Degradation of anti-inflammatory drugs in municipal wastewater by heterogeneous photocatalysis and electro-Fenton process.

Non-steroidal anti-inflammatory drugs (NSAID) are compounds frequently found in municipal wastewater and their degradation by conventional wastewater treatment plants (WWTP) is generally incomplete. This study compared the efficiency of two advanced oxidation processes (AOP), namely heterogeneous photocatalysis (HP) and electro-Fenton (EF), in the degradation of a mixture of common NSAID (diclofenac, ibuprofen and naproxen) dissolved in either deionized water or effluent from a WWTP. Both processes were effective in degrading the NSAID mixture and the trend of degradation was as follows, diclofenac > naproxen > ibuprofen. EF with a current density of 40 mA cm-2 and 0.3 mmol Fe2+ L-1 was the most efficient process to mineralize the organic compounds, achieving up to 92% TOC removal in deionized water and 90% in the WWTP effluent after 3 h of reaction. HP with 1.4 g TiO2 L-1 at pH 7 under sunlight, produced 85% TOC removal in deionized water and 39% in WWTP effluent also after 3 h treatment. The lower TOC removal efficiency shown by HP with the WWTP effluent was attributed mainly to the scavenging of reactive species by background organic matter in the wastewater. On the contrary, inorganic ions in the wastewater may produce oxidazing species during the EF process, which contributes to a higher degradation efficiency. EF is a promising option for the treatment of anti-inflammatory pharmaceuticals in municipal WWTP at competitive electrical energy efficiencies.

Photo-assisted electrochemical degradation of polychlorinated biphenyls with boron-doped diamond electrodes.

The capacity of the photo electro-Fenton (PEF) process to degrade a mixture of seven polychlorinated biphenyl (PCB) congeners was studied. Boron-doped diamond (BDD) sheets were used as anode and cathode in the experimental electrolytic cell that contained Na2SO4 0.05 M at pH 3 as supporting electrolyte for the electro generation of H2O2 at the cathode. The effects of UV light intensity (254 and 365 nm), current density (8, 16 and 24 mA cm-2) and ferrous ion dosage (0.1, 0.2 and 0.3 mM) on PCB (C0 = 50 µg L-1) degradation were evaluated. The highest level of PCB degradation (97%) was achieved with 16 mA cm-2 of current density, 0.1 mM of ferrous ion and UV light at 365 nm as irradiation source after 6 h of reaction. PCB28, PCB52 and PCB101 were not detected after 0.5, 1.5 and 3 h of reaction, respectively. The degradation of PCB138, PCB153, PCB180 and PCB209 was also high (>95%). The PEF system outperformed other oxidation processes (electro-Fenton, anodic oxidation, Fenton, photo-Fenton and UV photolysis) in terms of reaction rate and degradation efficiency. These results demonstrate for the first time the degradation of PCB209, the most highly chlorinated PCB congener, by an advanced electrochemical oxidation process.

[Agroindustrial wastes methanization and bacterial composition in anaerobic digestion]. / Residuos agroindustriales con potencial para la producción de metano mediante la digestión anaerobia.

The tons of organic waste that are annually generated by agro-industry, can be used as raw material for methane production. For this reason, it is important to previously perform biodegradability tests to organic wastes for their full scale methanization. This paper addresses biodegradability, methane production and the behavior of populations of eubacteria and archaeabacteria during anaerobic digestion of banana, mango and papaya agroindustrial wastes. Mango and banana wastes had higher organic matter content than papaya in terms of their volatile solids and total solid rate (94 and 75% respectively). After 63 days of treatment, the highest methane production was observed in banana waste anaerobic digestion: 63.89ml CH4/per gram of chemical oxygen demand of the waste. In the PCR-DGGE molecular analysis, different genomic footprints with oligonucleotides for eubacteria and archeobacteria were found. Biochemical methane potential results proved that banana wastes have the best potential to be used as raw material for methane production. The result of a PCR- DGGE analysis using specific oligonucleotides enabled to identify the behavior of populations of eubacteria and archaeabacteria present during the anaerobic digestion of agroindustrial wastes throughout the process.

