Screening of semi-volatile compounds in plants treated with coated cerium oxide nanoparticles by comprehensive two-dimensional gas chromatography.

Literature data about semi-volatile organic compounds in plants and the effect of cerium oxide nanoparticles on them are scarce. Surface modification of nanoparticles may change nanoparticle-environment interaction, and therefore affects compounds in plants. In this research, uncoated and glucose-, levan-, and pullulan-coated cerium oxide nanoparticles were used for wheat and pea treatment during the growth. The aim was the screening of semi-volatile organic compounds from plants' shoots using comprehensive two-dimensional gas chromatography-mass spectrometry, a powerful separation technique allowing to reach unique separation resolution, and investigation of qualitative changes after the treatment with coated cerium oxide nanoparticles. The results were analyzed by the identification of individual peaks and fingerprint analysis by image processing. Wheat samples contained a higher number of semi-volatile organic compounds (108) compared to pea (77) but were less affected by the treatments with coated nanoparticles. The highest number of compounds was detected in wheat after the treatment with levan- and pullulan-coated nanoparticles, and in pea after treatment with levan-coated nanoparticles. This article reports a successful application of a semi-volatile organic compounds profile presented only as categorical variables and unique fingerprint images for the inter-cultivar recognition. This method may be useful in screening nanoparticles' effects on different plants.

Hydrochemistry of groundwater contaminated by petroleum hydrocarbons: the impact of biodegradation (Vitanovac, Serbia).

Aquifer contamination by petroleum hydrocarbons leads to measurable changes of groundwater hydrochemistry, primarily due to the microbiological activity. This study analyzes this phenomenon at an historical kerosene-contaminated site in Vitanovac (central Serbia). Due to the long-term hydrocarbon contamination and exposure to aerobic and anaerobic biodegradation mechanisms, the lowest concentrations of O2, NO3-, and SO42- (electron acceptors) and the highest concentrations of Mn and Fe (products of microbial metabolic activity) overlap. The terminal redox-accepting processes in groundwater ranged from oxygen reduction to sulfate reduction. The most anoxic processes were registered in piezometers closest to the source of contamination, as was also confirmed by the redox potential (Eh) measurements. High electrical conductivity values and the highest TOC, SiO2, and Al concentrations also overlap in the contaminated zone close to the source of contamination. Scanning electron microscopy study of quartz grains from the zone undergoing the impact of biodegradation confirmed the occurrence of weathering microscale processes on mineral surfaces. Taking all these factors together, it seems reasonable to assume that microbiological activity has caused the enhanced weathering of silicate minerals.

Capillary zone electrophoresis determination of fluoride in seawater using transient isotachophoresis.

We developed capillary zone electrophoresis (CZE) with indirect UV detection for the determination of fluoride (F-) in seawater using transient isotachophoresis (tITP) as an on-line concentration procedure. A method of correcting sample salinity effects was also proposed so that F- concentrations were obtained using a calibration graph. The proposed method is simple: it requires no sample pretreatment aside from dilution. The following optimum conditions were established: background electrolyte (BGE), 5 mM 2,6-pyridinedicarboxylic acid (PDC) adjusted to pH 3.5 containing 0.03% m/v hydroxypropyl methylcellulose (HPMC); detection wavelength, 200 nm; vacuum (50 kPa) injection period of sample, 5 s (254 nL); and applied voltage, 23 kV with the sample inlet side as the cathode. The limit of detection (LOD, S/N = 3) and limit of quantification (LOQ, S/N = 10) for F- reached 0.024 and 0.070 mg/L, respectively. The respective values of the relative standard deviation (RSD) of the peak area, peak height, and migration time for F- were 2.5, 3.4, and 0.30%. The proposed method was applied for the determination of F- in seawater samples collected from coastal waters of western Japan during August 26-28, 2014. Both results obtained using standard addition method and a calibration graph agreed with those obtained using a conventional spectrophotometric method.

Natural attenuation of petroleum hydrocarbons-a study of biodegradation effects in groundwater (Vitanovac, Serbia).

