Removal of phenanthrene in aqueous solution containing photon competitors by TiO2-C-Ag film supported on fiberglass.

Surface interactions with pollutants and photons are key factors that affect the applications of TiO2 in environmental remediation. In this study, the solubilizing agents dimethylsulfoxide and polyoxyethylene sorbitan monooleate, which act as photon competitors, had no effect on the photocatalytic activity of TiO2-C-Ag film in phenanthrene (PHE) removal. Fiberglass with TiO2-C-Ag coating removed 91.1 ± 5.2 and 99.7 ± 0.4% of PHE in treatments using UVA (365-465 nm) and UVC (254 nm) irradiation, respectively. The use of fiberglass as a support increased the superficial area, thus allowing PHE sorption. C and Ag, which are electrically active impurities in TiO2, enhanced its photocatalytic activity and thus the attraction of the pollutant to its surface. The use of high-frequency UV light (UVC) decreased the amount of carbon species deposited on the TiO2CAg film surface. X-ray photoelectron spectroscopy of the TiO2-C-Ag film revealed extensive oxidation of the carbon deposited on the film under UVC light and loss of electrons from Ag clusters by conversion of Ag0 to Ag3+.

Production of a halotolerant biofilm from green coffee beans immobilized on loofah fiber (Luffa cylindrica) and its effect on phenanthrene degradation in seawater.

A biofilm developed from low quality green coffee beans was tested for its capacity to degrade the polynuclear aromatic hydrocarbon (PAH), phenanthrene (Phe), in seawater. Microorganisms were immobilized on two types of Luffa cylindrica (with three and four placental cavities), and the effects of moisture content (20, 30 and 40% of water holding capacity) and particle size (<0.42 mm, 0.42-0.86 mm and 0.86-2.0 mm) of green coffee beans on microbial activity were considered. Biofilm growth determined by respirometry showed a highest microbial activity at a moisture content of 40% and particle size of 0.42-0.86 mm. The loofah fiber with three placental cavities showed the highest adherence of microorganisms. The kinetics of microbial growth in both seawater and distilled water and the scanning electron microscopies indicated that the microorganisms associated with green coffee beans are halotolerant. In fact, I-GCB-SW-G biofilm degraded 67.56% of Phe (50 mg L-1) in seawater, at a significantly higher rate than in distilled water (I-GCB-DW-W).

The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species.

The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process.

Long-term response on growth, antioxidant enzymes, and secondary metabolites in salicylic acid pre-treated Uncaria tomentosa microplants.

OBJECTIVE: To obtain micro propagated Uncaria tomentosa plantlets with enhanced secondary metabolites production, long-term responses to salicylic acid (SA) pre-treatments at 1 and 100 µM were evaluated after propagation of the plantlets in a SA-free medium. RESULTS: SA pre-treatments of single node cuttings OF U. tomentosa produced long-term responses in microplants grown for 75 days in a SA-free medium. Reduction in survival rate, root formation, and stem elongation were observed only with 100 µM SA pre-treatments with respect to the control (0 + DMSO).Both pre-treatments enhanced H2O2 and inhibited superoxide dismutase and catalase activities, while guaiacol peroxidase was increased only with 1 µM SA. Also, both pre-treatments increased total monoterpenoid oxindole alkaloids by ca. 55 % (16.5 mg g(-1) DW), including isopteropodine, speciophylline, mitraphylline, isomitraphylline, rhynchopylline, and isorhynchopylline; and flavonoids by ca. 21 % (914 µg g(-1) DW), whereas phenolic compounds were increased 80 % (599 µg g(-1) DW) at 1 µM and 8.2 % (359 µg g(-1) DW) at 100 µM SA. CONCLUSION: Pre-treatment with 1 µM SA of U.tomentosa microplants preserved the survival rate and increased oxindole alkaloids, flavonoids, and phenolic compounds in correlation with H2O2 and peroxidase activity enhancements, offering biotechnological advantages over non-treated microplants.

Scenedesmus incrassatulus CLHE-Si01: a potential source of renewable lipid for high quality biodiesel production.

The potential of microalgal oil from Scenedesmus incrassatulus as a feedstock for biodiesel production was studied. Cell concentration of S. incrassatulus and lipid content obtained during mixotrophic growth were 1.8 g/L and 19.5 ± 1.5% dry cell weight, respectively. The major components of biodiesel obtained from S. incrassatulus oil were methyl palmitate (26%) and methyl linoleate (49%), which provided a strong indication of high quality biodiesel. Fuel properties were determined by empirical equations and found to be within the limits of biodiesel standard ASTM D6751 and EN 14214. The quality properties of the biodiesel were high cetane number (62), low density (803 kg/m(3)), low viscosity (3.78 mm(2)/s), oxidation stability (9h) and cold filter plugging point (-4°C). Hence, S. incrassatulus has potential as a feedstock for the production of excellent quality biodiesel.

