Degradation of caffeine by conductive diamond electrochemical oxidation

The use of Conductive-Diamond Electrochemical Oxidation (CDEO) and Sonoelectrochemical Oxidation (CDSEO) has been evaluated for the removal of caffeine of wastewater. Effects of initial concentration, current density and supporting electrolyte on the process efficiency are assessed. Results show that caffeine is very efficiently removed with CDEO and that depletion of caffeine has two stages depending on its concentration. At low concentrations, opposite to what it is expected in a mass-transfer controlled process, the efficiency increases with current density very significantly, suggesting a very important role of mediated oxidation processes on the removal of caffeine. In addition, the removal of caffeine is faster than TOC, indicating the formation of reaction intermediates. The number and relative abundance of them depend on the operating conditions and supporting electrolyte used. In chloride media, removal of caffeine is faster and more efficiently, although the occurrence of more intermediates takes place. CDSEO does not increase the efficiency of caffeine removal, but it affects to the formation of intermediates. A detailed characterization of intermediates by liquid chromatography time-of-flight mass spectrometry seems to indicate that the degradation of caffeine by CDEO follows an oxidation pathway similar to mechanism proposed by other advanced oxidation processes.     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10?g – in triplicate) were collected before herbicide application and 7, 14, 28 and 42?days after treatment (DAT), then 1?mL of ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ was trapped in 2?M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12?h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.     

Evaluation of the effect of different treatment methods on sugarcane vinasse remediation

Abstract

Sugarcane vinasse is a by-product obtained during ethanol production in sugar-ethanol plants. For each 1?L of ethanol produced approximately 11?L of vinasse are generated. As this residue is obtained in high amounts, it is used as fertilizer in sugarcane crops. However, despite being rich in nutrients, sugarcane vinasse is approximately one hundred times more polluting than domestic sewage, making it an environmental problem. Thus, the aim of the present study was to propose a treatment sequence for sugarcane vinasse and evaluate the possibility of energetic use of the generated sludge in the coagulation/flocculation stage. pH, conductivity, turbidity and decreases in UV/Vis absorption spectra were determined for each treatment step. In addition, the upper calorific value of the generated sludge was also determined, while ash (adsorption treatment) and catalyst (heterogeneous photocatalysis) characterizations were also carried out. At the end of the treatment, initial vinasse turbidity was reduced by 100% and pH and conductivity values were stabilized. The sludge presented a higher calorific value of approximately 3,000?kcal kg^?1 and the ash and catalyst displayed favorable characteristics to be applied to the sugarcane vinasse treatment stages.     

The environmental behaviour of polychlorinated phenols and its relevance to cork forest ecosystems: a review

Pentachlorophenol (PCP) has been used as a herbicide, biocide and preservative worldwide since the 1930s and as a result, extensive and prolonged contamination exists. The environmental impact increases when its many degradation products are taken into consideration. A number of chloroanisols and their related chlorophenols have been found in cork slabs collected from Portuguese oak tree forests before stopper manufacturing, and contamination by PCP and polychlorinated anisole (PCA) has been detected in Canadian forests. It is suggested that the use of polychlorinated phenols, in particular PCP, is thought to be a cause of the cork taint problem in wine, a major socio-economic impact not only for industry but on sensitive and highly biodiverse ecosystems. It also highlights particular issues relating to the regional regulation of potentially toxic chemicals and global economics world wide. To fully understand the impact of contamination sources, the mechanisms responsible for the fate and transport of PCP and its degradation products and assessment of their environmental behaviour is required. This review looks at the current state of knowledge of soil sorption, fate and bioavailability and identifies the challenges of degradation product identification and the contradictory evidence from field and laboratory observations. The need for a systematic evaluation of PCP contamination in relation to cork forest ecosystems and transfer of PCP between trophic levels is emphasised by discrepancies in bioaccumulation and toxicity. This is essential to enable long term management of not only transboundary contaminants, but also the sustainable management of socially and economically important forest ecosystems.     

Adsorption behavior of alpha -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.     

Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel

In this study, particulate matter (PM) were characterized from a place impacted by heavy-duty vehicles (Bus Station) fuelled with diesel/biodiesel fuel blend (B3) in the city of Londrina, Brazil. Sixteen priority polycyclic aromatic hydrocarbons (PAH) concentrations were analyzed in the samples by their association with atmospheric PM, mass size distributions and major ions (fluorite, chloride, bromide, nitrate, phosphate, sulfate, nitrite, oxalate; fumarate, formate, succinate and acetate; lithium, sodium, potassium, magnesium, calcium and ammonium). Results indicate that major ions represented 21.2% particulate matter mass. Nitrate, sulfate, and ammonium, respectively, presented the highest concentration levels, indicating that biodiesel may also be a significant source for these ions, especially nitrate. Dibenzo[a,h]anthracene and indeno[1,2,3,-cd]pyrene were the main PAH found, and a higher fraction of PAH particles was found in diameters lower than 0.25 μm in Londrina bus station. The fine and ultrafine particles were dominant among the PM evaluated, suggesting that biodiesel decreases the total PAH emission. However, it does also increase the fraction of fine and ultrafine particles when compared to diesel.     

