An anion-exchange high-performance liquid chromatography method coupled to total organic carbon determination for the analysis of water-soluble organic aerosols.

The chemical composition of water-soluble organic carbon (WSOC) in atmospheric aerosol particles is largely unexplored, due to the myriad of individual compounds, which has hampered attempts to attain a full characterization at the molecular level. An alternative approach, focusing on the analysis of a few main chemical classes, allowed the quantitative fractionation of WSOC into neutral compounds (NC), mono- and di-acids (MDA) and polyacids (PA) through an anion-exchange liquid chromatographic method. Previous attempts to quantify NC, MDA and PA relied on a low-pressure chromatographic technique using a volatile buffer, followed by total organic carbon (TOC) analysis of the fractions, or alternatively on a faster HPLC-UV method which provided a quantification of the fractions based on empirical relationships between UV signal and TOC concentration. Here, we report an upgraded anion-exchange HPLC technique, allowing direct TOC analysis of the eluted fractions, without any pre-treatment, thus permitting a great simplification of quantitative analysis and preventing sample losses. The new HPLC-TOC methodology, employing completely inorganic eluents shows the same efficiency of the former HPLC-UV method employing organic additives, with the exception of phenolic compounds, which are retained on the column by secondary interactions, and low-molecular weight tricarboxylic acids, which are recovered among MDA. The new anion-exchange liquid chromatographic method can recover a substantial amount (86-100%) of water-soluble organic carbon from atmospheric aerosol extracts, thus allowing a higher retention and fractionation capacity with respect to alternative techniques, like solid phase extraction.

Uptake and toxicity of Cr(III) in celery seedlings.

The present study shows that in celery Cr(III) induces deleterious effects on seedling development and morphology, and a number of metabolic responses related to stress. Exogenous CrCl3 from 0.01 to 1 mM increasingly inhibited seed germination and hypocotyl elongation, or completely blocked it (10 mM), while the root apparatus was dramatically damaged even at the lowest dose. Seedlings took up exogenous Cr(III) in a dose-dependent manner, roots being the site of major metal accumulation; translocation towards the hypocotyl and cotyledonary leaves was also detected. Either total or chlorophyll a content was significantly reduced by chromium as low as 0.01 mM. A large accumulation of free and, to a lesser extent, conjugated polyamines occurred in all segments of treated plants. A dose-dependent relationship linking actual amounts of Cr(III) recovered in the entire seedling or organ and the respective polyamine titre was evidenced. Free putrescine, in particular, was the polyamine exhibiting the highest rate of increase, and cotyledonary leaves the organ where the major response occurred. A marked increase in ubiquitin-protein conjugates after Cr(III) treatment was also observed, particularly in roots. Thus, the study suggests for the first time a possible relationship between ubiquitination and Cr(III)-stress. The putative function of polyamines as a stress response, and the recruitment of the ubiquitin pathway to remove damaged or aberrant proteins which might have been produced in metal-treated seedlings are discussed.

Partitioning of metals between the aqueous phase and suspended insoluble material in fog droplets.

This paper discusses the partitioning of metals (K, Na, Ca, Mg, Al, Cu, Fe, Pb and Zn) between the aqueous phase and the suspended insoluble material in fog samples collected in the Po Valley during two extensive fields campaigns. Metals represent on average 11% of the mass of suspended insoluble matter, while the main component is carbon (both organic carbon, OC = 35%, and black carbon, BC = 8%). The unaccounted suspended matter mass is very high, on average 46%, and is attributable to non metallic species, such as O and N and of Si. The principal metals in the insoluble suspended fraction are Fe and Al (2-5%), while the contributions of other metals (Na, Mg, Cu, Pb and Zn) are lower than 1%. Ca and K exhibited high blank values and could not be detected above blank detection limit threshold. The main components in the aqueous phase are NO3- (34%), WSOC (23%), SO4(2-) (18%) and NH4+ (19%), while trace metals and remaining cations and anions accounted for less than 1% of solute mass. The main dissolved trace metals in fog droplets are Zn, Al and Fe, while the main metallic cations are Na and Ca. Fe and Al are the only metals preferentially distributed in the suspended insoluble matter of fog droplets (partitioning ratio respectively 37% and 33%). All other metals are mostly dissolved in the aqueous phase (mean partitioning ratios of Mg, Pb, Zn, Cu and Na are 69%, 70%, 77%, 81% and 87%). These findings are in agreement with literature data on metal speciation in cloud and rain samples. The dependence of partitioning ratios on pH is investigated for the different metals, with only Al showing a clear partitioning ratio decrease with increasing pH. Conversely, the other metals show no dependence or a complex and highly variable behaviour. The partitioning ratio of iron (mean 37%) observed in the Po Valley fog samples is much higher than the water extractable iron in aerosol particles (typically 1-2 %): this fact can be explained by differences in the aerosol sources and composition among sites and by chemical processes in the aqueous phase, such as complexation and redox reactions involving organic ligands (oxalate, or other organic acids as humic-like organic matter) which may promote Fe solubility.