH<3) a significant broadening (noticeable effect of dual fluorescence) and shifting of the band was observed. Whereas, for water and polar (protic) solvents, we observed a very interesting phenomenon of dual fluorescence never before reported for this particular group of analogues (with the specific substituent system). Based on the results of the experiments, it was observed that the presented effects may be related both with conformational effects (related to the possible positioning of the-OH group on the side of the carbonyl system, which facilitates the possibility of proton transfer) as well as, most importantly, the effects of excited state intramolecular proton transfer (ESIPT-Excited State Intramolecular Proton Transfer) related in this case with the necessary (new/previously unobserved in published literature) presence of ionic and non-ionic forms of the compound). Both the conducted quantum-mechanical [TD]DFT-Time-Dependent Density Functional Theory) calculations and excited state dipole moment change calculations for the analyzed molecule in solvents with varying pH confirmed the association between the observed fluorescence phenomena and the two aforementioned effects.

Investigation of chlorophyll degradation by tetracycline.

Antibiotics represent a novel type of environment pollutants which modify chlorophyll content in plants. Spectroscopic methods were employed to investigate the effect of tetracycline on chlorophyll degradation. Changes in absorbance and fluorescence demonstrated that tetracycline reaction with chlorophyll results in the formation of pheophytin, which was confirmed by new bands typical of pheophytin which appeared in the absorbance spectrum. The rate of pheophytin formation depended on ratio tetracycline to chlorophyll concentration in solution. In solutions with chlorophyll concentration of C = 1 × 10-5 M and tetracycline concentrations of C = 1 × 10-3 M and C = 1 × 10-2 M, pheophytin was formed after 28 h and 25 min, respectively. The obtained lifetime for pheophytin formed during chlorophyll reaction - with tetracycline hydrochloride was τ = 5.71 ±â€¯0.02 ns and its value coincides, within the error limits, with the value obtained for pure pheophytin purchased from ChromaDex. The experiment demonstrated two mechanisms of chlorophyll degradation to pheophytin by tetracycline hydrochloride, i.e. 1) loss of Mg2+ ions from the chlorophyll molecule as a result of the presence of H+ ions in solution (i.e. as a result of medium acidification), and 2) removal of Mg2+ ions directly from chlorophyll by tetracycline which binds Mg2+ ions from the chlorophyll. We demonstrated that magnesium occurring in low concentrations attached to a tetracycline molecule in the BCD ring, and that the second ion of Mg2+ may attach to the A ring of tetracycline at higher Mg2+ concentrations. Two fluorescence bands appeared which indicated such magnesium attachments indeed occurred.

Influence of light and Fe(III) ions on tetracycline degradation.

Tetracycline (TC) is an antibiotic produced on the largest scale in the world and used for the treatment of both humans and animals. Its removal from the circulation chain between the natural environment and animals is still a serious problem. Fe(III) ions can be used to break this chain. Fe(III) ions appear in water in spite of irradiation of Fe(III)-Cit complex and oxidation by oxygen present in water. Fe(III)-Cit was a reservoir of Fe(III) ions from which they were continuously released. Therefore, in this paper we studied an interaction between tetracycline (TC) and Fe(III) ions under fluorescent light at 20 °C and 30 °C in the water environment. This interaction leads to TC + Fe(III) coordinating complex formation. Changes caused by this process were monitored within 1860 min by measuring absorption and fluorescence spectra. The absorption spectra showed a charge-transfer stacking band(s) of oxidized and non-oxidized form of TC above 400 nm; in turn the fluorescence spectra revealed decay of initial bands and formation of the new ones. The initial, main fluorescence band at 16,660 cm-1 associated with the intramolecular proton transfer has gradually disappeared after Fe(III) ions binding to oxygen atoms in the BCD system rings of a TC molecule. Gaussian decomposition of all fluorescence spectra allowed extracting new bands, their evolution in time and calculating the rate of the first reaction step. Temperature rise of 10 °C caused more than a ten-fold increase in the first-order reaction rate.

A Strong Impact of Soil Tetracycline on Physiology and Biochemistry of Pea Seedlings.

