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Basic dye decomposition kinetics in a photocatalytic slurry reactor.

Wastewater effluent from textile plants using various dyes is one of the major water pollutants to the environment. Traditional chemical, physical and biological processes for treating textile dye wastewaters have disadvantages such as high cost, energy waste and generating secondary pollution during the treatment process. The photocatalytic process using TiO2 semiconductor particles under UV light illumination has been shown to be potentially advantageous and applicable in the treatment of wastewater pollutants. In this study, the dye decomposition kinetics by nano-size TiO2 suspension at natural solution pH was experimentally studied by varying the agitation speed (50-200 rpm), TiO2 suspension concentration (0.25-1.71 g/L), initial dye concentration (10-50 ppm), temperature (10-50 degrees C), and UV power intensity (0-96 W). The experimental results show the agitation speed, varying from 50 to 200 rpm, has a slight influence on the dye decomposition rate and the pH history; the dye decomposition rate increases with the TiO2 suspension concentration up to 0.98 g/L, then decrease with increasing TiO2 suspension concentration; the initial dye decomposition rate increases with the initial dye concentration up to a certain value depending upon the temperature, then decreases with increasing initial dye concentration; the dye decomposition rate increases with the UV power intensity up to 64 W to reach a plateau. Kinetic models have been developed to fit the experimental kinetic data well.

Coloring Agents↗

Monitoring urbanization of Iskenderun, Turkey, and its negative implications.

This study aimed to analyze long-term urban land use (LU) change and its negative implications on the coastal environment of Iskenderun, Turkey. Information on urban LU change for the 144-year period between 1858 and 2002 was extracted from a historic city plan, black-white monoscopic aerial photographs, and Landsat ETM+ imagery. According to the results, areal extent of urban areas has increased approximately 40 times during the past 144 years. The population growth as a result of industrial developments and permanent migration was main driving force to the urbanization. Environmental problems that resulted from rapid development in the region such as air, water and soil pollution were highlighted and some recommendations were made in the light of qualitative and quantitative information on the urbanization and its negative consequences.

Environmental Monitoring↗

Photoprotection.

UNLABELLED: Many agents affect the transmission of ultraviolet light to human skin. These include naturally occurring photoprotective agents (ozone, pollutants, clouds, and fog), naturally occurring biologic agents (epidermal chromophores), physical photoprotective agents (clothing, hats, make-ups, sunglasses, and window glass), and ultraviolet light filters (sunscreen ingredients and sunless tanning agents). In addition, there are agents that can modulate the effects of ultraviolet light on the skin (antioxidants and others). All of the above are reviewed in this article. LEARNING OBJECTIVE: At the conclusion of this learning activity, participants should be able to provide an overview of all aspects of photoprotection.

4-Aminobenzoic Acid↗

Evaluation of the effects of diuron and its derivatives on Lemna gibba using a fluorescence toxicity index.

The herbicide diuron (DCMU) [3-(3,4-dichlorophenyl)-1,1-dimethylurea] is largely used in agricultural practices which contribute to water pollution in large areas. Its degradation induced by light or microbial activity is known to be a slow process, and may result in the accumulation of DCMU derivatives in the environment. In this report we used the yield of PSII variable fluorescence of Lemna gibba affected by the DCMU derivatives DCPMU [1-(3,4-dichlorophenyl)-3-methylurea], DCPU [1-(3,4-dichlorophenyl)urea], and DCA [3,4-dichloroaniline] to calculate the fluorescence toxicity index. We found the fluorescence toxicity index to be a useful parameter to evaluate the inhibitory effect on PSII electron transport in L. gibba exposed to DCMU and its derivatives. The variations observed for the inhibitory effect between DCMU and its derivatives seem to be caused by the modification of the dimethylurea group within the DCMU molecule. The fluorescence toxicity index demonstrated a strong quantitative dependency between the inhibitory effect of PSII electron transport and pollutant concentrations. We propose the fluorescence toxicity index to be a useful tool for future bioassays in evaluating the quality of water polluted with herbicides that induce an inhibition to PSII photochemistry.

