Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Natural organic matter fractionation along the treatment of water for human consumption

The main objective of this study was to characterize the organic matter present in raw water and along the treatment process, as well as its seasonal variation. A natural organic matter fractionation approach has been applied to Lever water treatment plant located in Douro River, in Oporto (Portugal). The process used was based on the sorption of dissolved organic matter in different types of ion exchange resins, DAX-8, DAX-4 and IRA-958, allowing its separation into four fractions: very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), charged hydrophilic (CHA) and hydrophilic neutral (NEU). The dissolved organic carbon (DOC) determination was used to quantify dissolved organic matter. Samples were collected monthly, during approximately one year, from raw water captured at the surface and under the bed of the river, and after each step of the treatment: pre-filtration in sand/anthracite filters, ozonation, coagulation/flocculation, counter current dissolved air flotation and filtration (CoCoDAFF) and chlorination. The NEU fraction showed a seasonal variation, with maximum values in autumn for the sampling points corresponding to raw water captured at the surface and under the bed of the river. It was usually the predominating fraction and did not show a significant decrease throughout the treatment. Nevertheless their low concentration, the same occurred for the CHA and VHA fractions. There was an overall decrease in the SHA fraction throughout the water treatment (especially after CoCoDAFF and ozonation) as well as in the DOC. The TSUVA254 values obtained for raw water generally varied between 2.0 and 4.0 L mgC-1 m-1 and between 0.75 and 1.78 L mgC-1 m-1 for treated water. It was observed a decrease of TSUVA values along the treatment, especially after ozonation. These results may contribute to a further optimization in the process of treating water for human consumption.

Occupational exposure to particulate matter and fungi in a composting plant: case study in Portugal

The handling of waste can be responsible for occupational exposure to particles and fungi. The aim of this study was to characterize exposure to particles and fungi in a composting plant. Measurements of particulate matter were performed using portable direct-reading equipment. Air samples of 50L were collected through an impaction method with a flow rate of 140L/min onto malt extract agar supplemented with chloramphenicol (0.05%). Surfaces samples were also collected. All the samples were incubated at 27ºC for 5 to 7 days. Particulate matter data showed higher contamination for PM, and PM10 sizes. Aspergillus genus presents the highest air prevalence (90.6%). Aspergillus niger (32.6%), A. fumigatus (26.5%) and A. flavus (16.3%) were the most prevalent fungi in air sampling, and Mucor sp. (39.2%), Aspergillus niger (30.9%) and A. fumigatus (28.7%) were the most found in surfaces. the results obtained claim the attention to the need of further research.

As questões de género nas práticas educativas do Pré-Escolar e Ensino do 1.º Ciclo do Ensino Básico no âmbito do estágio pedagógico : os estereótipos nos materiais escolares

Dissertação de Mestrado, Educação Pré-Escolar e Ensino do 1.º Ciclo do Ensino Básico, 16 de Junho de 2015, Universidade dos Açores.

Impact on human health of particulate matter emitted from burnings in the Brazilian Amazon region

OBJECTIVE: To analyze the impact on human health of exposure to particulate matter emitted from burnings in the Brazilian Amazon region. METHODS: This was an ecological study using an environmental exposure indicator presented as the percentage of annual hours (AH%) of PM2.5 above 80 μg/m3. The outcome variables were the rates of hospitalization due to respiratory disease among children, the elderly and the intermediate age group, and due to childbirth. Data were obtained from the National Space Research Institute and the Ministry of Health for all of the microregions of the Brazilian Amazon region, for the years 2004 and 2005. Multiple regression models for the outcome variables in relation to the predictive variable AH% of PM2.5 above 80 μg/m3 were analyzed. The Human Development Index (HDI) and mean number of complete blood counts per 100 inhabitants in the Brazilian Amazon region were the control variables in the regression analyses. RESULTS: The association of the exposure indicator (AH%) was higher for the elderly than for other age groups (β = 0.10). For each 1% increase in the exposure indicator there was an increase of 8% in child hospitalization, 10% in hospitalization of the elderly, and 5% for the intermediate age group, even after controlling for HDI and mean number of complete blood counts. No association was found between the AH% and hospitalization due to childbirth. CONCLUSIONS: The indicator of atmospheric pollution showed an association with occurrences of respiratory diseases in the Brazilian Amazon region, especially in the more vulnerable age groups. This indicator may be used to assess the effects of forest burning on human health.

Exposure to volatile organic compounds, particulate matter and fungi in a composting plant

Composting is an important process of solid waste management and it can be used for treatment of a variety of different wastes (green waste, household waste, sewage sludge and more). This process aims to: 1. Reduce the volumes of waste and; 2. Create a valuable product which can be recycled as a soil amendment in agriculture and gardening. A natural self-heating process involving the biological degradation of organic matter under aerobic conditions. The handling of waste and compost is responsible for the release of airborne microorganisms and their compounds in the air. Possible contaminants: a) Dust; b) Mesophilic and thermophilic microorganisms; c) Volatile organic compounds; d) Endotoxins and mycotoxins…. Aim: assess exposure/contamination to: a) Volatile organic compounds (VOCs); b) Particulate matter (PM); c) Fungi. In a composting plant located in Lisbon. An additional goal was to identify the workplace with higher level of contamination. In a totally indoor composting plant. The composting operations consisted: 1º Waste already sorted is unloaded in a reception area; 2º Pretreatment - remove undesirable materials from the process (glass, rocks, plastics, metals…); 3º Anaerobic digestion; 4º Dehydration; 5º Open composting with forced aeration. All the process takes thirteen weeks.

