Forecasting human exposure to atmospheric pollutants in Portugal – A modelling approach

Air pollution has become one main environmental concern because of its known impact on human health. Aiming to inform the population about the air they are breathing, several air quality modelling systems have been developed and tested allowing the assessment and forecast of air pollution ambient levels in many countries. However, every day, an individual is exposed to different concentrations of atmospheric pollutants as he/she moves from and to different outdoor and indoor places (the so-called microenvironments). Therefore, a more efficient way to prevent the population from the health risks caused by air pollution should be based on exposure rather than air concentrations estimations. The objective of the present study is to develop a methodology to forecast the human exposure of the Portuguese population based on the air quality forecasting system available and validated for Portugal since 2005. Besides that, a long-term evaluation of human exposure estimates aims to be obtained using one-year of this forecasting system application. Additionally, a hypothetical 50% emission reduction scenario has been designed and studied as a contribution to study emission reduction strategies impact on human exposure.To estimate the population exposure the forecasting results of the air quality modelling system MM5-CHIMERE have been combined with the population spatial distribution over Portugal and their time-activity patterns, i.e. the fraction of the day time spent in specific indoor and outdoor places. The population characterization concerning age, work, type of occupation and related time spent was obtained from national census and available enquiries performed by the National Institute of Statistics. A daily exposure estimation module has been developed gathering all these data and considering empirical indoor/outdoor relations from literature to calculate the indoor concentrations in each one of the microenvironments considered, namely home, office/school, and other indoors (leisure activities like shopping areas, gym, theatre/cinema and restaurants). The results show how this developed modelling system can be useful to anticipate air pollution episodes and to estimate their effects on human health on a long-term basis. The two metropolitan areas of Porto and Lisbon are identified as the most critical ones in terms of air pollution effects on human health over Portugal in a long-term as well as in a short-term perspective. The coexistence of high concentration values and high population density is the key factor for these stressed areas. Regarding the 50% emission reduction scenario, the model results are significantly different for both pollutants: there is a small overall reduction in the individual exposure values of PM₁₀ (<10 μg m^?3 h), but for O₃, in contrast, there is an extended area where exposure values increase with emission reduction. This detailed knowledge is a prerequisite for the development of effective policies to reduce the foreseen adverse impact of air pollution on human health and to act on time.     

Procedures for estimation of modelling uncertainty in air quality assessment

The main objectives of this work focus, firstly, on a review of the current existent methodologies to estimate air quality modelling uncertainty, and, secondly, in the preparation of guidelines for modelling uncertainty estimation, which can be used by local and regional authorities responsible for air quality management. From the application exercise, it was concluded that it is possible to define a subset of statistical parameters able to reproduce the general uncertainties estimation. Concerning the quality indicators defined by EU directives, the results show that the legislated uncertainty estimation measures are ambiguous and inadequate in several aspects, mainly in what concerns the error measures for hourly and daily indicators based on the highest observed concentration. A relative error at the percentile correspondent to the allowed number of exceedances of the limit value was suggested and tested, showing that is a more robust and appropriate parameter for model performance evaluation.     

Five years of formaldehyde and acetaldehyde monitoring in the Rio de Janeiro downtown area – Brazil

The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8 μg m^?3 with SD 28.4 μg m^?3) to 2009 (average of 49.3 μg m^?3 with SD 27.4 μg m^?3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9 μg m^?3 with SD 8.0 μg m^?3) to 2009 (average of 26.8 μg m^?3 with SD 11.5 μg m^?3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.     

Synergistic effects caused by atrazine and terbuthylazine on chlorpyrifos toxicity to early-life stages of the zebrafish Danio rerio

This study examined the effects of three widely used pesticides that have been previously detected in aquatic systems neighbouring agricultural fields on the early-life stages of the zebrafish Danio rerio. Tests involving single exposures and binary combinations of the s-triazine herbicides (atrazine and terbuthylazine) and the organophosphate insecticide chlorpyrifos were performed. Several endpoints, such as swimming behaviour, morphological abnormalities and mortality, were studied. In addition, the inhibition of acetylcholinesterase (AChE) activity was investigated in order to evaluate the mode of action and toxicity of chlorpyrifos in the presence of these herbicides. Results indicate that both binary mixtures elicited synergistic responses on the swimming behaviour of zebrafish larvae. Moreover, although the herbicides were not effective inhibitors of the AChE on their own, a synergistic inhibition of the enzyme activity was obtained by exposure to mixtures with chlorpyrifos. We observed a correlation between impairment of swimming behaviour of the larvae and inhibition of AChE activity. This study supports previous studies concerning the risk assessment of mixtures since the toxicity may be underestimated when looking only at the single toxicants and not their mixtures.     

