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Identification and characterization of tebuconazole transformation products in soil by combining suspect screening and molecular typology
2016
Storck, Veronika | Lucini, Luigi | Mamy, Laure | Ferrari, Federico | Papadopoulou, Evangelia S. | Nikolaki, Sofia | Karas, Panagiotis A. | Servien, Remi | Karpouzas, Dimitrios G. | Trevisan, Marco | Benoit, Pierre | Martin-Laurent, Fabrice
Pesticides generate transformation products (TPs) when they are released into the environment. These TPs may be of ecotoxicological importance. Past studies have demonstrated how difficult it is to predict the occurrence of pesticide TPs and their environmental risk. The monitoring approaches mostly used in current regulatory frameworks target only known ecotoxicologically relevant TPs. Here, we present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. We used an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry, followed by structural proposition through a molecular structure correlation program. In silico molecular typology was then used to group TPs according to common molecular descriptors and to indirectly elucidate their environmental parameters by analogy to known pesticide compounds with similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in soil during a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected, and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be investigated towards a more comprehensive environmental risk assessment scheme.
Afficher plus [+] Moins [-]Sources of hydrocarbons in urban road dust: Identification, quantification and prediction
2016
Mummullage, Sandya | Egodawatta, Prasanna | Ayoko, G. A. (Godwin A.) | Goonetilleke, Ashantha
Among urban stormwater pollutants, hydrocarbons are a significant environmental concern due to their toxicity and relatively stable chemical structure. This study focused on the identification of hydrocarbon contributing sources to urban road dust and approaches for the quantification of pollutant loads to enhance the design of source control measures. The study confirmed the validity of the use of mathematical techniques of principal component analysis (PCA) and hierarchical cluster analysis (HCA) for source identification and principal component analysis/absolute principal component scores (PCA/APCS) receptor model for pollutant load quantification. Study outcomes identified non-combusted lubrication oils, non-combusted diesel fuels and tyre and asphalt wear as the three most critical urban hydrocarbon sources. The site specific variabilities of contributions from sources were replicated using three mathematical models. The models employed predictor variables of daily traffic volume (DTV), road surface texture depth (TD), slope of the road section (SLP), effective population (EPOP) and effective impervious fraction (EIF), which can be considered as the five governing parameters of pollutant generation, deposition and redistribution. Models were developed such that they can be applicable in determining hydrocarbon contributions from urban sites enabling effective design of source control measures.
Afficher plus [+] Moins [-]Diazo-coupling spectrophotometric determination of nitrogen oxides in the air
2016
Huang, Yingying | Shi, Wenjian | Zhang, Caihong | Li, Liang | Wen, Haifeng
A new accurate, sensitive, rapid and convenient measurement for the determination of nitrogen oxides in the air was established. After being oxidized by chromium trioxide (CrO3), nitrogen oxides in the air existed in the form of NO2, then forming nitrite and nitrate after being absorbed by the alkaline aqueous solution. Under acidic condition, the diazo reaction is specific to the nitrite and primary aromatic amine. In this paper, the structure of diazo and coupling compounds were selected and tested through the experiments. The relationship between the azo compound's molecular structure and the sensitivity of the method as well as the electronic flow direction in the conjugated system of azo compounds were studied. A theory that conjugated system's electron cloud in azo compound's molecule flowed from coupling compounds to diazo compounds through nitrogen and nitrogen double bond was proposed. This theory had a guiding function for exploiting highly sensitive chromogenic agents. Furthermore, the conditions and methods of diazo reaction and coupling chromogenic reaction were investigated. A spectrophotometry that p-aminobenzenesulfonic acid as diazo compound and 2-amino-5-naphthol-7-sulfonic acid (J acid) as coupling compound for the determination of nitrogen oxides in the air was established. The maximum absorption wavelength of p-aminobenzenesulfonic acid-J acid azo compound was at 480 nm. And the molar absorptivity was 4.01 × 104 L mol−1 cm−1 with recovery of 98.5%–100.9% and R.S.D. of 1.82%. In addition, the determination limit of measurement was 0.017 mg m−3 nitrogen oxides and the determination range was 0.027–2.0 mg m−3 nitrogen oxides. This method can be easily applied to the determination of the nitrogen oxides in the air.
