FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

Influence of uncertain reaction rates on ozone sensitivity to emissions

Air quality models rely upon simplified photochemical mechanisms to efficiently represent the thousands of chemical species that interact to form air pollution. Uncertainties in the chemical reaction rate constants and photolysis frequencies that comprise those mechanisms can generate uncertainty in the estimation of pollutant concentrations and their responsiveness to emission controls. A high-order sensitivity analysis technique is applied to quantify the extent to which reaction rate uncertainties influence estimates of ozone concentrations and their sensitivities to precursor emissions during an air pollution episode in Houston, Texas. Several reactions were found to have much larger proportional effects on ozone’s sensitivities to emissions than on its concentrations. In particular, uncertainties in photolysis frequencies and in the rate of reaction between NO₂ and OH to form nitric acid can significantly influence the magnitude and sign of peak ozone sensitivity to nitrogen oxide (NO_x) emissions. Ozone sensitivity to VOCs exhibits a much more muted response to uncertainties in the reaction rate constants and photolysis frequencies considered here. The results indicate the importance of accurate reaction rate constants to predicting the ozone impacts resulting from NO_x emission controls.     

Evaluation of a detailed model of secondary organic aerosol formation from α-pinene against dark ozonolysis experiments

BOREAM, a detailed model for the gas-phase oxidation of α-pinene and its subsequent formation of Secondary Organic Aerosol (SOA), is tested against a large set of SOA yield measurements obtained in dark ozonolysis experiments. For the majority of experiments, modelled SOA yields are found to agree with measured yields to within a factor 2. However, the comparisons point to a general underestimation of modelled SOA yields at high temperatures (above 30 °C), reaching an order of magnitude or more in the worst cases, whereas modelled SOA yields are often overestimated at lower temperature (by a factor of about 2). Comparisons of results obtained using four different vapour pressure prediction methods indicate a strong sensitivity to the choice of the method, although the overestimated temperature dependence of the yields is found in all cases. Accounting for non-ideality of the aerosol mixture (based on an adapted UNIFAC method) has significant effects, especially at low yields. Our simulations show that the formation of oligomers through the gas-phase reactions of Stabilised Criegee Intermediates (SCI) with other molecular organic products could increase the SOA yield significantly only at very low relative humidity (below 1%). Further tests show that the agreement between model and measurements is improved when the ozonolysis mechanism includes additional production of non-volatile compounds.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Environmental copper: Behaviour when involved in physical adsorption at several interfaces

From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl_2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.     

Biomonitoring perfluorinated compounds in Catalonia,Spain: concentrations and trends in human liver and milk samples

Background, aim and scope  

Perfluorinated compounds (PFCs) are global environmental pollutants that bioaccumulate in wildlife and humans. Laboratory experiments have revealed toxic effects such as delayed development, humoral suppression, and hepatotoxicity. Although numerous human blood levels have been reported, little is known about distribution in the human body. Knowledge about PFC distribution and accumulation in the human body is crucial to understanding uptake and subsequent effects as well as to conduct risk assessments. The present study reports PFC levels in human liver and breast milk from a general population living in Catalonia, Spain. Liver and milk levels are compared to previously reported levels in blood from the same geographic area as well as to other existing reports on human liver and milk levels in other countries.     

Integrated emergy,energy and economic evaluation of rice and vegetable production systems in alluvial paddy fields: Implications for agricultural policy in China

