Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry

Environmental Science and Pollution Research - The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl,...     

Water quality in Lis river, Portugal

In the past 30?years, the Lis river basin has been subjected to constant ecological disasters mainly due to piggery untreated wastewater discharges. The aim of this study was to evaluate the effect of existing domestic, agricultural, and industrial activities on the water quality, and to propose a watershed plan to protect and manage surface water resources within the Lis river basin. For this purpose, 16 monitoring stations have been strategically selected along the Lis river stretch and its main tributaries to evaluate the water quality in six different sampling periods (2003–2006). All samples were characterized in terms of organic material, nutrients, chlorophyll, and pathogenic bacteria. Generally, the Lis river presents poor water quality, according to environmental quality standards for surface water, principally in terms of dissolved oxygen, biochemical oxygen demand, total nitrogen, and fecal coliform, which can be associated mainly with the contamination source from pig-breeding farms.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes

Different advanced oxidation processes (AOPs) were applied to the treatment of a real cotton-textile dyeing wastewater as a pre-oxidation step to enhance the biodegradability of the recalcitrant compounds, which can be further oxidized using a biological process. Tests were conducted on a lab-scale prototype using artificial solar radiation and at pilot scale with compound parabolic collectors using natural solar radiation. The cotton-textile dyeing wastewater presents a lilac color, with a maximum absorbance peak at 641 nm, alkaline pH (pH?=?8.2), moderate organic content (DOC?=?152 mg C L^?1, COD?=?684 mg O₂ L^?1) and low-moderate biodegradability (40 % after 28 days in Zahn–Wellens test). All the tested processes contributed to an effective decolorization and mineralization, but the most efficient process was the solar-photo-Fenton with an optimum catalyst concentration of 60 mg Fe²⁺ L^?1, leading to 98.5 % decolorization and 85.5 % mineralization after less than 0.1 and 5.8 kJ_UV L^?1, respectively. In order to achieve a final wastewater with a COD below 250 mg O₂ L^?1 (discharge limit into water bodies imposed by the Portuguese Legislation-Portaria no. 423/97 of 25 June 1997), considering the combination of a solar-photo-Fenton reaction with a biological process, the phototreatment energy required is 0.5 kJ_UV L^?1, consuming 7.5 mM hydrogen peroxide, resulting in 58.4 % of mineralization $ \left({t}_{30\mathrm{W}}=3.2\ \min; \overline{T}=30.7\ {}^{\circ}\mathrm{C};\overline{\mathrm{pH}}=2.80;{\overline{\mathrm{UV}}}_{G,n}={13\ \mathrm{W}\ \mathrm{m}}^{-2}\right). $      

Water quality modelling of Lis River, Portugal

The aim of the study was to predict the impact of flow conditions, discharges and tributaries on the water quality of Lis River using QUAL2Kw model. Calibration of the model was performed, based on data obtained in field surveys carried out in July 2004 and November 2006. Generally the model fitted quite well the experimental data. The results indicated a decrease of water quality in the downstream area of Lis River, after the confluence of Lena, Milagres and Amor tributaries, as a result of discharges of wastewaters containing degradable organics, nutrients and pathogenic organisms from cattle-raising wastewaters, domestic effluents and agricultural runoff. The water quality criteria were exceeded in these areas for dissolved oxygen, biochemical oxygen demand, total nitrogen and faecal coliforms. Water quality modelling in different scenarios showed that the impact of tributaries on the quality of Lis River water was quite negligible and mainly depends on discharges, which are responsible by an increase of almost 45, 13 and 44 % of ultimate carbonaceous biochemical oxygen demand (CBOD_u), ammonium nitrogen and faecal coliforms, for winter simulation, and 23, 33 and 36 % for summer simulation, respectively, when compared to the real case scenario.     

Comparative analysis of trace contaminants in leachates before and after a pre-oxidation using a solar photo-Fenton reaction

