Soil fertility in slash and burn agricultural systems in central Mozambique.

Slash and burn is a land use practice widespread all over the world, and nowadays it is formally recognized as the principal livelihood system in rural areas of South America, Asia, and Africa. The practice consists of a land rotation where users cut native or secondary forest to establish a new crop field and, in some cases, build charcoal kilns with the cut wood to produce charcoal. Due to several socio-economic changes in developing countries, some scientists and international organizations have questioned the sustainability of slash and burn since in some cases, crop yield does not justify the soil degradation caused. To estimate the soil quality in agricultural and forest soils at different ages of the forest-fallow period (25, 35, and 50 years), this survey investigated rural areas in three locations in Manica province, central Mozambique: Vanduzi, Sussundenga, and Macate. Soil profiles were trenched and sampled with a pedological approach under crop fields and forest-fallow. The chronosequence was selected to test the hypothesis that the increase in forest-fallow age causes an improvement of soil fertility. Results highlighted discrete variations among locations in mineralogy, Al- and Fe-oxyhydroxides, sand, silt, pH, total organic carbon, humic carbon, total nitrogen, available phosphorous, chloride, nitrate, fluoride, and ammonium. Few differences in mineralogy, Fe-oxyhydroxides, available P, chloride, and nitrate were detected between crop fields and forest-fallow within the same location. Such differences were mostly ascribed to intrinsic fertility inherited from the parent material rather than a longer forest-fallow period. However, physicochemical soil property improvement did not occur under a forest age of 50 years (the longest forest-fallow considered), indicating that harmonization of intrinsic fertility and agronomic practices may increase soil organic matter and nutrient contents more than a long forest-fallow period.

Potentially Toxic Substances and Associated Risks in Soils Affected by Wildfires: A Review.

The presence of toxic substances is one of the major causes of degradation of soil quality. Wildfires, besides affecting various chemical, physical, and biological soil properties, produce a mixture of potentially toxic substances which can reach the soil and water bodies and cause harm to these media. This review intends to summarise the current knowledge on the generation by wildfires of potentially toxic substances, their effects on soil organisms, and other associated risks, addressing the effects of fire on metal mobilisation, the pyrolytic production of potentially toxic compounds, and the detoxifying effect of charcoal. Numerous studies ascertained inhibitory effects of ash on seed germination and seedling growth as well as its toxicity to soil and aquatic organisms. Abundant publications addressed the mobilisation of heavy metals and trace elements by fire, including analyses of total concentrations, speciation, availability, and risk of exportation to water bodies. Many publications studied the presence of polycyclic aromatic hydrocarbons (PAH) and other organic pollutants in soils after fire, their composition, decline over time, the risk of contamination of surface and ground waters, and their toxicity to plants, soil, and water organisms. Finally, the review addresses the possible detoxifying role of charcoal in soils affected by fire.

Rational Design of Copper(II)-Uracil Nanoprocessed Coordination Polymers to Improve Their Cytotoxic Activity in Biological Media.

This work is focused on the rational structural design of two isostructural Cu(II) nano-coordination polymers (NCPs) with uracil-1-acetic acid (UAcOH) (CP1n) and 5-fluorouracil-1-acetic acid (CP2n). Suitable single crystals for X-ray diffraction studies of CP1 and CP2 were prepared under hydrothermal conditions, enabling their structural determination as 1D-CP ladder-like polymeric structures. The control of the synthetic parameters allows their processability into water colloids based on nanoplates (CP1n and CP2n). These NCPs are stable in water at physiological pHs for long periods. However, interestingly, CP1n is chemically altered in culture media. These transformations provoke the partial release of its building blocks and the formation of new species, such as [Cu(UAcO)2(H2O)4]·2H2O (Cu(II)-complex), and species corresponding to the partial reduction of the Cu(II) centers. The cytotoxic studies of CP1n versus human pancreatic adenocarcinoma and human uveal melanoma cells show that CP1n produces a decrease in the cell viability, while their UAcOH and Cu(II)-complex are not cytotoxic under similar conditions. The copper reduction species detected in the hydrolysis of CP1n are closely related to the formation of the reactive oxygen species (ROS) detected in the cytotoxic studies. These results prompted us to prepare CP2n that was designed to improve the cytotoxicity by the substitution of UAcO by 5-FUAcO, taking into account the anticancer activity of the 5-fluorouracil moiety. The new CP2n has a similar behavior to CP1n both in water and in biological media. However, its subtle structural differences are vital in improving its cytotoxic activity. Indeed, the release during the hydrolysis of species containing the 5-fluorouracil moiety provokes a remarkable increase in cellular toxicity and a significant increase in ROS species formation.

Phosphate sorption and desorption by two contrasting volcanic soils of equatorial Africa.