Antibiotics are a new type of contaminants found in the environment. They are increasingly used in farm animal production systems and may accumulate in crops, limiting the plant growth rate and nutritive value. The aim of this study was to determine the effects of tetracycline (TC) on physiological and biochemical properties of pea seedlings. The presence of TC in the soil during 24 hours did not result in any distinct changes of the seedlings. However, after five days (120 h) of soil TC action, the seedling appearance and metabolic activities were significantly affected. Leaves lost their green coloration as a result of a 38% degradation of their chlorophyll. Total protein was isolated from shoots of pea grown for 120 h in TC-supplemented perlite (250 mg × L-1) or perlite with no TC (control plants). The 2D electrophoretic maps of proteins from non-TC shoots contained 326 spots, whereas maps of shoot proteins from TC-treated seedlings contained only 316 spots. The identity of 26 proteins was determined. The intensity of most proteins (62%) increased. This was particularly visible with diphosphate kinase, superoxide dismutase [Cu-Zn], peroxiredoxin, and glutathione S-transferase. A distinctly increased quantity of a protein involved in photosynthesis (photosystem II stability/assembly factor HCF136) was also noted. One protein was detected only in shoots of TC-treated plants (as opposed to controls); however, it could not be identified. Moreover, at the highest concentration of TC (250 mg × L-1 of perlite), a sharp increase in free-radical content was observed along with the amount of callose deposited in vascular bundles of leaves and roots and the occurrence of masses of dead cells in roots. It was found, therefore, that tetracycline which has been known for inhibiting predominantly the attachment of aminoacyl-tRNA to the ribosomal acceptor in bacteria can disturb diverse metabolic pathways in plants.

Uptake and reaction to roundup ultra 360 SL in soybean seedlings.

Due to the widespread and frequent use of Roundup Ultra 360 SL in crops production, the active substance glyphosate is often present (in the soil or in post-harvest remnants) and may be toxic to plants, including the non-target species. The aim of the current study was to determine the sensitivity of young soybean seedlings to glyphosate in concentrations ranging from 0 to 10 µM. It was demonstrated that the seedlings take small quantities of soil glyphosate up. More of the active substance was found in the shoots than in the roots. From the doses applied, the plant absorbs up to 4% of soil glyphosate, while over 96% remains in the soil. This suggests that only 4% of glyphosate taken up from the soil affects plant seedling development and water management. It modifies the contents of the biogenic amines cadaverine and putrescine as well as the activity of enzymes involved in their biosynthesis, i.e. ornithine decarboxylase and lysine decarboxylase. The free radical content of the roots increased with increasing herbicide doses and time of exposure. The main enzyme involved in the rapid removal of free radicals was superoxide peroxidase, activated by the herbicide treatment, while catalase was not significantly stimulated.

Proteins in Relation to Vigor and Viability of White Lupin (Lupinus albus L.) Seed Stored for 26 Years.

The aim of the study was to evaluate the vigor and viability as well as to determine and compare the contents of selected protein fractions of white lupin (Lupinus albus L.) seeds stored for 26 years at temperatures of -14°C and +20°C. The seeds stored at -14°C germinated in 86.3%, while the seeds stored at +20°C did not germinate at all. The viability evaluation was confirmed by the measuring electroconductivity of seed exudates. In seeds stored at -14°C the contents of γ, δ, and ß conglutin were 14, 4 and 69 mg g-1 fresh mass, respectively, while in seed stored at +20°C they were 15.5, 3, 65 mg g-1 fresh mass, respectively. One-dimensional electrophoresis of γ and δ conglutin fractions indicated the presence of several intense polypeptide bands with molecular weights from 23.0 to 10.3 kDa. Polypeptide bands with a molecular weight of 22.4 and 19.8 kDa exhibited almost two times higher expression in the seeds stored at -14°C compared to the seeds stored at +20°C. Electrophoresis revealed 310 protein spots on the maps generated for seeds stored at -14°C, and 228 spots for seeds stored at +20°C. In seeds stored at +20°C most polypeptide subunits had a pI ranging from 4.5 to 7 and a molecular weight of 10-97 kDa. The greatest differences in the contents of polypeptides between the analyzed variants was observed within the range of 20-45 kDa (-14°C: 175, +20°C: 115 protein spots) and within the range of 65-97 kDa (-14°C: 103, +20°C: 75 protein spots). In seeds stored at +20°C, a clear decline in basic (8-10 pI) polypeptides was observed. The study demonstrated that the polypeptides identified as γ and δ conglutins are probably closely related to vigor and viability of seeds.

Levofloxacin is phytotoxic and modifies the protein profile of lupin seedlings.

