Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative

Sensitized P25 TiO₂ was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N′-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO₂ allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ?>?400 nm) simulated solar radiation in O₂ atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO₂.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Adsorption of nutrients and cadmium by different minerals: experimental studies and modelling

This work analyses cadmium sorption by natural vermiculite, zeolite, and pumice, which have been recently considered for their potential use in remediation of contaminated soils. Batch experiments were performed to investigate the interactions between the mineral surfaces and the main nutritive cations of Hoagland solution. In addition to their ameliorative effect of reducing metal mobility, these minerals are able to interact to different extents with various components of the nutrient solution and can change the availability of essential nutrients in solution. Therefore, the minerals were also exposed to a range of cadmium doses to compare their different affinities for this element and to analyse the cadmium–nutrient interactions. The results showed that the nutrient solution composition was significantly modified by contact with zeolite and vermiculite, and to a minor extent with pumice. The ionic equilibrium between the solid and aqueous phases was attained at several time points depending on the cation. Ammonium and potassium ions were almost entirely absorbed by zeolite, while in vermiculite endogenous magnesium ions were exchanged with the liquid phase calcium ions. The amount of cadmium adsorbed on mineral surfaces equilibrated with the nutrient solution showed the following sequence zeolite>vermiculite>pumice, and the cation concentrations of the fluid phase were sensitive to cadmium addition.     

Environmental release and mass flux partitioning of PCDD/Fs during normal and transient operation of full scale waste to energy plants

The paper reports on global release and mass partitioning in the flux of residues of PCDD/Fs, evaluated with dedicated field campaigns at a municipal solid waste incineration plant during normal and transient operation. Results are compared with those obtained in other installations equipped with furnaces, energy recovery options and flue gas treatment technologies representative of most of the European incineration plants currently in operation. Levels of the pollutants of interest were determined in all the solid, liquid and gaseous residues produced by every single facility, and the results analysed in terms of the effects arising from the fed waste and the configuration of the plant. PCDD/Fs total release between 1.5 and 45 microg I-TEQ per ton of burned waste was evaluated, with lower values resulting from the adoption of catalytic conversion process for flue gas treatment. Most of the mass flux emitted is associated with solid residues deriving from activated carbon PCCD/F dry removal options, with significant contributions also from fly ash produced by particulate removal devices located immediately downstream the boiler and from scrubber blowdowns treatment sludge. During transient operating conditions the dioxin total release may increase by 50% with comparison to steady-state functioning.     

Degradation of cyprodinil, fludioxonil, cyfluthrin and pymetrozine on lettuce after different application methods

Degradation of two fungicides (cyprodinil and fludioxonil) and two insecticides (cyfluthrin and pymetrozine) applied on iceberg and romaine lettuce under field conditions with different methods (portable mistblower and chemigation) was studied field data showed that both distribution methods and lettuce cultivar affect the degradation trends of examined pesticides. In these trials the residues of all active ingredients after pre-harvest time were less than fifty's maximum residue levels; the values in the romaine cultivar were generally higher than those in iceberg lettuce. After pre-harvest time residues of pesticides applied on romaine lettuce by portable motor sprayer were always higher than those obtained by the chemigation system.     

Mapping Soil Gas Radon Concentration: A Comparative Study of Geostatistical Methods

Understanding soil gas radon spatial variations can allow the constructor of a new house to prevent radon gas flowing from the ground. Indoor radon concentration distribution depends on many parameters and it is difficult to use its spatial variation to assess radon potential. Many scientists use to measure outdoor soil gas radon concentrations to assess the radon potential. Geostatistical methods provide us a valuable tool to study spatial structure of radon concentration and mapping. To explore the structure of soil gas radon concentration within an area in south Italy and choice a kriging algorithm, we compared the prediction performances of four different kriging algorithms: ordinary kriging, lognormal kriging, ordinary multi-Gaussian kriging, and ordinary indicator cokriging. Their results were compared using an independent validation data set. The comparison of predictions was based on three measures of accuracy: (1) the mean absolute error, (2) the mean-squared error of prediction; (3) the mean relative error, and a measure of effectiveness: the goodness-of-prediction estimate. The results obtained in this case study showed that the multi-Gaussian kriging was the most accurate approach among those considered. Comparing radon anomalies with lithology and fault locations, no evidence of a strict correlation between type of outcropping terrain and radon anomalies was found, except in the western sector where there were granitic and gneissic terrain. Moreover, there was a clear correlation between radon anomalies and fault systems.     

