Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd²⁺ ions by nZVI through adsorption. Cd²⁺ adsorption decreased in the presence of competitive cations in the order: Zn²⁺?>?Co²⁺?>?Mg²⁺?>?Mn²⁺?=?Cu²⁺?>?Ca²⁺?>?Na²⁺?=?K⁺. Higher concentrations of Cl^? significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd²⁺ adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI–Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.     

Temporal and geographical genetic variation in the amphipod Melita plumulosa (Crustacea: Melitidae): Link of a localized change in haplotype frequencies to a chemical spill

Anthropogenic effects such as contamination affect the genetic structure of populations. This study examined the temporal and geographical patterns of genetic diversity among populations of the benthic crustacean amphipod Melita plumulosa in the Parramatta River (Sydney, Australia), following an industrial chemical spill. The spill of an acrylate/methacrylate co-polymer in naphtha solvent occurred in July 2006. M. plumulosa were sampled temporally between December 2006 and November 2009 and spatially in November 2009. Genetic variation was examined at the mitochondrial cytochrome c oxidase subunit I locus. Notably, nucleotide diversity was low and Tajima’s D was significantly negative amongst amphipods collected immediately downstream from the spill for 10 months. We hypothesize that the spill had a significant localized effect on the genetic diversity of M. plumulosa. Alternate explanations include an alternate and unknown toxicant or a localized sampling bias. Future proposed studies will dissect these alternatives.     

Teleconnections,midlatitude cyclones and Aegean Sea turbulent heat flux variability on daily through decadal time scales

We analyze daily wintertime cyclone variability in the central and eastern Mediterranean during 1958–2001 and identify four distinct “cyclone states,” corresponding to the presence or absence of cyclones in each basin. Each cyclone state is associated with wind flows that induce characteristic patterns of cooling via turbulent (sensible and latent) heat fluxes in the eastern Mediterranean basin and Aegean Sea. The relative frequency of occurrence of each state determines the heat loss from the Aegean Sea during that winter, with largest heat losses occurring when there is a storm in the eastern but not central Mediterranean (eNOTc) and the smallest occurring when there is a storm in the central but not eastern Mediterranean (cNOTe). Time series of daily cyclone states for each winter allow us to infer Aegean Sea cooling for winters prior to 1985, the earliest year for which we have daily heat flux observations. We show that cyclone states conducive to Aegean Sea convection occurred in 1991/1992 and 1992/1993, the winters during which deepwater formation was observed in the Aegean Sea, and also during the mid-1970s and the winters of 1963/1964 and 1968/1969. We find that the eNOTc cyclone state is anticorrelated with the North Atlantic Oscillation (NAO) prior to 1977/1978. After 1977/1978, the cNOTe state is anticorrelated with both the NAO and the North Caspian Pattern, showing that the area of influence of large-scale atmospheric teleconnections on regional cyclone activity shifted from the eastern to the central Mediterranean during the late 1970s. A trend toward more frequent occurrence of the positive phase of the NAO produced less frequent cNOTe states since the late 1970s, increasing the number of days with strong cooling of the Aegean Sea surface waters.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

Ash from the combustion of wood treated with inorganic wood preservatives: Element composition and leaching

Wood samples impregnated with inorganic wood preservatives containing the elements arsenic, boron, chromium, copper, fluorine, and/or zinc were burned in a furnace. Three different kinds of ash were collected: furnace, boiler, and so-called fly ash. Analyses showed that the ash contained large amounts of elements originating from the inorganic wood preservatives. Further interest was focused on the leachability of the above-mentioned elements. For this purpose a laboratory batch leaching test according to the German Standard DIN 38 414 part 4 was chosen. The results indicate that the leachability is in a range where the release of these elements to the environment from deposited ash can be considered as detrimental.     

Temporal and spatial variation of RNA content in nymphs of the mayfly, Stenonema femoratum (Say)

Temporal variation of RNA: weight, RNA: protein, RNA: DNA, and protein: DNA ratios in Stenonema femoratum (Say) was assessed by monitoring at the same site in a small midwestern stream over a two-year period. Variation components were estimated using a two-way mixed model analysis of variance with weight class and collection date as main effects. About 30% of the variation in RNA concentration was within-cell variation associated with differences among individuals and analytical error. Temporal variation accounted for about 50% of the total variability in RNA concentration data. RNA: weight had 11% and RNA: protein had 17% variation attributed to weight class effects indicating that these ratios were dependent on the size of the mayfly. RNA: DNA ratios were not influenced by mayfly weight, suggesting that this ratio would be the most appropriate for comparing populations based on means of mixed individual sizes. Comparison of mean RNA: DNA ratios among collection dates yielded significant increases in the ratio during late fall in two consecutive years. Spatial variations in RNA: DNA ratios of S. femoratum collected from sites of similar habitats were not significantly different. These data encourage the future development of RNA concentration as an in situ biochemical indicator of growth rate and possibly of stress related effects on growth rate.     

The effect of vinasse on the growth of Helianthus annuus and Pisum sativum: part I--The effects on some enzymes and chlorophyll and protein content

In this study, the composition of vinasse was first analysed. It was found to contain 8.43% dry matter, 3.3% total ash, 4% crude protein and 0.95% total carbohydrates; BOD load was determined as 63 g litre(-1). Subsequently, the effects of vinasse in various concentrations (1, 2.5, 5, 10, 25, 50, 75 and 100%) on the activity of cellulase and pectin methyl esterase and the chlorophyll and protein contents of Pisum sativum and Helianthus annuus were investigated. The activity of these enzymes and the protein and chlorophyll contents in potted plants showed a gradual increase from the control up to 2.5% concentration of vinasse, but decreased at higher concentrations. These different effects of the effluent may be due to the high BOD load and the presence of cell wall cations in it.