NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7

A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS).     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

Immersed solid phase microextraction to measure chemical activity of lipophilic organic contaminants in fatty tissue samples

It is known that solid phase microextraction (SPME) fibers can be equilibrated directly within environmental matrices such as water, sediment and soil slurries. Here it is shown that this method can also be applied to biological tissue. SPME extraction of biological matrices reportedly causes lipophilic fouling of the fiber. However, we found no significant measurement bias when combining equilibrium sampling with fiber surface cleaning. The uptake of lipophilic organic pollutants from the tissue and into the SPME fiber coating was characterized by fast equilibrium partitioning without sample depletion and without impacting the sorptive properties of the fiber. The precision of the method when applied to hexachlorobenzene and several PCB congeners in harbor porpoise blubber was 15%, which includes the variation between SPME samplings, manual injections and the instrumental analysis. A good correlation (r(2)=0.95) was obtained between SPME measurements of PCB 153 in blubber and concentrations obtained via a traditional analytical approach. These results indicate that SPME is a promising technique for measuring chemical activity in biological tissue, which would make it a useful tool for studying chemical distribution in organisms as well as biodilution and biomagnification phenomena.     

Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy

A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23-30 pg WHO-TEQ g(-1), lipid base, for subjects in the 27-54 year age groups, while concentrations increased to 40-44 pgTEQ g(-1) for the two 55-67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six "indicator" congeners were in the range 240-300 ng g(-1), lipid base, for subjects in the 27-54 year age groups. A raise in NDL-PCB body burden (430-470 ng g(-1), lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements.     

Uphill permeation of Cr(VI) using Hostarex A327 as ionophore by membrane-solvent extraction processing

The transport of chromium by the emulsion pertraction technology (EPERT) using Hostarex A327 (tertiary amine) as a carrier has been investigated. The permeation of the metal is studied as a function of various experimental variables: hydrodynamic conditions, concentration of Cr(VI) and HCl in the source phase, carrier concentration and diluent in the organic phase, strippant concentration in the stripping phase and support characteristics of the membrane. The mass transfer coefficient and the thickness of the aqueous source boundary layer were estimated from the experimental data. Furthermore, the selectivity of the Hostarex A327-bases EPERT towards different metal ions and the behaviour of the system against other carriers are presented.     

Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in blood and breast milk collected from 60 mothers in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs), and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) in paired samples of blood and breast milk collected from 60 mothers in Sapporo City, Hokkaido Prefecture, Japan. The present study is one of the few studies in which PCDDs, PCDFs, and dioxin-like PCBs have been measured in blood and breast milk collected from 60 same mothers. Of these 60 mothers, 30 were primipara (mean: 30.1 years, median: 28.0 years) and 30 were multipara (mean: 32.2 years, median: 32.5 years). The arithmetic mean TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the primiparous mothers were 9.0, 3.3, 5.7, and 0.4 pg TEQ g(-1) lipid, respectively, and 5.2, 2.2, 4.5, and 0.4 pg TEQ g(-1) lipid, respectively, with the total TEQ concentrations of these dioxin-like compounds being 9.3-42.9 (mean: 18.4, median: 17.3) and 7.0-41.1 (mean: 12.3, median: 11.4) pg TEQ g(-1) lipid, respectively. In the case of multiparous mothers, the arithmetic mean TEQ concentrations of these dioxin-like compounds in blood and breast milk were 7.1, 2.7, 5.3, and 0.4 pg TEQ g(-1) lipid, respectively, and 3.9, 1.7, 3.8, and 0.4 pg TEQ g(-1) lipid, respectively, with the total TEQ concentrations being 3.4-28.1 (mean: 15.5, median: 13.9) and 2.7-20.0 (mean: 9.8, median: 9.2)pg TEQ g(-1) lipid, respectively. The total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of primiparous mothers in Sapporo City appeared to be generally lower than those recently surveyed throughout the greater area of Japan. Significant correlations were observed between age and the total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in the blood of primiparae and multiparae, and significant correlations were also observed between age and the total TEQ concentrations of these dioxin-like compounds in the breast milk of primiparae and multiparae. The total TEQ concentrations of PCDDs, PCDFs, and dioxin-like PCBs in the blood of primiparous mothers showed a close correlation to those in their breast milk and also showed good correlations between the total TEQ concentrations of these dioxin-like compounds in the blood of multiparous mothers and those in their breast milk. The result of a comparison of the arithmetic mean concentrations of each congener of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk indicated that the transfer of octachlorodibenzo-p-dioxin (OCDD) from the blood to the breast milk was lower than those of other congeners. In contrast, among mono-ortho PCBs congeners, the arithmetic mean concentrations of 2,3',4,4',5-pentachlorobiphenyl (PentaCB) (#118) and 2,3,3',4,4'-PentaCB (#105) in the breast milk were slightly higher than those in the blood, which suggested that breast-fed infants may be at higher risk from mono-ortho PCBs.     

