Modeling Inorganic Aerosols and Their Response to Changes in Precursor Concentration in Mexico City

Abstract

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM_2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM_2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

A high-resolution historical sediment record of nutrients,trace elements and organochlorines (DDT and PCB) deposition in a drinking water reservoir (Lake Brêt,Switzerland) points at local and regional pollutant sources

The ¹³⁷Cs and ²¹⁰Pb dating of a 61-cm long sediment core retrieved from a drinking water reservoir (Lake Brêt) located in Switzerland revealed a linear and relatively high sedimentation rate (～1 cm year^?1) over the last decades. The continuous centimeter scale measurement of physical (porewater and granulometry), organic (C_org, P, N, HI and OI indexes) and mineral (C_min and lithogenic trace elements) parameters therefore enables reconstructing the environmental history of the lake and anthropogenic pollutant input (trace metals, DDT and PCBs) at high resolution. A major change in the physical properties of the lowermost sediments occurred following the artificial rise of the dam in 1922. After ca. 1940, there was a long-term up-core increase in organic matter deposition attributed to enhance primary production and anoxic bottom water conditions due to excessive nutrient input from a watershed predominantly used for agriculture that also received domestic effluents of two wastewater-treatment plants. This pattern contrasts with the terrigenous element input (Eu, Sc, Mg, Ti, Al, and Fe) which doubled after the rising of the dam but continuously decreased during the last 60 years. By comparison, the trace metals (Cu, Pb and Hg) presented a slight enrichment factor (EF) only during the second part of the 20th century. Although maximum EF Pb (>2) occurred synchronously with the use of leaded gasoline in Switzerland (between ca. 1947 and 1985) the Hg and Cu profiles exhibited a relatively similar trend than Pb during the 20th century, therefore excluding the alkyl-lead added to petrol as the dominant (atmospheric) source of lead input to Lake Brêt. Conversely, the Cu profile that did not follow the decrease registered in Pb and Hg during the last 10 years, suggests an additional source of Cu probably linked to the impact of agricultural activities in the area. In absence of heavy industries in the catchment, the atmospheric deposition of DDT and PCBs via surface runoff followed the historical emissions of POPs in Switzerland. Such result highlights the regional contamination of freshwater resources by the large-scale emission of toxic industrial chemicals in the 1960s and 1970s as well as the efficiency of the regulatory measures subsequently taken.     

Evolutionary relationships of deep-sea mussels inferred by mitochondrial DNA sequences

In order to elucidate the evolutionary process of deep-sea Bathymodiolus mussels, we investigated the phylogenetic relationships of 16 species worldwide by analyzing nucleotide sequences of the mitochondrial COI and ND4 genes. Deep-sea mussels were clustered into three groups by basal trichotomous divergence. The first was composed of four species found in Japanese waters and one species from the Gulf of Mexico, which contain methanotrophic endosymbiotic bacteria. The second included nine species distributed in the West and East Pacific, Indian, and Atlantic Oceans. Members of the second group were trichotomously divided into the Indo-West Pacific, Atlantic, and East Pacific subclusters. The Indo-West Pacific subcluster was composed of three very closely related species with mutual genetic distances at the intraspecific level (av. 0.019 in COI and 0.009 in ND4 relative to av. 0.156 in COI and 0.265 in ND4 among Bathymodiolus species other than Cluster A species), suggesting some gene flow among these species. The third consisted of two West Pacific species. Species in the second and third groups contain mainly thioautotrophic endosymbionts, including some species harboring both methanotrophs and thioautotrophs.     

Organic speciation of atmospheric particles in Alvão Natural Park (Portugal)

PM₁₀ continental rural background aerosols were collected during a summer field campaign (August–September 2006) at Lamas de Ôlo in the upper zone of the Alvão Natural Park, a mountain region of northern Portugal. In addition to the determination of the carbonaceous content by a thermal–optical method, the organic speciation of aerosols was performed by gas chromatography–mass spectrometry in an effort to evaluate photo-oxidation products of biogenic volatile organic compounds and other markers for source characterization. The detailed analysis revealed relatively high concentrations of polyols and short-chain dicarboxylic, tricarboxylic, hydroxycarboxylic, and oxocarboxylic acids, many of which are thought to be indicators of secondary aerosol formation, accounting for about 70% of global chromatographically resolved mass. Major photo-oxidation products of α- and β-pinene have been detected. The tracers for the photo-oxidation of isoprene comprise two diastereoisomeric 2-methyltetrols, C₅-alkene triols, and 2-methylglyceric acid, which have only recently been elucidated. In addition, the occurrence of levoglucosan and other biomass combustion tracers indicates that the site was affected by wildfires. This source contributed to more than 80% of the organic carbon mass during a period of strong forest fire influence.     

Experimental exposure of juvenile savannah monitors (Varanus exanthematicus) to an environmentally relevant mixture of three contaminants: effects and accumulation in tissues

Using varanids as indicators of pollution in African continental wetlands was previously proposed. The present study aimed at understanding experimentally how monitors absorb and accumulate pollutants and how they are affected. The relevance of non-destructive sampling was also evaluated. Savannah monitors (Varanus exanthematicus) were orally exposed during 6 months to a mixture of lead, 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and chlorpyrifos-ethyl (CPF) or to the vehicle only. Proportionally to their mass, exposed monitors received the same dose: 20 then 10 mg lead?kg^?1, 2 then 0.5 mg CPF?kg^?1 and 4 mg 4,4′-DDT?kg^?1. Individuals surviving contamination were euthanized after 4 or 6 months of experiment. Tissues were analysed for lead by atomic absorption spectrophotometry and for DDT and CPF by gas chromatography. Exposed monitors absorbed all three pollutants but only lead (essentially in bone, tail tips and phalanxes) and 4,4′-DDT plus its main metabolites (essentially in fat and liver) accumulated. CPF killed ten individuals. Clear correlations occurred between the total quantity of lead or 4,4′-DDT administered and concentrations in tissues. Tail tips and skin samples are recommended non-destructive indicators for lead and organochlorine pesticides contamination, respectively. This work confirms that monitors can be used as relevant indicators of environmental pollution by lead and organochlorine pesticides. Although varanids withstand heavy lead and DDT contamination, our results suggest that CPF can be lethal at very low doses to the herpetofauna and emphasize the importance of considering all taxa in impact assessment studies, including reptiles.     

A study on As, Cu, Pb and Zn (bio)availability in an abandoned mine area (São Domingos, Portugal) using chemical and ecotoxicological tools

The aim of this study was to relate the results obtained by chemical methods, used to assess environmental (bio)availability, with the ecotoxic response and bioaccumulation of trace elements (TE) by the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils from a sulphide mine. The extracting solution 0.5 M NH₄CH₃COO, 0.5 M CH₃COOH and 0.02 M EDTA (pH 4.7), was able to predict environmental bioavailability of TE to E. fetida. However, the toxicological bioavailability could not be predicted from the results of the chemical extractions or from the bioaccumulation results: E. fetida reproduction was higher in soils where environmental bioavailability of TE and bioaccumulation values were also higher. In this study, the toxic response of the organism seemed to be more influenced by the overall nutritional status of the soil (e.g. pH, organic matter, plant nutrient availability and cation exchange capacity) than by its TE contamination. In the case of anthropogenic multi-contaminated sites, the different soil characteristics exert an important and confounding influence in the toxic response and the relationship between different bioavailable fractions cannot be easily established, emphasising the need to combine results from chemical methods with those from bioassays when evaluating the bioavailability of TE in these soils.