China is the largest rice producing and consuming country in the world, but rice production has given way to the production of vegetables during the past twenty years. The government has been trying to stop this land-use conversion and increase the area in rice-vegetable rotation. Important questions that must be answered to determine what strategy is best for society are, “What is the reason behind this conversion?”; “Which system is more productive and which is more sustainable?”; and “How can economic policy be used to adjust the pattern of farmland use to attain sustainable development?” To answer these questions, a combined evaluation of these agricultural production systems was done using emergy, energy and economic methods. An economic analysis clearly showed that the reason for this conversion was simply that the economic output/input ratio and the benefit density of the vegetable production system were greater than that of rice. However, both energy and emergy evaluations showed that long-term rice was the best choice for sustainable development, followed by rotation systems. The current price of rice is lower than the em-value of rice produced from the long-term rice system, but higher than that of rice produced from the rotation system. Scenario analysis showed that if the government increases the price of rice to the em-value of rice produced from the long-term rice system, US$0.4/kg, and takes the value of soil organic matter into account, the economic output/input ratios of both the rice and rotation systems will be higher than that of the vegetable system. The three methods, energy, emergy and economics, are different but complementary, each revealing a different aspect of the same system. Their combined use shows not only the reasons behind a system’s current state or condition, but also the way to adjust these systems to move toward more sustainable states.     

The evolution of the Canadian mining industry: The role of regulatory punctuation

In this study, we analyze the evolution of Canada's mining industry from 1929 to 2006, focussing on the determinants of the number of firms in the industry and why this number changed over that period. Most empirical studies of industry evolution have focused on manufacturing industries that share similar structural characteristics. Perhaps because of this, extant models of industry evolution tend to ignore industry-specific and national-specific factors that can cause atypical trajectories, that is, heterogeneous industry evolution. Initial inspection of the Canadian mining industry shows that it is atypical in that it exhibits “negative skew” over time in the number of firms rather than the typical “positive skew.” We review two dominant theoretical approaches to industry evolution: the density-dependence theory and variants of industrial organization economics. We also consider possible sources of industry evolution heterogeneity, focussing particularly on “regulatory punctuation”. Using Canadian mining data, we find that the traditional models do not fully explain the changes in population size in Canada's mining industry. As a result, we introduce a number of hybrid models. The results from these hybrid models suggest that Canadian-specific regulatory punctuations, particularly the introduction of significant new taxes, environmental legislation, and incentives have shaped the trajectory of mining firm participation.     

Factors Influencing Prymnesium parvum Population Dynamics During Bloom Initiation: Results from In-lake Mesocosm Experiments1

Roelke, Daniel L., Leslie Schwierzke, Bryan W. Brooks, James P. Grover, Reagan M. Errera, Theodore W. Valenti, Jr., and James L. Pinckney, 2010. Factors Influencing Prymnesium parvum Population Dynamics During Bloom Initiation: Results from In-Lake Mesocosm Experiments. Journal of the American Water Resources Association (JAWRA) 46(1):76-91. DOI: 10.1111/j.1752-1688.2009.00392.x Abstract: The alga Prymnesium parvum forms large fish-killing blooms in many Texas lakes. In some of these lakes, however, P. parvum occurs but does not develop blooms. In this study, we investigated factors that may influence bloom initiation by conducting a series of in-lake experiments involving mixing of waters from Lake Whitney, which has a history of P. parvum blooms, with waters from Lake Waco where no blooms have occurred. In all experiments, the addition of Lake Waco waters resulted in a poorer performance of P. parvum. Various experimental treatments and field data show that differences in grazing, pathogens, nutrients, and salts between the two lakes were not likely factors that contributed to this observation. Industrial and agricultural contaminants, allelochemicals and algicidal chemicals were not measured as a part of this research. However, anthropogenic contaminants other than nutrients were not observed at levels exceeding water quality standards in Lake Waco in recent years. On the other hand, nuisance cyanobacteria are common in Lake Waco, where Microcystis sp. and Anabaena sp. were abundant during the initiation of our experiments, both taxa are known to produce chemicals with allelopathic properties. In addition, the emergent field of algal-heterotrophic bacteria interactions suggests that chemicals produced by heterotrophic bacteria should not be overlooked. Further research focusing on the chemical interactions between cyanobacteria and P. parvum, as well as the potential role of algicidal bacteria, in the initiation of P. parvum blooms is necessary, as it may be important to the management of these blooms.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.