Copper (Cu) speciation in organic-waste (OW) amended soil: Instability of OW-borne Cu(I) sulfide and role of clay and iron oxide minerals.

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cutotal = 122 mg·kg-1) was amended over 11 years with Cu-rich pig slurry in which Cu was 100 % Cu(I) sulfide. Natural Cu associated with clay and iron oxide minerals persisted in the amended soil, but the exogenous Cu(I) sulfide was unstable. The increase in Cu concentration in the amended soil to 174 mg·kg-1 was accounted for the increase of Cu sorbed to kaolinite and Cu bound to organic matter. These results are important for better understanding the natural occurrence of Cu in soils and for assessing the environmental impacts of organic waste recycling in agricultural fields.

Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles.

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.

Copper and zinc accumulation and fractionation in a clayey Hapludox soil subject to long-term pig slurry application.

Pig slurry (PS) recycling as fertilizer is commonly practiced as an option for minimizing livestock waste. Successive PS applications on the soil can lead to crop toxicity and environmental risk. Despite extensive investigation of macronutrient behavior, the fate of trace metals remains uncertain and only a few long-term field studies have been reported to date. This study was designed to assess the impact of 11-year continuous PS spreading on Cu and Zn accumulation and fractionation in a Brazilian clayey Hapludox soil. Three different PS application rates--50, 100 and 200m3 ha(-1)year(-1)--were monitored at six soil depths in comparison to a non-amended control soil. The modified Geological Survey of Canada sequential extraction protocol was applied. A statistically significant increase in Cu and Zn total concentration (assessed by the sum of fractions) was noted only within the 0-5 cm soil layer for the 50 and 100 m3 ha(-1) year(-1) (PS50 and PS100) treatments, and up to 10-15 cm for the 200 m3 ha(-1)year(-1) (PS200) treatment. The mass balance, determined for the 22 PS amendments over the period, confirmed the overall exogenous Cu and Zn accumulation within the surface layers. More than 70% of the natural heavy metal content was originally in the residual fraction. However, this was the only fraction not influenced by the PS amendments. After PS input, the exogenous Cu was mainly detected in the fraction bound to organic matter (66.4%) within the PS200 0-5 cm soil layer. Exogenous Zn was mainly distributed between the adsorbed fraction (36.7%) and the organic matter fraction (32.0%) within the PS200 0-5 cm layer.

Potential of carbon accumulation in no-till soils with intensive use and cover crops in southern Brazil.

The area under no-till (NT) in Brazil reached 22 million ha in 2004-2005, of which approximately 45% was located in the southern states. From the 1970s to the mid-1980s, this region was a source of carbon dioxide to the atmosphere due to decrease of soil carbon (C) stocks and high consumption of fuel by intensive tillage. Since then, NT has partially restored the soil C lost and reduced the consumption of fossil fuels. To assess the potential of C accumulation in NT soils, four long-term experiments (7-19 yr) in subtropical soils (Paleudult, Paleudalf, and Hapludox) varying in soil texture (87-760 g kg(-1) of clay) in agroecologic southern Brazil zones (central region, northwest basaltic plateau in Rio Grande Sul, and west basaltic plateau in Santa Catarina) and with different cropping systems (soybean and maize) were investigated. The lability of soil organic matter (SOM) was calculated as the ratio of total organic carbon (TOC) to particulate organic carbon (POC), and the role of physical protection on stability of SOM was evaluated. In general, TOC and POC stocks in native grass correlated closely with clay content. Conversely, there was no clear effect of soil texture on C accumulation rates in NT soils, which ranged from 0.12 to 0.59 Mg ha(-1) yr(-1). The C accumulation was higher in NT than in conventional-till (CT) soils. The legume cover crops pigeon pea [Cajanus cajan (L.) Millsp] and velvet beans (Stizolobium cinereum Piper & Tracy) in NT maize cropping systems had the highest C accumulation rates (0.38-0.59 Mg ha(-1) yr(-1)). The intensive cropping systems also were effective in increasing the C accumulation rates in NT soils (0.25-0.34 Mg ha(-1) yr(-1)) when compared to the double-crop system used by farmers. These results stress the role of N fixation in improving the tropical and subtropical cropping systems. The physical protection of SOM within soil aggregates was an important mechanism of C accumulation in the sandy clay loam Paleudult under NT. The cropping system and NT effects on C stocks were attributed to an increase in the lability of SOM, as evidenced by the higher POC to TOC ratio, which is very important to C and energy flux through the soil.