Radon alpha track counting on solid state nuclear track detector by an ImageJ-based software macro.

Radon (222Rn) is a radioactive gas emanating from geological materials. Inhalation of this gas is closely related to an increase in the probability of lung cancer if the levels are high. The usual methodology for the quantification of radon by passive methods is the use of etched solid-state nuclear track detectors, frequently in combination with optical microscopes or image scanning for image acquisition and software-based image processing for track counting. Currently available commercial instrumentation, as the Radosys microscopy system, is quite expensive, so the development of alternative methodologies is desirable. In this work, a simple, fast and low-cost image acquisition system for the determination of tracks in chemically etched CR-39 solid-state nuclear track detectors to quantify 222Rn alpha tracks has been proposed. The image of the detector surface is obtained by a conventional light stereoscopic microscope, transmitted by a CCD camera into the computer, and analyzed by the ImageJ open-source software. This methodology was employed to analyze 45 samples collected in dwellings and caves located in the region of Extremadura (Southwest Spain). Results show a good correlation coefficient of r2 = 0.98 between the reference and purposed methodology and excellent repeatability, demonstrating that the system enables routine counting tracks for radon measurement as an alternative to the Radosys microscopy instrument.

Presence of 236U and 239,240Pu in soils from Southern Hemisphere.

236U, 239Pu and 240Pu are present in soils mainly as a result of the local- and global-fallout from the atmospheric nuclear weapons tests carried out mainly in the 1950's and 1960's. In this work we provide new data on the presence of 236U and 239,240Pu in surface soils (i.e. up to 5 cm depth) from Chile and Africa. The results were obtained by low-energy Accelerator Mass Spectrometry (AMS). In the case of the Chilean samples, 236U/239Pu atom ratios show a high variability and are in general higher than the reported value for the global fallout in the Northern Hemisphere, ranging from 0.2 to 1.5. The 236U atomic concentrations range from 3.5 × 106 to 9.1 × 106 atoms/g, and are at least two orders of magnitude lower than the reported values in the Northern Hemisphere. The measured 240Pu/239Pu atom ratio in soils from South-Africa and Mozambique are of about 0.17, in agreement with the expected one for global-fallout at those coordinates. To best knowledge of the authors the present work is the first publication on 236U concentrations and 236U/239Pu atom ratios in soils from South-America and Africa.

Disposable sputtered-bismuth screen-printed sensors for voltammetric monitoring of cadmium and lead in atmospheric particulate matter samples.

We report here the use of commercial screen-printed disposable sensors comprising a sputtered bismuth working electrode, a silver pseudo reference electrode and a carbon auxiliary electrode (whole set referred as BispSPE), as a new and advantageous alternative for reliable and convenient monitoring of Cd and Pb in atmospheric particulate matter (PM10 fraction) by anodic stripping voltammetry after acid digestion. After a detailed exploration of surface composition and depth profiles of the BispSPE by SEM, EDX, XPS and EIS, chemical and instrumental variables have been optimized to develop a reliable method capable of measuring Cd and Pb with detection limits of 11.8ngmL-1 and 6.1ngmL-1 respectively. These detection limits are useful for pollution monitoring of these elements in ambient air under the requirements of international health and environmental protection standards. The accuracy of the method was assessed by voltammetric measurements of Cd and Pb in ERM®-CZ120 Fine dust (PM10-like) and ERM® 1648a Urban Particulate Matter certified reference materials. The applicability of the method to Cd and Pb determination in real samples was demonstrated by analysis of PM10 samples from the air quality network in Extremadura, with a good correlation respect to the standard ICP-MS methodology. Our work constitutes the first reference about the use of disposable sensors based on BispSPE for the determination of heavy metals in atmospheric particulate matter samples.

Spatial gradient of human health risk from exposure to trace elements and radioactive pollutants in soils at the Puchuncaví-Ventanas industrial complex, Chile.

The Punchuncaví Valley in central Chile, heavily affected by a range of anthropogenic emissions from a localized industrial complex, has been studied as a model environment for evaluating the spatial gradient of human health risk, which are mainly caused by trace elemental pollutants in soil. Soil elemental profiles in 121 samples from five selected locations representing different degrees of impact from the industrial source were used for human risk estimation. Distance to source dependent cumulative non-carcinogenic hazard indexes above 1 for children (max 4.4 - min 1.5) were found in the study area, ingestion being the most relevant risk pathway. The significance of health risk differences within the study area was confirmed by statistical analysis (ANOVA and HCA) of individual hazard index values at the five sampling locations. As was the dominant factor causing unacceptable carcinogenic risk levels for children (<10-4) at the two sampling locations which are closer to the industrial complex, whereas the risk was just in the tolerable range (10-6 - 10-4) for children and adults in the rest of the sampling locations at the study area. Furthermore, we assessed gamma ray radiation external hazard indexes and annual effective dose rate from the natural radioactivity elements (226Ra, 232Th and 40K) levels in the surface soils of the study area. The highest average values for the specific activity of 232Th (31 Bq kg-1), 40K (615 Bq kg- 1), and 226Ra (25 Bq kg-1) are lower than limit recommended by OECD, so no significant radioactive risk was detected within the study area. In addition, no significant variability of radioactive risk was observed among sampling locations.