The toxicity of levofloxacin to yellow lupin plants was evaluated in this study. Recommended indexes of plant (roots and shoots) growth were determined and new indexes were proposed which better characterise the phytotoxicity of levofloxacin. These were, in particular, the activity of antioxidative enzymes, the content of free radicals, as well as the root protein content and the root protein profile. The results showed that levofloxacin considerably affected EC50, measured as the activity of catalase in roots, and leaves (1.05 and 0.069 mM, respectively). The activity of peroxidase in the roots and the dry weight of seedlings were the least sensitive parameters (EC50 was 1.8 and 1.76 mM, respectively). Units of toxicity clearly showed that the activity of catalase is a better measure of toxicity for low concentrations of the drug, and it is a better index of plant physiological state than the morphological parameters of seedlings. Moreover, levofloxacin changed the location of free radicals and the protein profile in plants. The changes in location of reactive oxygen species in roots were an important symptom of the drug toxicity to lupin seedlings. Our results have shown that the toxicity of levofloxacin was manifested mainly by changes in the protein profile. The content of the glyceraldehyde-3-phosphate dehydrogenase, 14-3-3-like protein A, expansin-B3-like precursor, fructose-bisphosphate aldolase, lipoxygenase, nucleotide-binding subunit of vacuolar ATPase and pyruvate dehydrogenase were found to decrease. On the other hand, plant exposure to levofloxacin resulted in an increase in the content of enolase, protein LlR18A, class III chitinase, ascorbate peroxidase, aspartate aminotransferase, alcohol dehydrogenase 1, leghemoglobin reductase-like 17 and heat shock cognate protein 80-like.

Instability of chlorophyll in yellow lupin seedlings grown in soil contaminated with ciprofloxacin and tetracycline.

With increasing soil concentrations of ciprofloxacin and tetracycline a decrease of leaf chlorophyll content was observed. Tetracycline was more detrimental than ciprofloxacin. The chlorophyll content in plants growing for ten days on a tetracycline containing soil decreased by 68%. The decrease of chlorophyll concentration was even sharper in new leaves that formed after application of the antibiotic (up to 81% drop). The comparison of absorption spectra of commercial, reagent grade chlorophyll, alone and incubated with antibiotics, has shown that ciprofloxacin and tetracycline can react directly with chlorophyll and decrease its concentration by 47.7% and 48.5%, respectively. The changes in fluorescence spectra confirmed the formation of chlorophyll degradation product. The chlorophyll decay was a second order reaction and depended on antibiotic concentration and duration of exposure. Reaction rate constants differed with antibiotics and their soil concentrations. With increasing contents of antibiotics in soil the constant of chlorophyll degradation rate in lupin plants increased from k = 870 M-1day-1 for 3 mg ciprofloxacin to k = 2490 M-1day-1 for 90 mg ciprofloxacin, and in the case of tetracycline the reaction rate constant increased from k = 1330 M-1day-1 to k = 2910 M-1day-1. The sensitivity of chlorophyll to ciprofloxacin and tetracycline was confirmed by determining EC and TU indices.

Content of biogenic amines in Lemna minor (common duckweed) growing in medium contaminated with tetracycline.

Aquatic plants are continuously exposed to a variety of stress factors. No data on the impact of antibiotics on the biogenic amines in duckweed (Lemna minor) have been available so far, and such data could be significant, considering the ecological role of this plant in animal food chains. In the tissues of control (non-stressed) nine-day-old duckweed, the following biogenic amines were identified: tyramine, putrescine, cadaverine, spermidine and spermine. Based on the tetracycline contents and the computed EC values, the predicted toxicity units have been calculated. The obtained results demonstrated phytoxicity caused by tetracycline in relation to duckweed growth rate, yield and the contents of chlorophylls a and b. The carotenoid content was not modified by tetracycline. It was found that tetracycline as a water pollutant was a stress factor triggering an increase in the synthesis of amines. Tetracycline at 19, 39 and 78µM concentrations increased biogenic amine synthesis by 3.5 times. Although the content of tyramine increased fourteen times with the highest concentration of the drug (and of spermidine - only three-fold) the increase of spermidine was numerically the highest. Among the biogenic amines the most responsive to tetracycline were spermine and tyramine, while the least affected were putrescine and spermidine. Despite putrescine and spermidine being the least sensitive, their sum of contents increased five-fold compared to the control. These studies suggest that tetracycline in water reservoirs is taken up by L. minor as the antibiotic clearly modifies the metabolism of this plant and it may likely pose a risk.

Phytotoxicity of sulfamethazine soil pollutant to six legume plant species.

The effect of traces of sulfamethazine (SMZ) in soil (0.01, 0.1, 0.25, 1, 5, 15, and 20 mM) on cellular distribution of cytochrome c oxidase activity, shoot and root growth, and leachate electroconductivity was analyzed in germinating seeds of yellow lupin, pea, lentil, soybean, adzuki bean, and alfalfa. Results showed that a high activity of cytochrome c oxidase in mitochondria correlated with high seed vigor and viability. The appearance of necroses and root decay was associated with a decrease in the activity of mitochondrial cytochrome c oxidase but was accompanied by an increase in cytosolic cytochrome c oxidase activity. A short exposure period of seeds (3 and 6 d) to sulfamethazine did not influence germination. Elongation of roots and stems was more sensitive than germination rate as an indicator of soil contamination by sulfamethazine. Among all tested leguminous plants, yellow lupin was the most reliable bioindicator of SMZ contaminated soil.