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.

Actualities on Nuclear Medicine Applications in Sports Medicine

Aims: This paper aims to address some of the main possible applications of actual Nuclear Medicine Imaging techniques and methodologies in the specific context of Sports Medicine, namely in two critical systems: musculoskeletal and cardiovascular. Discussion: At the musculoskeletal level, bone scintigraphy techniques proved to be a mean of diagnosis of functional orientation and high sensibility compared with other morphological imaging techniques in the detection and temporal evaluation of pathological situations, for instance allowing the acquisition of information of great relevance in athletes with stress fractures. On the other hand, infection/inflammation studies might be of an important added value to characterize specific situations, early diagnose of potential critical issues – so giving opportunity to precise, complete and fast solutions – while allowing the evaluation and eventual optimization of training programs. At cardiovascular system level, Nuclear Medicine had proved to be crucial in differential diagnosis between cardiac hypertrophy secondary to physical activity (the so called "athlete's heart") and hypertrophic cardiomyopathy, in the diagnosis and prognosis of changes in cardiac function in athletes, as well as in direct - and non-invasive - in vivo visualization of sympathetic cardiac innervation, something that seems to take more and more importance nowadays, namely in order to try to avoid sudden death episodes at intense physical effort. Also the clinical application of Positron Emission Tomography (PET) has becoming more and more widely recognized as promising. Conclusions: It has been concluded that Nuclear Medicine can become an important application in Sports Medicine. Its well established capabilities to early detection of processes involving functional properties allied to its high sensibility and the actual technical possibilities (namely those related with hybrid imaging, that allows to add information provided by high resolution morphological imaging techniques, such as CT and/or MRI) make it a powerful diagnostic tool, claiming to be used on an each day higher range of clinical applications related with all levels of sport activities. Since the improvements at equipment characteristics and detection levels allows the use of smaller and smaller doses, so minimizing radiation exposure it is believed by the authors that the increase of the use of NM tools in the Sports Medicine area should be considered.

Image upsampling algorithms applied on Nuclear Medicine: comparision of hqnx and nxSaI algorithms families with two interpolation algorithms - nearest neighbour and bicubic interpolation

Introduction: Image resizing is a normal feature incorporated into the Nuclear Medicine digital imaging. Upsampling is done by manufacturers to adequately fit more the acquired images on the display screen and it is applied when there is a need to increase - or decrease - the total number of pixels. This paper pretends to compare the “hqnx” and the “nxSaI” magnification algorithms with two interpolation algorithms – “nearest neighbor” and “bicubic interpolation” – in the image upsampling operations. Material and Methods: Three distinct Nuclear Medicine images were enlarged 2 and 4 times with the different digital image resizing algorithms (nearest neighbor, bicubic interpolation nxSaI and hqnx). To evaluate the pixel’s changes between the different output images, 3D whole image plot profiles and surface plots were used as an addition to the visual approach in the 4x upsampled images. Results: In the 2x enlarged images the visual differences were not so noteworthy. Although, it was clearly noticed that bicubic interpolation presented the best results. In the 4x enlarged images the differences were significant, with the bicubic interpolated images presenting the best results. Hqnx resized images presented better quality than 4xSaI and nearest neighbor interpolated images, however, its intense “halo effect” affects greatly the definition and boundaries of the image contents. Conclusion: The hqnx and the nxSaI algorithms were designed for images with clear edges and so its use in Nuclear Medicine images is obviously inadequate. Bicubic interpolation seems, from the algorithms studied, the most suitable and its each day wider applications seem to show it, being assumed as a multi-image type efficient algorithm.

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.

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.

Trace metals in size-fractionated particulate matter in a Portuguese hospital: exposure risks assessment and comparisons with other countries

Hospitals are considered as a special and important type of indoor public place where air quality has significant impacts on potential health outcomes. Information on indoor air quality of these environments, concerning exposures to particulate matter (PM) and related toxicity, is limited though. This work aims to evaluate risks associated with inhalation exposure to ten toxic metals and chlorine (As, Ni, Cr, Cd, Pb, Mn, Se, Ba, Al, Si, and Cl) in coarse (PM2.5–10) and fine (PM2.5) particles in a Portuguese hospital in comparison with studies representative of other countries. Samples were collected during 1 month in one urban hospital; elemental PM characterization was determined by proton-induced X-ray emission. Noncarcinogenic and carcinogenic risks were assessed according to the methodology provided by the United States Environmental Protection Agency (USEPA; Region III Risk-Based Concentration Table) for three different age categories of hospital personnel (adults, >20, and <65 years) and patients (considering nine different age groups, i.e., children of 1–3 years to seniors of >65 years). The estimated noncarcinogenic risks due to occupational inhalation exposure to PM2.5-bound metals ranged from 5.88×10−6 for Se (adults, 55–64 years) to 9.35×10−1 for As (adults, 20–24 years) with total noncarcinogenic risks (sum of all metals) above the safe level for all three age categories. As and Cl (the latter due to its high abundances) were the most important contributors (approximately 90 %) to noncarcinogenic risks. For PM2.5–10, noncarcinogenic risks of all metals were acceptable to all age groups. Concerning carcinogenic risks, for Ni and Pb, they were negligible (<1×10−6) in both PM fractions for all age groups of hospital personnel; potential risks were observed for As and Cr with values in PM2.5 exceeding (up to 62 and 5 times, respectively) USEPA guideline across all age groups; for PM2.5–10, increased excess risks of As and Cr were observed particularly for long-term exposures (adults, 55–64 years). Total carcinogenic risks highly (up to 67 times) exceeded the recommended level for all age groups, thus clearly showing that occupational exposure to metals in fine particles pose significant risks. If the extensive working hours of hospital medical staff were considered, the respective noncarcinogenic and carcinogenic risks were increased, the latter for PM2.5 exceeding the USEPA cumulative guideline of 10−4. For adult patients, the estimated noncarcinogenic and carcinogenic risks were approximately three times higher than for personnel, with particular concerns observed for children and adolescents.