Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland

Concentration and distribution of PCBs, PCB 11, and PBDEs in both surficial sediment and soil samples, taken from a zone subject to recent accelerated development, were investigated to assess the environmental quality and understand both natural and anthropogenic processes that influence contaminant behaviors. Values of PCB and PBDE are in the lower range of those reported in literature, typical of low impacted coastal zones. This could be due to efficient processes of resuspension and removal. Contaminants in the lagoon showed higher concentrations in sediments from sites close to the city and the outfalls of the industrial area, while soils showed maximum values in the northern samples. In addition, congener patterns and statistical analyses suggest the presence of effective degradation processes, especially for PBDEs, with the exception of the most concentrated samples that may indicate a direct input. PCB 11 is a significant component (up to 18%) in most lagoon sediments. Its presence is strongly associated with fine particles, thus the distribution seems to be driven mainly by the system hydrodynamic and does not trace the sources. Due to evaporation, only flooded agricultural soils show a similar relative abundance of this congener.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Relationship between leaf antioxidants and ozone injury in Nicotiana tabacum ‘Bel-W3’ under environmental conditions in São Paulo,SE – Brazil

Previous studies have reported that the extent of leaf injury in Nicotiana tabacum “Bel-W3” exposed to environmental conditions in the city of São Paulo is influenced by weather conditions. This influence may occur by means of antioxidant responses. Thus, this study aimed to evaluate whether daily antioxidant responses to environmental variations interfere on the progression of leaf injury on plants of this cultivar during their exposure in a state park of São Paulo and to determine a linear combination of variables, among antioxidants and environmental factors, which mostly explain this visible response. Plants were exposed at the mentioned site for 14 days in four different experiments. During each experiment, three plants were daily sampled to determine the accumulated percentage of leaf area affected by necrosis and antioxidant responses (concentrations of total ascorbic acid (AA) and activity of superoxide dismutase (SOD) and peroxidases (POD)). Ozone concentrations and weather conditions were also daily measured. Pearson correlations and multivariate analyses assessed the relationship between biological and environmental variables. Leaf injury appeared between the 3rd and 6th days of exposure and increased over the exposure periods. The daily concentrations of AA tended to decrease with time of exposure in all experiments, but the activity of SOD and POD oscillated during plant exposure. Positive correlations were observed between AA or SOD and O₃ concentrations, as well as negative correlations between AA and air temperature. The increasing percentage of leaf necrosis across the whole period was explained by decreasing levels of AA 2 days before injury estimation and by higher O₃ concentrations 5 days before (R² = 0.36; p < 0.001). The use of N. tabacum Bel-W3 as a bioindicator can be restricted by leaf antioxidant responses to both atmospheric contamination and weather conditions.     

An investigation of ergonomics analysis tools used in industry in the identification of work-related musculoskeletal disorders.

Web-based surveys were sent to Canadian certified ergonomists, Joint Health and Safety Committees (JHSCs) and health and safety certification trainers to understand better which ergonomics analysis tools were used in industry and help JHSCs obtain the necessary training required to reduce work-related musculoskeletal disorders (WMSDs). The results showed that most of the certified ergonomists used the Snook/Mital tables, the National Institute of Occupational Safety and Health (NIOSH) equation and rapid upper limb assessment (RULA) /rapid entire body assessment (REBA). The most frequently used methods by JHSCs to identify ergonomics risk were injury reports and worker complaints. The surveys for the health and safety certification trainers revealed that most curricula did not include ergonomics analysis tools. There appears to be a gap between what is recommended by certified ergonomists for JHSC, what is taught in training and what is used by JHSCs for ergonomics risk analysis. A better understanding, modifications in training curricula and education of JHSCs are needed to help reduce WMSDs.     

