Influence of digestion methods on the recovery of Iron, Zinc, Nickel, Chromium, Cadmium and Lead contents in 11 organic residues

There are currently many devices and techniques to quantify trace elements (TEs) in various matrices, but their efficacy is dependent on the digestion methods (DMs) employed in the opening of such matrices which, although "organic", present inorganic components which are difficult to solubilize. This study was carried out to evaluate the recovery of Fe, Zn, Cr, Ni, Cd and Pb contents in samples of composts and cattle, horse, chicken, quail, and swine manures, as well as in sewage sludges and peat. The DMs employed were acid digestion in microwaves with HNO3 (EPA 3051A); nitric-perchloric digestion with HNO3 + HClO4 in a digestion block (NP); dry ashing in a muffle furnace and solubilization of residual ash in nitric acid (MDA); digestion by using aqua regia solution (HCl:HNO3) in the digestion block (AR); and acid digestion with HCl and HNO3 + H2O2 (EPA 3050). The dry ashing method led to the greatest recovery of Cd in organic residues, but the EPA 3050 protocol can be an alternative method for the same purpose. The dry ashing should not be employed to determine the concentration of Cr, Fe, Ni, Pb and Zn in the residues. Higher Cr and Fe contents are recovered when NP and EPA 3050 are employed in the opening of organic matrices. For most of the residues analyzed, AR is the most effective method for recovering Ni. Microwave-assisted digestion methods (EPA3051 and 3050) led to the highest recovery of Pb. The choice of the DM that provides maximum recovery of Zn depends on the organic residue and trace element analyzed.

Iron oxides and quality of organic matter in sugarcane harvesting systems

Improvements in working conditions, sustainable production, and competitiveness have led to substantial changes in sugarcane harvesting systems. Such changes have altered a number of soil properties, including iron oxides and organic matter, as well as some chemical properties, such as the maximum P adsorption capacity of the soil. The aim of this study was to characterize the relationship between iron oxides and the quality of organic matter in sugarcane harvesting systems. For that purpose, two 1 ha plots in mechanically and manually harvested fields were used to obtain soil samples from the 0.00-0.25 m soil layer at 126 different points. The mineralogical, chemical, and physical results were subjected to descriptive statistical analyses, such as the mean comparison test, as well as to multivariate statistical and principal component analyses. Multivariate tests allowed soil properties to be classified in two different groups according to the harvesting method: manual harvest with the burning of residual cane, and mechanical harvest without burning. The mechanical harvesting system was found to enhance pedoenvironmental conditions, leading to changes in the crystallinity of iron oxides, an increase in the humification of organic matter, and a relative decrease in phosphorus adsorption in this area compared to the manual harvesting system.

Organic Matter Fractions and Quality of the Surface Layer of a Constructed and Vegetated Soil After Coal Mining. I - Humic Substances and Chemical Characterization

After open coal mining, soils are “constructed”, which usually contain low levels and quality of organic matter (OM). Therefore, the use of plant species for revegetation and reclamation of degraded areas is essential. This study evaluated the distribution of carbon (C) in the chemical fractions as well as the chemical characteristics and humification degree of OM in a soil constructed after coal mining under cultivation of perennial grasses. The experiment was established in 2003 with the following treatments: Hemarthria altissima (T1), Paspalum notatum (T2), Cynodon dactilon (T3), Urochloa brizantha (T4), bare constructed soil (T5), and natural soil (T6). In 2009, soil samples were collected from the 0.00-0.03 m layer and the total organic carbon stock (TOC) and C stock in the chemical fractions: acid extract (CHCl), fulvic acid (CFA), humic acid (CHA), and humin (CHU) were determined. The humic acid (HA) fraction was characterized by infrared spectroscopy and the laser-induced fluorescence index (ILIF) of OM was also calculated. After six years, differences were only observed in the CHA stocks, which were highest in T1 (0.89 Mg ha-1) and T4 (1.06 Mg ha-1). The infrared spectra of HA in T1, T2 and T4 were similar to T6, with greater contribution of aliphatic organic compounds than in the other treatments. In this way, ILIF decreased in the sequence T5>T3>T4>T1>T2>T6, indicating higher OM humification in T3 and T5 and more labile OM in the other treatments. Consequently, the potential of OM quality recovery in the constructed soil was greatest in treatments T1 and T4.

Organic matter processing and soil evolution in a braided river system

Traditionally, braided river research has considered flow, sediment transport processes and, recently, vegetation dynamics in relation to river morphodynamics. However, if considering the development of woody vegetated patches over a time scale of decades, we must consider the extent to which soil forming processes, particularly related to soil organic matter, impact the alluvial geomorphic-vegetation system. Here we quantify the soil organic matter processing (humification) that occurs on young alluvial landforms. We sampled different geomorphic units, ranging from the active river channel to established river terraces in a braided river system. For each geomorphic unit, soil pits were used to sample sediment/soil layers that were analysed in terms of grain size (<2mm) and organic matter quantity and quality (RockEval method). A principal components analysis was used to identify patterns in the dataset. Results suggest that during the succession from bare river gravels to a terrace soil, there is a transition from small amounts of external organic matter supply provided by sedimentation processes (e.g. organic matter transported in suspension and deposited on bars), to large amounts of autogenic in situ organic matter production due to plant colonisation. This appears to change the time scale and pathways of alluvial succession (bio-geomorphic succession). However, this process is complicated by: the ongoing possibility of local sedimentation, which can serve to isolate surface layers via aggradation from the exogenic supply; and erosion which tends to create fresh deposits upon which organic matter processing must re-start. The result is a complex pattern of organic matter states as well as a general lack of any clear chronosequence within the active river corridor. This state reflects the continual battle between deposition events that can isolate organic matter from the surface, erosion events that can destroy accumulating organic matter and the early ecosystem processes necessary to assist the co-evolution of soil and vegetation. A key question emerges over the extent to which the fresh organic matter deposited in the active zone is capable of significantly transforming the local geochemical environment sufficiently to accelerate soil development.