Residuos agroindustriales con potencial para la producción de metano mediante la digestión anaerobia / Agroindustrial wastes methanization and bacterial composition in anaerobic digestion

Las toneladas de residuos orgánicos que se generan anualmente en la agroindustria pueden aprovecharse como materia prima para la producción de metano. Para que los residuos orgánicos se puedan convertir a metano a gran escala, es importante que previamente se realicen sobre ellos pruebas de biodegradabilidad; un parámetro importante que conviene establecer es su potencial bioquímico de metano. En el presente trabajo se estudió la biodegradabilidad, la producción de metano y el comportamiento de poblaciones de eubacterias y arqueobacterias durante la digestión anaerobia de residuos de plátano, mango y papaya provenientes de la agroindustria, adicionando un inóculo microbiano. Los residuos de mango y plátano tenían mayor contenido de materia orgánica (94 y 75 %, respectivamente) que el residuo de papaya con base en su relación sólidos volátiles/sólidos totales. Después de 63 días de tratamiento, la mayor producción de metano se observó en la digestión anaerobia del residuo de plátano: 63,89 ml de metano por g de demanda química de oxígeno del residuo. Los resultados del potencial bioquímico de metano demostraron que el residuo de plátano tiene el mejor potencial para ser usado como materia prima en la producción de metano. A través de un análisis por PCR-DGGE con oligonucleótidos específicos se logró evaluar el tamaño y la composición de las poblaciones de eubacterias y arqueobacterias presentes en la digestión anaerobia de residuos agroindustriales a lo largo del proceso.

The tons of organic waste that are annually generated by agro-industry, can be used as raw material for methane production. For this reason, it is important to previously perform biodegradability tests to organic wastes for their full scale methanization. This paper addresses biodegradability, methane production and the behavior of populations of eubacteria and archaeabacteria during anaerobic digestion of banana, mango and papaya agroindustrial wastes. Mango and banana wastes had higher organic matter content than papaya in terms of their volatile solids and total solid rate (94 and 75 % respectively). After 63 days of treatment, the highest methane production was observed in banana waste anaerobic digestion: 63.89 ml CH4/per gram of chemical oxygen demand of the waste. In the PCR-DGGE molecular analysis, different genomic footprints with oligonucleotides for eubacteria and archeobacteria were found. Biochemical methane potential results proved that banana wastes have the best potential to be used as raw material for methane production. The result of a PCR- DGGE analysis using specific oligonucleotides enabled to identify the behavior of populations of eubacteria and archaeabacteria present during the anaerobic digestion of agroindustrial wastes throughout the process.

Levels of organochlorine pesticides in blood plasma from residents of malaria-endemic communities in Chiapas, Mexico.

Organochlorine (OC) pesticides have been extensively used for pest control in agriculture and against malaria vectors in the region of Soconusco, Chiapas, in southern Mexico. Our study aimed to identify whether the inhabitants of four Soconusco communities at different locations (i.e., altitudes) and with different history of use of OC pesticides, have been similarly exposed to residues of these pesticides. In particular, we analyzed the potential relationship between levels of OC pesticides in plasma and the age, gender, and residence of the study population (n = 60). We detected seven pesticides in total (γ-HCH, ß-HCH, heptachlor, p,p'-DDE, p,p'-DDT, ß-endosulfan, endrin aldehyde). Of these, p,p'-DDE and ß-endosulfan were the most frequently found (in 98% and 38% of the samples, respectively). The low-altitude (<20 m above sea level; masl) and mid-altitude (520 masl) locations had the highest levels of p,p'-DDE, with geometric means of 50.6 µg/L and 44.46 µg/L, respectively. The oldest subjects (>60 years) had the highest p,p'-DDE level (56.94 ± 57.81 µg/L) of all age groups, while men had higher p,p'-DDE (34.00 ± 46.76 µg/L) than women. Our results demonstrate that residents of the Soconusco region are exposed to p,p'-DDE because of high exposure to DDT in the past and current environmental exposure to this DDT-breakdown product.

Occurrence of glyphosate in water bodies derived from intensive agriculture in a tropical region of southern Mexico.

Glyphosate is an agrochemical widely used to control weeds. However, glyphosate spreads to water bodies by spray-drift, run-off and leaching, potentially causing detrimental effects on non-target biota. There is no information on the occurrence of this herbicide in water bodies near crop fields in Mexico, although it is the most commonly used pesticide in this country. To fill this gap, we quantified glyphosate in water bodies from twenty-three locations, including natural protected areas and agricultural areas in southern Mexico, during the dry and the rainy seasons. We expected (1) higher concentrations during the dry season due to reduced dilution by precipitation and, (2) absence of glyphosate in the protected areas. In agreement with our expectation, concentration of glyphosate was higher during the dry season (up to 36.7 µg/L). Nonetheless, glyphosate was detected in all samples-including natural protected areas. These results emphasize the need for an evaluation of the impact of glyphosate on native species as well as regulate its use.

Shearing of biofilms enables selective layer based microbial sampling and analysis.