Araceae↗

Photocatalytic oxidation of volatile organic compounds using fluorescent visible light.

Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a highly attractive alternative technology for purification and deodorization of indoor air. The main objectives of this study were to demonstrate that a common fluorescent visible light (FVL) lamp can be used to effectively remove by PCO low concentrations of VOCs from slightly contaminated air and to provide some fundamental and technical details on the process. The target VOC was n-butanol, which is a standard reference odorant. Its PCO was studied under a long residence time in a 3.7-L cylindrical reactor with commercial titanium dioxide (TiO2) as the reference photocatalyst and using mostly FVL for illumination. For comparison only, a UV (black) light lamp was used. The gas-phase products were detected and quantified online by gas chromatography (GC). The effects of reactor residence time, of inlet concentration, and of the relative light intensity on the efficiency of the process were also evaluated. At a high n-butanol concentration (0.1 vol %), butanal and propanal were identified as the intermediate products of the process; ethanal appeared when the initial concentration was < or = 850 ppm(v). This indicates that PCO leading to CO2 and H2O is relatively slow and proceeds in a stepwise manner. Although the efficiency of the process with an FVL lamp was significantly lower than when using a UV black light, complete PCO of low concentrations was achieved for 100 ppm(v). In a search for a material with photoactivation extended to higher wavelengths or increased photoactivity, several samples of transition metal- or silver ion-doped (2 atomic %) TiO2 as well as SrTi(1-x-)Fe(x)O3 (x = 0.1 and 0.15) perovskites were included in the study. None of these materials was more active than pure TiO2. The results of this study open new horizons in the area of in door air quality (IAQ) control.

Air Pollutants↗

The combination of photocatalysis and ozonolysis as a new approach for cleaning 2,4-dichlorophenoxyaceticacid polluted water.

Treatment of 2,4-D polluted waters with photocatalysis leads to the buildup of high concentrations of the long living intermediate 2,4-DCP. A new approach using a combination of ozonolysis and photocatalysis gave better degradation results with lower intermediate concentrations. The advantages of photocatalysis giving a constant decline in TOC and of ozonolysis giving no buildup of high intermediate concentrations were combined. Degradation data of 2,4-D for photocatalysis, ozonolysis and the combination of both for different pH ranges are given. Data on the main intermediate 2,4-DCP are given for the three different approaches.

2,4-Dichlorophenoxyacetic Acid↗

Photoirradiation of representative polycyclic aromatic hydrocarbons and twelve isomeric methylbenz[a]anthracene with UVA light: formation of lipid peroxidation.

Polycyclic aromatic hydrocarbons (PAHs) are widespread genotoxic environmental pollutants, which require metabolic activation in order to exert biological activities, including mutagenicity and carcinogenicity. Photoactivation is another activation pathway that can lead to PAH genotoxicity. In this paper, we demonstrate that photoirradiation of a series of representative PAHs, with and without bearing a methyl substituent, with UVA light in the presence of methyl linoleate resulted in the formation of methyl linoleate hydroperoxides (a lipid peroxide). The lipid peroxide formation was inhibited by dithiothreitol (DTT) (free radical scavenger), NaN3 (singlet oxygen and free radical scavenger), and superoxide dismutase (SOD) (superoxide scavenger), but was enhanced by the presence of deuterium oxide (D2O) (extends singlet oxygen lifetime). These results suggest that photoirradiation of PAHs by UVA light generates reactive oxygen species (ROS), which induce lipid peroxidation.

Benz(a)Anthracenes↗

PM2.5 mass and light extinction reconstruction in IMPROVE.