Strictosidine-related enzymes involved in the alkaloid biosynthesis of Uncaria tomentosa root cultures grown under oxidative stress.

The activity and gene expression of strictosidine-related enzymes in Uncaria tomentosa root cultures exposed to oxidative stress were studied. Elicitation with 0.2 mM hydrogen peroxide (H2 O2 ) or a combination of 0.8 mM buthionine sulfoximine and 0.2 mM jasmonic acid (BSO-JA) increased peroxidase activities by twofold at Day 8 and glutathione reductase by 1.4-fold at Day 5 in H2 O2 elicited cultures respect to the control. Production of monoterpenoid oxindole alkaloids (MOA), 3α-dihydrocadambine, and dolichantoside was stimulated after H2 O2 elicitation, reaching levels of 886.4 ± 23.6, 847.7 ± 25.4, and 87.5 ± 7.2 µg/g DW, at Day 8 which were 1.7-, 2.1-, and 2.3-fold higher relative to control. BSO-JA elicited cultures produced about twice alkaloids than H2 O2 -treated cultures, following a biphasic pattern with maxima at 0.5 and 8 days. Alkaloid production was preceded by increase in strictosidine synthase (STR) and strictosidine glucosidase (SGD) activities. After elicitation with H2 O2 or BSO-JA, the STR activity (pKat/mg protein) increased by 1.9-fold (93.8 ± 17.8 at 24 h) or 2.5-fold (102.4 ± 2.2 at 6 h) and the SGD activity (pKat/mg protein) by 2.8-fold (245.2 ± 14.4 at 6 h) or 4.2-fold (421.2 ± 1.8 at 18 h) relative to control. STR and SGD transcripts were upregulated after elicitation. H2 O2 -treated roots showed higher levels of STR at 48-192 h and SGD at 24-48 h, while BSO-JA treatments showed STR increased at 12 h and SGD at 24 h. Also, LC/ESI-MS confirmed the biosynthesis of dolichantoside from N-ω-methyltryptamine and secologanin by U. tomentosa protein extracts.

Application of 2III7-3 fractional factorial experimental design to enhance enzymatic activities of Pleurotus ostreatus with high concentrations of polychlorinated biphenyls.

A 2(III)(7-3) fractional factorial experimental design was used to establish 16 culture media, with and without PCBs to enhance the activities of laccase (Lac), manganese peroxidase (MnP), and versatile peroxidase (VP) produced by the white rot fungus Pleurotus ostreatus. The culture was added to 10,000 mg L(-1) of transformer oil, containing 71% of the identified Arochlor 1242. The culture conditions were established with eight variables at two values (levels); pH (4 and 6), agitation (100 and 200 rpm), CuSO(4) (150 and 250 mg L(-1)), MnSO(4) (50 and 200 mg L(-1)), Tween 80 (13 and 3500 mg L(-1)), wheat straw (0 and 2.5 g L(-1)), sugarcane bagasse (0 and 2.5 g L(-1)),and Arochlor 1242 (0 and 7100 mg L(-1)) at 4, 8, 12, 16 and 20 days old culture. Laccase activity was enhanced at a high value of pH and low value of agitation (P<0.001) and correlated positively (R(2)= 0.9; α=0.05) with the removal of polychlorinated biphenyls (PCBs). VP activity was enhanced 27-fold with PCBs, Tween 80 and pH. The MnP activity was increased 1.2-fold with PCBs. The fractional factorial experimental design methodology allowed us to determine the P. ostreatus culture media conditions to enhance Lac and VP activities for efficient removal of Arochlor 1242 (one of the most recalcitrant organochloride pollutants). The factors that shown the greatest effect on Lac activity were: pH, agitation and high concentrations of Arochlor 1242.

Small microcapsules of crystal proteins and spores of Bacillus thuringiensis by an emulsification/internal gelation method.

This paper describes a microencapsulation process of a spore crystal aggregate produced by Bacillus thuringiensis var. kurstaki HD-1. The methodology is based on the emulsification/internal gelation method, and was implemented to produce microcapsules of small diameter (< 10 µm) with the capacity to protect the spore crystal aggregate from extreme ultraviolet radiation. The diameter of microcapsules was in the range of 3.1 ± 0.2-6.8 ± 0.4 µm, which is considered adequate for biological control purposes. The protective effect of the alginate coat was verified by the remaining 60 ± 2% and 40 ± 1% of spore viability and protein activity, respectively, after UV-B radiation of 236 J, and with bioassays with Spodoptera frugiperda. It is expected that the protective effect of the alginate coat will improve the effectiveness of the Bt-HD1 formulated as small diameter microcapsules, and their yield, once they are released into the environment, will also be improved.

