Determination of mercury in agroindustrial samples by flow-injection cold vapor atomic absorption spectrometry using ion exchange and reductive elution

A flow-injection system with a Chelite-S® cationic resin packed minicolumn is proposed for the determination of trace levels of mercury in agroindustrial samples by cold vapor atomic absorption spectrometry. Improved sensitivity and selectivity are attained since mercuric ions are on-line concentrated whereas other potential interferents are discarded. With on-line reductive elution procedure, concentrated hydrochloric acid could be replaced by 10% w/v SnCl2, in 6 M HCl as eluent. The reversed-intermittent stream either carries the atomic mercury, to the flow cell in the forward direction or removes the residue from reactor/gas liquid separator to a discarding flask in the opposite direction. Concentration and volume of reagent, acidity, flow rates, commutation times and potential interfering species were investigated. For 120 s preconcentration time, the proposed system handles about 25 samples h-1 (50.0 500 ng l-1), consuming about 10 ml sample and 5 mg SnCl2 per determination. The detection limit is 0.8 ng l-1 and the relative standard deviation (RSD) (n = 12) of a 76.7 ng l-1 sample is about 5%. Results are in agreement with certified value of standard materials at 95% confidence level and good recoveries (97-128%) of spiked samples were found. (C) 2000 Elsevier Science B.V.

Mitigation of N2O emissions from grassland by nitrification inhibitor and actilith F2 applied with fertilizer and cattle slurry

Nitrous oxide (N2O) is involved in both ozone destruction and global warming. In agricultural soils it is produced by nitrification and denitrification mainly after fertilization. Nitrification inhibitors have been proposed as one of the management tools for the reduction of the potential hazards of fertilizer-derived N2O. Addition of nitrification inhibitors to fertilizers maintains soil N in ammonium form, thereby gaseous N losses by nitrification and denitrification are less likely to occur and there is increased N utilization by the sward. We present a study aimed to evaluate the effectiveness of the nitrification inhibitor dicyandiamide (DCD) and of the slurry additive Actilith F2 on N2O emissions following application of calcium ammonium nitrate or cattle slurry to a mixed clover/ryegrass sward in the Basque Country. The results indicate that large differences in N2O emission occur depending on fertilizer type and the presence or absence of a nitrification inhibitor. There is considerable scope for immediate reduction of emissions by applying DCD with calcium ammonium nitrate or cattle slurry. DCD, applied at 25 kg ha-1, reduced the amount of N lost as N2O by 60% and 42% when applied with cattle slurry and calcium ammonium nitrate, respectively. Actilith F2 did not reduce N2O emissions and it produced a long lasting mineralization of previously immobilized added N.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

Air quality and emissions management in the State of São Paulo, Brazil

The São Paulo State has 36 million people, 25 million living in three metropolitan areas. Only the São Paulo Metropolitan Region (SPMR) includes the state capital (São Paulo City) plus 38 cities, where ≈ 18 million people live, affected by frequent episodes of ozone, NOx, and fine particulate matter. In 2003, it was estimated that 15.1% of the SPMR vehicles used ethanol and 70.2% used the local gasoline. Natural gas vehicles have witnessed a booming participation in the last years, mainly through conversion of gasoline cars, and the present fleet is almost one million vehicles. To face the problems generated by light vehicles emissions the Federal Government set a program called PROCONVE - Program of Air Pollution Control from Vehicles - in 1986 and since then until now a significant reduction was reached, but the growth of the fleet hides most of the emission cuts. A discussion covers the evolution of the air pollution management in São Paulo; and innovative tools for air pollution management - both for mobile and stationary sources. This is an abstract of a paper presented at the 98th AWMA Annual Conference and Exhibition (Minneapolis, MN 6/21-24/2005).

Evaluating quality of life in mercury intoxicated people in urban-industrial environments through short-form 36 application

Context and objective: Records of contact with mercury (Hg) exist for more than 3500 years and several problems related to the use of this element can be noticed. Considering inexistence of current reports about it, quality of life perception evaluation was studied in people chronically intoxicated by mercury in an industrial environment. Design and setting: This is a cross-sectional descriptive observational study. Information from 47 urban-industrial workers from lamps manufacturing in São Paulo, clinically diagnosed as intoxicated by mercury and currently followed by the Occupational Health Service of Faculdade de Medicine da Universidade de São Paulo, with average age of 41.7 years old, was considered. Methods: SF36 questionnaire application was performed, with inferences tested by χ-square proof, by Spearman linear correlation and Mann-Whitney non-parametric test, adopting p < 0.05 as significant level. Results: In the eight domains, observed medians are 40% for physical functioning; 0 for physical function; 30% for body pain; 30% for general health; 22.2% for vitality; 50% for social functioning; 0 for emotional role and 36% for mental health. Correlation between age and SF36 domains does not reveal statistical significance, except for physical functioning, indicating that lower scores presented by older people in this domain are not followed by changes on other ones. Conclusions: Values obtained in people chronically intoxicated by mercury are actually lower, in the motor and mental scope components. Some instruments domains are higher for men than for women. Older ages are inversely associated to good performance in physical function domain. © Copyright Moreira Jr. Editora. Todos os direitos reservados.