Temporal and spatial variation of trace elements in atmospheric deposition around the industrial area of Puchuncaví-Ventanas (Chile) and its influence on exceedances of lead and cadmium critical loads in soils.

Fractionation of elemental contents in atmospheric samples is useful to evaluate pollution levels for risk assessment and pollution sources assignment. We present here the main results of long-term characterization of atmospheric deposition by using a recently developed atmospheric elemental fractionation sampler (AEFS) for major and trace elements monitoring around an important industrial complex located in Puchuncaví region (Chile). Atmospheric deposition samples were collected during two sampling campaigns (2010 and 2011) at four sampling locations: La Greda (LG), Los Maitenes (LM), Puchuncaví (PU) and Valle Alegre (VA). Sample digestion and ICP-MS gave elements deposition values (Al, As, Ba, Cd, Co, Cu, Fe, K, Mn, Pb, Sb, Ti, V and Zn) in the insoluble fraction of the total atmospheric deposition. Results showed that LG location, the closest location to the industrial complex, was the more polluted sampling site having the highest values for the analyzed elements. PU and LM were the next more polluted and, finally, the lowest elements concentrations were registered at VA. The application of Principal Component Analysis and Cluster Analysis identified industrial, traffic and mineral-crustal factors. We found critical loads exceedances for Pb at all sampling locations in the area affected by the industrial emissions, more significant in LG close to the industrial complex, with a trend to decrease in 2011, whereas no exceedances due to atmospheric deposition were detected for Cd.

Fractionation of trace elements in total atmospheric deposition by filtrating-bulk passive sampling.

We have developed and validated a new simple and effective methodology for fractionation of soluble and insoluble forms of trace elements in total atmospheric deposition. The proposed methodology is based on the modification of a standard total deposition passive sampler by integrating a quartz fiber filter that retains the insoluble material, allowing the soluble fraction to pass through and flow to a receiving bottle. The quartz filter containing the insoluble fraction and the liquid containing the soluble fraction are then separately assayed by standardized ICP-MS protocols. The proposed atmospheric elemental fractionation sampler (AEFS) was validated by analyzing a Coal Fly Ash reference material with proper recoveries, and tested for field fractionation of a set of 10 key trace elements in total atmospheric deposition at the industrial area of Puchuncaví-Ventanas, Chile. The AEFS was proven useful for pollution assessment and also to identify variability of the soluble and insoluble fractions of the selected elements within the study area, improving the analytical information attainable by standard passive samplers for total deposition without the need of using sophisticated and high cost wet-only/dry only collectors.

Miniaturized voltammetric stripping on screen printed gold electrodes for field determination of copper in atmospheric deposition.

The applicability of commercial screen-printed gold electrodes (SPGEs) connected to a portable potentiostat and a laptop has been explored to optimize a new square wave anodic stripping voltammetric method for on-site determination of soluble Cu(II) in atmospheric deposition samples taken around an industrial complex. Electrode conditioning procedures, chemical and instrumental variables have been optimized to develop a reliable method capable of measuring dissolved copper with a detection limit of 3.7 ng mL(-1), useful for pollution monitoring or screening purposes. The proposed method was tested with the SLRS-5 River Water for Trace Metals (recoveries 109.9-113.1%) and the SPS-SW2 Batch 121 Elements in Surface Waters (recoveries 93.2-97.6%). The method was applied to soluble Cu(II) measurement in liquid samples taken by a total atmospheric deposition collector modified with a quartz filter for soluble and insoluble elemental speciation. The voltammetric measurements on field samples were tested in the lab by a reference ICP-MS method, with good agreement. The proposed method proved capability for field operation during a two weeks monitoring campaign.

Determination of mercury in indoor dust samples by ultrasonic probe microextraction and stripping voltammetry on gold nanoparticles-modified screen-printed electrodes.