Granules are large, self-supporting biofilms that form naturally in high-rate anaerobic treatment systems and are extremely important to reactor functionality. Granules exhibit functional and phylogenetic layering, interesting to both scientists and technologists. Until now, it has only been possible to analyze layering through sectioning and microscopic analysis with fluorescent in situ hybridization, or to analyze the whole granule through DNA extraction and microbial community profiling methods. This means different functional and spatial layers cannot be analyzed separately, including next generation sequencing techniques, such as pyrotag sequencing. In this work, we describe a method to remove microbes selectively from successive spatial layers through hydraulic shearing and demonstrate its application on anaerobic granules of three different types (VFA-, carbohydrate-, protein-fed) in size ranges 0.6-2 mm. Outer layers in particular could be selectively sheared as confirmed by FISH. TRFLP was used as an example bulk DNA method on selectively sheared fractions. A shift in dominant population was found from presumptive acidogens (such as Bacteroidetes and Anaerolinea) in outer layers to syntrophs (such as Syntrophomonas and Geobacter) in inner layers, with progressive changes through the depth. The strength of the shear-bulk molecular method over FISH was that a deeper phylogenetic profile could be obtained, even with TRFLP, and that prior knowledge of the community is not required.

Production of prodigiosin and chitinases by tropical Serratia marcescens strains with potential to control plant pathogens.

The potential of three Serratia marcescens strains (CFFSUR-B2, CFFSUR-B3 and CFFSUR-B4) isolated from tropical regions in Mexico to inhibit the mycelial growth and conidial germination of Colletotrichum gloeosporioides, causal agent of fruit anthracnose, was evaluated. The ability of these strains to produce prodigiosin and chitinases when cultivated in oil seed-based media (peanut, sesame, soybean and castor bean) and in Luria-Bertani medium was determined. All of the strains exhibited similar fungal antagonistic activities and inhibited myceliar growth by more than 40% while inhibiting conidial germination by 81-89% (P = 0.01). The highest level of prodigiosin (40 µg/ml) was produced in the peanut-based medium while growth in soybean-based medium allowed the highest production of chitinases (56 units/ml), independent of the strain used. Strain CFFSUR-B2 grown in peanut medium was used to evaluate the effect of inoculum density and initial pH on metabolite production. The amount of prodigiosin produced increased with greater inoculum densities, with an initial density of 1 × 10(12) resulting in the highest production (60 µg/ml). Prodigiosin production was not affected by pH. The strains studied have the advantage of being adapted to tropical climates and are able to produce chitinases in the absence of chitin induction in vitro. These characteristics suggest their potential as biocontrol agents for fungal pathogens in tropical regions of the world.

Use of spent substrate after Pleurotus pulmonarius cultivation for the treatment of chlorothalonil containing wastewater.

Lignocellulosic materials are used as substrate for the cultivation of the edible mushroom Pleurotus pulmonarius. After two or three flushes of mushrooms, the spent substrate is discarded although it still has an important enzymatic activity that can be used for several purposes. In this study, we sought to determine the technical feasibility of using spent substrate from P. pulmonarius to degrade chlorothalonil. Reaction mixture was prepared with 6 ml of pesticide aqueous solution (2 mg active ingredient/l) and 3 ml of enzymatic extract obtained from spent P. pulmonarius substrate. The enzymatic reaction (27 °C, pH 7.4) was conducted for 1 h with sampling at 15 min intervals. The effect of storage time and temperature (freezing or refrigerating) of spent substrate and enzymatic extract, respectively, on the activity over chlorothalonil was determined. Freshly obtained spent substrate extract was able to reduce 100% of the initial concentration of chlorothalonil (2 mg/l) after 45 min of reaction. Storage time had a negative effect on the stability of the enzymatic activity: with spent substrate stored for a week, chlorothalonil concentration was reduced in 49.5% after 1 h reaction and with substrate stored for two and three weeks, the degradation efficiency decreased to 9.15% and 0%, respectively. Cooling and freezing the spent substrate extract also had a negative effect on chlorothalonil degradation.

Soil and water pollution in a banana production region in tropical Mexico.

The effects of abundant Mancozeb (Mn, Zn-bisdithiocarbamate) applications (2.5 kg ha⁻¹week⁻¹ for 10 years) on soil and surface-, subsurface- and groundwater pollution were monitored in a banana production region of tropical Mexico. In soils, severe manganese accumulation was observed, wheras the main metabolite ethylenethiourea was near the detection limit. Surface and subsurface water was highly polluted with ethylenethiourea, the main metabolite of Mancozeb (22.5 and 4.3 µg L⁻¹, respectively), but not with manganese. In deep ground water, no ethylenethiourea was detected. The level of pollution in the region presents a worrisome risk for aquatic life and for human health.

Performance of staged and non-staged up-flow anaerobic sludge bed (USSB and UASB) reactors treating low strength complex wastewater.