Sanitary landfill leachates are a complex mixture of high-strength organic and inorganic persistent contaminants, which constitute a serious environmental problem. In this study, trace contaminants present in leachates were investigated by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector before and after a pre-oxidation step using a solar photo-Fenton process. More than 40 organic compounds were detected and identified as benzene (0.09?±?0.07 mg?L^-1), trichlorophenol (TCP) (0.18?±?0.12 mg?L^-1), phthalate esters (Di-n-butyl phthalate (DBP), Butyl benzyl phthalate (BBP), Di(2-ethylhexyl) phthalate (DEHP)) (DBP: 0.47?±?0.01 mg?L^-1; BBP: 0.36?±?0.02 mg?L^-1; DEHP: 0.18?±?0.01 mg?L^-1), among others. Toluene, pentachlorophenol, dimethyl phthalate, diethyl phthalate, and Di-n-octyl phthalate were never detected in any of the samples. After the photo-Fenton treatment process, TCP decreased to levels below its detection limit, benzene concentration increased approximately three times, and DBP concentration decreased about 77 % comparatively to the raw leachate sample. The solar photo-Fenton process was considered to be very efficient for the treatment of sanitary landfill leachates, leading to the complete elimination of 24 of the detected micropollutants to levels below their respective detection limits and low to significant abatement of seven other organic compounds, thus resulting in an increase of the leachate biodegradability.     

Assessment of indoor airborne contamination in a wastewater treatment plant

The main objective of this work was to quantify and characterize the major indoor air contaminants present in different stages of a municipal WWTP, including microorganisms (bacteria and fungi), carbon dioxide, carbon monoxide, hydrogen sulfide ammonia, formaldehyde, and volatile organic compounds (VOCs). In general, the total bacteria concentration was found to vary from 60 to >52,560 colony-forming units (CFU)/m³, and the total fungi concentration ranged from 369 to 14,068 CFU/m³. Generally, Gram-positive bacteria were observed in higher number than Gram-negative bacteria. CO₂ concentration ranged from 251 to 9,710 ppm, and CO concentration was either not detected or presented a level of 1 ppm. H₂S concentration ranged from 0.1 to 6.0 ppm. NH₃ concentration was <2 ppm in most samples. Formaldehyde was <0.01 ppm at all sampling sites. The total VOC concentration ranged from 36 to 1,724 μg/m³. Among the VOCs, toluene presented the highest concentration. Results point to indoor/outdoor ratios higher than one. In general, the highest levels of airborne contaminants were detected at the primary treatment (SEDIPAC 3D), secondary sedimentation, and sludge dehydration. At most sampling sites, the concentrations of airborne contaminants were below the occupational exposure limits (OELs) for all the campaigns. However, a few contaminants were above OELs in some sampling sites.     

Water quality in Minho/Miño River (Portugal/Spain)

Minho River, also called Miño (in Spain), extends to about 300 km from Spain to Portugal. The source of the river lies in Spain and in the last 75 km, the river defines the border between Portugal and Spain. Under the scope of a cooperation project between North Portugal and Galicia region of Spain, titled: “Valorization of the natural resources of the Minho/Miño drainage basin”, seven water-sampling campaigns were carried out during the last 2 years in Minho River basin. Seven sampling sites were selected along the international stretch, and five were chosen in the main Portuguese and Spanish tributaries of Minho River. Water quality based on the physicochemical and microbial parameters was assessed. According to the Portuguese legislation for surface waters, the international section of Minho River presents a reasonably good water quality (BOD₅ <5 mg/L, TNK <2 mg/L, and total phosphorous <1 mg P/L). Valença and Louro were found to be the most polluted sampling sites and Louro the most polluted tributary (maximum values observed: TSS?=?26 mg/L, BOD₅?=?6.6 mg O₂/L, COD?=?20.8 mg O₂/L, total nitrogen?=?9.9 mg N/L; minimum value observed: OD?=?1.3 mg O₂/L). A one-dimensional stream water quality model QUAL2Kw was calibrated using data measured in field surveys along the international stretch of Minho River. QUAL2Kw was also used to predict the impact of flow conditions, discharges, and tributaries on the water quality of international stretch of Minho River, essential to establish proposals for management and planning of Minho River Basin.     

Functional ANOVA starting from discrete data: an application to air quality data

A nonparametric functional approach is proposed to compare the mean functions of $k$ k samples of curves. In practice, curves data are usually collected in a discrete form and hence they must be pre-processed to use purely functional techniques. However, in the context of $k$ k -sample tests, the pre-processing step can have effects in terms of power reduction. Hall and Van Keilegom (Stat Sin 17:1511–1531, 2007) proposed a methodology to minimizing these effects in the context of tests for the equality of two distribution functions. Their procedure is here extended to the case of $k$ k -sample hypothesis tests. The asymptotic validity of the procedure is established and its finite sample performance is analyzed through Monte Carlo experiments. As an illustration, the method is applied to air quality data collected from several monitoring stations placed at different geographical locations at the center of Spain.