The role of natural attenuation processes in groundwater contamination by petroleum hydrocarbons is of intense scientific and practical interest. This study provides insight into the biodegradation effects in groundwater at a site contaminated by kerosene (jet fuel) in 1993 (Vitanovac, Serbia). Total petroleum hydrocarbons (TPH), hydrochemical indicators (O2, NO3-, Mn, Fe, SO42-, HCO3-), δ13C of dissolved inorganic carbon (DIC), and other parameters were measured to demonstrate biodegradation effects in groundwater at the contaminated site. Due to different biodegradation mechanisms, the zone of the lowest concentrations of electron acceptors and the zone of the highest concentrations of metabolic products of biodegradation overlap. Based on the analysis of redox-sensitive compounds in groundwater samples, redox processes ranged from strictly anoxic (methanogenesis) to oxic (oxygen reduction) within a short distance. The dependence of groundwater redox conditions on the distance from the source of contamination was observed. δ13C values of DIC ranged from - 15.83 to - 2.75‰, and the most positive values correspond to the zone under anaerobic and methanogenic conditions. Overall, results obtained provide clear evidence on the effects of natural attenuation processes-the activity of biodegradation mechanisms in field conditions.

Interactions of the metal tolerant heterotrophic microorganisms and iron oxidizing autotrophic bacteria from sulphidic mine environment during bioleaching experiments.

Iron and sulfur oxidizing chemolithoautotrophic acidophilic bacteria, such as Acidithiobacillus species, hold the dominant role in mine environments characterized by low pH values and high concentrations of reduced sulfur and iron compounds, such as ores, rocks and acid drainage waters from mines. On the other hand, heterotrophic microorganisms, especially their biofilms, from these specific niches are receiving increased attention, but their potential eco-physiological roles have not been fully understood. Biofilms are considered a threat to human health, but biofilms also have beneficial properties as they are deployed in waste recycling and bioremediation systems. We have analyzed interactions of the metal tolerant heterotrophic microorganisms in biofilms with iron oxidizing autotrophic bacteria both from the sulphidic mine environment (copper mine Bor, Serbia). High tolerance to Cu(2+), Cd(2+) and Cr(6+) and the presence of genetic determinants for the respective metal tolerance and biofilm-forming ability was shown for indigenous heterotrophic bacteria that included strains of Staphylococcus and Rhodococcus. Two well characterized bacteria- Pseudomonas aeruginosa PAO1 (known biofilm former) and Cupriavidus metallidurans CH34 (known metal resistant representative) were also included in the study. The interaction and survivability of autotrophic iron oxidizing Acidithiobacillus bacteria and biofilms of heterotrophic bacteria during co-cultivation was revealed. Finally, the effect of heterotrophic biofilms on bioleaching process with indigenous iron oxidizing Acidithiobacillus species was shown not to be inhibitory under in vitro conditions.

Microbial fuel cells as an electrical energy source for degradation followed by decolorization of Reactive Black 5 azo dye.

The problem of wastewater has long been ubiquitous and has great consequences for the environment and its inhabitants. Microbial fuel cells (MFCs) have enormous potential for the treatment of wastewaters polluted with azo dyes. The amount of energy that can be produced from a single-chamber MFC is sufficient to perform decolorization and degradation of such dyes, which are widely used in the textile industry. This study on the azo dye, reactive black 5 (RB5), provides an alternative method through three parallel-connected MFCs to obtain electricity that directly serves for the dye's electrochemical degradation. We examined degradation followed by decolorization of RB5 using Fe and Pt electrodes, together with H2O2, to achieve the electro-Fenton process. The amount of voltage produced (295 mV), the current density (276 mA m-3) and the power density (50 mW m-3) were sufficient to degrade 25 mg L-1 RB5 dye with 0.5 mM H2O2 in just 2 h. The dye degradation mechanism was investigated using UV-VIS, FT-IR and HPLC-MS/MS. The ecotoxicity of the degradation products was assessed using a bacterial model, Aliivibrio fischeri. These tests showed that there was successful degradation of the dye to products whose toxicity is less than that of RB5.