The use of anaerobic processes to treat low-strength wastewater has been increasing in recent years due to their favourable performance-costs balance. For optimal results, it is necessary to identify reactor configurations that are best suited for this kind of application. This paper reports on the comparative study carried out with two high-rate anaerobic reactor systems with the objective of evaluating their performances when used for the treatment of low-strength, complex wastewater. One of the systems is the commonly used up-flow anaerobic sludge blanket (UASB) reactor. The other is the up-flow staged sludge bed (USSB) system in which the reactor was divided longitudinally into 3, 5 and 7 compartments by the use of baffles. The reactors (9 l) were fed with a synthetic, soluble and colloidal waste (chemical oxygen demand (COD) < 1000 mg/l) and operated at 28 degrees C and 24 h hydraulic retention time. Intermediate flow hydraulics, between plug-flow and completely-mixed, in the UASB and 7 stages USSB reactors allowed efficient degradation of substrates with minimum effluent concentrations. Low number of compartments in the USSB reactors increased the levels of short-circuiting thus reducing substrate removal efficiencies. All reactors showed high COD removal efficiencies (93-98%) and thus can be regarded as suitable for the treatment of low strength, complex wastewater. Staged anaerobic reactors can be a good alternative for this kind of application provided they are fitted with a large enough (> or =7) number of compartments to fully take advantage of their strengths. Scale factors seem to have influenced importantly on the comparison between one and multi staged sludge-bed reactors and, therefore, observations made here could change at larger reactor volumes.

Comparative ecological risks of pesticides used in plantation production of papaya: application of the SYNOPS indicator.

Pesticides are used intensively for crop protection in tropical fruit plantations. Assessments of the relative risks posed by pesticides are needed to assist in the development of management plans that minimize ecological impacts. In this study, the risk indicator SYNOPS_2 was used to compare risks to aquatic ecosystems by pesticides commonly used in papaya plantations. Plant interception and spray drift were measured during six applications of three pesticides (chlorothalonil, chloropyrifos, and malathion) using a turbo fan driven sprayer. Plant interception was estimated to be higher (42.6+/-12.7%; p=0.04) in late (8-14 months old) than in early (4 months old) trees (20.1+/-25.3%). Chlorothalonil concentrations of up to 11.0 microg L(-1) were found in water from an adjacent ditch after field application. Concentrations of this pesticide (7.4+/-4.1 microg L(-1)) in runoff water were also significantly (p<0.01) higher than those of malathion (2.4+/-1.9 microg L(-1)) and chlorpyrifos (0.8+/-0.5 microg L(-1)). Good correlation between measured and predicted values (r2=0.56-0.85, p<0.01) showed that SYNOPS_2 is able to describe trends in runoff pollution in papaya plantations. Linear equations were obtained in order to correct numerical disagreement between measured and calculated runoff concentrations. An independent test showed a reasonable agreement between measured chlorothalonil concentrations and the predicted values using the proposed equations. Fifteen pesticides used in papaya cultivation were ranked according to their calculated chronic biological risk index. Pesticides with the highest risk index for non-target organisms were: chlorothalonil for algae, lambda cyahalotrin for Daphnia and fish, and malathion for earthworms. Chlorothalonil was the pesticide with the highest exposure level in water and therefore represents a high risk for aquatic life. Results show that SYNOPS_2 can be used as a pesticide risk indicator on papaya and possibly other tropical fruit plantations.

Water quality and presence of pesticides in a tropical coastal wetland in southern Mexico.

The water quality of the Pozuelos-Murillo lagoon system in southern Mexico was evaluated during three periods between March and October 2002, with particular emphasis on the detection of organochlorine and organophosphorous pesticide residues in water and sediments. Physicochemical and microbiological parameters of water were also measured and integrated in a water quality index (WQI). Multivariate analysis was used to regionalise the lagoon system as a function of the behaviour of all measured parameters. Solid phase micro-extraction followed by gas chromatography (SPME-GC) was used for pesticide analysis. The concentration of phosphorous was found to be higher than that of nitrogenous compounds. This, besides a deficiency in dissolved oxygen and a high organic matter concentration (as COD), reflects eutrophication processes in some areas of the system. Measured levels of faecal coliforms and oils and greases were above the limits established by Mexican law and comparable to the concentrations reported for other highly polluted systems in Mexico. Residues of DDD (2.0 microg L(-1)) in water and DDE (247 ng g(-1)) and endosulfan I (814 ng g(-1)) sediments were detected by SPME-GC. The spatial distribution of these contaminants implies major potential risks because the most polluted sites were found to be those with the highest fishing activity. Although in general the WQI is on acceptable levels (65-80%), some contamination problems are evident.