Encystment of Azotobacter nigricans grown diazotrophically on kerosene as sole carbon source.

Encystment of Azotobacter nigricans was induced by its diazotrophic cultivation on kerosene. Its growth and nitrogenase activity were affected by kerosene in comparison to cultures grown on sucrose. Electron microscopy of vegetative cells showed that when nitrogenase activity was higher and the poly-beta-hydroxybutyrate granules were not present to a significant extent, peripheral bodies were abundant. After 8 days of culture on kerosene, the presence of cysts with intracellular bunches of poly-beta-hydroxybutyrate granules was observed. Germination of cysts bears germinating multicelled yet unbroken capsule cysts with up to three cells inside. This is the first report of encystment induction of Azotobacter species grown on kerosene.

Short-term accumulation of atrazine by three plants from a wetland model system.

This work describes the accumulation and distribution of the herbicide atrazine in soil, water, and roots from three wetland model systems using the monocots Typha domingensis, Sagittaria lancifolia, and Echinochloa pyramidalis. Results were analyzed from a 3(3) full factorial experimental design, in order to describe the effect of accumulation of atrazine and times of exposure in the species evaluated. We found that accumulation depends on the species and the herbicide concentration; about 30% was accumulated in soil, 40% in roots, and 10-20% in water. By the end of the experiment, E. pyramidalis accumulated 8.47 mg/l of atrazine and 14.39 mg/l T. domingensis; in all cases, adsorption accounted for 1.4%, fitting a Langmuir model with a k(d) of 14.47.

Fenton (H2O2/Fe) reaction involved in Penicillium sp. culture for DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation.

The purpose of this work was to demonstrate that a Fenton (H(2)O(2)/Fe) reaction was involved in DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation in a culture of Penicillium sp. spiked with FeSO(4). A commercial DDT mixture (10% DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], 30% o,p-DDT and 60% of p,p' -DDT) of 10 mg L(-1) was used. Hydrogen peroxide (H(2)O(2)), tartaric acid and oxalic acid were identified at 18 h in culture media, with and without added DDT; this correlated positively with lowering of pH from 5.8 to 2.7. Lower concentrations of oxalic acid and H(2)O(2) (7.9 and 52.6 mg L(-1), respectively) occurred in media with DDT at 30 h, in comparison to that one without DDT mixture (27.9 and 65.3 mg L(-1), respectively), at this time there was maximum degradation (87.7, 91.7 and 94.2%) for DDE, o,p-DDT and p,p'-DDT, respectively. We propose that the degradation of the DDT mixture by Penicillium sp. was through a Fenton reaction (H(2)O(2)/Fe) under acidic conditions produced in situ during the fungal culture amended with FeSO(4).

Comportamiento adsortivo-desortivo del lindano en un suelo agrícola / Adsorptive-desorptive benhaviour of lindane in an agricultural soil

El objetivo de este trabajo fue estudiar el comportamiento adsortivo-desortivo del pesticida lindano en un suelo agrícola con importante contenido de materia orgánica, utilizando el coeficiente de histéresis diferencial (CHPoggi). Además se obtuvo una expresión analítica simple del CHPoggi para el caso mixto, cuando la isoterma de adsorción sigue el modelo lineal y la isoterma de desorción sigue el modelo de Langmuir. Se obtuvo una isoterma de adsorción lineal, q= 3,91·C y una isoterma de desorción de tipo Langmuir, q= (32,9·C)/(1+1,11·C). Utilizando ambas isotermas y la definición del coeficiente de histéresis diferencial, se dedujo una expresión matemática para éste en un punto de interés (qj, Cj) de la forma CHPoggi= a·b/kl , donde a: capacidad máxima de la curva de desorción en mg·kg-1; b: coeficiente relacionado a la razón de crecimiento de la curva de desorción, en l·mg-1; y kl: coeficiente de adsorción lineal en l·kg-1. El valor del coeficiente de histéresis para un punto de interés q= 24,5mg·kg-1 y C= 6,0mg·l-1, utilizando las tangentes de ambas isotermas dió un valor de 6,6, y utilizando la expresión matemática se obtuvo un valor de 8,4 indicando una buena aproximación al primer método al considerar los errores experimentales. El valor de CHPoggi indica que la histéresis lindano-suelo agrícola fue moderada a alta

Phenotypic plasticity in Scenedesmus incrassatulus (Chlorophyceae) in response to heavy metals stress.