Study of spatial and temporal distribution of antimicrobial in water and sediments from caging fish farms by on-line SPE-LC-MS/MS

An on-line solid phase extraction liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of 12 antimicrobials in sediment and surface water was developed and validated. Furthermore, the spatial and temporal antimicrobials distributions in the sediment and in the water of four fish farms located in the hydroelectric dam of Ilha Solteira Reservoir in Brazil were investigated over four seasons in three sampling sites: at the fish cages, 100 and 1,000 m downstream far from the cages. The method was performed using an Agilent Zorbax 80 SB-C8 column (9.4 × 15 mm, 5 µm) as the loading column, and the Agilent Zorbax Eclipse Plus C18 column (3.0 × 100 mm, 3.5 µm) as a separation column within a run time of 13 min. The limits of quantification were less than 9 ng·L^?1 for the antibiotics in water and 16 µg·kg^?1 in sediment; the recovery ranged from 80 to 119%, with a variation coefficient less than 11%, and the repeatability was lower than 15%. Oxytetracycline was found in the water in all sample seasons. However, florfenicol was identified in April and October 2013 and January 2014, and tetracycline was present in July 2013. Regarding the sediment, oxytetracycline and tetracycline were found in all sampling periods, but chlortetracycline was only identified in January 2014. The spatial distribution of antimicrobials showed that the main pollution source came from the fish farms. This study demonstrated that the proposed method is reliable for the monitoring of antimicrobials in water and sediments and it showed contamination in both matrices from Ilha Solteira Reservoir.     

Bias Correction Techniques to Improve Air Quality Ensemble Predictions: Focus on O3 and PM Over Portugal

Five air quality models were applied over Portugal for July 2006 and used as ensemble members. Each model was used, with its original set up in terms of meteorology, parameterizations, boundary conditions and chemical mechanisms, but with the same emission data. The validation of the individual models and the ensemble of ozone (O₃) and particulate matter (PM) is performed using monitoring data from 22 background sites. The ensemble approach, based on the mean and median of the five models, did not improve significantly the skill scores due to large deviations in each ensemble member. Different bias correction techniques, including a subtraction of the mean bias and a multiplicative ratio adjustment, were implemented and analysed. The obtained datasets were compared against the individual modelled outputs using the bias, the root mean square error (RMSE) and the correlation coefficient. The applied bias correction techniques also improved the skill of the individual models and work equally well over the entire range of observed O₃ and PM values. The obtained results revealed that the best bias correction technique was the ratio adjustment with a 4-day training period, demonstrating significant improvements for both analysed pollutants. The increase in the ensemble skill found comprehends a bias reduction of 88 % for O₃, and 92 % for PM10, and also a decrease in 23 % for O₃ and 43 % for PM10 in what concerns the RMSE. In addition, a spatial bias correction approach was also examined with successful skills comparing to the uncorrected ensemble for both pollutants.     

Spatial variation of mercury levels in nesting Bonelli's eagles from Southwest Portugal: effects of diet composition and prey contamination

Mercury (Hg) was determined in adult Bonelli's eagles (Hieraaetus fasciatus) and their avian prey, from samples of feathers collected between 1992 and 2001 at the nesting sites of 21 pairs in Southwest Portugal. Eagle Hg levels showed great variation, reflecting primarily differences in diet composition and food chain biomagnification. Concentrations were positively correlated with the dietary proportion of insectivorous and omnivorous birds (e.g. egrets, corvids and thrushes), with very low levels for pairs feeding mainly on herbivores (e.g. rabbits, pigeons and partridges). Differences in prey contamination among breeding territories added to dietary effects in determining variation of Hg levels in eagles, shaping a spatial pattern that was largely consistent with a source of contamination in a coal-burning power-plant lying upwind of the study area. Despite this presumed contamination, Hg levels seemed to be of little concern to this eagle population, though there might be subtle deleterious effects on the reproductive output of a few pairs. This study emphasizes the need to account for dietary effects when biomonitoring Hg contamination using birds of prey.