Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.
Over the past several decades, the Brazilian State of Rondônia has been the destination of many rural migrants drawn from Brazil's middle southern regions by massive government colonization projects. Factors such as explosive population growth, logging, mining, small-scale farming and ranching have synergistically fuelled deforestation in the state. The total area deforested in Rondônia in 1978 was 4200 km2. In 1988, the area increased to 30 000 km2, in 1998 to 53 300 km2 and by the year 2003, a total of 67 764 km2 of Rondônia was deforested. In response to the high rate of deforestation observed in Rondônia and other Amazonian states, state and federal agencies worked to create a network of conservation units (CUs) in Brazil during the 1990s that was signed into law(Law 9985/00) in 2000. The ability of these CUs to reduce the rate of deforestation was analysed. Remotely-sensed data from Landsat and thematic coverages were used to measure deforestation inside all CUs in Rondônia. A more detailed analysis of CUs with the highest levels of deforestation, including an analysis between soil types and deforestation and a forecast of potential future deforestation, was conducted. The creation of conservation units in Rondônia has been useful in curbing deforestation within their boundaries; however, many CUs face pressure from the combined activities of illegal loggers, cattle ranchers and small-scale farmers seeking new sources of timber and agricultural land. For example, an exponential increase in the amount of deforestation was observed in Rondônia's Bom Futuro National Forest between 1992 and 2000. A regression model indicated a total of 20 500 ha deforested by 2002, while measurements from 2002 imagery showed an actual total deforestation of 20 720 ha. Should this trend persist, Bom Futuro National Forest could be completely deforested by 2017. CUs in Rondônia must be developed and implemented jointly by all stakeholders through the creation of partnerships between local communities, non-governmental organizations and government agencies.
Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.
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