Toward verifying fossil fuel CO2 emissions with the CMAQ model: Motivation,model description and initial simulation

Motivated by the question of whether and how a state-of-the-art regional chemical transport model (CTM) can facilitate characterization of CO₂ spatiotemporal variability and verify CO₂ fossil-fuel emissions, we for the first time applied the Community Multiscale Air Quality (CMAQ) model to simulate CO₂. This paper presents methods, input data, and initial results for CO₂ simulation using CMAQ over the contiguous United States in October 2007. Modeling experiments have been performed to understand the roles of fossil-fuel emissions, biosphere–atmosphere exchange, and meteorology in regulating the spatial distribution of CO₂ near the surface over the contiguous United States. Three sets of net ecosystem exchange (NEE) fluxes were used as input to assess the impact of uncertainty of NEE on CO₂ concentrations simulated by CMAQ. Observational data from six tall tower sites across the country were used to evaluate model performance. In particular, at the Boulder Atmospheric Observatory (BAO), a tall tower site that receives urban emissions from Denver, CO, the CMAQ model using hourly varying, high-resolution CO₂ fossil-fuel emissions from the Vulcan inventory and CarbonTracker optimized NEE reproduced the observed diurnal profile of CO₂ reasonably well but with a low bias in the early morning. The spatial distribution of CO₂ was found to correlate with NOx, SO₂, and CO, because of their similar fossil-fuel emission sources and common transport processes. These initial results from CMAQ demonstrate the potential of using a regional CTM to help interpret CO₂ observations and understand CO₂ variability in space and time. The ability to simulate a full suite of air pollutants in CMAQ will also facilitate investigations of their use as tracers for CO₂ source attribution. This work serves as a proof of concept and the foundation for more comprehensive examinations of CO₂ spatiotemporal variability and various uncertainties in the future.

Implications: Atmospheric CO₂ has long been modeled and studied on continental to global scales to understand the global carbon cycle. This work demonstrates the potential of modeling and studying CO₂ variability at fine spatiotemporal scales with CMAQ, which has been applied extensively, to study traditionally regulated air pollutants. The abundant observational records of these air pollutants and successful experience in studying and reducing their emissions may be useful for verifying CO₂ emissions. Although there remains much more to further investigate, this work opens up a discussion on whether and how to study CO₂ as an air pollutant.     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

The use of multivariate statistical methods for optimization of the surface water quality network monitoring in the Paraopeba river basin,Brazil

This study sought to evaluate and propose adjustments to the water quality monitoring network of surface freshwaters in the Paraopeba river basin (Minas Gerais, Brazil), using multivariate statistical methods. A total of 13,560 valid data were analyzed for 19 water quality parameters at 30 monitoring sites, over a period of 5 years (2008–2013). The cluster analysis grouped the monitoring sites in eight groups based on similarities of water quality characteristics. This analysis made it possible to detect the most relevant monitoring stations in the river basin. The principal components analysis associated with non-parametric tests and the analysis of violation of the standards prescribed by law, allowed for identifying the most relevant parameters which must be maintained in the network (thermotolerant coliforms, total manganese, and total phosphorus). The discharge of domestic sewage and industrial wastewater, that from mining activities and diffuse pollution from agriculture and pasture areas are the main sources of pollution responsible for the surface water quality deterioration in this basin. The BP073 monitoring site presents the most degraded water quality in the Paropeba river basin. The monitoring sites BP094 and BP092 are located geographically close and they measure similar water quality, so a possible assessment of the need to maintain only one of the two in the monitoring network is suggested. Therefore, multivariate analyses were efficient to assess the adequacy of the water quality monitoring network of the Paraopeba river basin, and it can be used in other watersheds.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.     

Decomposition of hazardous organic materials in the solidification/stabilization process using catalytic-activated carbon

The application of a catalytic-activated carbon to the solidification/stabilization (S/S) process for immobilization of phenol and 2-chlorophenol and catalytic decomposition was investigated. The effect of the catalytic-activated carbon, in amounts of 0.25-1% (by dry sand wt.), on the leaching of phenol and 2-chlorophenol was studied. H2O2 was added as a source of oxygen in the amounts of 1 or 5%, with respect to liquid solution weight. Toxicity characteristic leaching procedure (TCLP) leaching tests showed that adding the catalytic-activated carbon to the S/S matrix significantly reduced the leachability of both phenol and 2-chlorophenol. Only trace amounts of phenol were found in the leaching solution, while the concentration of 2-chlorophenol was below the detection limit of the gas chromatography (GC). Without addition of the catalytic-activated carbon, 87% of the phenol and 92% of the 2-chlorophenol leached. Additional tests on TCLP leachate solutions using GC-mass spectrometry indicated the existence of simple, less hazardous, hydrocarbons, including alcohol. Catalytic-activated carbons treated with phenol in the presence of H2O2 were also analyzed using time of flight-secondary ion mass spectroscopy (TOF-SIMS). Results indicate that the phenol aromatic ring was broken by the catalytic reaction.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76-128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

