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.     

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.     

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.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Airborne pollutants along a roadside: assessment using snow analyses and moss bags

Vertical snow sampling and moss bag transplants were used to estimate the local inorganic and organic pollutant load deposited from traffic along a major highway in Finland. The pH and concentrations of Cl(-), NO(3)(-), SO(4)(2-), Ca(2+), Na(+) and polyaromatic hydrocarbons (PAHs) were determined from snow samples collected in winter at different sites along the highway. In summer, moss bags containing 20 g of fresh red-stemmed feather moss (Pleurozium schreberi) were transplanted at the same sites. The moss bag transplants remained exposed to roadside traffic for a period of one month following which the samples were collected and the PAH profiles and concentrations were analysed. The deposition of inorganic and organic pollutants from road traffic was observed up to 60 m from the road. The prevailing winds had a significant effect on the dispersion of pollutants. Snow appears to be a good collector of inorganic pollutants from the atmosphere and can be used to monitor local airborne pollution from road traffic. Snow packs can also be used as passive collectors of organic pollutant loads from road traffic on a local scale. To monitor organic PAH deposition from the road traffic, moss bags appeared to be better indicators compared to snow sampling. The efficiency of moss bags in accumulating PAH compounds indicate that vegetation may be an important sink for traffic pollution.