Compliance under the Regional Haze Rule of 1999 is based on Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing aerosol mass and light extinction from aerosol chemical concentrations measured in the IMPROVE network. The accuracy, consistency, and potential biases in these formulations were examined using IMPROVE aerosol chemistry and light extinction data from 1988-1999. Underestimation of particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) by the IMPROVE mass reconstruction formula by 12%, on average, appears to be related to the exclusion of sodium, chlorine, and other elements and to artifacts associated with the measurement of organic carbon, but not to absorption of water by sulfates and nitrates on IMPROVE Teflon filters during weighing. Light scattering measured by transmissometry is not consistent with nephelometer scattering or single-scatter albedos expected for remote locations. Light scattering was systematically overestimated by 34%, on average, with the IMPROVE particle scattering (Bsp) reconstruction formula. The use of climatologically based hygroscopic growth factors f(RH) suggested for compliance with the Haze Rule contributes significantly to this overestimation and increases the amount of light extinction attributable to sulfates for IMPROVE samples between 1993 and 1999 by 5 percentage points.

Air Pollutants↗

Photocatalytic degradation of polystyrene plastic under fluorescent light.

Plastic is used widely all over the world, due to the fact that it is low cost, is easily processable, and has lightweight properties. However, the hazard of discarding waste plastic, so-called "white pollution", is becoming more and more severe. In this paper, solid-phase photocatalytic degradation of polystyrene (PS) plastic, one of the most common commercial plastics, over copper phthalocyanine (CuPc) sensitized TiO2 photocatalyst (TiO2/CuPc) has been investigated under fluorescent light irradiation in the air. UV-vis spectra show that TiO2/CuPc extends its photoresponse range to visible light, contrasting to only UV light absorption of pure TiO2. The PS photodegradation experiments exhibit that higher PS weight loss rate, lower PS average molecular weight, less amount of volatile organic compounds, and more CO2 can be obtained in the system of PS-(TiO2/CuPc), in comparison with the PS-TiO2 system. Therefore, PS photodegradation over TiO2 CuPc composite is more complete and efficient than over pure TiO2, suggesting the potential application of dye-sensitized TiO2 catalyst in the thorough photodegradation of PS plastic under fluorescent light. During the photodegradation of PS plastic, the reactive oxygen species generated on TiO2 or TiO2/CuPc particle surfaces play important roles in chain scission. The present study demonstrates that the combination of polymer plastic with dye-sensitized TiO2 catalyst in the form of thin film is a practical and useful way to photodegrade plastic contaminants in the sunlight.

Catalysis↗

Canines as sentinel species for assessing chronic exposures to air pollutants: part 2. Cardiac pathology.

The principal objective of this study is to evaluate by light and electron microscopy (LM, EM) the heart tissues in stray southwest and northeast metropolitan Mexico City (SWMMC, NEMMC) dogs and compare their findings to those from 3 less polluted cities (Cuernavaca, Tlaxcala, and Tuxpam). Clinically healthy mongrel dogs, including 109 from highly polluted SWMMC and NEMMC, and 43 dogs from less polluted cities were studied. Dogs residing in cities with lower levels of pollutants showed little or no cardiac abnormalities. Mexico City and Cuernavaca dogs exhibited LM myocardial alterations including apoptotic myocytes, endothelial and immune effector cells, degranulated mast cells associated with scattered foci of mononuclear cells in left and right ventricles and interventricular septum, and clusters of adipocytes interspersed with mononuclear cells. Vascular changes included scattered polymorphonuclear leukocytes (PMN) margination and microthrombi in capillaries, and small venous and arteriolar blood vessels. Small veins exhibited smooth muscle cell hyperplasia, and arteriolar blood vessels showed deposition of particulate matter (PM) in the media and adventitia. Unmyelinated nerve fibers showed endoneural and epineural degranulated mast cells. EM examination of myocardial mast cells showed distended and abundant rough endoplasmic reticulum with few secretory granules. Myocardial capillaries exhibited fibrin deposition and their endothelial cells displayed increased luminal and abluminal pinocytic activity and the formation of anemone-like protrusions of the endothelium into the lumen. A close association between myocardial findings, lung epithelial and endothelial pathology, and chronic inflammatory lung changes was noted. The myocardial changes described in dogs exposed to ambient air pollutants may form the basis for developing hypothesis-driven mechanistic studies that might explain the epidemiological data of increased cardiovascular morbidity and mortality in people exposed to air pollutants.