Environmental impacts caused by cemeteries and crematoria,new funeral technologies,and preferences of the Northeastern and Southern Brazilian population as for the funeral process

Cemeteries and crematoria are the main funeral ways used in the world nowadays. It is a little-studied segment in the present days, mainly as for the possible environmental impacts in the environment, such as those derived from dental amalgam, prostheses, and dioxins, among other. This article aimed to identify the environmental impacts caused by cemeteries and crematoria and to point out new trends in funeral processes such as freeze-drying and alkaline hydrolysis. The study is justified due to the large part of the Brazilian population that do not know the environmental impacts caused by cemeteries and crematoria, as well as to bring information about the new processes. For that, a research was carried out with 400 people. The main results show that among all the funeral processes, the new freeze-drying process was opted by 33% of the sample. We also identified that the main reasons for choosing the funeral process were less environmental impact (28%), no after-death expenses (grave payment) (16.1%), and the possibility of putting away or throwing away the remains wherever you want (14.9%). Finally, new funeral processes were well accepted by the Brazilian population—those who were interviewed—due to their benefits.     

Evaluation of violations in water quality standards in the monitoring network of São Francisco River basin,the third largest in Brazil

The São Francisco River is the largest river located entirely within Brazil, and water scarcity problems have been a major concern of Brazilian society and government. Water quality issues are also a concern and have worsened with the recent intensification of urbanization and industrialization. In this study, violations to water quality standards established by local legislation were calculated as a percentage for 26 selected parameters over a monitoring period of 14 years. The violation percentages were analyzed spatially using the Kruskal-Wallis test, followed by multiple comparison analysis. Temporal analysis was performed using the Mann-Kendall test and Spearman correlation. Some parameters could be identified as cause for concern due to high violation levels, such as the fecal coliform indicator (FCI) and phosphorus—both related to domestic and effluent disposal without treatment or with insufficient treatment—and color, turbidity, manganese, and total suspended solids—which can be affected by erosive processes of natural and anthropogenic causes. The study found that these violations are concentrated in the most urbanized and industrialized areas of the basin. Some metallic parameters, such as iron and arsenic violations, may be related to mining activities in the rich soil of the Iron Quadrangle area located within the Minas Gerais State. Trend analysis results indicated that most monitoring stations did not have significant modification (elevation or reduction) trends over time, which, together with the high violation percentages, might indicate the maintenance of a scenario of constant pressure upon water resources, in particular in those more urbanized areas.     

The complexation of Cu(II) by anthropogenic fulvic acids extracted from composted urban and livestock wastes

Abstract

The fulvic acid (fua) fractions of two samples of composted solid wastes [urban (urfua) and livestock (lsfua) wastes], commercialized to be used in agriculture as organic correctives or fertilizers, were analyzed for their affinity towards Cu(II) at pH=6. Molecular fluorescence spectroscopy (synchronous mode) was used to monitor the quenching caused by the complexation upon addition of Cu(II) to fua. Spectral data were preprocessed by a chemometric self‐modeling mixture analysis method (SIMPLISMA) to detect the number of different types of fluorescent binding sites that exist in each fua, their spectra and the corresponding quenching profiles [fluorescence intensity as function of the total Cu(II) concentration]. From the analysis of the quenching profiles, the amount of binding sites (Cl) and the corresponding conditional stability constants (K') were calculated. Both fua samples have approximately Cl = 0.21 mmol/g and the logarithms of K’ are 4.21(3) and 4.51(8), respectively for urfua and lsfua. The differences detected between these fua samples and those extracted from natural soils can be attributed mainly to the relatively small humification extent of the present anthropogenic fua samples.     

Only carapace or the entire cephalothorax: which is best to obtain chitosan from shrimp fishery waste?

Journal of Material Cycles and Waste Management - The polysaccharide chitin (CHIT), extracted mainly from exoskeletons of crustaceans, can be obtained from shrimp fishery waste. It is the source of...