Use of biological indicators to assess water quality of the Ul River (Portugal)

Diatoms and macroinvertebrates have been extensively used as water quality indicators in Europe for the last two decades. In Portugal, the use of biological indicators to assess water quality in rivers has increased greatly. The aim of this work was to assess the water quality and ecological status of the Ul River in order to evaluate its ability for the establishment of a fluvial beach, using periphytic diatoms and macroinvertebrates as indicators. Four sites were selected along the Ul River. At each site, biological, physical, and chemical parameters were investigated. Epilithic diatoms and macroinvertebrates were sampled. The Specific Polluosensitivity Index and the Biological Diatom Index were applied to diatom data, while for macroinvertebrates, the Iberian Biological Monitoring Working Party (IBMWP) was used. According to the results obtained, it was possible to conclude that up to now, this river does not possess the ideal conditions for the establishment of a fluvial beach. We concluded that epilithic diatoms and macroinvertebrates provided consistent information on water quality assessment and can be used as biological indicators of the water quality in Ul River.     

Chlorination in a wastewater treatment plant: acute toxicity effects of the effluent and of the recipient water body

This study investigates the impact of wastewater treatment plant (WWTP) effluent on the toxicity of the recipient water body and the effectiveness of the disinfection treatment applied (sodium hypochloride) to assure the compliance of both microbiological and toxicological emission limits. No toxicity was found in the majority of samples collected from the recipient river, upstream and downstream of the WWTP, using three different toxicity tests (Vibrio fischeri, Daphnia magna, and Pseudokirchneriella subcapitata). Only three samples presented toxic unit (TU) values with V. fischeri, and one presented TU with P. subcapitata. The influent toxicity ranged from slightly toxic to toxic (TU = 0.68–4.47) with V. fischeri, while only three samples presented TU values with the other tests. No toxicity was found in the absence of chlorination, while the mean toxicity was 3.42 ± 4.12 TU with chlorination in the effluent. Although no toxicity or very slight toxicity was found in the receiving water, its residual toxicity was higher than the US EPA Quality Standard in two samples. Escherichia coli concentration had a lower mean value in the chlorinated effluent: 13,993 ± 12,037 CFU/100 mL vs. 62,857 ± 80,526 CFU/100 mL for the not chlorinated effluent. This difference was shown to be significant (p < 0.05). E. coli in ten chlorinated samples was higher than the limit established by European and Italian Legislation. The mean highest trihalomethanes (THMs) value was found in the influent samples (2.79 ± 1.40 μg/L), while the mean highest disinfection by-products (DBPs) was found in the effluent samples (1.85 ± 2.25 μg/L). Significant correlations were found between toxicity, sodium hypochlorite, THMs, DBPs, E. coli, and residual chlorine. In conclusion, this study highlighted that the disinfection of wastewater effluents with sodium hypochlorite determines the increase of the toxicity, and sometimes is not enough to control the E. coli contamination.     

Spatial variability of air pollutants in the city of Taranto, Italy and its potential impact on exposure assessment

Epidemiological studies typically use monitored air pollution data from a single station or as averaged data from several stations to estimate population exposure. In industrialized urban areas, this approach may present critical issues due to the spatial complexities of air pollutants which are emitted by different sources. This study focused on the city of Taranto, which is one of the most highly industrialized cities in southern Italy. Epidemiological studies have revealed several critical situations in this area, in terms of mortality excess and short-term health effects of air pollution. The aims of this paper are to study the variability of air pollutants in the city of Taranto and to interpret the results in relation to the applicability of the data in assessing population exposure. Meteorological and pollution data (SO2, NO2, PM10), measured simultaneously and continuously during the period 2006–2010 in five air quality stations, were analyzed. Relative and absolute spatial concentration variations were investigated by means of statistical indexes. Results show significant differences among stations. The highest correlation between stations was observed for PM10 concentrations, while critical values were found for NO2. The worst values were observed for the SO2 series. The high values of 90th percentile of differences between pairs of monitoring sites for the three pollutants index suggest that mean concentrations differ by large amounts from site to site. The overall analysis supports the hypothesis that various parts of the city are differently affected by the different emission sources, depending on meteorological conditions. In particular, analysis revealed that the influence of the industrial site may be primarily identified with the series of SO2 data which exhibit higher mean concentration values and positive correlations with wind intensity when the monitoring station is downwind from the industrial site. Results suggest evaluating the population exposure to air pollutants in industrialized cities by taking into account the possible zones of influence of different emission sources. More research is needed to identify an indicator, which ought to be a synthesis of several pollutants, and take into account the meteorological variables.     

Monitoring pollution in River Mureş, Romania, part II: metal accumulation and histopathology in fish

As a part of an exposure and effect monitoring conducted along the river Mureş, Western Romania in 2004, the health status of two indigenous fish species, sneep (Chondrostoma nasus) and European chub (Leuciscus cephalus) was investigated upstream and downstream the city of Arad. In fish, histopathology was assessed in liver and gills, and heavy metals (cadmium, copper, lead and zinc) were analyzed in liver samples. In both fish species, histopathological reactions in the gills (epithelial lifting, focal proliferation of epithelial cells of primary and secondary lamellae and resulting fusion of secondary lamellae, hyperplasia and hypertrophy of mucous cells, focal inflammation and necrosis of epithelial cells) were most severe at the two sampling sites upstream Arad city, which were shown to be polluted by copper, cadmium, faecal coliforms and streptococci in a parallel study. At these two sites, also histopathology in the liver of L. cephalus was more prominent than at the two downstream sites. In C. nasus, symptoms in the liver (focal inflammation with lymphocytic infiltrations, macrophage aggregates and single cell necrosis) were also highly pronounced at the sampling site located directly downstream the municipal sewage treatment plant of Arad. With the exception of copper accumulation in L. cephalus caught at the most upstream sampling site, in both fish species cadmium and copper accumulation were exceptionally high and did not differ significantly between the four sampling sites.