Mitigation of ammonia and greenhouse gases emissions from urea coated with oil shale residues in a silvopastoral system.

The objective of this work was to investigate the viability of using retorted oil shale as urea coating (U + ROS) in the decrease of N losses by ammonia (NH3-N) volatilization. The experiment was carried out in a silvopastoral system with a randomized block design with split-plots. The main treatments consisted of spatial arrangements of the trees, while the subdivision of the plots constituted the surface application of common urea (U) and retorted oil shale-coated urea (U + ROS) for the pasture. In addition to NH3 measurements, fluxes of N2O and CH4 in the soil were determined, as well as soil moisture and contents of mineral N (0-5 cm). Independently of tree spacing, the use of ROS along with urea (U + ROS) showed a mean decrease of 15.9% in the accumulated NH3 volatilization and 24.1% in the peaks of emission, although it was not significantly different from the U treatment (P < 0.10). In addition, it did not increase significantly the N2O and CH4 emissions, evidencing a potential to decrease N losses by ammonia volatilization, with no impact on greenhouse gases emissions from the soil.

Agricultural use and pH correction of anaerobic sewage sludge with acid pH.

Agricultural use is the main way of recycling sewage sludge. Besides providing nutrients and organic matter to crops and soils, it is an important alternative for recycling this residue. However, problems during the sewage treatment process may generate sludge batches with an acidic pH. Thus, it is essential to understand the consequences of using such sludge on soils and plants, and to explore ways to overcome this limitation. The objective of this study was to evaluate addition rates of anaerobic sewage sludge (ASS) with acidic compositions on the soil fertility and performance of lettuce plants. Additionally, a methodology for pH correction of ASS with acidic pH is proposed. An agronomic experiment was conducted in a greenhouse using seven addition rates of ASS (0.0, 0.25, 0.5, 1, 2, 4 and 8 g kg-1 in dry basis), treated with an additional step of disinfection (solarization), and applied in an Albaqualf soil cultivated with lettuce (Lactuca sativa). Soil and leaf chemical composition, as well as chlorophyll index and the dry matter of lettuce leaves were evaluated. Failures during the acidogenesis phase of the anaerobic digestion process were probably the cause of ASS acidification. Although this ASS increased soil fertility indicators and plant dry matter, it significantly reduced soil pH, thereby requiring a complementary assay to correct its pH up to 6.0, which was achieved through liming. Anaerobic sewage sludges with an acidic pH can be effectively used in agriculture after being dried and disinfected through solarization, followed by pH correction, avoiding negative impacts on soil chemical attributes and plant response.

Preconcentration of polar phenolic compounds from water samples and soil extract by liquid-phase microextraction and determination via liquid chromatography with ultraviolet detection.

This work proposes a liquid-phase microextraction (LPME) method to extract the highly polar compounds phenol (Ph), o-cresol (o-Cr), m-cresol (m-Cr), p-cresol (p-Cr), and 2,4-dimethylphenol (2,4-DMP) from aqueous matrices. The first extraction step of the LPME method employed a common volumetric flask and n-octanol, and the second extraction step used NaOH as the acceptor phase. The optimized extraction conditions were 900 µL of n-octanol as the extraction solvent, NaOH at 0.60 mol L(-1) as the acceptor phase, an extraction time of 5.0 min, HCl at 0.01 mol L(-1) and NaCl at 20.0% as the donor phase, and an extraction temperature of 20.0°C. The analysis of 50.0 mL of aqueous sample, pretreated under the optimized LPME conditions, afforded a limit of detection (LOD) between 0.3 and 3.5 µg L(-1), a limit of quantification (LOQ) between 1.2 and 11.6 µg L(-1), and a linear range from 2.50 to 50.0 µg L(-1) for Ph, o-Cr, m-Cr and p-Cr and from 12.5 to 250 µg L(-1) for 2,4-DMP. The proposed LPME method was a successful sample preparation strategy, and allowed for precise and accurate quantification of polar phenolic compounds in aqueous matrices such as tap water, river water, groundwater, and seawater, and also in a soil extract. The recovery values ranged from 72.5% to 126.0%, and the relative standard deviation was between 0.3 and 11.5%.

Transfer of atrazine degradation capability to mineralize aged ¹4C-labeled atrazine residues in soils.