Photon-induced multiple particle emissions of Zr90 and natZr from 10 to 140 MeV

A comprehensive analysis of electrodisintegration yields of protons on Zr90 is proposed taking into account the giant dipole resonance, isovector giant quadrupole resonance (IVGQR), and quasideuteron contributions to the total photoabsorption cross section from 10 to 140 MeV. The calculation applies the MCMC intranuclear cascade to address the direct and pre-equilibrium emissions and another Monte Carlo-based algorithm to describe the evaporation step. The final results of the total photoabsorption cross section for Zr90 and relevant decay channels are obtained by fitting the (e,p) measurements from the National Bureau of Standards and show that multiple proton emissions dominate the photonuclear reactions at higher energies. These results provide a consistent explanation for the exotic and steady increase of the (e,p) yield and also a strong evidence of a IVGQR with a strength parameter compatible with the E2 energy-weighted sum rule. The inclusive photoneutron cross sections for Zr90 and natZr, derived from these results and normalized with the (e,p) data, are in agreement within 10% with both Livermore and Saclay data up to 140 MeV. © 2007 The American Physical Society.

Seasonal behavior of mercury species in waters and sediments from the Negro River Basin, Amazon, Brazil

Total (HgT), reactive (HgR) and organic (Hg ORG) mercury species have been quantified in non-filtered waters collected from the Negro River Basin, Amazon (from January/2002 through January/2004), in both black and white water bodies. Black waters presented the highest HgT, HgORG and HgR concentration (29.1 ng L-1, 1.63 ng L-1 and 3.9 ng L-1, respectively), while, white waters presented the lowest HgT, Hg ORG and HgR concentration (8.8 ng L-1, 0.49 ng L-1 and 1.2 ng L-1, respectively). An inverse correlation between HgT and the water level over the basin was obtained, although the HgORG concentration has increased in the first rainy months and then decreased as the water level rose. Total mercury in surface sediments (0-10 cm) ranged from 70 to 271 mg kg-1 being the methylmercury 0.47-1.79 % of this stock. The results indicate that HgR and the labile dissolved organic matter were introduced into the aquatic environment during the flooding season, especially in the earlier stages, thus contributing to mercury methylation. ©2007 Sociedade Brasileira de Química.

Multiple particle and cluster emissions from Zr following intermediate energies photo absorption

A new approach based on a N-a cluster photoabsorption model is proposed for the understanding of the puzzling steady increase behavior of the 90Zr (e, α) yield measured at the National Bureau of Standards (NBS) within the Giant Dipole Resonance and quasideuteron energy range. The calculation takes into account the pre-equilibrium emissions of protons, neutrons and alpha particles in the framework of an extended version of the multicollisional intranuclear cascade model (MCMC). Another Monte Carlo based algorithm describes the statistical decay of the compound nucleus in terms of the competition between particle evaporation (p, n, d, α, 3He and t) and nuclear fission. The results reproduce quite successfully the 90Zr (e,α) yield, suggesting that emissions of a particles are essential for the interpretation of the exotic increase of the cross sections.

Voltammetry of mercury (II) based on an organo-clay modified graphite electrode

Organo-clay complex of ligand-hexadecyltrimethylammonium with montmorillonite was made for the purpose of application as a preconcentration agent in a chemically modified carbon paste electrode for determination of mercury (II) in aqueous solution. It was found out that the adsorption of Hg(II) by organo-clay complex is independent of the pH of the solution. It was also found out that the adsorption of the remaining metals Cd(II), Ps(II), Cu(II), Zn(II), and Ni(II) was dependent on the changes in pH solutions and increased when it varies from 1 to 8. The resultant material was characterized by cyclic and differential pulse anodic voltammetry using a modified graphite paste electrode in different supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, possible interferences and other variables.

Mercury, copper, and zinc concentrations in extracted human teeth

Amalgam has been used as a filling material for over 150 years. Mercury, copper, and zinc are present in restoration. The aim of this study was to compare mercury, copper, and zinc concentrations in extracted human teeth with amalgam restorations and teeth without restorations. Thirty-two teeth, 15 restored with dental amalgam and 17 without restorations, were chemically analyzed in an Optima 3300 DV (Perkin Elmer) plasma emission spectrometer. Mercury, copper, and zinc were found in human teeth regardless of the presence of amalgam restorations. The highest mercury concentrations were found in the coronary portions of the teeth with amalgam restorations. Copper concentrations were very high. Zinc concentrations in the teeth without restoration were lower than those seen in the coronary portion of the teeth with restorations. © 2009 Heldref Publications.

