Calibration Approaches for Measurement of Aerosol Multielemental Concentration using Spark Emission Spectroscopy.

A multivariate calibration approach, using partial least squares regression, has been developed for measurement of aerosol elemental concentration. A training set consisting of 25 orthogonal aerosol samples with 9 factors (elements: Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb, Ti) and 5 levels (elemental concentrations) was designed. Spectral information was obtained for each aerosol sample using aerosol spark emission spectroscopy (ASES) at a time resolution of 1 minute. Simultaneous filter samples were collected for determination of elemental concentration using an inductively coupled plasma mass spectrometry (ICP-MS) analysis. Two regression models, PLS1 and PLS2, were developed to predict mass concentration from spectral measurements. Prediction ability of the models improved substantially when only signature wavelengths were included instead of the entire spectrum. The PLS1 model with 45 selected spectral variables (PLS1-45 model) presented the lowest relative root mean square error of cross validation (RMSECV; 16 - 35%). The detection limits using the PLS1-45 model, for the nine elements were in the range of 0.16 - 0.50 µg/m3. The performance of both multivariate and univariate regression models were tested for an unknown sample of welding fume aerosol. The multivariate model did not provide significantly better prediction compared to the univariate model. In spite of the difference in matrices of calibration aerosol and the unknown test aerosol, the results from PLS model show good agreement with those from filter measurements. The relative root mean square error of prediction (RMSEP) obtained from PLS1-45 model was 13% for Cr, 23% for Fe, 22% for Mn and 12% for Ni. The study shows that in spite of lower spectral resolution and lack of sample preparation, reliable and robust measurements can be obtained using the proposed calibration method based on PLS regression.

Impact of leaching conditions on constituents release from Flue Gas Desulfurization Gypsum (FGDG) and FGDG-soil mixture.

The interest in using Flue Gas Desulfurization Gypsum (FGDG) for land applications has increased recently. This study evaluates the leaching characteristics of trace elements in "modern" FGDG (produced after fly ash removal) and FGDG-mixed soil (SF) under different environmental conditions using recently approved EPA leaching methods (1313-1316). These methods employ various pH and liquid-solid (LS) ratios under batch leaching, column percolation and diffusion controlled release scenarios. Toxicity Characteristic Leaching Protocol (TCLP) and Synthetic Precipitation Leaching Protocol (SPLP) were used for comparison. The data obtained from new EPA methods provide broad insight into constituent release from FGDG and SF when compared to TCLP and SPLP. The release of toxic elements such as Hg, As, Pb, Co, Cd and Cr from SF was negligible. High release of B from FGDG was observed under all tested conditions; however, its release from SF was low. Both FGDG and SF released Se under all pH conditions (2-13) and LS ratios (1-10) in low concentrations (0.02-0.2mg/L). The data from this study could be used to investigate potential use of "modern" FGDG for new beneficial land applications.

Magnetically recoverable TiO2-WO3 photocatalyst to oxidize bisphenol A from model wastewater under simulated solar light.

A novel magnetically recoverable, visible light active TiO2-WO3 composite (Fe3O4@SiO2@TiO2-WO3) was prepared to enable the photocatalyst recovery after the degradation of bisphenol A (BPA) under simulated solar light. For comparison, the photocatalytic activity of other materials such as non-magnetic TiO2-WO3, Fe3O4@SiO2@TiO2, TiO2, and the commercial TiO2 P25 was also evaluated under the studied experimental conditions. The structure and morphology of the synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and electron dispersion spectroscopy (EDS). Moreover, Brunauer-Emmett-Teller (BET) surface area and magnetic properties of the samples were determined. The Fe3O4@SiO2@TiO2-WO3 and TiO2-WO3 led to a BPA degradation of 17.50 and 27.92 %, respectively, after 2 h of the simulated solar light irradiation. Even though their activity was lower than that of P25, which degraded completely BPA after 1 h, our catalysts were magnetically separable for their further reuse in the treatment. Furthermore, the influence of the water matrix in the photocatalytic activity of the samples was studied in municipal wastewater. Finally, the identification of reaction intermediates was performed and a possible BPA degradation pathway was proposed to provide a better understanding of the degradation process. Graphical abstract ᅟ.