Water-sanitation-health nexus in the Indus-Ganga-Brahmaputra River Basin: need for wastewater surveillance of SARS-CoV-2 for preparedness during the future waves of pandemic.

The Indus-Ganga-Brahmaputra River Basin (IGBRB) is a trans-boundary river basin flowing through four major countries in South Asia viz., India, Pakistan, Bangladesh, and Nepal. Contamination of surface water by untreated or inadequately treated wastewater has been a huge problem for pathogenic microorganisms in economies in transition. Recent studies have reported that sewage surveillance can provide prior information of the outbreak data, because faeces can contain the novel coronavirus (SARS-CoV-2) shed by infected humans. Hence, in this study we geo-spatially mapped the COVID-19 hotspots during the peak time in the first and second wave of pandemic to demonstrate the need and usefulness of wastewater surveillance strategy in IGBRB during ongoing pandemic. Further we discussed the status of sanitation, health and hand-hygiene in the IGBRB along with characterization of the challenges posed by the pandemic in achieving the United Nations Sustainable Development Goals (UN-SDGs). Monthly Geographical Information System (GIS) mapping of COVID-19 hotspots in the IGBRB showed an increase in the spread along the direct sewage discharge points. The social inequalities expose the vulnerabilities of the urban poor in terms of the burden, risks and access to Water, Sanitation, and Hygiene (WASH) needs. Such an evidence-based image of the actual SARS-CoV-2 viral load in the community along the IGBRB can provide valuable insights and recommendations to deal with the future waves of COVID-19 pandemic in this region that can go a long way in achieving the UN-SDGs.

Toxicity investigation of CeO2 nanoparticles coated with glucose and exopolysaccharides levan and pullulan on the bacterium Vibrio fischeri and aquatic organisms Daphnia magna and Danio rerio.

Cerium oxide nanoparticles (nCeO2) have widespread applications, but they can be hazardous to the environment. Some reports indicate the toxic effect of nCeO2 on tested animals, but literature data are mainly contradictory. Coating of nCeO2 can improve their suspension stability and change their interaction with the environment, which can consequently decrease their toxic effects. Herein, the exopolysaccharides levan and pullulan, due to their high water solubility, biocompatibility, and ability to form film, were used to coat nCeO2. Additionally, the monosaccharide glucose was used, since it is a common material for nanoparticle coating. This is the first study investigating the impact of carbohydrate-coated nCeO2 in comparison to uncoated nCeO2 using different model organisms. The aim of this study was to test the acute toxicity of carbohydrate-coated nCeO2 on the bacterium Vibrio fischeri NRRL B-11177, the crustacean Daphnia magna, and zebrafish Danio rerio. The second aim was to investigate the effects of nCeO2 on respiration in Daphnia magna which was performed for the first time. Finally, it was important to see the relation between Ce bioaccumulation in Daphnia magna and Danio rerio and other investigated parameters. Our results revealed that the coating decreased the toxicity of nCeO2 on Vibrio fischeri. The coating of nCeO2 did not affect the nanoparticles' accumulation/adsorption or mortality in Daphnia magna or Danio rerio. Monitoring of respiration in Daphnia magna revealed changes in CO2 production after exposure to coated nCeO2, while the crustacean's O2 consumption was not affected by any of the coated nCeO2. In summary, this study revealed that, at 200 mg L-1, uncoated and carbohydrate-coated nCeO2 are not toxic for the tested organisms, however, the CO2 production in Daphnia magna is different when they are treated with coated and uncoated nCeO2. The highest production was in glucose and levan-coated nCeO2 according to their highest suspension stability. Daphnia magna (D. magna), Danio rerio (D. rerio), Vibrio fischeri (V. fischeri).

Fungal transformation and reduction of phytotoxicity of grape pomace waste.