Volcanic soils cover 1% of the Earth's surface but support 10% of the world's population. They are among the most fertile soils in the world, due to their excellent physical properties and richness in available nutrients. The major limiting factor for plant growth in volcanic soils is phosphate fixation, which is mainly attributable to active species of aluminium and iron. The sorption and desorption of phosphate is studied on the surface horizons of two African agricultural soils, a silandic Andosol (Rwanda) and a vitric Andosol (São Tomé and Principe). Both soils are slightly acid. The silandic Andosol is rich in active aluminium forms, while the vitric Andosol has high amounts of crystalline iron and aluminium oxides. Sorption isotherms were determined by equilibrating at 293K soil samples with phosphate solutions of concentrations between 0 and 100 mg P L-1 in NaNO3; phosphate was determined by visible spectrophotometry in the equilibrium solution. To study desorption, the soil samples from the sorption experiment were equilibrated with 0.02 M NaNO3. The isotherms were adjusted to mathematical models. In almost all the concentration range, the adsorption of phosphate by the silandic Andosol was greater than 90% of the amount added, being lower in the vitric Andosol but always higher than 65%. The high sorption by the silandic Andosol is attributed to its richness in non-crystalline Fe and Al, while in the vitric Andosol crystalline iron species seem to play a relevant role in the adsorption. The sorption isotherms of both soils fitted to the Temkin model, the adjustment to the Langmuir or Freundlich models being unsatisfactory; throughout the range studied, the sorption increases with increasing phosphorus concentration, a maximum sorption is not predictable (as occurs when the sorption is adjusted to the Langmuir model). For an added P concentration of 100 mg L-1 (3.2 mmol L-1), the sorption is 47.7 µmol P g-1 in the silandic Andosol and 41.6 µmol P g-1 in the vitric Andosol. The desorption is low and the comparison of the sorption and desorption isotherms reveals a pronounced hysteresis, that is, the irreversibility of the sorption. The high phosphate sorption and its irreversibility are comparable to those published for other volcanic soils with high contents of allophane, active aluminium and free iron. The strong phosphate adsorption is a serious limiting factor for plant growth, which requires a careful management of phosphorus fertilization.

Unprecedented H-atom transfer from water to ketyl radicals mediated by Cp(2)TiCl.

The H-atom transfer (HAT) from water to ketyl radicals, mediated by titanocene(iii) aqua-complexes, can explain the Ti(III)-promoted reduction of ketones in aqueous medium better than the conventional House mechanism. Moreover, we also report novel evidences supporting the existence of these titanocene(iii) aqua-complexes.

Electronic communication through a poly-yne carbonyldicobalt complex containing an open linear triosmium cluster.

The oxidative coupling of 2-[Co(2)(CO)(4)(micro-X){micro(2)-eta(2)-(SiMe(3)C(2))}]-5-(C[triple bond]CH)C(4)H(2)S (X = dppa (1), dppm (2)) and 3-[Co(2)(CO)(4)(micro-dmpm){micro(2)-eta(2)-(SiMe(3)C(2))}]-4-(C[triple bond]CH)C(4)H(2)S (3) using standard Eglinton-Glaser conditions yielded 2,2'-[Co(2)(CO)(4)(micro-X){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-5,5'-(C[triple bond]C)(2) (X = dppa (4), dppm (5)) and 3,3'-[Co(2)(CO)(4)(micro-dmpm){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-4,4'-(C[triple bond]C)(2) (6), respectively (dppa = (Ph(2)P)(2)NH; dmpm = (Me(2)P)(2)CH(2); dppm = (Ph(2)P)(2)CH(2)). The reaction of 5 with [Os(3)(CO)(11)(CH(3)CN)] afforded 2,2'-[Co(2)(CO)(4)(micro-dppm){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-5,5'-[Os(3)(CO)(11)(micro(3)-eta(4)-(C[triple bond]C)(2)] (7), where the triosmium cluster is open and coordinated as a linear chain to both triple bonds. The electrochemical study of 7 shows that the "Os(3)" unit significantly enhances the electronic communication between the "Co(2)" redox centres as compared with 5. Complex 6 was characterized by single-crystal X-ray diffraction analyses.

Source identification of heavy metals in pastureland by multivariate analysis in NW Spain.

Arable layer of pastureland in Galicia (NW Spain) was monitored for total content of heavy metals, and analysed by multivariate statistical techniques, in order to investigate the different origin that metals may have in pasture soils. Principal component analysis (PCA), cluster analysis (CA) and correlation matrix (CM) were applied to 65 samples in which the total concentrations of Mn, Fe, Zn, Cu, Cr, Co, Ni, Cd and Pb were measured. Four significant components were extracted by PCA, explaining 78.830% of total variance. Mn, Co and Ni (and partially Cu), and Fe and Cr, were associated in two lithogenic components, respectively, while an anthropogenic origin was identified for Cd, Pb and Zn. Zn (and Cu) were mainly associated with soil fertilisation by cattle slurry or with other activities regarding cattle management. Although the origin of Cd and Pb was also attributed to slurry application, other sources like commercial fertilisers, vehicle exhaust or aerial deposition were not discarded as possible contributors. CA confirmed and completed the results obtained by PCA, classifying the data in four groups representing different areas. Group 1 represented samples corresponding to areas were the application of manure was moderate, while Group 2 included samples of lithogenic origin. Highest contents of anthropogenic metals were included in Group 3, although soils in this cluster were not considered as polluted. The last cluster grouped the samples with the lowest content of all the metals analysed, representing areas correctly managed and not affected by other external sources. Finally, the results obtained by CM agreed with PCA and CA, also helping in elucidating individual relationships between metals.