The microalgae genus Scenedesmus is commonly found in freshwater bodies, wastewater facilities and water polluted with heavy metals. Phenotypic plasticity in Scenedesmus has been documented in response to a wide variety of conditions; however, heavy metals have not been comprehensively documented as phenotypic plasticity inducers. In this study, we report the phenotypic plasticity of Scenedesmus incrassatulus (a non-spiny, four-cell coenobium forming species) in response to EC(50) value of copper, cadmium and hexavalent chromium. S. incrassatulus was grown in batch cultures in the presence of each metal. Chlorophyll-a content, cell size, parameters derived from the schematic energy-flux model for photosystem II, and morphotype expressions were recorded. Divalent cation metals induced unicellular forms, and hexavalent chromium produced out-of-shape coenobia corresponding to various stages of autospore formation. The changes induced by divalent metals were interpreted as phenotypic plasticity, because they were always associated to population doublings and were reversible when toxicant pressure was removed (only for Cu). Copper was the best inductor of unicellular forms and also affected significantly all the photosynthetic parameters measured. The developed morphotypes could confer ecological advantages to S. incrassatulus in metal stressed environments.

Remoción de percloroetileno en dos tipos de sistemas anaerobios continuos

Se evaluó y comparó el desempeño de dos reactores mesofílicos metanogénicos de mezcla completa escala laboratorio (RMC1, RMC2) y un reactor metanogénico de lecho fluidizado (RANLEF, con carbón activado granular como soporte) para remoción de percloretileno (PCE) tras adicionar una moderada cantidad de metanol en el afluente. Los reactores fueron operados con cargas de 0,07 y 1gDQO·l-1·d-1, y tiempos de retención hidráulica de 15 y 1d, respectivamente. El diseño experimental consistió en tres períodos de operación: régimen metanogénico con metanol como fuente de C (periodo 1), igual con aclimatación a 20mgPCE·l-1 (periodo 2.1) o 40mgPCE·l-1 (2.2), e igual con 40mgPCE·l-1 en RANLEF y RMC1, y 20mgPCE·l-1 en RMC2 (periodo 3). La eficiencia de PCE y DQO fue más alta en RANLEF en el primer periodo; el CH4 en biogás y el incremento de cloro fueron similares en los tres reactores. Durante el periodo 2.2 la remoción de PCE alcanzó 81% en RANLEF, sugestivo de buena aclimatación a mayor entrada de PCE; la remoción de DQO se mantuvo alta, y el contenido de CH4 en biogás alcanzó un valor medio de 64% v/v, indicando un régimen metanogénico satisfactorio. Los RMCs experimentaron un deterioro drástico en su desempeño al aumentar PCE de 20 a 40mg·l-1, por lo que se regresó el RMC1 a 20mg·l-1. El desempeño de RMC2 se mantuvo bajo, sugiriendo un impacto negativo sobre la metanogénesis y remoción de PCE. En contraste, el RMC1 con 20mg·l-1 se recuperó del estado transitorio negativo, exhibiendo desempeño similar al RANLEF alimentado con 40mg·l-1. En el período 3, el RANLEF con 40mg·l-1 y el RMC1 con 20mg·l-1 mostraron desempeño similar, mientras que el RMC2 con 40mg·l-1 exhibió una disminución en la eficiencia de remoción de DQO, baja productividad de biogás y contenido de CH4 en biogás, pero la remoción de PCE estuvo cerca de RANLEF y RMC1. La eficiencia de descloración del RMC2 fue significativamente menor que la del RANLEF, el cual fue más robusto y estable en el proceso anaerobio de remoción de alta concentración de PCE.