Efficient photocatalytic degradation of organics present in gas and liquid phases using Pt-TiO2/Zeolite (H-ZSM).

TiO2-encapsulated H-ZSM photocatalysts were prepared by physical mixing of TiO2 and zeolites. Pt was immobilized on the surface of the TiO2-encapsulated zeolite (H-ZSM) catalysts by a simple photochemical reduction method. Different weight ratios of both TiO2 and Pt were hybridized with H-ZSM and the catalytic performance of the prepared catalysts was investigated for 2-propanol oxidation in liquid phase and acetaldehyde in gas phase reaction. Around 5-10 wt% TiO2-encapsulated H-ZSM catalysts was found to be optimal amount for the effective oxidation of the organics. Prior to light irradiation, Pt-TiO2-H-ZSM showed considerable amount of catalytic degradation of 2-propanol in the dark, forming acetone as an intermediate. In this study, Pt has played a major and important role on the total oxidation of 2-propanol as well as acetaldehyde. As a result, no residual organics were present in the pores of the zeolites. The catalysts could be reused more than three times without losing their catalytic activity in both phases. The Pt-TiO2-H-ZSM photocatalysts could overcome the problem of strong adsorption of organics in the zeolite pores (after the reaction). Thus, Pt-TiO2-H-ZSM can be used as a potential catalyst for both liquid and gas phase oxidation of organic pollutants.

Erythromycin oxidation and ERY-resistant Escherichia coli inactivation in urban wastewater by sulfate radical-based oxidation process under UV-C irradiation.

This study evaluates the feasibility of UV-C-driven advanced oxidation process induced by sulfate radicals SO4(.)- in degrading erythromycin (ERY) in secondary treated wastewater. The results revealed that 10 mg L(-1) of sodium persulfate (SPS) can result in rapid and complete antibiotic degradation within 90 min of irradiation, while ERY decay exhibited a pseudo-first-order kinetics pattern under the different experimental conditions applied. ERY degradation rate was strongly affected by the chemical composition of the aqueous matrix and it decreased in the order of: ultrapure water (kapp = 0.55 min(-1)) > bottled water (kapp = 0.26 min(-1)) > humic acid solution (kapp = 0.05 min(-1)) > wastewater effluents (kapp = 0.03 min(-1)). Inherent pH conditions (i.e. pH 8) yielded an increased ERY degradation rate, compared to that observed at pH 3 and 5. The contribution of hydroxyl and sulfate radicals (HO. and SO4(.)-) on ERY degradation was found to be ca. 37% and 63%, respectively. Seven transformation products (TPs) were tentatively elucidated during ERY oxidation, with the 14-membered lactone ring of the ERY molecule being intact in all cases. The observed phytotoxicity against the tested plant species can potentially be attributed to the dissolved effluent organic matter (dEfOM) present in wastewater effluents and its associated-oxidation products and not to the TPs generated from the oxidation of ERY. This study evidences the potential use of the UV-C/SPS process in producing a final treated effluent with lower phytotoxicity (<10%) compared to the untreated wastewater. Finally, under the optimum experimental conditions, the UV-C/SPS process resulted in total inactivation of ERY-resistant Escherichia coli within 90 min.

Dissolved effluent organic matter: Characteristics and potential implications in wastewater treatment and reuse applications.