Synthesis of zirconia-immobilized copper chelates for catalytic decomposition of hydrogen peroxide and the oxidation of polycyclic aromatic hydrocarbons

Chelating sorbents with diethylenetriaminepenta(methylene-phosphonic acid) (DTPMPA) and ethylenediaminetetraacetic acid ligands immobilized on zirconia matrix were prepared and subsequently saturated with Cu(II). All the Cu chelates catalyzed decomposition of H(2)O(2) yielding highly reactive hydroxyl radicals. All of them were also able to catalyze degradation of polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[b]fluoranthene). The most effective DTPMPA-based catalysts G-32 and G-35 (10 mg ml(-1) with 100 mmol H(2)O(2)) caused almost complete decomposition of 15 ppm anthracene and benzo[a]pyrene during a five day catalytic cycle at 30 degrees C. Anthracene-1,4-dione was the main product of anthracene oxidation by all catalysts. The catalysts were active in several cycles without regeneration.     

Proinflammatory effect of fine and ultrafine particulate matter using size-resolved urban aerosols from Paris

Epidemiological and experimental studies have underlined that exposure to particulate matter (PM) leads mainly to airway inflammation, but the roles of particle size and chemical composition associated to such adverse health outcomes need to be better investigated. This study was performed to validate novel strategies of particle sampling, recovery and cell exposure in order to evaluate the pro-inflammatory potential of fine and ultrafine particles from a fractionated aerosol. Samplings of Paris background aerosols using 13-stage low pressure impactors (0.03-10 microm) gave bimodal mass distributions with an accumulation mode centered on a median diameter of 0.42 microm and a coarse one on 3.25 microm. PM 1 accounted for 70% and PM 0.1 for 12% of PM 10. The latter mainly comprised carbon-chained aggregates. The development of an efficient and reproducible method to recover fine (PM 1-0.1) and ultrafine (PM 0.1-0.03) particulate matter has permitted experimental comparison of the impact of such particles on human bronchial epithelial cells (HBECs). In this study we have compared the relative effects of fine and ultrafine particles at non-cytotoxic concentrations over 24h on the production of the pro-inflammatory cytokine GM-CSF by HBECs. Combining two cell exposure strategies to the size-fraction particles according to either their proportion (isovolume exposure) or their quantity in the aerosol (isomass exposure), we showed that both ultrafine and fine particles induced a concentration-dependent GM-CSF release by HBECs which is significant from 1 microg cm(-2). In conclusion, short duration samplings using 13-stage impactors enable to obtain size-resolved PM in sufficient quantities to carry out toxicological investigations. These findings are promising in view to conduct a more intensive study joining chemical and toxicological assays.     

Performance evaluation of a biotrickling filter treating a mixture of oxygenated VOCs during intermittent loading

Laboratory scale-studies on the biodegradation of a 1:1:1 weight mixture of three oxygenated volatile organic compounds (VOCs), ethanol, ethyl acetate, and methyl-ethyl ketone (MEK) in a biotrickling filter (BTF) were carried out using two identically sized columns, filled with different polypropylene rings. The performance of the BTFs was examined for a period of 10 months applying several operational strategies. Similar performance was obtained for both supports. Intermittent flow rate of trickling liquid was shown beneficial to improve the removal efficiency (RE). Continuous feeding of VOC resulted in an excessive accumulation of biomass so high pressure drop was developed in less than 20-30 d of operation. Intermittent VOC loading with night and weekend feed cut-off periods passing dry air, but without addition of water, was shown as a successful operational mode to control the thickness of the biofilm. In this case, operation at high inlet loads (ILs) was extended for more than 75 d maintaining high REs and low pressure drops. Outlet emission concentrations lower than 100 mg Cm(-3) were obtained for ILs up to 100 g Cm(-3)h(-1) working at 15s of empty bed residence time. The most easily biodegradable compounds ethanol and ethyl acetate were used primarily than MEK. After a 3-wk-starvation period, the system performance was almost restored since the first d of operation, being the removal of the less biodegradable compound, MEK, partially deteriorated.