Performance was evaluated and compared in two lab-scale mesophilic methanogenic complete mix reactors (RMC1, RMC2) and a methanogenic fluidized bed reactor (RANLEF) for removal of perchloroethylene (PCE) when fed a moderate concentration of methanol. The RMCs and RANLEF were operated at loading rates of 0.07 and 1gCOD·l-1·d-1, and hydraulic retention times of 15 and 1 day, respectively. The experimental design consisted of three periods of operation: methanogenic regime with methanol as carbon source (1); same with acclimation to 20 (2.1) or 40mgPCE·l-1 (2.2); and same with 40mgPCE·l-1 in RANLEF and RMC1 and 20 mgPCE·l-1 in RMC2 (3). In the first period both PCE and COD removals were higher in RANLEF; biogas CH4 content and chloride increase were similar in the three reactors. During period 2.2, PCE removal increased up to 81% in RANLEF, suggesting a good acclimation to the higher inflow PCE concentration; COD reduction remained high, and CH4 in biogas indicated a satisfactory methanogenic regime. The RMCs experienced drastic performance impairments upon increase of inflow PCE (20 to 40mg·l-1), and RMC1 was returned to operate with 20mgPCE·l-1. RMC2 performance remained poor, showing a drastic deterioration of methanogenesis and PCE removal. By contrast, RMC1 with 20mgPCE·l-1 recovered from the negative transient state and exhibited similar performance to that of RANLEF fed 40mg·l-1. In period 3, RANLEF with 40mg·l-1 and RMC1 with 20mg·l-1 showed similar performances, whereas RMC2 kept with 40mg·l-1 exhibited impaired COD removal, lower biogas productivity and CH4 biogas content, but a PCE removal very close to RANLEF and RMC1. The dehalogenation efficiency of RMC2 was significantly lower than that of the RANLEF, which appears to be a more robust and stable anaerobic process for the effective removal of high concentrations of PCE.

Avaliou-se e comparou-se o desempenho de dois reatores mesofílicos metanogênicos de mistura completa escala laboratório (RMC1, RMC2) e um reator metanogênico de leito fluidizado (RANLEF, com carvão ativado granular como suporte) para remoção de percloretileno (PCE) depois de adicionar uma moderada quantidade de metanol no afluente. Os reatores foram operados com cargas de 0,07 e 1gDQO·l-1·d-1, e tempos de retenção hidráulica de 15 e 1d, respectivamente. O projeto experimental consistiu em três períodos de operação: regime metanogênico com CH4 como fonte de carbono (1), igual com aclimatação a 20mgPCE·l-1 (2.1) ou 40mgPCE·l-1 (2.2), e igual com 40mgPCE·l-1 em RANLEF e RMC1, e 20mgPCE·l-1 em RMC2 (3). A eficiência de PCE e DQO foi mais alta em RANLEF no primeiro período; o CH4 em biogás e o incremento de cloro foram similares nos três reatores. Durante o período 2.2 a remoção de PCE alcançou 81% em RANLEF, sugestivo de boa aclimatação a maior entrada de PCE; a remoção de DQO se manteve alta, e o conteúdo de CH4 em biogás alcançou um valor médio de 64% v/v, indicando um regime metanogênico satisfatório. Os RMCs experimentaram um deterioro drástico no seu desempenho ao aumentar PCE de 20 a 40mg·l-1, pelo que se regressou o RMC1 a 20mg·l-1. O desempenho de RMC2 se manteve baixo, sugerindo um impacto negativo sobre a metanogênesis e remoção de PCE. Em contraste, o RMC1 com 20mg·l-1 se recuperou do estado transitório negativo, exibindo desempenho similar ao RANLEF alimentado com 40mg·l-1. No período 3, o RANLEF com 40mg·l-1 e o RMC1 com 20mg·l-1 mostraram desempenho similar, enquanto que o RMC2 com 40mg·l-1 exibiu uma diminuição na eficiência de remoção de DQO, baixa produtividade de biogás e conteúdo de CH4 em biogás, mas a remoção de PCE esteve perto de RANLEF e RMC1. A eficiência de descloração do RMC2 foi significativamente menor que a do RANLEF, o qual foi mais robusto e estável no processo anaeróbio de remoção de alta concentração de PCE.

Specific synthesis of 5,5'-dicapsaicin by cell suspension cultures of capsicum annuum var. annuum (chili Jalapeño chigol) and their soluble and NaCl-extracted cell wall protein fractions.

HPLC-UV, (1)H NMR, (13)C NMR, and (1)H-(1)H COSY analyses revealed that exogenous capsaicin was specifically converted into 5,5'-dicapsaicin by both cell suspension cultures of Capsicum annuum var. annuum (chili Jalapeño chigol) and their soluble and NaCl-extracted cell wall protein fractions under oxidative conditions. In cell suspension cultures 5,5'-dicapsaicin was found only in biomass of capsaicin-fed cultures. This compound has not been detected before either in fresh fruits or in in vitro cultures of Capsicum. The transformation of capsaicin by different protein fractions revealed that most of the enzymatic activity was located in the NaCl-extracted, or ionic cell wall bound, protein, and that it was strictly dependent on H(2)O(2). These results might in part explain some previously described features of capsaicin production by in vitro cultures of Capsicum. The implications of the results regarding the catabolism of capsaicinoids are discussed.