RESUMO
Chemical characterization of PM2.5 and PM10 is important to identify potential compounds that induce biological responses that translate into cardio-respiratory health problems. This study shows the reliability of the use of crystalline phases, identified in samples from receptor sites, as source markers, helping researchers to infer the main sources of air pollution, even without the use of receptor models. PM2.5 and PM10 samples were collected at two sites in an urban industrialized region located at southeast of Brazil and analyzed by Synchrotron X-ray Diffraction to identify crystalline compounds. Results show 5 PM10 and PM2.5 species not previously reported in the literature. We propose reaction mechanisms for these species and identify specific sources for each crystalline phase found: BaTiO3 was found in PM10 receptor samples and proved to be a vehicular marker formed during brake action; maghemite (γ-Fe2O3), pyracmonite [(NH4)3Fe(SO4)3], ammonium perchlorate (NH3OHClO4) and potassium ferrate (K2Fe2O4) were found in PM2.5 proved to be markers of industrial activities. The crystalline phases found in PM samples from receptor sites and the mechanisms of reactions showed the reliability of the use of crystalline phases as source markers in the identification of potential sources of air pollution without misinterpretation of the likely source.
Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar/análise , Monitoramento Ambiental/métodos , Material Particulado/análise , Material Particulado/química , Sulfato de Amônio/análise , Compostos de Bário/análise , Brasil , Compostos Férricos/análise , Indústrias , Compostos de Ferro/análise , Tamanho da Partícula , Percloratos/análise , Compostos de Potássio/análise , Compostos de Amônio Quaternário/análise , Reprodutibilidade dos Testes , Síncrotrons , Titânio/análise , Difração de Raios X/métodosRESUMO
In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10-7-1.0×10-3mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10-10mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods.
Assuntos
Naftalenos/análise , Nitrocompostos/análise , Percloratos/análise , Éteres Fenílicos/análise , Poliaminas/análise , Potenciometria/métodos , Verduras/química , Compostos de Anilina , Naftalenos/química , Nitrocompostos/química , Éteres Fenílicos/química , Plastificantes , Poliaminas/química , Cloreto de Polivinila , UrináliseRESUMO
Since the 1990s, a large number of studies around the world have reported the presence of perchlorate in different types of environmental matrices. In view of their inherent characteristics, such as high solubility, mobility, persistence, and low affinity for the surface of soil, perchlorates are mobilized through the water-soil system and accumulate in edible plant species of high human consumption. However, the ingestion of food products containing perchlorate represents a potential health risk to people due to their adverse effects on thyroid, hormone, and neuronal development, mainly in infants and fetuses. At present, research has been centered on determining sources, fates, and remediation methods and not on its real extension in vegetables under farming conditions. This review presents a comprehensive overview and update of the frequent detection of perchlorate in fruits and vegetables produced and marketed around the world. Additionally, the impact of fertilizer on the potential addition of perchlorate to soil and its mobility in the water-soil-plant system is discussed. This review is organized into the following sections: sources of perchlorate, mobility in the water-soil system, presence in fruits and vegetables in different countries, international regulations, and toxicological studies. Finally, recommendations for future studies concerning perchlorate in fruits and vegetables are presented.
Assuntos
Monitoramento Ambiental , Contaminação de Alimentos/análise , Frutas/química , Percloratos/análise , Verduras/química , Solo/química , Poluentes do Solo/análise , Água/química , Poluentes Químicos da Água/análiseRESUMO
Perchlorate is a widespread environmental contaminant and potent thyroid hormone disrupting compound. Despite this, very little is known with regard to the occurrence of this compound in indoor dust and the exposure of humans to perchlorate through dust ingestion. In this study, 366 indoor dust samples were collected from 12 countries, the USA, Colombia, Greece, Romania, Japan, Korea, Pakistan, Kuwait, Saudi Arabia, India, Vietnam, and China, during 2010-2014. Dust samples were extracted by 1% (v/v) methylamine in water. Analyte separation was achieved by an ion exchange (AS-21) column and analysis was performed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The overall concentrations of perchlorate in dust were in the range of 0.02-104µg/g (geometric mean: 0.41µg/g). The indoor dust samples from China contained the highest concentrations (geometric mean: 5.38µg/g). No remarkable differences in perchlorate concentrations in dust were found among various microenvironments (i.e., car, home, office, and laboratory). The estimated median daily intake (EDI) of perchlorate for toddlers through dust ingestion in the USA, Colombia, Greece, Romania, Japan, Korea, Pakistan, Kuwait, Saudi Arabia, India, Vietnam, and China was 1.89, 0.37, 1.71, 0.74, 4.90, 7.20, 0.60, 0.80, 1.55, 0.70, 2.15, and 21.3ng/kgbodyweight (bw)/day, respectively. Although high concentrations of perchlorate were measured in some dust samples, the contribution of dust to total perchlorate intake was <5% of the total perchlorate intake in humans. This is the first multinational survey on the occurrence of perchlorate in indoor dust.
Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Poeira/análise , Percloratos/análise , Adolescente , Adulto , Criança , Pré-Escolar , China , Cromatografia Líquida de Alta Pressão , Colômbia , Ingestão de Alimentos , Exposição Ambiental/análise , Grécia , Humanos , Índia , Lactente , Japão , Kuweit , Paquistão , República da Coreia , Romênia , Arábia Saudita , Espectrometria de Massas em Tandem , Estados Unidos , Vietnã , Adulto JovemRESUMO
Trace analysis is usually associated with high-sensitivity analysis instrumentation. It became fully established from the 1960s following consensus among different groups of practitioners over protocols, reference materials, sensitivity, and accuracy and precision. As a consequence, wet chemical methods have been relegated to a secondary role, contrasting with their tremendous historical significance in detecting, identifying, and estimating small amounts of material. This is particularly relevant to the state-of-the-science analytical determinations stimulated by the effect of minor components in commodities of commercial importance. Here, I select a single example: attempts made during the 1890s to determine the amount of potassium perchlorate (KCIO4) that occurs in Chile saltpetre (sodium nitrate). The application of titrimetry, particularly the adaptation of Volhard's method for chloride analysis, was crucial in the efforts to estimate perchlorate in the nitrate used for explosives and to track the impact of perchlorate concentrations on certain important agricultural crops.
Assuntos
Nitratos/história , Percloratos/história , Compostos de Potássio/história , Titulometria/história , História do Século XIX , Nitratos/análise , Percloratos/análise , Compostos de Potássio/análiseRESUMO
Various studies have evaluated the accumulation of ClO4(-) in lettuce (Lactuca sativa), but very few have dealt with the variables that can interfere with its capture. The present study evaluates the transfer of ClO4(-) in two L. sativa varieties: butter head (L. sativa var. capitata) and cos lettuce (L. sativa var. crispa) under hydroponic conditions. The ClO4(-) concentrations used correspond to levels (1 and 2mgL(-1)), measured in irrigation water in the Iquique region in the north of Chile. Results indicate that the capture of ClO4(-) is dependent on its concentration, lettuce genotype, and temperature. The butter head variety accumulates the highest perchlorate concentrations. Anion competition involving NO3(-) (16 and 48mM), Cl(-) (23 and 56mM), and SO4(2-) (10 and 20mM) was evaluated, being NO3(-) (48mM), the most significant competition reducing the concentration of ClO4(-) in tissues of L. sativa varieties.
Assuntos
Lactuca/química , Lactuca/genética , Percloratos/química , Temperatura , Ânions/química , Chile , Genótipo , Lactuca/metabolismo , Percloratos/análise , Folhas de Planta/química , Folhas de Planta/metabolismo , Raízes de Plantas/química , Raízes de Plantas/metabolismoRESUMO
Perchlorate is an anion that originates as a contaminant in ground and surface waters. The presence of perchlorate in soil and water samples from northern Chile (Atacama Desert) was investigated by ion chromatography-electrospray mass spectrometry. Results indicated that perchlorate was found in five of seven soils (cultivated and uncultivated) ranging from 290 ± 1 to 2,565 ± 2 µg/kg. The greatest concentration of perchlorate was detected in Humberstone soil (2,565 ± 2 µg/kg) associated with nitrate deposits. Perchlorate levels in Chilean soils are greater than those reported for uncultivated soils in the United States. Perchlorate was also found in superficial running water ranging from 744 ± 0.01 to 1,480 ± 0.02 µg/L. Perchlorate water concentration is 30-60 times greater than levels established by the United States Environmental Protection Agency (24.5 µg/L) for drinking.
