Study of Meteorological Aspects and Urban Concentration of SO2 in Atmospheric Environment of La Plata, Argentina

This article presents and discusses SO₂ (ppbv) concentration measurements combined with meteorological data (mainly wind speed and direction) for a five-year campaign (1996 to 2000), in a site near an oil refinery plant close to the city of La Plata and surroundings (aprox. 740.000 inh.), considered one of the six most affected cities by air pollution in the country. Since there is no monitoring network in the area, the obtained results should be considered as medium term accumulated data that enables to determine trends by analyzing together gas concentrations and meteorological parameters. Preliminary characterization of the behaviour of the predominant winds of the region in relation with potential atmospheric gas pollutants from seasonal wind roses is possible to carry out from the data. These results are complemented with monthly averaged SO₂ measurements. In particular, for year 2000, pollutant roses were determined which enable predictions about contamination emission sources. As a general result we can state that there is a clear increase in annual SO₂ concentration and that the selected site should be considered as a key site for future survey monitoring network deployment. Annual SO₂ average concentration and prevailing seasonal winds determined in this work, together with the potential health impact of SO₂ reveals the need for a comprehensive and systematic study involving particulate matter an other basic pollutant gases.     

Organochlorine and mercury residues in Swainson's and ferruginous hawk eggs collected in North and South Dakota, 1974–79

Residues of organochlorine pesticides, polychlorinated biphenyls (PCBs), and mercury were measured in eggs of Swainson's hawks (Buteo swainsoni) and ferruginous hawks (B. regalis) collected in North and South Dakota during 1974–79. DDE was the most common compound detected in the eggs, but residues were below levels known to have adverse effects on reproduction. Other organochlorine compounds and mercury were found at low levels. Eggs of ferruginous hawks tended to contain more compounds with higher residues than eggs of Swainson's hawks.     

Second derivative spectroscopy for the determination of volatilized ammonia from urea-amended soil

A second derivative spectrometer custom fitted with a 1 m stainless steel White cell and maintained at 105°C is used to make real-time measurements of volatilized NH₃ from urea-amended soil. Comparison of the technique to impinger data shows a 5–16% discrepancy between the two techniques; however, other experiments presented suggests that this is not real. Sulfur dioxide and nitrous oxide interferences are discussed, though they were not found to be present in this study. Instrument response time is shown to be fast if 67% of the total response is achieved in less than 5 min. Fast response is achieved for ammonia if wall-adsorption effects are minimal and if ammonia mass flow is maintained at 0.2 μg min^-1.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.     

The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Matrix diffusion effects in the cleanup of heterogeneous aquifers

Simple mathematical models are developed to account for the rather slow mass transport of nonaqueous phase liquid (NAPL) into aqueous solution in groundwater during flushing operations. The models are based on the assumption that this bottleneck in the process is associated with diffusion in the aqueous phase in the porous medium from the location of the NAPL drops/ganglia in a region of relatively low permeability out into a region of substantially higher permeability, somewhat analogous to diffusion from a block of porous rock into a nearby fracture, where the fracture system overwhelmingly dominates the overall permeability. The models include batch flushing, flushing in a laboratory column, and a one-dimensional model for flushing by means of a single recovery well.     

Optimizing the removal of small fish passage barriers

Removing small artificial barriers that hinder upstream migrations of fish is a major problem in riparian habitat restoration. Because of budgetary limitations, it is necessary to prioritize barrier removal and repair decisions. These have usually been based on scoring and ranking procedures, which, although simple to use, can be very inefficient in terms of increasing the amount of accessible instream habitat. We develop a novel decision-making approach, based on integer programming techniques, which optimizes repair and removal decisions. Results show based on real datasets of barrier culverts located in Washington State that scoring and ranking is over 25% below the optimum on average and a full 100% below in the worst case, producing no net habitat gain whatsoever. This is compared to a dynamic programming method that was able to find optimal solutions in less than a second, even for problems with up to several hundred variables, and a heuristic method, which found solutions with less than a 1% average optimality gap in even less time.