High temperature and nib acidification during cacao-controlled fermentation improve cadmium transfer from nibs to testa and the liquor's flavor.

Migration of nib Cd to the testa during fermentation can be achieved with high temperatures (> 45 °C) and low nib pH values (< 5.0) using spontaneous fermentation. However, this low pH can lead to low flavor quality. This study used three controlled temperature fermentation treatments on three cacao genotypes (CCN 51, ICS 95, and TCS 01) to test its effects on the nib pH, the migration of nib Cd to the testa, and the liquor flavor quality. All treatments were effective in reducing the total nib Cd concentration. Nevertheless, the treatment with the higher mean temperature (44.25 °C) and acidification (pH 4.66) reached the highest mean nib Cd reductions throughout fermentation, a 1.37 factor in TCS 01, promoting the development of fine-flavor cocoa sensorial notes. In unfermented beans, the Cd concentration of nibs was higher than that of the testa, and the Cd migration proceeded down the total concentration gradient. However, Cd migration was observed against the concentration gradient (testa Cd > nib Cd) from the fourth day. Cd migration could increase by extensive fermentation until the sixth day in high temperatures and probably by the adsorbent capacity of the testa. Genotype-by-treatment interactions were present for the nib Cd reduction, and a universal percentage of decrease of Cd for each genotype with fermentation cannot be expected. Selecting genotypes with highly adsorbent testa combined with controlled temperatures would help reduce the Cd concentration in the cacao raw material, improving its safety and quality.

Pesticide residues on lettuce (Lactuca sativa L.) in Cundinamarca-Colombia.

Lettuce is Colombia's most widely cultivated leafy vegetable, but in the absence of good agricultural practices, there is the risk of some pesticide residues that affect its safety and quality. This work aimed to identify the pesticides used by farmers for the lettuce crop, the iceberg variety (Lactuca sativa var. capitata), in some municipalities of Cundinamarca (Colombia) and to investigate their residues by sampling and analysis. The farmers reported in the survey 44 active ingredients, most fungicides (54%), while the laboratory analysis showed 23 chemical compounds (52% insecticides, 39% fungicides and 9% herbicides). In addition, dithiocarbamates, procymidone and some organophosphates were among the active ingredients that exceeded the maximum residue limits (MRLs). About 80% of the identified pesticides were not registered with the regulatory entity Instituto Colombiano Agropecuario (ICA) for their use in lettuce, but some were in commercial products legally registered in Latin American and Caribbean countries.

Dynamics of cocoa fermentation and its effect on quality.

Several research efforts on cocoa have been focused on parameters for controlling the transformation process to guarantee homogeneity and quality of cocoa beans, the main raw material in the chocolate industry. The main changes that determine the final quality of cocoa-and also the product's homogeneity-occur during fermentation, given the great number of factors that affect the process. This research seeks to identify the most relevant factors affecting quality in order to offer higher-quality and more homogeneous cocoa for the chocolate industry. The dynamics of the fermentation process were observed in three contrasting locations, monitoring different variables and evaluating the final quality of the cocoa. Results show that temperature and pH profile are the key factors to be monitored and controlled in order to achieve high-quality cocoa beans.

Comparative effectiveness of activated dolomite phosphate rock and biochar for immobilizing cadmium and lead in soils.

Sandy soils in Florida are vulnerable to toxic metal pollution, and it is necessary to identify desirable amendments for the remediation of metal contaminated soils. Sorption and incubation experiments were conducted to compare the effectiveness of dolomite phosphate rock (DPR), humic acid activated dolomite phosphate rock (ADPR) and biochar (BC) in immobilizing Cd2+ and Pb2+ in two representative agricultural soils in south Florida (Alfisol-Riviera and Spodosol -Ankona series). The results showed that the soils had a low sorption capacity for metals with maximum sorption of 0.767-3.30 mg/g. Application of amendments increased the maximum sorption by 4.2-4.8 times for Pb2+ and 1.5-2.2 times for Cd2+ in Alfisol soil, and 7.1-7.9 times for Pb2+ and 1.7-3.1 times for Cd2+ in Spodosol soil. ADPR was the most effective amendment for increasing the soil's sorption capacity for Cd2+ and Pb2+. 0.01 M CaCl2 extractable metals in the contaminated soils were significantly decreased by all the amendments, especially ADPR, which reduced extractable Cd2+ and Pb2+by 87.2 and 76.0% in Alfisol and 91.3 and 76.3% in Spodosol soil as compared to control. The amounts of extractable Cd2+ and Pb2+ were negatively correlated with soil pH and available P, indicating that the change of soil characteristics by amendments was the dominant mechanism for enhanced immobilization of metals in the contaminated soils. These results indicate that ADPR has great potential for remediating toxic levels of Cd2+ and Pb2+ in contaminated soils.

Reactivity of iron(II)-bound nitrosyl hydride (HNO, nitroxyl) in aqueous solution.

The reactivity of coordinated nitroxyl (HNO) has been explored with the [Fe(II)(CN)(5)HNO](3-) complex in aqueous medium, pH 6. We discuss essential biorelevant issues as the thermal and photochemical decompositions, the reactivity toward HNO dissociation, the electrochemical behavior, and the reactions with oxidizing and reducing agents. The spontaneous decomposition in the absence of light yielded a two-electron oxidized species, the nitroprusside anion, [Fe(II)(CN)(5)NO](2-), and a negligible quantity of N(2)O, with k(obs)≈5×10(-7)s(-1), at 25.0°C. The value of k(obs) represents an upper limit for HNO release, comparable to values reported for other structurally related L ligands in the [Fe(II)(CN)(5)L](n-) series. These results reveal that the FeN bond is strong, suggesting a significant σ-π interaction, as already postulated for other HNO-complexes. The [Fe(II)(CN)(5)HNO](3-) ion showed a quasi-reversible oxidation wave at 0.32 V (vs normal hydrogen electrode), corresponding to the [Fe(II)(CN)(5)HNO](3-)/[Fe(II)(CN)(5)NO](3-),H(+) redox couple. Hexacyanoferrate(III), methylviologen and the nitroprusside ion have been selected as potential oxidants. Only the first reactant achieved a complete oxidation process, initiated by a proton-coupled electron transfer reaction at the HNO ligand, with nitroprusside as a final oxidation product. Dithionite acted as a reductant of [Fe(II)(CN)(5)HNO](3-), in a 4-electron process, giving NH(3). The high stability of bound HNO may resemble the properties in related Fe(II) centers of redox active enzymes. The very minor release of N(2)O shows that the redox conversions may evolve without disruption of the FeN bonds, under competitive conditions with the dissociation of HNO.

Three redox states of nitrosyl: NO+, NO*, and NO-/HNO interconvert reversibly on the same pentacyanoferrate(II) platform.

Not so elusive: [Fe(II)(CN)(5)(HNO)](3-) has been characterized spectroscopically after the two-electron reduction of nitroprusside (see scheme). The complex is stable at pH 6, slowly decomposing to [Fe(CN)(6)](4-) and N(2)O. It is deprotonated at increasing pH value with oxidation of bound NO(-) to [Fe(II)(CN)(5)(NO)](3-). [Fe(II)(CN)(5)(HNO)](3-) is the first non-heme iron-nitroxyl complex prepared in aqueous solution that is reversibly redox-active under biologically relevant conditions.