Wastewater reuse is currently considered globally as the most critical element of sustainable water management. The dissolved effluent organic matter (dEfOM) present in biologically treated urban wastewater, consists of a heterogeneous mixture of refractory organic compounds with diverse structures and varying origin, including dissolved natural organic matter, soluble microbial products, endocrine disrupting compounds, pharmaceuticals and personal care products residues, disinfection by-products, metabolites/transformation products and others, which can reach the aquatic environment through discharge and reuse applications. dEfOM constitutes the major fraction of the effluent organic matter (EfOM) and due to its chemical complexity, it is necessary to utilize a battery of complementary techniques to adequately describe its structural and functional character. dEfOM has been shown to exhibit contrasting effects towards various aquatic organisms. It decreases metal uptake, thus potentially reducing their bioavailability to exposed organisms. On the other hand, dEfOM can be adsorbed on cell membranes inducing toxic effects. This review paper evaluates the performance of various advanced treatment processes (i.e., membrane filtration and separation processes, activated carbon adsorption, ion-exchange resin process, and advanced chemical oxidation processes) in removing dEfOM from wastewater effluents. In general, the literature findings reveal that dEfOM removal by advanced treatment processes depends on the type and the amount of organic compounds present in the aqueous matrix, as well as the operational parameters and the removal mechanisms taking place during the application of each treatment technology.

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light.

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO(2)) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO(2) nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO(2) by direct incorporation into the sol-gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO(2)-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO(2) +monodisperse TiO(2) (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO(2)-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO(2)-P25. Using NF-TiO(2) layer-by-layer with monodisperse TiO(2) (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5 × 10(-3) min(-1) for caffeine, 12.5 and 9.0 × 10(-3) min(-1) for carbamazepine, and 10.9 and 5.8 × 10(-3) min(-1) for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO(2)-based films compared to the direct addition of nanoparticles into the sol.

Double-side active TiO2-modified nanofiltration membranes in continuous flow photocatalytic reactors for effective water purification.

A chemical vapour deposition (CVD) based innovative approach was applied with the purpose to develop composite TiO(2) photocatalytic nanofiltration (NF) membranes. The method involved pyrolytic decomposition of titanium tetraisopropoxide (TTIP) vapor and formation of TiO(2) nanoparticles through homogeneous gas phase reactions and aggregation of the produced intermediate species. The grown nanoparticles diffused and deposited on the surface of γ-alumina NF membrane tubes. The CVD reactor allowed for online monitoring of the carrier gas permeability during the treatment, providing a first insight on the pore efficiency and thickness of the formed photocatalytic layers. In addition, the thin TiO(2) deposits were developed on both membrane sides without sacrificing the high yield rates. Important innovation was also introduced in what concerns the photocatalytic performance evaluation. The membrane efficiency to photo degrade typical water pollutants, was evaluated in a continuous flow water purification device, applying UV irradiation on both membrane sides. The developed composite NF membranes were highly efficient in the decomposition of methyl orange exhibiting low adsorption-fouling tendency and high water permeability.

Photocatalytic degradation and mineralization of microcystin-LR under UV-A, solar and visible light using nanostructured nitrogen doped TiO2.

In an attempt to face serious environmental hazards, the degradation of microcystin-LR (MC-LR), one of the most common and more toxic water soluble cyanotoxin compounds released by cyanobacteria blooms, was investigated using nitrogen doped TiO(2) (N-TiO(2)) photocatalyst, under UV-A, solar and visible light. Commercial Degussa P25 TiO(2), Kronos and reference TiO(2) nanopowders were used for comparison. It was found that under UV-A irradiation, all photocatalysts were effective in toxin elimination. The higher MC-LR degradation (99%) was observed with Degussa P25 TiO(2) followed by N-TiO(2) with 96% toxin destruction after 20 min of illumination. Under solar light illumination, N-TiO(2) nanocatalyst exhibits similar photocatalytic activity with that of commercially available materials such as Degussa P25 and Kronos TiO(2) for the destruction of MC-LR. Upon irradiation with visible light Degussa P25 practically did not show any response, while the N-TiO(2) displayed remarkable photocatalytic efficiency. In addition, it has been shown that photodegradation products did not present any significant protein phosphatase inhibition activity, proving that toxicity is proportional only to the remaining MC-LR in solution. Finally, total organic carbon (TOC) and inorganic ions (NO(2)(-), NO(3)(-) and NH(4)(+)) determinations confirmed that complete photocatalytic mineralization of MC-LR was achieved under both UV-A and solar light.

The effect of UV/H2O2 treatment on disinfection by-product formation potential under simulated distribution system conditions.