Air Pollutants↗

Canines as sentinel species for assessing chronic exposures to air pollutants: part 1. Respiratory pathology.

A complex mixture of air pollutants is present in the ambient air in urban areas. People, animals, and vegetation are chronically and sequentially exposed to outdoor pollutants. The objective of this first of 2 studies is to evaluate by light and electron microscopy the lungs of Mexico City dogs and compare the results to those of 3 less polluted cities in MEXICO: One hundred fifty-two clinically healthy stray mongrel dogs (91 males/61 females), including 43 dogs from 3 less polluted cities, and 109 from southwest and northeast metropolitian Mexico City (SWMMC, NEMMC) were studied. Lungs of dogs living in Mexico City and Cuernavaca exhibited patchy chronic mononuclear cell infiltrates along with macrophages loaded with particulate matter (PM) surrounding the bronchiolar walls and extending into adjacent vascular structures; bronchiolar epithelial and smooth muscle hyperplasia, peribronchiolar fibrosis, microthrombi, and capillary and venule polymorphonuclear leukocytes (PMN) margination. Ultrafine PM was seen in alveolar type I and II cells, endothelial cells, interstitial macrophages (Mtheta), and intravascular Mtheta-like cells. Bronchoalveolar lavage showed significant numbers of alveolar macrophages undergoing proliferation. Exposure to complex mixtures of pollutants-predominantly particulate matter and ozone-is causing lung structural changes induced by the sustained inflammatory process and resulting in airway and vascular remodeling and altered repair. Cytokines released from both, circulating inflammatory and resident lung cells in response to endothelial and epithelial injury may be playing a role in the pathology described here. Deep concern exists for the potential of an increasing rise in lung diseases in child populations exposed to Mexico City's environment.

Age Distribution↗

Oxidative stress and usnic acid content in Parmelia caperata and Parmelia soredians (Lichenes).

High light levels together with Paraquat treatment or exposure to pollutants (e.g. SO2) can cause oxidative stress in epiphytic lichens. In some cases, a significant increase in ascorbic acid and other antioxidant metabolites, sometimes occurring in lichens only, was observed. In this study, usnic acid was measured by HPLC in Parmelia caperata and Parmelia soredians thalli treated with Paraquat, a herbicide which transfers electrons from various transport systems to oxygen, producing O2*- superoxide radicals. In light, Paraquat acts by generating active oxygen species within the chloroplast, thus simulating the oxidative component of environmental stress. The significant increase in the usnic acid content measured in P. soredians thalli (+ 36.3%) is in line with the hypothesis that it has an antioxidant action, but it is in contrast to the limited increase measured in P. caperata thalli (+ 13.7%). These apparently contradictory results confirm those found in the literature, which attribute different functions to usnic acid depending on the lichen species considered and on whether they have other detoxifying substances in their thalli. These studies are of potential application-oriented interest in relation to research into new active principles to be used in the pharmaceutical, food and cosmetic fields and/or in environmental biomonitoring.

Air Pollutants, Occupational↗

Petroleum pollutant degradation by surface water microorganisms.