Afficher plus [+] Moins [-]Preliminary characterization of biosurfactant produced by a PAH-degrading Paenibacillus sp. under thermophilic conditions
2016
Mesbaiah, Fatma Zohra | Eddouaouda, Kamel | Badis, Abdelmalek | Chebbi, Alif | Hentati, Dorra | Sayadi, Sami | Chamkha, Mohamed
The capacities of a biosurfactant producing and polycyclic aromatic hydrocarbon (PAH) utilizing bacterium, namely, strain 1C, isolated from an Algerian contaminated soil, were investigated. Strain 1C belonged to the Paenibacillus genus and was closely related to the specie Paenibacillus popilliae, with 16S rRNA gene sequence similarity of 98.4 %. It was able to produce biosurfactant using olive oil as substrate. The biosurfactant production was shown by surface tension (32.6 mN/m) after 24 h of incubation at 45 °C and 150 rpm. The biosurfactant(s) retained its properties during exposure to elevated temperatures (70 °C), relatively high salinity (20 % NaCl), and a wide range of pH values (2–10). The infrared spectroscopy (FTIR) revealed that its chemical structure belonged to lipopeptide class. The critical micelle concentration (CMC) of this biosurfactant was about 0.5 g/l with 29.4 mN/m. In addition, the surface active compound(s) produced by strain 1C enhanced PAH solubility and showed a significant antimicrobial activity against pathogens. In addition to its biosurfactant production, strain 1C was shown to be able to utilize PAHs as the sole carbon and energy sources. Strain 1C as hydrocarbonoclastic bacteria and its interesting surface active agent may be used for cleaning the environments polluted with polyaromatic hydrocarbons.
Afficher plus [+] Moins [-]Achromobacter xylosoxidans as a new microorganism strain colonizing high-density polyethylene as a key step to its biodegradation
2016
Kowalczyk, Anna | Chyc, Marek | Ryszka, Przemysław | Latowski, Dariusz
This study presents results of research on isolation new bacteria strain Achromobacter xylosoxidans able to effect on the structure of high-density polyethylene (HDPE), polymer resistant to degradation in environment. New strain of A. xylosoxidans PE-1 was isolated from the soil and identified by analysis of the 16S ribosome subunit coding sequences. The substance to be degraded was HDPE in the form of thin foil films. The foil samples were analyzed with Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) as well as scanning electron microscope (SEM), and the results revealed degradation of chemical structure of HDPE. About 9 % loss of weight was also detected as a result of A. xylosoxidans PE-1 effect on HDPE foil. On the basis of comparative spectral analysis of the raw material before the bacteria treatment and the spectrum from a spectra database, it was assumed that the HDPE was the only source of carbon and energy for the microorganisms. No fillers or other additives used in the plastic processing were observed in HDPE before experiments. This is the first communication showing that A. xylosoxidans is able to modify chemical structure of HDPE, what was observed both on FTIR, in mass reduction of HDPE and SEM analysis. We also observed quite good growth of the bacteria also when the HDPE was the sole carbon source in the medium. These results prove that A. xylosoxidans is an organism worth applying in future HDPE biodegradation studies.
Afficher plus [+] Moins [-]Thermodynamic entropy of organic oxidation in the water environment: experimental evaluation compared to semi-empirical calculation
2016
Luo, Li | Wang, Xiaochang C. | Ngo, Huu Hao | Guo, Wenshan
Residual organic matters in the secondary effluent are usually less biodegradable in terms of the total organic carbon content, and when discharged into a receiving water body, their further decomposition most likely mainly occurs due to chemical oxidation. Using this scenario, a semi-empirical method was previously developed to calculate the thermodynamic entropy of organic oxidation to quantitatively evaluate the impact of organic discharge on the water environment. In this study, the relationship between the entropy increase (ΔSC) and excess organic mass (ΔTOC) was experimentally verified via combustion heat measurement using typical organic chemicals and mixtures. For individual organic chemicals, a linear relationship was detected between ΔSC and ΔTOC with the same proportionality coefficient, 54.0 kJ/g, determined in the previous semi-empirical relationship. For the organic mixtures, a linear relationship was also identified; however, the proportionality coefficient was 69.2 kJ/g, indicating an approximately 28 % increase in the oxidation heat required to decompose the same organic mass. This increase in energy can likely be attributed to the synergistic effects of hydrogen bonding, hydrophobic interactions, π–π interactions, and van der Waals interactions between functional groups of different organic compounds. Intermolecular interactions may result in 17–32 % more dissociation energy for organic mixtures compared to the organic components’ chemical structures. Because organics discharged into a water body are always a mixture of organic compounds, the proportionality coefficient obtained using organic mixtures should be adopted to modify the previously proposed semi-empirical equation.