Advanced oxidation with ultraviolet light and hydrogen peroxide (UV/H(2)O(2)) produces hydroxyl radicals that have the potential to degrade a wide-range of organic micro-pollutants in water. Yet, when this technology is used to reduce target contaminants, natural organic matter can be altered. This study evaluated disinfection by-product (DBP) precursor formation for UV/H(2)O(2) while reducing trace organic contaminants in natural water (>90% for target pharmaceuticals, pesticides and taste and odor producing compounds and 80% atrazine degradation). A year-long UV/H(2)O(2) pilot study was conducted to evaluate DBP precursor formation with varying water quality. The UV pilot reactors were operated to consistently achieve 80% atrazine degradation, allowing comparison of low pressure (LP) and medium pressure (MP) lamp technologies for DBP precursor formation. Two process waters of differing quality were used as pilot influent, i.e., before and after granular activated carbon adsorption. DBP precursors increased under most of the conditions studied. Regulated trihalomethane formation potential increased through the UV/H(2)O(2) reactors from 20 to 118%, depending on temperature and water quality. When Post-GAC water served as reactor influent, less DBPs were produced in comparison to conventionally treated water. Haloacetic acid (HAA5) increased when conventionally treated water served as UV/H(2)O(2) pilot influent, but only increased slightly (MP lamp) when GAC treated water served as pilot influent. No difference in 3-day simulated distribution system DBP concentration was observed between LP and MP UV reactors when 80% atrazine degradation was targeted.

Regeneration of three-way automobile catalysts using biodegradable metal chelating agent--S, S-ethylenediamine disuccinic acid (S, S-EDDS).

Regeneration of the activity of three-way catalytic converters (TWCs) was tested for the first time using a biodegradable metal chelating agent (S, S-ethylenediamine disuccinic acid (S, S-EDDS). The efficiency of this novel environmentally friendly solvent in removing various contaminants such as P, Zn, Pb, Cu and S from commercial aged three-way catalysts, and improving their catalytic performance towards CO and NO pollutants removal has been investigated. Four samples of catalysts from the front and rear inlets of two different TWCs with different mileages and aged under completely different driving conditions were investigated. The catalysts were characterized using various techniques, such as X-ray diffraction (XRD), Scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area measurements (N(2) adsorption at 77 K). Quantitative ICP-MS analyses and SEM-EDS studies show the removal of Zn, P and Pb. SEM-EDS images obtained at low magnification (50 µm) showed considerable differences in the surface morphology and composition after washing with S, S-EDDS. However, XRD studies indicated neither little to no removal of major contaminant compound phases nor major structural changes due to washing. Correspondingly, little or no enhancement in BET surface area was observed between the used and washed samples. Light-off curves show that the regeneration procedure employed can effectively improve the catalytic performance towards NO pollutant.

Visible light induced wetting of nanostructured N-F co-doped titania films.

Nitrogen and fluorine co-doped TiO(2) films have been prepared by dip coating of a modified titania sol-gel based on a nitrogen precursor and a nonionic fluorosurfactant as pore template and fluorine source. The modified NF-TiO(2) films absorb in the visible spectral range, between 400-510 nm and undergo reversible hydrophilic conversion under visible light to a final contact angle of 8°, in contrast to the UV limited optical response of their undoped anatase TiO(2) analogues. The phenomenon takes place at a rate slower than the corresponding one observed for the UV stimulated superhydrophilic effect. The wetting response of the N-F doped TiO(2) films correlates well with the variation of their optical properties and surface morphological characteristics and most importantly with their photocatalytic activity, rendering these materials very promising for self-cleaning applications under visible light.

The effect of UV/H2O2 treatment on biofilm formation potential.