Soil remediation time to achieve clean-up goals II: influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8–13 h) and decreased the remediation efficiency (RE) (99–90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8–4.9 h) and decreased the RE (99–97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: influence of air flow rate, water and natural organic matter content

Abstract This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.

Occupational exposure to particulate matter in 2 Portuguese waste-sorting units

Objectives - This study intended to characterize work environment contamination by particles in 2 waste-sorting plants. Material and Methods - Particles were measured by portable direct-reading equipment. Besides mass concentration in different sizes, data related with the number of particles concentration were also obtained. Results - Both sorting units showed the same distribution concerning the 2 exposure metrics: particulate matter 5 (PM5) and particulate matter 10 (PM10) reached the highest levels and 0.3 μm was the fraction with a higher number of particles. Unit B showed higher (p < 0.05) levels for both exposure metrics. For instance, in unit B the PM10 size is 9-fold higher than in unit A. In unit A, particulate matter values obtained in pre-sorting and in the sequential sorting cabinet were higher without ventilation working. Conclusions - Workers from both waste-sorting plants are exposed to particles. Particle counting provided additional information that is of extreme value for analyzing the health effects of particles since higher values of particles concentration were obtained in the smallest fraction.

Influence of traffic emissions on the carcinogenic polycyclic aromatic hydrocarbons in outdoor breathable particles

Because polycyclic aromatic hydrocarbons (PAHs) have been proven to be toxic, mutagenic, and/or carcinogenic, there is widespread interest in analyzing and evaluating exposure to PAHs in atmospheric environments influenced by different emission sources. Because traffic emissions are one of the biggest sources of fine particles, more information on carcinogenic PAHs associated with fine particles needs to be provided. Aiming to further understand the impact of traffic particulate matter (PM) on human health, this study evaluated the influence of traffic on PM10 (PM with aerodynamic diameter <10 µm) and PM2.5 (PM with aerodynamic diameter <2.5 µm), considering their concentrations and compositions in carcinogenic PAHs. Samples were collected at one site influenced by traffic emissions and at one reference site using lowvolume samplers. Analysis of PAHs was performed by microwave-assisted extraction combined with liquid chromatography (MAE-LC); 17 PAHs, including 9 carcinogenic ones, were quantified. At the site influenced by traffic emissions, PM10 and PM2.5 concentrations were, respectively, 380 and 390% higher than at the background site. When influenced by traffic emissions, the total concentration of nine carcinogenic compounds (naphthalene, chrysene, benzo(a)anthracene, benzo(b) fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and dibenzo(a,l)pyrene) was increased by 2400 and 3000% in PM10 and PM2.5, respectively; these nine carcinogenic compounds represented 68 and 74% of total PAHs (ƩPAHs) for PM10 and PM2.5, respectively. All PAHs, including the carcinogenic compounds, were mainly present in fine particles. Considering the strong influence of these fine particles on human health, these conclusions are relevant for the development of strategies to protect public health.

Forest fires in Northern region of Portugal: impact on PM levels

Every year European citizens become victims of devastating fires, which are especially disastrous for Southern European countries. Apart from the numerous health and economic consequences, fires generate hazardous pollutants that are introduced into the environment, thus representing serious risks for public health. In that regard, particulate matter (PM) is of amajor concern. Thus, the objectives of thisworkwere to characterize the trend of forest fire occurrences and burnt area during the period of 2005 and 2010 and to study the influence of forest fires on levels of particulatematter PM10 and PM2.5. In 2010, 22,026 forest fires occurred in Portugal. The northern region was the most affected by forest fires, with 27% of occurrences in Oporto district. The annual means of PM10 and PM2.5 concentrations at two urban background sites were 25±14 μg m−3 and 8.2±4.9 μg m−3, and 17±13 μg m−3 and 7.3±5.9 μg m−3, respectively. At both sites the highest levels of PMfractionswere observed during July and August of 2010, corresponding to the periods when majority (66%) of forest fires occurred. Furthermore, PM10 daily limit at the two sites was exceeded during 20 and 5 days, respectively; 56%, and respectively 60% of those exceedances occurred during the forest fire season. Considering that the risks of forest fire ignition and severity are enhanced with elevated temperatures, the climate change might increase the environmental impacts of forest fires.

