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.     

TXRF analysis of soils and sediments to assess environmental contamination

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.     

Influence of natural events on the concentration and composition of atmospheric particulate matter

A ten-month field study aimed to determine the contribution of natural events (i.e. sea-salt and mineral dust events) to urban PM concentration was carried out at six sampling sites in Central Italy (Lazio region). Four indicators have been used to identify natural events during the period of the study. The first one is constituted by the ratio between number of particles in the coarse to the accumulation mode. It is simple, cheap, and the information are given in quasi-real time, but the nature of the event (sea-salt or mineral dust) is not detectable. The second indicator relies on the chemical analysis of the collected PM by X-ray fluorescence (XRF) and allows a robust identification of sea-salt and crustal components. The third one is based on diagnostic ratios of elemental fractions: Mg_extractable/Ti_residue for sea-salt and Ti_residue/Sb_residue for mineral dust. It requires skilled staff but it is most accurate and sensible. The last indicator, constructed on the basis of natural radioactivity data, is not diagnostic for the nature of the event but it is able to estimate the increase in PM concentration with respect to the expected concentration in the absence of natural events.The relevance of natural events and the variations in PM concentration and composition during the study are discussed. The joined use of the four indicators allowed the identification of about 20 natural PM episodes. In general, sea-salt aerosol events did not cause exceedance of the daily EU limit value for PM₁₀. Saharan dust events, instead, were in most cases responsible for the exceedance of the limit value at all stations.     

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.     

Biochemical composition of a meso-bathyal lobster

To characterise some traits of the life strategies of Polycheles typhlops, a deep-sea small lobster usually encountered as by-catch within deep trawls in the Southern Tyrrhenian Sea (Mediterranean Sea), we analysed the biochemical composition of the caudal muscles of 49 specimens collected in March and April 2007. Differences in the biochemical composition between females and males were weak, but relevant differences in protein (>90% of the organic C) and lipid (4–6%) contents were observed between developmental stages both in females and males. These differences are likely to be related to different food items and/or to the metabolic shifts associated with their reproduction. We argue that this deep-sea lobster could cover a relevant role in the meso-pelagic food webs and attract future commercial interest.     

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.     

Evaluation of concentration efficiency of the Pseudomonas aeruginosa phage PP7 in various water matrixes by different methods

Enteric viruses monitoring in surface waters requires the concentration of viruses before detection assays. The aim of this study was to evaluate different methods in terms of recovery efficiencies of bacteriophage PP7 of Pseudomonas aeruginosa, measured by real-time PCR, using it as a viral control process in water analysis. Different nucleic acid extraction methods (silica–guanidinium thiocyanate, a commercial kit (Qiagen Viral RNA Kit) and phenol–chloroform with alcohol precipitation) exhibited very low recovery efficiencies (0.08–4.18 %), being the most efficient the commercial kit used for subsequent experiments. To evaluate the efficiency of three concentration methods, PBS (as model for clean water) and water samples from rivers were seeded to reach high (HC, 10⁶ pfu ml^?1) and low concentrations (LC, 10⁴ pfu ml^?1) of PP7. Tangential ultrafiltration proved to be more efficient (50.36?±?12.91, 17.21?±?9.22 and 12.58?±?2.35 % for HC in PBS and two river samples, respectively) than adsorption–elution with negatively charged membranes (1.00?±?1.34, 2.79?±?2.62 and 0.05?±?0.08 % for HC in PBS and two river samples, respectively) and polyethylene glycol precipitation (15.95?±?7.43, 4.01?±?1.12 and 3.91?±?0.54 %, for HC in PBS and two river samples, respectively), being 3.2–50.4 times more efficient than the others for PBS and 2.7–252 times for river samples. Efficiencies also depended on the initial virus concentration and aqueous matrixes composition. In consequence, the incorporation of an internal standard like PP7 along the process is useful as a control of the water concentration procedure, the nucleic acid extraction, the presence of inhibitors and the variability of the recovery among replicas, and for the calculation of the sample limit of detection. Thus, the use of a process control, as presented here, is crucial for the accurate quantification of viral contamination.     

Trace metal levels in Prochilodus lineatus collected from the La Plata River, Argentina

Most of the industrial, urban and sewage discharges are released into the La Plata River, Argentina without any previous treatment. However, few works have investigated the extent of metal contamination. The aim of this study was to assess the levels of cadmium, copper, lead and zinc in liver and gills of adults Prochilodus lineatus collected from three sampling stations along the coast of the La Plata River: Berazategui, Berisso and Atalaya (from north to south). Samplings were performed during 2002 and 2004. Berazategui and Berisso were located nearby the main ducts that discharge the urban and domestic waste disposal from the cities of Buenos Aires and La Plata, respectively. The third station, Atalaya, was free of sewage discharges. Levels of cadmium and copper in liver were always higher than those found in gills. Instead, for lead and zinc, high levels were observed either in liver or gills, depending on the sampling station and the sampling period. In both tissues, the concentrations of metals did not differ significantly between male and female fish. In liver samples, the concentrations of cadmium, copper and zinc tended to increase from north to south. Instead, the levels of lead followed an opposite pattern. No clear tendencies were observed in gill samples. The data may be useful as reference levels of metal contaminants in P. lineatus, the most important fish species in the La Plata River system.     

Carbon, nitrogen, and phosphorus stoichiometry of plankton and the nutrient regime in Cabo Frio Bay, SE Brazil

This long-term study, performed during the years 2003–2005 and 2008–2009, investigated the carbon (C), nitrogen (N), and phosphorus (P) contents of the phyto- and zooplankton communities and the nutrient regime of Cabo Frio Bay, SE Brazil. The information intends to serve as baseline of the plankton C, N, and P stoichiometry for the calibration of biogeochemical and ecological models in support to future findings related to the local and regional phenomena of climatic change. Cabo Frio Bay is a small semienclosed system set adjacent to a region subject to sporadic coastal upwelling. Zooplankton exhibited average annual C, N, and P contents of 11.6?±?6.9 %, 2.8?±?1.8 %, and 0.18?±?0.08 %, and phytoplankton (>20 μm) 6.8?±?6.0 %, 1.6?±?1.5 %, and 0.09?±?0.08 %, respectively. The C/N/P ratios correspond to the lowest already found to date for a marine environment. The low C contents must have been brought about by a predominance of gelatinous zooplankton, like Doliolids/ Salps and also Pteropods. Average annual nutrient concentrations in the water were 0.21?±?0.1 μM for phosphate, 0.08?±?0.1 μM for nitrite, 0.74?±?1.6 μM for nitrate, and 1.27?±?1.1 μM for ammonium. N/P ratios were around 8:1 during the first study period and 12:1 during the second. The plankton C/N/P and N/P nutrient ratios and elemental concentrations suggest that the system was oligotrophic and nitrogen limited. The sporadic intrusions of upwelling waters during the first study period had no marked effect upon the systems metabolism, likely due to dilution effects and the short residence times of water of the bay.