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.     

Universal criteria for assessing the ecological state of soil algocenoses

A set of criteria allowing demarcation between algocenoses is proposed. These criteria characterize the species composition, group of dominants, and taxonomic and ecological structure of algocenoses.     

Phenotypic variation and adaptive reaction to the presence of predator in two Daphnia species (Daphniiformes, <Emphasis Type="Italic">Daphnia</Emphasis>) in Lake Baikal

The effect of invertebrate predation pressure by the cladoceran Leptodora kindti on the population structure of Daphnia galeata and D. hyalina has been estimated by analyzing the occurrence frequency of the normal and spined morphotypes in Lake Baikal. It is shown that the growth of L. kindti population density leads to an increase in the proportion of the spined morphotype, while that of that of the normal morphotype decreases.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

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.     

Application of 15N–18O double stable isotope tracer technique in an agricultural nonpoint polluted river of the Yangtze Delta Region

One strategy to combat nitrate (NO₃-N) contamination in rivers is to understand its sources. NO₃-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a ¹⁵N–¹⁸O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO₃-N are present in both the main channel and the major tributaries, and NO₃-N was one of the most important N forms in water. Analysis of isotopic compositions (δ ¹⁸O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ ¹⁵N-NO₃ (?1.4 to 12.4 ‰) and a narrow range of δ ¹⁸O-NO₃ (3.7 to 9.0 ‰) in the main channel waters. The δ ¹⁵N and δ ¹⁸O-NO₃ values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ ¹⁵N and δ ¹⁸O-NO₃ values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO₃-N in most of the samples had relatively low δ ¹⁵N and δ ¹⁸O-NO₃ values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO₃-N pollution in the rivers at the tributary scale.     

Beyond selectivity: Are behavioral avoidance and hormesis likely causes of pyrethroid-induced outbreaks of the southern red mite Oligonychus ilicis?

Secondary pest outbreak is a counterintuitive ecological backlash of pesticide use in agriculture that takes place with the increase in abundance of a non-targeted pest species after pesticide application against a targeted pest species. Although the phenomenon was well recognized, its alternative causes are seldom considered. Outbreaks of the southern red mite Oligonychus ilicis are frequently reported in Brazilian coffee farms after the application of pyrethroid insecticides against the coffee leaf miner Leucoptera coffeella. Selectivity favoring the red mite against its main predatory mites is generally assumed as the outbreak cause, but this theory has never been tested. Here, we assessed the toxicity (and thus the selectivity) of deltamethrin against both mite species: the southern red mite and its phytoseid predator Amblyseius herbicolus. Additionally, behavioral avoidance and deltamethrin-induced hormesis were also tested as potential causes of red mite outbreak using free-choice behavioral walking bioassays with the predatory mite and life-table experiments with both mite species, respectively. Lethal toxicity bioassays indicated that the predatory mite was slightly more susceptible than its prey (1.5×), but in more robust demographic bioassays, the predator was three times more tolerant to deltamethrin than its prey, indicating that predator susceptibility to deltamethrin is not a cause of the reported outbreaks. The predator did not exhibit behavioral avoidance to deltamethrin; however insecticide-induced hormesis in the red mite led to its high population increase under low doses, which was not observed for the predatory mite. Therefore, deltamethrin-induced hormesis is a likely cause of the reported red mite outbreaks.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.