Spatial and temporal variability in soil CO2-C emissions and relation to soil temperature at King George Island, maritime Antarctica

Few studies have examined the effects of temperature on spatial and temporal trends in soil CO2-C emissions in Antarctica. In this work, we present in situ measurements of CO2-C emissions and assess their relation with soil temperature, using dynamic chambers. We found an exponential relation between CO2 emissions and soil temperature, with the value of Q10 being close to 2.1. Mean emission rates were as low as 0.026 and 0.072 g of CO2-C m-2 h-1 for bare soil and soil covered with moss, respectively, and as high as 0.162 g of CO2-C m-2 h-1 for soil covered with grass, Deschampsia antarctica Desv. (Poaceae). A spatial variability analysis conducted using a 60-point grid, for an area with mosses (Sannionia uncianata) and D. antarctica, yielded a spherical semivariogram model for CO2-C emissions with a range of 1 m. The results suggest that soil temperature is a controlling factor on temporal variations in soil CO2-C emissions, although spatial variations appear to be more strongly related to the distribution of vegetation types. © 2010 Elsevier B.V. and NIPR.

Lidar observation campaign of sugar cane fires and industrial emissions in the State of São Paulo, Brazil

Brazil has an important role in the biomass burning, with the detection of approximately 100,000 burning spots in a single year (2007). Most of these spots occur in the southern part of the Amazon basin during the dry season (from August to november) and these emissions reach the southeast of the country, a highly populated region and with serious urban air pollution problems. With the growing demand on biofuels, sugarcane is considerably expanding in the state of São Paulo, being a strong contributor to the bad air quality in this region. In the state of São Paulo, the main land use are pasture and sugarcane crop, that covers around 50% and 10% of the total area, respectively. Despite the aerosol from sugarcane burning having reduced atmospheric residence time, from a few days to some weeks, they might get together with those aerosol which spread over long distances (hundreds to thousands of kilometers). In the period of June through February 2010 a LIDAR observation campaign was carried in the state of São Paulo, Brazil, in order to observe and characterize optically the aerosols from two distinct sources, namely, sugar cane biomass burning and industrial emissions. For this purpose 2 LIDAR systems were available, one mobile and the other placed in a laboratory, both working in the visible (532 nm) and additionally the mobile system had a Raman channel available (607 nm). Also this campaign counted with a SODAR, a meteorological RADAR specially set up to detect aerosol echoes and gas-particle analyzers. To guarantee a good regional coverage 4 distinct sites were available to deploy the instruments, 2 in the near field of biomass burning activities (Rio Claro and Bauru), one for industrial emissions (Cubatão) and others from urban sources (São Paulo). The whole campaign provide the equivalent of 30 days of measurements which allowed us to get aerosol optical properties such as backscattering/extinction coefficients, scatter and LIDAR ratios, those were used to correlate with air quality and meteorological indicators and quantities. In this paper we should focus on the preliminary results of the Raman LIDAR system and its derived aerosol optical quantities. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Emissions from sugar cane fires in the Central & Western State of São Paulo and aerosol layers over metropolitan São Paulo observed by IPEN's lidar: Is there a connection?

The central and western parts of the State of São Paulo are well-known for vast sugar cane plantations, which during the harvest time are traditionally burnt about 12 hours before manual cutting. This procedure causes the release of large quantities of aerosols and a variety of gases, which can be observed by IPMet's radars, located in Bauru and Presidente Prudente, on days with no or little rain. Depending on the distance of these plumes from the radar, they can be detected up to 5 km amsl or more, and are subsequently being transported by winds to other regions. During the dry winter season of 2008, such plumes, attributed to cane fires, were frequently observed by IPMet's radars and documented in terms of radar reflectivity, time and location during the period 10 th - 21 st July 2008. At the same time, IPEN's Elastic Backscatter Lidar in São Paulo observed layers of aerosols of variable strength and heights above the city. The most significant days, viz. 14 and 15 July 2008 had been selected for calculating backward, as well as forward trajectories, deploying the European Flextra 3.3 Trajectory Model, which was initiated with ECMWF historic data with a 0,25 o×0,25 o grid spacing. The results presented here show an excellent match between the radar-detected sources of the plumes on 11 th July 2008 in the central parts of the State and the observations by IPEN's Lidar over Metropolitan São Paulo on 14 th July 2008, both in terms of forward and backward trajectories, as well as their heights, with a transport duration of approximately 70 hours under the prevailing meteorological conditions. © Sociedad Española de Óptica.

Climate change and reduction of CO2 emissions: the role of developing countries in carbon trade markets

Includes bibliography

Ammonia emissions in tunnel-ventilated broiler houses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)