Ethanol, acetaldehyde, and methanol in the gas phase and rainwater in different biomes and urban regions of Brazil.

In the context of the increasing global use of ethanol biofuel, this work investigates the concentrations of ethanol, methanol, and acetaldehyde, in both the gaseous phase and rainwater, across six diverse urban regions and biomes in Brazil, a country where ethanol accounts for nearly half the light-duty vehicular fuel consumption. Atmospheric ethanol median concentrations in São Paulo (SP) (12.3 ± 12.1 ppbv) and Ribeirão Preto (RP) (12.1 ± 10.9 ppbv) were remarkably close, despite the SP vehicular fleet being ∼13 times larger. Likewise, the rainwater VWM ethanol concentration in SP (4.64 ± 0.38 µmol L-1) was only 26 % higher than in RP (3.42 ± 0.13 µmol L-1). This work demonstrated the importance of evaporative emissions, together with biomass burning, as sources of the compounds studied. The importance of biogenic emissions of methanol during forest flooding was identified in campaigns in the Amazon and Atlantic forests. Marine air masses arriving at a coastal site led to the lowest concentrations of ethanol measured in this work. Besides vehicular and biomass burning emissions, secondary formation of acetaldehyde by photochemical reactions may be relevant in urban and non-urban regions. The combined deposition flux of ethanol and methanol was 6.2 kg ha-1 year-1, avoiding oxidation to the corresponding and more toxic aldehydes. Considering the species determined here, the ozone formation potential (OFP) in RP was around two-fold higher than in SP, further evidencing the importance of emissions from regional distilleries and biomass burning, in addition to vehicles. At the forest and coastal sites, the OFP was approximately 5 times lower than at the urban sites. Our work evidenced that transition from gasoline to ethanol or ethanol blends brings the associated risk of increasing the concentrations of highly toxic aldehydes and ozone, potentially impacting the atmosphere and threatening air quality and human health in urban areas.

Quantification and risk assessment of pesticides in southern Brazilian air samples using low-volume sampling and rapid ultrasound-assisted extraction.

Brazil is one of the largest pesticide consumers in the world. In the last few years, the use of permissive environmental laws and newly authorized pesticide formulations has been enlarged. Thus, the intensive and inadequate use of pesticides may present a risk to human health since these compounds may move between environmental compartments. Outdoor air samples were collected using low-volume samplers at Arapongas city in the state of Paraná, Brazil, between February and November of 2017. Polyurethane foam (PUF) cartridges were presented as a good choice to collect pesticides from atmospheric gas phase samples when compared to styrene-divinylbenzene (XAD-2). Lower limits of quantitation were obtained with PUF cartridges, which allowed a greater number of samples to be quantified in PUF than in XAD-2. Atrazine and trifluralin were quantified for the first time in Brazilian air samples. The levels of concentration ranged between 192-1731 pg m-3 (chlorpyrifos), 136-1345 pg m-3 (atrazine) and 184-1189 pg m-3 (trifluralin). Alachlor has been out of market in Brazil since 2013, and thus it was not detected in any gas phase sample. The highest daily inhalation exposure was observed in infants, 1 × 10-6 mg kg-1 d-1 for atrazine, chlorpyrifos and trifluralin. None of the analyzed pesticides were associated with a hazardous quotient (HQ) > 1, considering the worst-case scenario for infants, indicating that there is no risk associated with the exposed population. Cancer risk assessment for trifluralin resulted in values below 1 × 10-6, therefore not indicating any significant risk to human health.