A miniaturized, fast, and efficient ultrasonic probe assisted method for Hg(II) extraction from indoor dust samples, in hydrochloric acid medium, was developed. The combination of the extraction method with the electrochemical determination of mercury by square-wave anodic stripping voltammetry (SWASV) on gold nanoparticles-modified screen-printed carbon electrodes (AuNPs-SPCEs) resulted in a convenient method for rapid, sensitive, and reliable mercury monitoring. Parameters involved in the extraction such as acid concentration, sonication amplitude, and sonication time were optimized using a Face-centered cube Central Composite Design. ICP-MS was also used to contrast the methodology and good agreement with electrochemical results was verified. Optimization and validation of the procedure were carried out by using NIST Standard Reference Material(®) 2583 Trace Elements in Indoor Dust. Finally, the proposed methodology was successfully applied for Hg(II) determination in dust samples collected at different indoor ambients.

Determination of mercury in ambient water samples by anodic stripping voltammetry on screen-printed gold electrodes.

The applicability of commercial screen-printed gold electrodes (SPGEs) for the determination of Hg(II) in ambient water samples by square wave anodic stripping voltammetry has been demonstrated. Electrode conditioning procedures, chemical and instrumental variables have been optimized to develop a reliable method capable of measuring dissolved mercury in the low ng mL(-1) range (detection limit 1.1 ng mL(-1)), useful for pollution monitoring or screening purposes. The proposed method was tested with the NIST 1641d Mercury in Water Standard Reference Material (recoveries 90.0-110%) and the NCS ZC 76303 Mercury in Water Certified Reference Material (recoveries 82.5-90.6%). Waste water samples from industrial origin and fortified rain water samples were assayed for mercury by the proposed method and by a reference ICP-MS method, with good agreement. Screen printing technology thus opens a useful way for the construction of reliable electrochemical sensors for decentralized or even field Hg(II) testing.

Adsorption kinetics of zinc in multicomponent ionic systems.

Using commercial activated carbon as an adsorbent, the kinetics of adsorption of zinc from multicomponent ionic systems having cadmium and mercury has been studied and reported. The variables investigated have been the chemical nature, ionic strength, and pH of the adsorptive (Zn2+) solution. The adsorption of Zn2+ is speeded up by the presence of Cd2+ and Hg2+ ions provided that the concentration of these two ions is high as compared to the concentration of Zn2+. When the ionic strength of the solution in relative terms is high (i.e., > 3 x 10(-4) M), however, the adsorption of Zn2+ decelerates. Also, the adsorption process is greatly accelerated at pH 12, whereas at pH 2 it does not occur at all.

Potentiometric stripping analysis (PSA) for monitoring of antimony in samples of vegetation from a mining area.

A potentiometric stripping analysis (PSA) method has been developed and checked for the fast and reliable determination of antimony in vegetation samples of Cistus ladanifer from a mining area in Badajoz, Southwest Spain. The method, modified from previous PSA methods for Sb in environmental samples, is based on dry ashing of the homogenized leaves, dissolution in hydrochloric acid, and PSA analysis on a mercury film plated on to a glassy carbon disk electrode. The influence of experimental variables such as the deposition potential, the deposition time, the signal stability and the calibration parameters, has been investigated. The method has been compared with an independent technique (instrumental neutron activation analysis) by analysis of standards and reference materials and comparison of the results. As a result of automation of the PSA equipment, the proposed method enables unattended analysis of 20 digested samples in a total time of 2 h, thus providing a useful tool for Sb monitoring of a large number of samples.

Evaluation of the influence of physical activity on the plasma concentrations of several trace metals.

Our study was carried out with the aim of evaluating the influence that the degree of physical activity may have on plasma concentrations of essential and toxic elements. Copper and zinc, elements of known importance in basic cellular processes, have been analysed as essential, and cadmium and lead as toxic for the body in abnormal doses. The study was performed on a total population of 50 healthy individuals, 34 of them professional sportsmen and the rest who undertook moderate physical activity (control group), all of them living in a polluted environment (Madrid, Spain). Sampling was conducted at the beginning of the season (October). Electro-analytical techniques of proved reliability and accuracy were used for the determination of the metals. The results were related to data obtained using graphite furnace atomic absorption spectrophotometry and by use of biological reference materials. We found significantly higher zinc plasma concentrations in the sportsmen involved in anaerobic-type training (judo, fencing) compared to those undertaking aerobic activities (endurance, cycling) (P < 0.05). The values in both cases were higher than those found in the control group. Our study showed an increase of plasma copper concentrations in professional sportsmen, especially in those performing anaerobic activities, compared to those subjects undertaking moderate activity (control group) (P < 0.05). In summary, our results showed that there were no deficiencies of copper and zinc in the athletes studied at the beginning of the season. The levels were higher than those of the control population. As for the toxic metals, cadmium and lead, we observed lower levels in the athletes than in the control group (cadmium P < 0.005, lead P < 0.05). These results may indicate the existence of possible elimination systems for these metals in athletes, when they are training in a polluted environment.