Particulate matter distribution in selected Portuguese archives: a preliminary study

Particulate matter (PM) can have a significant impact on human health and on artifacts stored and kept inside museums and archives. To the author's knowledge, its immediate and/or longterm concentrations and distribution on Portuguese archives has never been determined. Four Portuguese archives (with and without HVAC/air filtration systems) were selected and the immediate concentration of airborne particulate matter was measured by active sampling. Indoor-outdoor ratios were also determined. International and national guidelines were used to ascertain the environment’s quality, both for the readers and staff and for the documents preserved in these institutions. Inside, PM2.5 ranged between 0.37μg/m3 and 27.61μg/m3, while PM10 ranged between 4.43μg/m3 and 285.52μg/m3. The lowest values were determined in storage rooms and the highest in reading rooms. In terms of human health, Portuguese guidelines for immediate PM10 concentration were not met in several locations. For conservation purposes, storage rooms were classified according to an original air quality grid. Air filtration systems proved valuable in maintaining a safe environment for our written heritage and the staff and readers that deal with it and care for it every day. This study constitutes the first snapshot of the particulate matter concentrations and distribution in Portuguese Archives.

Measurements of environmental background radiation in the surrounding area of a coal-fired power plant

Certain materials used and produced in a wide range of non-nuclear industries contain enhanced activity concentrations of natural radionuclides. In particular, electricity production from coal is one of the major sources of increased exposure to man from enhanced naturally occurring materials. Over the past decades there has been some discussion about the elevated natural background radiation in the area near coal-fired power plants due to high uranium and thorium content present in coal. This work describes the methodology developed to assess the radiological impact due to natural radiation background increasing levels, potentially originated by a coal-fired power plant’s operation. Gamma radiation measurements have been done with two different instruments: a scintillometer (SPP2 NF, Saphymo) and a gamma ray spectrometer with energy discrimination (Falcon 5000, Canberra). A total of 40 relevant sampling points were established at locations within 20 km from the power plant: 15 urban and 25 suburban measured stations. The highest values were measured at the sampling points near to the power plant and those located in the area within the 6 and 20 km from the stacks. This may be explained by the presence of a huge coal pile (1.3 million tons) located near the stacks contributing to the dispersion of unburned coal and, on the other hand, the height of the stacks (225 m) which may influence ash’s dispersion up to a distance of 20 km. In situ gamma radiation measurements with energy discrimination identified natural emitting nuclides as well as their decay products (212Pb, 214Pb, 226Ra 232Th, 228Ac, 234Th 234Pa, 235U, etc.). This work has been primarily done to in order to assess the impact of a coal-fired power plant operation on the background radiation level in the surrounding area. According to the results, an increase or at least an influence has been identified both qualitatively and quantitatively.

Particulate matter flux deposition in the vicinity of a coal-fired power plant

This paper describes the methodology adopted to assess local air quality impact in the vicinity of a coal power plant located in the south of Portugal. Two sampling areas were selected to assess the deposition flux of dust fallout and its potential spatial heterogeneity. The sampling area was divided into two subareas: the inner, with higher sampling density and urban and suburban characteristics, inside a 6-km circle centered on the stacks, and an outer subarea, mainly rural, with lower sampling density within a radius of 20 km. Particulate matter deposition was studied in the vicinity of the coal fired power plant during three seasonal sampling campaigns. For the first one, the average annual flux of dust fallout was 22.51 g/(m2 yr), ranging from 4.20 to 65.94 g/(m2 yr); for the second one was 9.47 g/(m2 yr), ranging from 0.78 to 32.72 g/(m2 yr) and for the last one was 38.42 g/(m2 yr), ranging from 1.41 to 117.48 g/(m2 yr). The fallout during the second campaign turned out to be much lower than for others. This was in part due to meteorological local patterns but mostly due to the fact that the power plant was not working at full power during the second sampling campaign.155

Impact of the Meteorology Conditions on the Particulate Matter Dispersion from an Industrial Complex into Urban and Suburban Areas

The aim of this work was to assess the influence of meteorological conditions on the dispersion of particulate matter from an industrial zone into urban and suburban areas. The particulate matter concentration was related to the most important meteorological variables such as wind direction, velocity and frequency. A coal-fired power plant was considered to be the main emission source with two stacks of 225 m height. A middle point between the two stacks was taken as the centre of two concentric circles with 6 and 20 km radius delimiting the sampling area. About 40 sampling collectors were placed within this area. Meteorological data was obtained from a portable meteorological station placed at approximately 1.7 km to SE from the stacks. Additional data was obtained from the electrical company that runs the coal power plant. These data covers the years from 2006 to the present. A detailed statistical analysis was performed to identify the most frequent meteorological conditions concerning mainly wind speed and direction. This analysis revealed that the most frequent wind blows from Northwest and North and the strongest winds blow from Northwest. Particulate matter deposition was obtained in two sampling campaigns carried out in summer and in spring. For the first campaign the monthly average flux deposition was 1.90 g/m2 and for the second campaign this value was 0.79 g/m2. Wind dispersion occurred predominantly from North to South, away from the nearest residential area, located at about 6 km to Northwest from the stacks. Nevertheless, the higher deposition fluxes occurred in the NW/N and NE/E quadrants. This study was conducted considering only the contribution of particulate matter from coal combustion, however, others sources may be present as well, such as road traffic. Additional chemical analyses and microanalysis are needed to identify the source linkage to flux deposition levels.