Pedestrian exposure to size-resolved particles in Milan

Measurement campaigns for airborne particles along a pedestrian route in the city center of Milan were performed by means of a portable instrument consisting of an optical particle counter and a global positioning system (GPS) signal receiver. Based on the size-resolved particle number concentration data and on proper density factors experimentally determined for Milan urban area, the mass concentrations were calculated in terms of particulate matter with aerodynamic diameters < or =10 microm (PM10), < or =2.5 pm (PM2.5), and < or =1 microm (PM1). Besides directly measuring the personal exposure to PM throughout the route, the measurement campaigns pointed out small spatial and temporal variations of the concentration ranges in the different urban microenvironments visited along the route as well as very peculiar features of the particles levels in the underground subway. These findings suggested that the personal exposure of pedestrians in the city center could be estimated by simply taking into account the exposure at the open air and in the subway. The comparison between measured and calculated exposures according to the microenvironment-based estimation results in reasonable accordance, even though the estimations tend to slightly underestimate (12%) the actual measured exposure.     

Soil carbon dynamics in a Mediterranean forest during the Kyoto Protocol commitment periods

The purpose of the present work is to asses the possibility of detecting changes in soil organic carbon (SOC) at the end of the 5-years of the first Commitment Period (CP) of the Kyoto Protocol of the United Nation’s Framework Convention on Climate Change (1 January, 2008–31 December, 2012), by both direct measurement and the use of an opportunely evaluated SOC model, CENTURY. The investigated soil is young, developed since 28 years on virtually C-free spoil banks and under the influence of two managed forest stands, one a mix of English oak (Quercus robur L.) and Italian alder (Alnus cordata Loisel.) and the other pure English oak. The SOC stock of either stand was monitored since the time the stands were planted in 1981, and it was used together with other parameters for the model evaluation, while the future projections for the end of the first (2012) and second (2017) CP were made according to two extreme IPCC climatic scenarios: A1F1, the most dramatic, and B2, among the less impacting. Direct SOC measurements performed at the beginning and at the end of a time frame equivalent to a commitment period (2004–2008) had not shown significant variations in either stands. Compared to the 2008 SOC stock, in both stands the model shows variations at the end of the first CP from 0.7 to 1.8 Mg C ha⁻¹ for the A1F1 scenario and from 0.3 to 1.7 Mg C ha⁻¹ for the B2. These variations are within the standard deviations of the C stocks measured in 2008. On the contrary, at the end of the second CP, the modelled SOC increments range from 2.5 to 3.6 Mg C ha⁻¹ (A1F1) or from 1.9 to 3.4 Mg C ha⁻¹ (B2), indicating the possibility to detect the SOC changes by direct measurement, since the values well agree with the minimum detectable variation estimated for both sites in 3.3–4.5 Mg C ha⁻¹. This work shows that SOC stock changes measured directly in the field can be minimal at the end of both CPs, and that CENTURY well simulates the SOC dynamics of the stands. The use of such a model, validated at long-term experimental sites, hence represents an effective tool for estimating future changes in SOC amounts in support of direct measurements when a short period of time, such as the CP, is considered.     

PCDD/F and dioxin-like PCB profiles in soils amended with sewage sludge,compost, farmyard manure,and mineral fertilizer since 1962

Background, aim, and scope  

Biowaste contains compounds of agricultural value such as organic carbon, nutrients, and trace elements and can partially replace mineral fertilizer (MIN) and improve the physical properties of the soil. However, the obvious benefits of land spreading need to be carefully evaluated against potential adverse effects on the environment and human health. Environmental contamination resulting from biowaste application is one of the key variables when assessing cost/benefits. This study provides data on the resulting concentration of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the soil column as a result of the different types of fertilizers.     

Electrochemical advanced oxidation and biological processes for wastewater treatment: a review of the combined approaches

As pollution becomes one of the biggest environmental challenges of the twenty-first century, pollution of water threatens the very existence of humanity, making immediate action a priority. The most persistent and hazardous pollutants come from industrial and agricultural activities; therefore, effective treatment of this wastewater prior to discharge into the natural environment is the solution. Advanced oxidation processes (AOPs) have caused increased interest due to their ability to degrade hazardous substances in contrast to other methods, which mainly only transfer pollution from wastewater to sludge, a membrane filter, or an adsorbent. Among a great variety of different AOPs, a group of electrochemical advanced oxidation processes (EAOPs), including electro-Fenton, is emerging as an environmental-friendly and effective treatment process for the destruction of persistent hazardous contaminants. The only concern that slows down a large-scale implementation is energy consumption and related investment and operational costs. A combination of EAOPs with biological treatment is an interesting solution. In such a synergetic way, removal efficiency is maximized, while minimizing operational costs. The goal of this review is to present cutting-edge research for treatment of three common and problematic pollutants and effluents: dyes and textile wastewater, olive processing wastewater, and pharmaceuticals and hospital wastewater. Each of these types is regarded in terms of recent scientific research on individual electrochemical, individual biological and a combined synergetic treatment.