BACKGROUND, AIMS AND SCOPE: It is well known that the composition of petroleum or some of its processing products changes in the environment mostly under the influence of microorganisms. A series of experiments was conducted in order to define the optimum conditions for an efficient biodegradation of petroleum pollutant, or bioremediation of different segments of the environment. The aim of these investigations was to show to what extent the hydrocarbons of a petroleum pollutant are degraded by microbial cultures which were isolated as dominant microorganisms from a surface water of a wastewater canal of an oil refinery and a nitrogen plant. Biodegradation experiments were conducted on one paraffinic, and one naphthenic type of petroleum during a three month period under aerobic conditions, varying the following parameters: Inorganic (Kp) or an organic medium (Bh) with or without exposition to light. METHODS: Microorganisms were analyzed in a surface water sample from a canal (Pancevo, Serbia), into which wastewater from an oil refinery and a nitrogen plant is released. The consortia of microorganisms were isolated from the water sample (most abundant species: Phormidium foveolarum--filamentous Cyanobacteria, blue-green algae and Achanthes minutissima, diatoms, algae). The simulation experiments of biodegradation were conducted with the biomass suspension and crude oils Sirakovo (Sir, paraffinic type) and Velebit (Ve, naphthenic type). After a three month period, organic substance was extracted by means of chloroform. In the extracts, the content of saturated hydrocarbons, aromatic hydrocarbons, alcohols and fatty acids was determined (the group composition). n-Alkanes and isoprenoid aliphatic alkanes, pristane and phytane, in the aliphatic fractions, were analyzed using gas chromatography (GC). Total isoprenoid aliphatic alkanes and polycyclic alkanes of sterane and triterpane types were analyzed by GC-MS. RESULTS AND DISCUSSION: Paraffinic type petroleums have a significant loss of saturated hydrocarbons. For naphthenic type petroleum, such a trend has not been observed. The most intensive degradation of n-alkanes and isoprenoid aliphatic alkanes (in paraffinic oil) and isoprenoids (in naphthenic oil) was observed using the inorganic medium Kp in the light; the microbial conversion is somewhat lower with Kp in the dark; with organic medium Bh in the light the degradation is of low intensity; with the same medium in the dark the degradation is hardly to be seen. Steranes and triterpanes were not affected by microbial degradation under the conditions used in our experiments. Obviously, the petroleum biodegradation was restricted to the acyclic aliphatics (n-alkanes and isoprenoids). CONCLUSION: Phormidium foveolarum (filamentous Cyanobacteria--blue-green algae) and Achanthes minutissima (diatoms, algae), microbial cultures isolated as dominant algae from a surface water in a wastewater canal of an oil refinery and a nitrogen plant, have degradable effects dominantly involving petroleum hydocarbons. Petroleum microbiological degradation is more intensive when inorganic medium (in the light) is applied. Having in mind that the inorganic pollutants have been released into the canal as well, this medium reflects more the natural environmental conditions. Polycyclic alkanes of sterane and triterpane type, in spite of the fact that these compounds could be degraded, have remained unchanged regarding abundance and distribution. Since this is the case even for naphthenic type petroleum (which is depleted in n-alkanes), it can be concluded that the biodegradation of petroleum type pollutants, under natural conditions, will be restrained to the n-alkane and isoprenoid degradation. RECOMMENDATION AND OUTLOOK: Performed experiments and simulations of petroleum microbiological degradation may serve for the prediction of the fate of petroleum type pollutants, as well as for definition of conditions for bioremediation of some environmental segments.

Biodegradation, Environmental↗

Real-world emission factors of fine and ultrafine aerosol particles for different traffic situations in Switzerland.

Extended field measurements of particle number (size distribution of particle diameters, D, in the range between 18 nm and 10 microm), surface area concentrations, and PM1 and PM10 mass concentrations were performed in Switzerland to determine traffic emissions using a comprehensive set of instruments. Measurements took place at roads with representative traffic regimes: at the kerbside of a motorway (120 km h(-1)), a highway (80-100 km h(-1)), and in an urban area with stop-and-go traffic (0-50 km h(-1)) regulated by light signals. Mean diurnal variations showed that the highest pollutant concentrations were during the morning rush hours, especially of the number density in the nanoparticle size range (D <50 nm). From the differences between up- and downwind concentrations (or differences between kerbside and background concentrations for the urban site), "real-life" emission factors were derived using NOx concentrations to calculate dilution factors. Particle number and volume emission factors of different size ranges (18-50 nm, 18-100 nm, and 18-300 nm) were derived for the total vehicle fleet and separated into a light-duty (LDV) and a heavy-duty vehicle (HDV) contribution. The total particle number emissions per vehicle were found to be about 11.7-13.5 x 10(14) particles km(-1) for constant speed (80-120 km h(-1) and 3.9 x 10(14) particles km(-1) for urban driving conditions. LDVs showed higher emission factors at constant high speed than under urban disturbed traffic flow. In contrast, HDVs emitted more air pollutants during deceleration and acceleration processes in stop-and-go traffic than with constant speed of about 80 km h(-1). On average, one HDV emits a 10-30 times higher amount of particulate air pollutants (in terms of both number and volume) than one LDV.

