Polycyclic aromatic hydrocarbons in biochar amended soils: Long-term experiments in Brazilian tropical areas.

The interest in charcoal for agricultural use (biochar) has sharply increased in recent years. However, biochar can contain groups of compounds such as polycyclic aromatic hydrocarbons (PAHs) that are considered persistent pollutants, and are formed concomitantly with biochar during its production by pyrolysis. Soil samples were collected in three experimental areas at different intervals (1, 3, 5 or 6 years) after the application of 16 Mg ha-1 of biochar. The total concentrations of PAHs; benzo[a]pyrene; and the estimated total cancer risk in biochar treated plots were larger than found in the control ones, but they decreased over time, equaling the control values after three years in the high C content soil (11.2 g C kg-1 soil), or after six years in the low C content soil (6.8 g C kg-1 soil). Nevertheless, the sum of PAH concentrations found in the biochar amended plots, in the range of 15.80-39.40 ng g-1, were around two orders of magnitude below the limits of prevention established by Brazilian legislation (8100 ng g-1) and some European regulations for soils (3000 ng g-1) and also lower than the observed in previous studies about biochar amended soils. Our results indicate that, under the conditions evaluated, the application of biochar to soil in the studied proportion (16 Mg ha-1, every six years) is safe concerning soil contamination by PAHs.

Polycyclic aromatic hydrocarbons (PAHs) in street dust of Rio de Janeiro and Niterói, Brazil: Particle size distribution, sources and cancer risk assessment.

Fifteen polycyclic aromatic hydrocarbons (PAHs) were analyzed in two fractions (<63µm and 63-850µm) of street dust samples collected in different urban areas of Rio de Janeiro and Niterói cities, Brazil. Individual PAH concentrations and total PAH concentrations (∑PAH) were evaluated considering geographic and particle size distributions, PAH source and cancer risk. In 53% of the samples, ∑PAH values were higher in the smallest particles than in the largest ones, whereas the inverse was true for 23.5% of the samples. In 23.5% of the samples, both classes of particles showed comparable ∑PAH. The highest ∑PAH concentrations were found in areas of limited air dispersion, resulting in PAH accumulation in street dust. The diagnostic ratios and principal component analysis (PCA) indicated a strong influence of pyrogenic sources on PAH concentration, mainly of vehicular emissions. The cancer risk levels for children and adults, for both particulate size fractions (<63µm and 63µm-850µm), were comparable for dermal contact and by ingestion, and ranged from 10-8 to 10-6, whereas in certain cases the cancer risk level for adults by dermal contact was 2 to 3 times larger than for children. The cancer risk levels via inhalation always ranged from 10-13 to 10-10, so this exposure pathway was almost 104 less severe than through ingestion and dermal contact, and thus negligible.

Development, validation, and application of a method for selected avermectin determination in rural waters using high performance liquid chromatography and fluorescence detection.

Avermectins (AVM) are macrocyclic lactones used in livestock and agriculture. A quantitative method of high performance liquid chromatography with fluorescence detection for the determination of eprinomectin, abamectin, doramectin and ivermectin in rural water samples was developed and validated. The method was employed to study samples collected in the Pito Aceso River microbasin, located in the Bom Jardim municipality, Rio de Janeiro State, Brazil. Samples were extracted by solid phase extraction using a polymeric stationary phase, the eluted fraction was re-concentrated under a gentle N2 flow and derivatized to allow AVM determination using liquid chromatography with fluorescence detection. The excitation and emission wavelengths of the derivatives were 365 and 470nm, respectively, and a total chromatographic run of 12min was achieved. Very low limits of quantification (22-58ngL(-1)) were found after re-concentration using N2. Recovery values varied from 85.7% to 119.2% with standard deviations between 1.2% and 10.2%. The validated method was applied in the determination of AVM in 15 water samples collected in the Pito Aceso River microbasin, but most of them were free of AVM or showed only trace levels of these compounds, except for a sample that contained doramectin (9.11µgL(-1)). The method is suitable for routine analysis with satisfactory recovery, sensitivity, and selectivity.

Development and validation of a method for the determination of low-ppb levels of macrocyclic lactones in butter, using HPLC-fluorescence.

An analytical method was developed and validated for the simultaneous determination of four macrocyclic lactones (ML) (abamectin, doramectin, ivermectin and moxidectin) in butter, using liquid chromatography with fluorescence detection. The method employed heated liquid-liquid extraction and a mixture of acetonitrile, ethyl acetate and water, with preconcentration and derivatization, to produce stable fluorescent derivatives. The chromatographic run time was <12.5 min, with excellent separation. The method validation followed international guidelines and employed fortified butter samples. The figures of merit obtained, e.g. recovery (72.4-106.5%), repeatability (8.8%), within-laboratory reproducibility (15.7%) and limits of quantification (0.09-0.16 µg kg(-1)) were satisfactory for the desired application. The application of the method to real samples showed that ML residues were present in six of the ten samples evaluated. The method proved to be simple, easy and appropriate for simultaneous determination of ML residues in butter. To our knowledge, this is the first method described for the evaluation of ML in butter.