Environmental copper: Behaviour when involved in physical adsorption at several interfaces

From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl_2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.     

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM_2.5 and PM₁₀) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM_2.5 and PM₁₀ fractions were collected using a dichotomous sampler (10 L min^?1, 24 h) with Teflon? filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM_2.5 in 2009) was 0.99 ng m^?3 (NHV) and 3.3 ng m^?3 (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m^?3 and 0.12 ng m^?3 for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaP_eq), where the overall toxicity of a PAH mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaP_eq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m^?3 and 1.2–1.4 ng m^?3 for the NHV and HV seasons, respectively. Considering that the maximum permissible BaP_eq in ambient air is 1 ng m^?3, related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern.     

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

Accumulation of arsenic, lead, copper, and zinc, and synthesis of phytochelatins by indigenous plants of a mining impacted area

Several native plants, able to grow in an unconfined mining impacted area that is now in close vicinity with urban areas, were evaluated for their ability to accumulate heavy metals. The main soil contaminants were As, Pb, Cu, and Zn. Sampling of the rhizospheric metal polluted soil showed that Euphorbia prostrata Aiton, Parthenium incanum Kunth, and Zinnia acerosa (DC.) A. Gray were able to grow in the presence of high amounts of mixtures of these elements. The plants accumulated the metals in the above ground parts and increased the synthesis of thiol molecules. E. prostrata showed the highest capacity for accumulation of the mixture of elements (588 μg g DW^?1). Analysis of the thiol-molecules profile showed that these plants synthesized high amounts of long-chain phytochelatins, accompanied by low amounts of monothiol molecules, which may be related to their higher resistance to As and heavy metals. The three plants showed translocation factors from roots to leaves >1 for As, Pb, Cu, and Zn. Thus, by periodically removing aerial parts, these plants could be useful for the phytoremediation of semi-arid and arid mining impacted areas, in which metal hyper-accumulator plants are not able to grow.     

Potential of the microbial community present in an unimpacted beach sediment to remediate petroleum hydrocarbons

The potential of the microbial communities present in the intertidal zone of an unimpacted beach (a beach that did not suffer any significant oil spill) to degrade hydrocarbons was investigated. For that, laboratory-based microcosms (50-ml flasks) were set up with sandy beach sediment spiked with crude oil and incubated with local seawater for 15 days in the dark. Three bioremediation treatments were tested (biostimulation (BS), autochthonous bioaugmentation (AB), and combined treatment of biostimulation + bioaugmentation (BS + AB)) and the results were compared with natural attenuation (NA). Visual inspection showed clearly an oil solubility increase (confirmed by a higher hydrocarbons concentration in supernatant solutions) for all tested treatments when compared to NA. Significant degradation of the oil, shown by different profiles of petroleum hydrocarbons, was also observed for the different treatments particularly for BS + AB. Therefore, the microbial community of this unimpacted beach sediment could respond to an oil spill, degrading hydrocarbons. But to increase the natural attenuation pace, obtained results indicated that BS + AB is an appropriate approach for the bioremediation of beaches recently impacted by an oil spill. The autochthonous microbial cultures can be obtained “before” or “after” the contamination of the target site, being inoculated into the site right after it contamination.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Earthworm ecotoxicological assessments of pesticides used to treat seeds under tropical conditions

Ecotoxicological laboratory tests (lower-tier tests) are fundamental tools for assessing the toxicity of pesticides to soil organisms. In this study, using these tests under tropical conditions, we quantified the impact of the insecticides imidacloprid, fipronil, and thiametoxam, and the fungicides captan and carboxin + thiram, all of which are used in the chemical treatment of crop seeds, on the survival, reproduction, and behavior of Eisenia andrei (Oligochaeta). With the exception of imidacloprid, none of the pesticides tested caused mortality in E. andrei in artificial soils. The LC₅₀ of imidacloprid was estimated as 25.53 mg active ingredient kg^?1 of dry soil. Earthworm reproduction rates were reduced by imidacloprid (EC₅₀ = 4.07 mg kg^?1), fipronil (EC₂₀ = 23.16 mg kg^?1), carboxin + thiram (EC₅₀ = 56.38 mg kg^?1), captan (EC₅₀ = 334.84 mg kg^?1), and thiametoxam (EC₅₀ = 791.99 mg kg^?1). Avoidance behavior was observed in the presence of imidacloprid (AC₅₀ = 0.11 mg kg^?1), captan (AC₅₀ = 33.54 mg kg^?1), carboxin + thiram (AC₅₀ = 60.32 mg kg^?1), and thiametoxam (AC₅₀ = >20 mg kg^?1). Earthworms showed a preference for soils with the insecticide fipronil. Imidacloprid was the most toxic of the substances tested for E. andrei. The avoidance test was the most sensitive test for most pesticides studied, but results varied between pesticides. These results offer new insights on the toxicity of pesticides used to treat seeds in tropical regions. However, they should be complemented with higher-tier tests in order to reduce the uncertainties in risk assessment.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

A New Tape Reagent for the Determination of Hydrogen Sulfide in Air

The lead acetate paper tape reagent method for the estimation of hydrogen sulfide in air has been reviewed with the conclusions that the colored spots on which the quantitative estimation is based are not stable and do not lend by themselves to accurate results. Although it may be retained for grab sampling work, the lead acetate paper tape reagent is not acceptable as a stoichiometric reagent in any case where long duration sampling periods are concerned like in air pollution studies. A new mercuric chloride paper tape reagent has been developed as a substitute. Due to the fact that the colored spots resulting from the action of hydrogen sulfide on mercuric chloride are sensitive and very stablet, this new paper tape reagent is proposed as an adequate and reliable analytical too for the estimation of hydrogen sulfide in air. Also, a more comprehensive application of the paper tape analytical system is proposed throughout a suitable control of the factor tape retention capacity vs sampling rate which imposes some restrictions in the selection of the practical working range of concentrations. Nevertheless this working range is still wide enough to encompass all the hydrogen sulfide concentrations normally encountered in the city atmosphere.