Aerosols↗

Perspectives in chronobiology of air pollution.

In a series of experiments, male and female Sprague Dawley rats, kept in light (L) from 06(00) to 18(00) alternating with darkness (LD 12:12) inhaled different concentrations of carbon monoxide (50-1,700 ppm) at each of two test times, 12 h apart. A decrease in flow of CO2 (VCO2) resulting from CO inhalation was greater in the active dark (D) than resting light (L) span. Experimental hypoxic mortality of male and female mice also shows circadian variations, being greater in the D than in the L span. Moreover, a difference of mortality was observed betwen hypoxic exposures performed at 12(00) (in LD or DL) and hypoxic exposures performed at 00(00) (in LD or DL). Such results await tests of any extent to which they model responses of human beings to air pollution. In human beings any external environmental circadian, circaseptan and circannual variations in air pollution as such may serve to variable extent as socioeconomic synchronizers of innate rhythms with a corresponding frequency, rather than as solely generators of time patterns in any physiopathologic response to air pollution.

Air Pollution↗

Performance of a substratum-irradiated photosynthetic biofilm reactor for the removal of sulfide from wastewater.

The performance of a sulfide-removal system based on biofilms dominated by green sulfur bacteria (GSB) has been investigated. The system was supplied with radiant energy in the band 720-780 nm, and fed with a synthetic wastewater. The areal net sulfide removal rate and the efficacy of the incident radiant energy for sulfide removal have been characterized over ranges of bulk sulfide concentration (1.6-11.5 mg L(-1)) and incident irradiance (0.21-1.51 W m(-2)). The areal net sulfide removal rate increased monotonically with both increasing incident irradiance and increasing bulk sulfide concentration. The efficacy of the radiant energy for sulfide removal (the amount of sulfide removed per unit energy supplied) also increased monotonically with rising bulk sulfide concentration, but exhibited a maximum value with respect to incident irradiance. The maximum observed values of this net removal rate and this efficacy were, respectively, 2.08 g m(-2) d(-1) and 2.04 g W(-1) d(-1). In-band changes in the spectral composition of the radiant energy affected this efficacy only slightly. The products of sulfide removal were sulfate and elemental-S. The elemental-S was scarcely released into the liquid, however, and reasons for this, such as sulfur reduction and polysulfide formation, are considered. Between 1.45 and 3.85 photons were needed for the net removal of one electron from S-species. Intact samples of the biofilm were characterized by microscopy, and their thicknesses lay between 39 +/- 9 and 429 +/- 57 microm. The use of the experimentally determined rates and efficacies for the design of a pilot-scale system is illustrated.

Biodegradation, Environmental↗

Light intensity influences chromium bioaccumulation and toxicity in Scenedesmus acutus (Chlorophyceae).

The influence of light intensity on chromium uptake was studied in two strains of the freshwater unicellular alga Scenedesmus acutus (Chlorophyceae) having different sensitivity to Cr poisoning and light intensity. The two strains were subjected to different Cr treatments at 3000 and 80 lux. Cr toxicity was assessed by algal growth rate, recovery test, methylene blue staining, and determination of photosynthetic activity. After 2 and 4 days of treatment, bioaccumulated chromium, cell dry mass, and protein and carbohydrate contents were also assessed. When the algae were treated at 3000 lux, different bioaccumulation patterns were obtained when Cr content was related to dry mass, cell number, or protein content. A direct relationship between Cr content and cell mortality was observed only when the amount of Cr was related to protein content. In both strains Cr uptake was slower in subdued light, suggesting that it is linked to energy-dependent processes. The difference between the strains in sensitivity to Cr poisoning was also evident in subdued light.

Cell Death↗