Grape pomace (GP) from Vitis labrusca, the main byproduct from "American table wine" production, is recalcitrant to degradation, and its accumulation is a serious problem with negative environmental impacts. In this work, transformation of grape pomace using a steam pretreatment followed by incubation of GP during a 90-day period with six different fungi were evaluated. Several fungi tested reduced the phytotoxicity of water-soluble fraction (WSFd) from steam-pretreated GP after 90 days' incubation to lettuce and tomato seeds. U. botrytis caused the largest effective phytotoxicity reduction of WSFd (used in the concentration range of 10-1.25% p/v) and was the only fungus causing the removal of monoaromatic compounds. Therefore, this procedure with U. botrytis effectively reduces the availability of phytotoxic monoaromatic compounds in GP, which opens a way for the development of guidelines for the management of these wastes and their potential use as organic amendments in agricultural soil.

Interaction of Carbohydrate Coated Cerium-Oxide Nanoparticles with Wheat and Pea: Stress Induction Potential and Effect on Development.

: Reports about the influence of cerium-oxide nanoparticles (nCeO2) on plants are contradictory due to their positive and negative effects on plants. Surface modification may affect the interaction of nCeO2 with the environment, and hence its availability to plants. In this study, the uncoated and glucose-, levan-, and pullulan-coated nCeO2 were synthesized and characterized. The aim was to determine whether nontoxic carbohydrates alter the effect of nCeO2 on the seed germination, plant growth, and metabolism of wheat and pea. We applied 200 mgL-1 of nCeO2 on plants during germination (Ger treatment) or three week-growth (Gro treatment) in hydroponics. The plant response to nCeO2 was studied by measuring changes in Ce concentration, total antioxidative activity (TAA), total phenolic content (TPC), and phenolic profile. Our results generally revealed higher Ce concentration in plants after the treatment with coated nanoparticles compared to uncoated ones. Considering all obtained results, Ger treatment had a stronger impact on the later stages of plant development than Gro treatment. The Ger treatment had a stronger impact on TPC and plant elongation, whereas Gro treatment affected more TAA and phenolic profile. Among nanoparticles, levan-coated nCeO2 had the strongest and positive impact on tested plants. Wheat showed higher sensitivity to all treatments.

Defluorination of perfluoroalkyl acids is followed by production of monofluorinated fatty acids.

We investigated the capability of microorganisms isolated from environments polluted with perfluoroalkyl acids (PFAAs) to conduct biotransformation of these emerging pollutants. Two different microbial consortia (chemoorganoheterotrophic bacteria and total yeast and molds) were isolated from two river sediments in Saitama and Osaka, Japan, known for long term pollution with perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). The microbial consortia were incubated in the presence of added PFOS and PFOA, and decreases in concentrations of these compounds were between 46-69% and 16-36%, respectively. Decreases in concentrations were, in part, due to sorption on biomass, but defluorinated PFOS and PFOA products were not detected. However, untargeted analysis suggested the presence of several metabolites found only in samples from consortia with PFOS and PFOA but not in the control samples. Molecular formula candidates were narrowed down to two options, C18H28O5F and C21H27O4. It was assumed that these formulas were associated with unsaturated monofluorinated fatty acids and hydrocarbons with multiple unsaturated bonds or ring structures.

Brachybacterium sp. CH-KOV3 isolated from an oil-polluted environment-a new producer of levan.

Various microorganisms isolated from polluted environments, such as Pseudomonas sp. and Micrococcus sp. can synthesize exopolysaccharides (EPSs) which are natural, non-toxic and biodegradable polymers. EPSs play a key role in protection of microbial cells under various external influences. For humans, these substances have potential use in many industries. EPSs can be applied as a flavor or a fragrance carrier, an emulsifier, a stabilizer, a prebiotic, an antioxidant or an antitumor agent. In this study, we characterized an environmental microorganism that produces EPS, optimized EPS production by this strain and characterized the EPS produced. Isolate CH-KOV3 was identified as Brachybacterium paraconglomeratum. The sucrose level in the growth medium greatly influenced EPS production, and the highest yield was when the microorganism was incubated in media with 500g/L of sucrose. The optimal temperature and pH were 28°C and 7.0, respectively. The nuclear magnetic resonance (NMR) results and GC-MS analysis confirmed that the residues were d-fructofuranosyl residues with ß-configuration, where fructose units are linked by ß-2,6-glycosidic bonds, with ß-2,1-linked branches. All these data indicate that the investigated EPS is a levan-type polysaccharide. Thus, it was concluded that Brachybacterium sp. CH-KOV3 could constitute a new source for production of the bioactive polysaccharide, levan.