Afficher plus [+] Moins [-]Immobilization of fungal laccase onto a nonionic surfactant-modified clay material: application to PAH degradation
2016
Chang, Yi-Tang | Lee, Jiunn-Fwu | Liu, Keng-Hua | Liao, Yi-Fen | Yang, Vivian
Nonionic surfactant-modified clay is a useful absorbent material that effectively removes hydrophobic organic compounds from soil/groundwater. We developed a novel material by applying an immobilized fungal laccase onto nonionic surfactant-modified clay. Low-water-solubility polycyclic aromatic hydrocarbons (PAHs) (naphthalene/phenanthrene) were degraded in the presence of this bioactive material. PAH degradation by free laccase was higher than degradation by immobilized laccase when the surfactant concentration was allowed to form micelles. PAH degradation by immobilized laccase on TX-100-modified clay was higher than on Brij35-modified clay. Strong laccase degradation of PAH can be maintained by adding surfactant monomers or micelles. The physical adsorption of nonionic surfactants onto clay plays an important role in PAH degradation by laccase, which can be explained by the structure and molecular interactions of the surfactant with the clay and enzyme. A system where laccase is immobilized onto TX-100-monomer-modified clay is a good candidate bioactive material for in situ PAHs bioremediation.
Afficher plus [+] Moins [-]Antibiofouling potential of quercetin compound from marine-derived actinobacterium, Streptomyces fradiae PE7 and its characterization
2016
Gopikrishnan, Venugopal | Radhakrishnan, Manikkam | Shanmugasundaram, Thangavel | Pazhanimurugan, Raasaiyah | Balagurunathan, Ramasamy
An attempt has been made to isolate, purify and characterize antifouling compound from Streptomyces fradiae PE7 isolated from Vellar estuarine sediment, Parangipettai, South India. The microbial identification was done at species level based on its phenotypic, cell wall and molecular characteristics. Strain PE7 produced high quantity of antifouling compounds in agar surface fermentation when compared to submerged fermentation. In fermentation optimization, wide range of sugars, amino acids, minerals, pH, temperature and NaCl concentration was found to influence the antifouling compound production from the strain PE7. Antifouling compound PE7-C was purified from the crude extract by preparative TLC, and its activity against biofouling bacteria was confirmed by bioautography. Based on the physico-chemical characteristics, the chemical structure of the antifouling compound PE7-C was identified as quercetin (C₁₅H₁₀O₇), a flavonoid class of compound with the molecular weight 302.23 g/mol. The purified quercetin was active against 18 biofouling bacteria with MIC range between 1.6 and 25 μg/ml, algal spore germination and mollusc foot adherence found at 100 μg/ml and 306 ± 19.6 μg ml⁻¹ respectively. The present study, for the first time, reported quercetin from marine-derived Streptomyces sp. PE7 with antifouling activity. This also leads to the repurposing of quercetin for the development of antifouling agent.
Afficher plus [+] Moins [-]Highly stable rice-straw-derived charcoal in 3700-year-old ancient paddy soil: evidence for an effective pathway toward carbon sequestration
2016
Wu, Mengxiong | Yang, Min | Han, Xingguo | Zhong, Ting | Zheng, Yunfei | Ding, Pin | Wu, Weixiang
Recalcitrant charcoal application is predicted to decelerate global warming through creating a long-term carbon sink in soil. Although many studies have showed high stability of charcoal derived from woody materials, few have focused on the dynamics of straw-derived charcoal in natural environment on a long timescale to evaluate its potential for agricultural carbon sequestration. Here, we examined straw-derived charcoal in an ancient paddy soil dated from ~3700 calendar year before present (cal. year BP). Analytical results showed that soil organic matter consisted of more than 25 % of charcoal in charcoal-rich layer. Similarities in morphology and molecular structure between the ancient and the fresh rice-straw-derived charcoal indicated that ancient charcoal was derived from rice straw. The lower carbon content, higher oxygen content, and obvious carbonyl of the ancient charcoal compared with fresh rice straw charcoal implied that oxidation occurred in the scale of thousands years. However, the dominant aromatic C of ancient charcoal indicated that rice-straw-derived charcoal was highly stable in the buried paddy soil due to its intrinsic chemical structures and the physical protection of ancient paddy wetland. Therefore, it may suggest that straw charcoal application is a potential pathway for C sequestration considering its longevity.
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