The degradation of environmentally long-term aged (22 years) ¹4C-labeled atrazine residues in soil stimulated by inoculation with atrazine-adapted soil from Belgium, the United States (U.S.), and Brazil at two different moisture regimes (50% WHCmax/slurried conditions) was evaluated. Inoculation of the soil containing the aged ¹4C-labeled atrazine residues with 5, 50, and 100% (w/w) Belgian, U.S., or Brazilian atrazine-adapted soil increased ¹4C-atrazine residue mineralization by a factor of 3.1-13.9, depending upon the amount of atrazine-adapted soil inocula and the moisture conditions. Aged ¹4C-atrazine residue mineralization varied between 2 and 8% for Belgian and between 1 and 2% for U.S. and Brazilian soil inoculum at 50% WHCmax but was increased under slurried conditions, accounting for 8-10% (Belgian soil), 2-7% (Brazilian soil), and 3% (American soil). The results show that an increased degradation of long-term aged ¹4C-labeled atrazine residues is possible by the transfer of atrazine-adapted soil microflora from different soils and regions to non-adapted soil.

Biochar-mediated [14C]atrazine mineralization in atrazine-adapted soils from Belgium and Brazil.

Biochar addition to soil has been reported to reduce the microbial degradation of pesticides due to sorption of the active compound. This study investigated whether the addition of hardwood biochar alters the mineralization of (14)C-labeled atrazine in two atrazine-adapted soils from Belgium and Brazil at different moisture regimens. Biochar addition resulted in an equally high or even in a significantly higher atrazine mineralization compared to the soils without biochar. Statistical analysis revealed that the extent of atrazine mineralization was more influenced by the specific soil than by the addition of biochar. It was concluded that biochar amendment up to 5% by weight does not negatively affect the mineralization of atrazine by an atrazine-adapted soil microflora.

Metabolism and persistence of atrazine in several field soils with different atrazine application histories.

To assess the potential occurrence of accelerated herbicide degradation in soils, the mineralization and persistence of (14)C-labeled and nonlabeled atrazine was evaluated over 3 months in two soils from Belgium (BS, atrazine-treated 1973-2008; BC, nontreated) and two soils from Germany (CK, atrazine-treated 1986-1989; CM, nontreated). Prior to the experiment, accelerated solvent extraction of bulk field soils revealed atrazine (8.3 and 15.2 µg kg(-1)) in BS and CK soils and a number of metabolites directly after field sampling, even in BC and CM soils without previous atrazine treatment, by means of LC-MS/MS analyses. For atrazine degradation studies, all soils were incubated under different moisture conditions (50% maximum soil water-holding capacity (WHC(max))/slurried conditions). At the end of the incubation, the (14)C-atrazine mineralization was high in BS soil (81 and 83%) and also unexpectedly high in BC soil (40 and 81%), at 50% WHC(max) and slurried conditions, respectively. In CK soil, the (14)C-atrazine mineralization was higher (10 and 6%) than in CM soil (4.7 and 2.7%), but was not stimulated by slurried conditions. The results revealed that atrazine application history dramatically influences its degradation and mineralization. For the incubation period, the amount of extractable atrazine, composed of residues from freshly applied atrazine and residues from former field applications, remained significantly greater (statistical significance = 99.5 and 99.95%) for BS and CK soils, respectively, than the amount of extractable atrazine in the bulk field soils. This suggests that (i) mostly freshly applied atrazine is accessible for a complex microbial community, (ii) the applied atrazine is not completely mineralized and remains extractable even in adapted soils, and (iii) the microbial atrazine-mineralizing capacity strongly depends on atrazine application history and appears to be conserved on long time scales after the last application.

Accelerated degradation of (14)C-atrazine in brazilian soils from different regions.

The repeated use of a given pesticide may induce a selection of the soil microbial population, resulting in a rapid degradation of the respective xenobiotic. Patterns of atrazine degradation (mineralization, formation of metabolites and nonextractable residues (NER)) were evaluated in two Brazilian soils with a history of atrazine application. Results were compared with those obtained from soils that had no agricultural use or herbicide application history. (14)C-Atrazine mineralization in unsaturated treated soils was high. By the 85th day of incubation, 82% of the applied (14)C-atrazine was mineralized in the Rhodic Hapludox and 74% in the Xanthic Haplustox. Mineralization remained low in nontreated soils (