Greater Cincinnati Water Works (GCWW) evaluated the efficacy of ultraviolet light/hydrogen peroxide advanced oxidation (UV/H(2)O(2)) for reducing trace organic contaminants in natural water with varying water qualities. A year-long UV/H(2)O(2) pilot study was conducted to examine a variety of seasonal and granular activated carbon (GAC) breakthrough conditions. The UV pilot-scale reactors were set to consistently achieve 80% atrazine degradation, allowing comparison of low pressure (LP) and medium pressure (MP) lamp technologies for by-product formation. Because hydroxyl radicals react non-selectively with organic compounds, unintended by-product formation occurred. Total assimilable organic carbon (AOC) concentration increased through the reactors from 14 to 33% on average, depending on water quality. Natural organic matter (NOM) contains the precursors for AOC production, so when post-GAC water (versus conventionally treated water) served as reactor influent, less AOC was produced. No appreciable difference in AOC concentration was observed between LP and MP UV reactors. The Spirillum strain NOX fraction of the AOC increased from 50 to 65% on average, depending on the quality of the water. The increase in this fraction of AOC occurred because oxidation of NOM yielded smaller more assimilable organic compounds such as organic acids that are necessary for NOX growth. The Pseudomonas fluorescens strain P17 AOC concentration increased only when conventionally treated plant water was used as pilot influent. This organism thrives in waters of differing organic energy sources, but does not thrive well in carboxylic acids alone. The CONV water had more overall TOC that could contribute to higher P17 AOC counts. Biofilm coupon studies indicated that biofilms with greater heterotrophic plate counts were observed in the granular activated carbon (GAC) effluent streams receiving UV/H(2)O(2) pre-treatment. Biofilm coupon studies additionally indicated that the effluent stream of the GAC column proceeded by the MP reactor exhibited more viable biofilm than the other GAC effluent streams based on an ATP-bioluminescence method. The increased viability of the biofilm produced by the MP UV reactor is likely a result of the multiple UV wavelengths and higher energy input characteristic of this technology.

An advanced discrete state-discrete event multiscale simulation model of the response of a solid tumor to chemotherapy: Mimicking a clinical study.

In this paper an advanced, clinically oriented multiscale cancer model of breast tumor response to chemotherapy is presented. The paradigm of early breast cancer treated by epirubicin according to a branch of an actual clinical trial (the Trial of Principle, TOP trial) has been addressed. The model, stemming from previous work of the In Silico Oncology Group, National Technical University of Athens, is characterized by several crucial new features, such as the explicit distinction of proliferating cells into stem cells of infinite mitotic potential and cells of limited proliferative capacity, an advanced generic cytokinetic model and an improved tumor constitution initialization technique. A sensitivity analysis regarding critical parameters of the model has revealed their effect on the behavior of the biological system. The favorable outcome of an initial step towards the clinical adaptation and validation of the simulation model, based on the use of anonymized data from the TOP clinical trial, is presented and discussed. Two real clinical cases from the TOP trial with variable molecular profile have been simulated. A realistic time course of the tumor diameter and a reduction in tumor size in agreement with the clinical data has been achieved for both cases by selection of reasonable model parameter values, thus demonstrating a possible adaptation process of the model to real clinical trial data. Available imaging, histological, molecular and treatment data are exploited by the model in order to strengthen patient individualization modeling. The expected use of the model following thorough clinical adaptation, optimization and validation is to simulate either several candidate treatment schemes for a particular patient and support the selection of the optimal one or to simulate the expected extent of tumor shrinkage for a given time instant and decide on the adequacy or not of the simulated scheme.

Critical parameters determining standard radiotherapy treatment outcome for glioblastoma multiforme: a computer simulation.

The aim of this paper is to investigate the most critical parameters determining radiotherapy treatment outcome in terms of tumor cell kill for glioblastoma multiforme tumors by using an already developed simulation model of in vivo tumor response to radiotherapy.

The genetic profile of a tumor as a determinant of its response to radiotherapy: a computer simulation of two different radiotherapeutic schemes.

The aim of this paper is to present comparative results of a tumor response to radiotherapy model, concerning two different fractionation schemes and the insulin-like growth factor I receptor expression. A clinical case of glioblastoma multiforme is selected. The model parameters are appropriately adjusted according to the literature. The results of the simulation procedure are three-dimensionally visualized and compared with clinical experience.