Integrating Remote Sensing Approach with Pollution Monitoring Tools for Aquatic Ecosystem Risk Assessment and Managment: A Case Study of Lake Victoria(UGANDA)

Aquatic ecosystems around the world, lake, estuaries and coastal areas are increasingly impacted by anthropogenic pollutants through different sources such as agricultural, industrial and urban discharges, atmospheric deposition and terrestrial drainage. Lake Victoria is the second largest lake in the world and the largest tropical lake. Bordered by Tanzania, Uganda, and Kenya, it provides a livelihood for millions of Africans in the region. However, the lake is under threat from eutrophication, a huge decline in the number of native fish species caused by several factors including loss of biodiversity, over fishing and pollution has been recently documented. Increasing usage of pesticides and insecticides in the adjacent agricultural areas as well as mercury contamination from processing of gold ore on the southern shores are currently considered among the most emergent phenomena of chemical contamination in the lake. By the application of globally consistent and comprehensive geospatial data-sets based on remote sensing integrated with information on heavy metals accumulation and insecticides exposure in native and alien fish populations, the present study aims at assessing the environmental risk associated to the contamination of the Lake Victoria water body on fish health, land cover distribution, biodiversity and the agricultural area surrounding the lake. By the elaboration of Landsat 7 TM data of November 2002 and Landsat 7 TM 1986 we have calculated the agriculture area which borders the Lake Victoria bay, which is an upland plain. This process has greatly enhanced nutrient loading to the soil, which is subsequently transported to the lake by rain or as dry fall. All the data has been insert in the Geographical information System (ARCGIS) to be upgraded and consulted. Heavy metals in fish fillets showed concentrations rather low except for mercury being higher than others as already described in previous investigations. In the same tissue, cholinesterases activity (ChE) as an indicator of insecticides exposure showed significant differences among fish species in both activity and sensitivity of selected inhibitor insecticides. This integrated approach aims at identifying and quantifying selected aquatic environmental issues which integrated with monitoring techniques such as contaminant concentrations and biological responses to insecticides exposure in fish populations will provide a scientific basis for aquatic zones management and assist in policy formulations at the national and international levels.     

Spectral cullet classification in the mid-infrared field for ceramic glass contaminants detection.

The presence of glass-like contaminants inside waste glass products, usually resulting from both industrial and differentiated urban waste collection, has greatly increased in recent years, due to the introduction to the market of a large amount of goods manufactured from ceramic glass. The presence of contaminants in the glass recycling streams reduces product quality and increases production costs. The detection of ceramic glass detection is an unresolved problem, as such material looks like normal glass and can only be detected by trained personnel. In this study an innovative approach to ceramic glass recognition, based on the spectral signature in the mid-infrared (MIR) field, was proposed and investigated. The study specifically addressed the spectral characterization of glass and ceramic glass fragments collected in a real recycling plant from two different production lines: coloured container glass and white container glass. To define suitable inspection strategies to separate the useful (glass) from the polluting (ceramic glass) materials at the recycling plants, fragments presenting different colour, thickness, size, shape and manufacturing were selected. Both dirty and clean cullet was considered. The analyses, carried out in the MIR spectral field (2280-4480 nm), show that ceramic glass and glass fragments can be recognized according to their different spectral signature. In particular, by selecting a specific wavelength ratio the two classes of materials can be rapidly recognized, suggesting the possibility of developing an integrated hardware and software sorting system for 'on-line' ceramic glass separation.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Imaging spectroscopy based strategies for ceramic glass contaminants removal in glass recycling

The presence of ceramic glass contaminants in glass recycling plants reduces production quality and increases production costs. The problem of ceramic glass inspection is related to the fact that its detectable physical and pictorial properties are quite similar to those of glass. As a consequence, at the sorting plant scale, ceramic glass looks like normal glass and is detectable only by specialized personnel. In this paper an innovative approach for ceramic glass recognition, based on imaging spectroscopy, is proposed and investigated. In order to define suitable inspection strategies for the separation between useful (glass) and polluting (ceramic glass) materials, reference samples of glass and ceramic glass presenting different colors, thicknesses, shapes and manufacturing processes have been selected. Reflectance spectra have been obtained using two equipment covering the visible and near infrared wavelength ranges (400-1000 and 1000-1700 nm). Results showed as recognition of glass and ceramic glass is possible using selected wavelength ratios, in both visible and near infrared fields.