Assuntos
Percloratos/análise , Poluentes do Solo/análise , Solo/química , Poluentes Químicos da Água/análise , Chile , Clima Desértico , Água Doce/químicaRESUMO
Perchlorate (ClO(4)(-)) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO(4)(-) appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO(4)(-) indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO(4)(-) (delta(18)O, Delta(17)O, delta(37)Cl) and associated NO(3)(-) (delta(18)O, Delta(17)O, delta(15)N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO(3)(-)-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO(4)(-) in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO(4)(-) from the Atacama Desert of Chile as well as all known synthetic ClO(4)(-). ClO(4)(-) in Death Valley caliche has a range of high Delta(17)O values (+8.6 to +18.4 per thousand), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O(3)). However, the Death Valley delta(37)Cl values (-3.1 to -0.8 per thousand) and delta(18)O values (+2.9 to +26.1 per thousand) are higher than those of Atacama ClO(4)(-). In contrast, ClO(4)(-) from western Texas and New Mexico has much lower Delta(17)O (+0.3 to +1.3 per thousand), with relatively high delta(37)Cl (+3.4 to +5.1 per thousand) and delta(18)O (+0.5 to +4.8 per thousand), indicating either that this material was not primarily generated with O(3) as a reactant or that the ClO(4)(-) was affected by postdepositional O isotope exchange. High Delta(17)O values in ClO(4)(-) (Atacama and Death Valley) are associated with high Delta(17)O values in NO(3)(-), indicating that both compounds preserve characteristics of O(3)-related atmospheric production in hyper-arid settings, whereas both compounds have low Delta(17)O values in less arid settings. Although Delta(17)O variations in terrestrial NO(3)(-) can be attributed to mixing of atmospheric (high Delta(17)O) and biogenic (low Delta(17)O) NO(3)(-), variations in Delta(17)O of terrestrial ClO(4)(-) are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO(4)(-) in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO(4)(-) formation mechanisms and(or) ClO(4)(-) isotopic exchange in biologically active environments.
Assuntos
Nitratos/análise , Percloratos/análise , California , Chile , Monitoramento Ambiental/métodos , Poluentes Ambientais , Isótopos , Solo , Poluentes do Solo/análise , Sudoeste dos Estados Unidos , Poluentes da Água/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodosRESUMO
BACKGROUND: Perchlorate is a common contaminant of drinking water and food. It competes with iodide for uptake into the thyroid, thus interfering with thyroid hormone production. The U.S. Environmental Protection Agency's Office of Solid Waste and Emergency Response (OSWER) set a groundwater preliminary remediation goal (PRG) of 24.5 microg/L to prevent exposure of pregnant women that would affect the fetus. This does not account for the greater exposure that is possible in nursing infants or for the relative source contribution (RSC), a factor normally used to lower the PRG due to nonwater exposures. OBJECTIVES: Our goal was to assess whether the OSWER PRG protects infants against exposures from breast-feeding, and to evaluate the perchlorate RSC. METHODS: We used Monte Carlo analysis to simulate nursing infant exposures associated with the OSWER PRG when combined with background perchlorate. RESULTS: The PRG can lead to a 7-fold increase in breast milk concentration, causing 90% of nursing infants to exceed the reference dose (RfD) (average exceedance, 2.8-fold). Drinking-water perchlorate must be < 6.9 microg/L to keep the median, and < 1.3 microg/L to keep the 90th-percentile nursing infant exposure below the RfD. This is 3.6- to 19-fold below the PRG. Analysis of biomonitoring data suggests an RSC of 0.7 for pregnant women and of 0.2 for nursing infants. Recent data from the Centers for Disease Control and Prevention (CDC) suggest that the RfD itself needs to be reevaluated because of hormonal effects in the general population. CONCLUSIONS: The OSWER PRG for perchlorate can be improved by considering infant exposures, by incorporating an RSC, and by being responsive to any changes in the RfD resulting from the new CDC data.