Adsorption and photocatalytic oxidation of formaldehyde on a clay-TiO2 composite.

We investigated the adsorption capacity and photocatalytic removal efficiency of formaldehyde using a hectorite-TiO(2) composite in a bench flow reactor. The same experimental conditions were applied to pure TiO(2) (Degussa P25) as a reference. The catalysts were irradiated with either a UVA lamp (365 nm) or with one of two UVC lamps of 254 nm and 254+185 nm, respectively. Formaldehyde was introduced upstream at concentrations of 100-500 ppb, with relative humidity (RH) in the range 0-66% and residence times between 50 and 500 ms. Under dry air and without illumination, saturation of catalyst surfaces was achieved after ≈ 200 min for P25 and ≈ 1000 min for hectorite-TiO(2). The formaldehyde uptake capacity by hectorite-TiO(2) was 4.1 times higher than that of P25, almost twice the BET surface area ratio. In the presence of humidity, the difference in uptake efficiency between both materials disappeared, and saturation was achieved faster (after ≈ 200 min at 10% RH and ≈ 60 min at 65% RH). Under irradiation with each of the three UV sources, removal efficiencies were proportional to the Ti content and increased with contact time. The removal efficiency decreased at high RH. A more complete elimination of formaldehyde was observed with the 254+185 nm UV source.

Oxidative stress, cytoxicity, and cell mortality induced by nano-sized lead in aqueous suspensions.

This paper reports on the effect of aqueous and nano-particulated Pb on oxidative stress (lipid peroxidation), cytoxicity, and cell mortality. As determined by the Thiobarbituric Acid Reactive Substances (TBARS) method, only 6h after incubation aqueous suspensions bearing nano-sized PbO(2), soluble Pb(II), and brain-homogenate only suspensions, were determined to contain as much as ca. 7, 5, and 1 nmol TBARS mg protein(-1), respectively. Exposure of human cells (central nervous system, prostate, leukemia, colon, breast, lung cells) to nano-PbO(2) led to cell-growth inhibition values (%) ca. ≤18.7%. Finally, as estimated by the Artemia salina test, cell mortality values were found to show high-survival larvae rates. Microscopic observations revealed that Pb particles were swallowed, but caused no mortality, however.

Determination of lipid peroxidation and cytotoxicity in calcium, magnesium, titanium and hectorite (SHCa-1) suspensions.

This paper reports data on the relative ability of CaO, CaCl2, MgO, MgCl2, TiO2, and hectorite (SHCa-1) to induce oxidative stress (as determined by lipid peroxidation, LP) in biological matrices. The effectiveness of structural (oxide form) versus soluble Ca and Mg to induce LP is compared. An assessment on cytotoxicity as affected by soluble and structural Ca, Mg, TiO2 and SHCa-1 is also addressed. LP was screened and monitored using the Thiobarbituric Acid Reactive Substances (TBARS). The extent of TBARS production was found to vary with the type and initial concentration of the soluble or structural cation, Ca or Mg respectively. Obtained results showed higher magnitude values for the latter set of experiments. In the presence of TiO2 no significant TBARS production was detected pointing out a negligible effect of TiO2 on LP. At solid concentrations ca. 100 ppm, CaO appears to be more effective than SHCa-1 to induce LP. By contrast at ca. 25 ppm, MgO appears to be more effective than the clay mineral. The SHCa-1 LP-inducing activity has been proven to closely relate to structural Ca. The prevalence of mechanisms that may induce LP but not cytotoxicity (as determined by cell growth inhibition) was also addressed. Results on cell growth inhibition as affected by soluble and structural Ca, Mg, TiO2 and hectorite provide evidence to support that structural Ca or Mg brings about significantly higher variations than soluble Ca.

Lipid peroxidation induced by expandable clay minerals.

Small-sized environmental particles such as 2:1 phyllosilicates induce oxidative stress, a primary indicator of cell damage and toxicity. Herein, potential hazards of clay particle uptake are addressed. This paper reports that the content and distribution of structural Fe influence the ability of expandable clay minerals to induce lipid peroxidation (LP), a major indicator of oxidative stress, in biological matrices. Three smectite clays, hectorite (SHCa-1) and two nontronites (NAu-1) and (NAu-2) containing varying total content and coordination environment of structural Fe, were selected. Screening and monitoring of LP was conducted using a thiobarbituric acid reactive substances (TBARS) assay. The higher content of TBARS in nontronites than that in SHCa-1 suspensions was explained because structural Fe contributes to LP. The observed lack of correlation between TBARS content and the extent of Fe dissolution indicated that the formation of TBARS is surface controlled. Results showing a high TBARS content in SHCa-1 but not in nontronite supematant solutions was explained because the former contains distinct, soluble chemical component(s) that could (i) induce LP by its (their) own right and (ii) whose chemical affinity for organic ligands used as inhibitors is weak. Clays serve as stronger inductors than 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) but are much weaker than FeSO4. The outcome of this work shows that LP is clay surface-controlled and dependent on clay structural composition.

Efficiency of clay--TiO2 nanocomposites on the photocatalytic elimination of a model hydrophobic air pollutant.

Clay-supported TiO2 photocatalysts can potentially improve the performance of air treatment technologies via enhanced adsorption and reactivity of target volatile organic compounds (VOCs). In this study, a benchtop photocatalytic flow reactor was used to evaluate the efficiency of hectorite-TiO2 and kaolinite-TiO2, two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations, and reacted under UVA (lamda(max) = 365 nm) or UVC (lamda(max) = 254 nm) irradiation. The UVC lamp generated secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-Ti02 composites was compared with that of pure TiO2 (Degussa P25), and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO2 composites and of P25 were prepared by a dip-coating method on the surface of Raschig rings, which were placed inside the flow reactor. An upstream toluene concentration of approximately 170 ppbv was generated by diluting a constant flow of toluene vapor from a diffusion source with dry air, or with humid air at 10, 33, and 66% relative humidity (RH). Toluene concentrations were determined by collecting Tenax-TA sorbent tubes downstream of the reactor, with subsequent thermal desorption--GC/MS analysis. The fraction of toluene removed, %R, and the reaction rate, Tr, were calculated for each experimental condition from the concentrations measured with and without UV irradiation. Use of UVC light (UV/TiO2/O3) led to overall higher reactivity, which can be partially attributed to the contribution of gas phase reactions by short-lived radical species. When the reaction rate was normalized to the light irradiance, Tr/Ilamda,the UV/TiO2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO2 (P25 and Hecto-TiO2), but notfor Kao-TiO2. In all cases, reaction rates peaked at 10% RH, with Tr values between 10 and 50% higherthan those measured under dry air. However, a net inhibition was observed as RH increased to 33% and 66%, indicating that water molecules competed effectively with toluene for reactive surface sites and limited the overall photocatalytic conversion. Compared to P25, inhibition by coadsorbed water was less significant for Kao-TiO2 samples, but was more dramatic for Hecto-TiO2 due to the high water uptake capacity of hectorite.