Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.     

The assessment and prediction of temporal variations in surface water quality—a case study

In order to optimize the processes of sampling, monitoring, and management, the initial aim of this paper was to develop a model for the definition and prediction of temporal changes of water quality. In the case of the Morava River Basin (Serbia), the patterns of temporal changes have been recognized by applying different multivariate statistical techniques. The results of the conducted cluster analysis are the indicators of the existence of the three monitoring periods: the low-water, transitional, and high-water periods, which is in accordance with changes in the water flow in the analyzed river basin. A possibility of reducing the initial data set and recognizing the main pollution sources was examined by carrying out the principal component/factor analysis. The results indicate that the natural factor has a dominant influence in temporal groups. In order to recognize the discriminatory water quality parameters, a discriminant analysis (DA) was carried out. Conducting the DA enabled a significant reduction in the data set by the extraction of two parameters (the water temperature and electrical conductivity). Furthermore, the artificial neural network technique was used for testing the possibility of predicting changes in the values of the discriminant factors in the monitoring periods. The reliability of this method for the prediction of temporal variations of both extracted parameters within all temporal clusters has been proven.     

Experimental arid land afforestation in Central Anatolia,Turkey

The afforestation of arid lands faces many challenges, and perhaps the most important key for success is choosing one or more species that are adapted well for local environmental conditions. We explored species that would be suitable for the steppe region of Central Anatolia. Intensive site preparation included ripping the subsoil (to 80 cm) and plowing the upper soil before planting seedlings of Elaeagnus angustifolia, Robinia pseudoacacia, Fraxinus angustifolia, and Pinus nigra were used as tree species. We also tested the success of several shrub species: Amygdalus orientalis, Calligonum polygonoides, and Spartium junceum. After five growing seasons, E. angustifolia showed the highest survival, with 80% of planted seedlings remaining. For the shrubs, A. orientalis was the most successful species with a 95% survival rate. Broad-leaved trees grew a cumulative average of 34 cm in height in 5 years, whereas P. nigra seedings grew only 9 cm. The greatest height growth occurred in the shrubs, with A. orientalis gaining 40 cm in height in 5 years. Overall, E. angustifolia and A. orientalis appeared best suited for afforestation in these areas. R. pseodoacacia and F. angustifolia may also be used as alternative species.     

Pond bank access as an approach for managing toxic cyanobacteria in beef cattle pasture drinking water ponds

Forty-one livestock drinking water ponds in Alabama beef cattle pastures during were surveyed during the late summer to generally understand water quality patterns in these important water resources. Since livestock drinking water ponds are prone to excess nutrients that typically lead to eutrophication, which can promote blooms of toxigenic phytoplankton such as cyanobacteria, we also assessed the threat of exposure to the hepatotoxin, microcystin. Eighty percent of the ponds studied contained measurable microcystin, while three of these ponds had concentrations above human drinking water thresholds set by the US Environmental Protection Agency (i.e., 0.3 μg/L). Water quality patterns in the livestock drinking water ponds contrasted sharply with patterns typically observed for temperate freshwater lakes and reservoirs. Namely, we found several non-linear relationships between phytoplankton abundance (measured as chlorophyll) and nutrients or total suspended solids. Livestock had direct access to all the study ponds. Consequently, the proportion of inorganic suspended solids (e.g., sediment) increased with higher concentrations of total suspended solids, which underlies these patterns. Unimodal relationships were also observed between microcystin and phytoplankton abundance or nutrients. Euglenoids were abundant in the four ponds with chlorophyll concentrations >?250 μg/L (and dominated three of these ponds), which could explain why ponds with high chlorophyll concentrations would have low microcystin concentrations. Based on observations made during sampling events and available water quality data, livestock-mediated bioturbation is causing elevated total suspended solids that lead to reduced phytoplankton abundance and microcystin despite high concentrations of nutrients, such as phosphorus and nitrogen. Thus, livestock could be used to manage algal blooms, including toxic secondary metabolites, in their drinking water ponds by allowing them to walk in the ponds to increase turbidity.     

Urban tracer dispersion experiments during the second DAPPLE field campaign in London 2004

As part of the DAPPLE programme two large scale urban tracer experiments using multiple simultaneous releases of cyclic perfluoroalkanes from fixed location point sources was performed. The receptor concentrations along with relevant meteorological parameters measured are compared with a three screening dispersion models in order to best predict the decay of pollution sources with respect to distance. It is shown here that the simple dispersion models tested here can provide a reasonable upper bound estimate of the maximum concentrations measured with an empirical model derived from field observations and wind tunnel studies providing the best estimate. An indoor receptor was also used to assess indoor concentrations and their pertinence to commonly used evacuation procedures.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

A land use regression model for predicting ambient volatile organic compound concentrations in Toronto,Canada

More than 25 studies have employed land use regression (LUR) models to estimate nitrogen oxides and to a lesser extent particulate matter indicators, but these methods have been less commonly applied to ambient concentrations of volatile organic compounds (VOCs). Some VOCs have high plausibility as sources of health effects and others are specific indicators of motor vehicle exhaust. We used LUR models to estimate spatial variability of VOCs in Toronto, Canada. Benzene, n-hexane and total hydrocarbons (THC) were measured from July 25 to August 9, 2006 at 50 locations using the TraceAir organic vapor monitors. Nitrogen dioxide (NO₂) was also sampled to assess its spatial pattern agreement with VOC exposures. Buffers for land use, population density, traffic density, physical geography, and remote sensing measures of greenness and surface brightness were also tested. The remote sensing measures have the highest correlations with VOCs and NO₂ levels (i.e., explains >36% of the variance). Our regression models explain 66–68% of the variance in the spatial distribution of VOCs, compared to 81% for the NO₂ model. The ranks of agreement between various VOCs range from 48 to 63% and increases substantially – up to 75% – for the top and bottom quartile groups. Agreements between NO₂ and VOCs are much smaller with an average rank of 36%. Future epidemiologic studies may therefore benefit from using VOCs as potential toxic agents for traffic-related pollutants.     

Economic damages of ozone air pollution to crops using combined air quality and GIS modelling

This study aims at presenting a combined air quality and GIS modelling methodological approach in order to estimate crop damages from photochemical air pollution, depict their spatial resolution and assess the order of magnitude regarding the corresponding economic damages. The analysis is conducted within the Greater Thessaloniki Area, Greece, a Mediterranean territory which is characterised by high levels of photochemical air pollution and considerable agricultural activity. Ozone concentration fields for 2002 and for specific emission reduction scenarios for the year 2010 were estimated with the Ozone Fine Structure model in the area under consideration. Total economic damage to crops turns out to be significant and estimated to be approximately 43 M€ for the reference year. Production of cotton presents the highest economic loss, which is over 16 M€, followed by table tomato (9 M€), rice (4.2 M€), wheat (4 M€) and oilseed rape (2.8 M€) cultivations. Losses are not spread uniformly among farmers and the major losses occur in areas with valuable ozone-sensitive crops. The results are very useful for highlighting the magnitude of the total economic impacts of photochemical air pollution to the area’s agricultural sector and can potentially be used for comparison with studies worldwide. Furthermore, spatial analysis of the economic damage could be of importance for governmental authorities and decision makers since it provides an indicative insight, especially if the economic instruments such as financial incentives or state subsidies to farmers are considered.     

Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.