Distribution of perfluoroalkyl compounds in Osaka Bay and coastal waters of Western Japan.

Perfluoroalkyl acids (PFAAs) including perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) were analyzed in sediment samples taken from Ajifu Waterway in Osaka city, from Osaka Bay, and from Kagoshima Bay, as well as in fifteen seawater samples collected from Osaka Bay and coastal waters of Western Japan. In all sediment samples, only PFCAs were detected, and the highest concentration was determined in Ajifu Waterway, where ΣPFAA was 58990 ng kg-1 dry weight. The total concentrations of PFAAs in sea water samples ranged between the limit of quantification and 53.4 ng L-1, and perfluorohexanoic acid was the most prevalent and had the highest concentration of 37 ng L-1. The changes in the patterns and concentrations of PFAAs in Osaka Bay and coastal waters of Western Japan indicate that the PFAAs in surface waters are influenced by sources from Keihanshin Metropolitan Area, mainly the Yodo River basin, and the dilution effect which naturally occurs during their transport to the Pacific Ocean.

Perfluorinated compounds in sediment samples from the wastewater canal of Pancevo (Serbia) industrial area.

Perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) were analyzed in sediment samples from the wastewater canal draining the industrial complex of Pancevo, Serbia (oil refinery, petrochemical plant, and fertilizer factory). The canal is directly connected to Europe's second largest river, the Danube, which drains its water into the Black Sea. Perfluorooctane sulfonate (PFOS) up to 5.7ngg(-1) dry weight (dw) and total Perfluorinated compounds (PFCs) up to 6.3ngg(-1) dw were detected. Compared to other reports, high levels of PFOS were found, even though PFCs are not used in the industrial production associated with this canal. The PFOS concentration in water was recalculated using the adsorption coefficient, KOC from literature. Using the average output of wastewater from the canal, a mass load of 1.38kg PFOS per year discharged in the Danube River has been calculated, which undoubtedly points to the contribution to global persistent organic pollution of surface waters originating from this industrial place.

Ex situ bioremediation of a soil contaminated by mazut (heavy residual fuel oil)--a field experiment.

Mazut (heavy residual fuel oil)-polluted soil was exposed to bioremediation in an ex situ field-scale (600 m(3)) study. Re-inoculation was performed periodically with biomasses of microbial consortia isolated from the mazut-contaminated soil. Biostimulation was conducted by adding nutritional elements (N, P and K). The biopile (depth 0.4m) was comprised of mechanically mixed polluted soil with softwood sawdust and crude river sand. Aeration was improved by systematic mixing. The biopile was protected from direct external influences by a polyethylene cover. Part (10 m(3)) of the material prepared for bioremediation was set aside uninoculated, and maintained as an untreated control pile (CP). Biostimulation and re-inoculation with zymogenous microorganisms increased the number of hydrocarbon degraders after 50 d by more than 20 times in the treated soil. During the 5 months, the total petroleum hydrocarbon (TPH) content of the contaminated soil was reduced to 6% of the initial value, from 5.2 to 0.3 g kg(-1) dry matter, while TPH reduced to only 90% of the initial value in the CP. After 150 d there were 96%, 97% and 83% reductions for the aliphatic, aromatic, and nitrogen-sulphur-oxygen and asphaltene fractions, respectively. The isoprenoids, pristane and phytane, were more than 55% biodegraded, which indicated that they are not suitable biomarkers for following bioremediation. According to the available data, this is the first field-scale study of the bioremediation of mazut and mazut sediment-polluted soil, and the efficiency achieved was far above that described in the literature to date for heavy fuel oil.