Distribuição de metais e caracterização das constantes de troca entre espécies metálicas e frações húmicas aquáticas de diferentes tamanhos moleculares

In this work the metal distribution and exchange constants between metal species and aquatic humic fractions with different molecular sizes were studied. The aquatic humic substances (AHS) were extracted by XAD-8 resin from water sample collected from Itapitanguí river, São Paulo State, Brazil. The AHS were fractionated in six fractions with different molecular sizes (>100 - <5 kDa) and characterized by several techniques. Molar ratios H/C suggested higher aromaticity for fractions F1 and F6 whereas molar ratios C/N didn´t show any differences regarding the humification degree between the fractions. The UV-Vis absorbance a254/a436 ratio showed higher results for F4 and F5, probably by less condensed features. FTIR studies showed high similarity in the functional groups in the fractions. The highest percentage of traces of Co, Al, Fe, Mn, Cu, Zn and Ni (determined by ICP-AES) was preferably complexed by fractions F3 and F4 with a greater amount of dissolved organic carbon (DOC). In addition, the exchange constants, determined by ultrafiltration method, showed complexes AHS-Fe and AHS-Al with higher stability than complexes AHS-Co in all fractions.

Use of the EPR technique to determine thermal stability of some humified organic substances found in soil organic-mineral fractions

In this work, using the EPR spectroscopy, we analysed the thermal stability of some organic-mineral compounds found in a Gleysoil from Rio Janeiro. It was observed a complete disappearance of the EPR signal around 600 °C for the < 2 µm fraction and a residual EPR signal of semiquinone free radical for the 2-20 µm and 20-53 µm fractions at the same temperature. Also, the experiments showed that the 2-20 µm fraction had a larger concentration of semiquinone free radical per g of carbon and a smaller line width indicated a larger humification of this fraction. This is an evidence that the soil organic matter of this fraction (2-20 µm) is more stable than the other ones.

Anéis aromáticos condensados e relação E4/E6: estudo de ácidos húmicos de gleissolos por RMN de 13C no estado sólido utilizando a técnica CP/MAS desacoplamento defasado

In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures.

Determinação da humificação da matéria orgânica de um latossolo e de suas frações organo-minerais

Laser-induced fluorescence spectroscopy was used to determine the humification degree of the organic matter of a whole soil, that is, soil without any physical or chemical treatment. Particle size was determined in physically separated fractions. The humification of organic matter, the depth of the soil and the planting system can be correlated. On the surface of the soil, no tillage provided the smallest humification in comparison with the conventional tillage and reduced tillage. The fractions of the superficial layer of the soil (0-20 cm) indicated larger humification in the fraction from 20 to 53 µm and the smallest in the fraction of <2 µm.

Matéria orgânica em quatro tipos de solos brasileiros: composição química e sorção de atrazina

Soil organic matter is the main sorptive soil compartment for atrazine in soils, followed in a minor scale by the inorganic fraction. In this study, the soil organic matter quality and atrazine sorption were investigated in four different soil types. The pedogenic environment affected the humification and therefore the chemical composition of the organic matter. The organic matter contribution to atrazine sorption was larger (60-83%) than that of the inorganic fraction. The organic matter capacity in retaining the herbicide was favoured by a higher decomposition degree and a smaller carboxylic substitution of the aliphatic chains.

Interferência da lignina na quantificação de radicais livres no processo de compostagem

In this work was studied composts and their humic acids (HA) to evaluate the use of EPR in the monitoring of the humification. It was observed increase in the concentration of organic free radical (OFR) in all the composts, but in L1 the increase was more significant than L2 and L3. Research more detailed of L1 showed that the lignin is main source of OFR. Then determination of these radicals in material in nature that contains high amount of lignin isn't a good indicator to monitor the humification process in the composting and yes the fraction HA of the composts.

Acompanhamento químico da vermicompostagem de lodo de esgoto doméstico

This research aims to monitor the humification process of domestic sewage sludge resulted from the vermicomposting, evaluating, also, the possibility of using the final product (vermicompost) in agricultural soils. The monitored chemical variables during the 90 days of vermicomposting were: humidity rate, organic matter content, nitrogen and phosphorus content, pathogenic organisms concentration, total organic carbon, acidity, CEC, C/N ratio, CEC/TOC ratio, and humic and fulvic acids content. The change in these variables during the vermicomposting process showed that this technique is effective for use in the maturation of the residue.

Influência das substâncias húmicas de sedimentos na biodisponibilidade de metais para o sistema aquático

In rivers, sediments act as sinks for retaining contaminants. This study evaluated the influence of sediment humic substances (HS) on the bioavailability of metals. The levels of metals in sediments and HS indicated that most are complexed with HS. Characterization of HS showed a high degree of humification. The complexation capacity of HS for metals established the affinity order:Pb2+

Application of fourier transform infrared spectroscopy, chemical and chemometrics analyses to the characterization of agro-industrial waste

Agroindustrial waste in general presents significant levels of nutrients and organic matter and has therefore been frequently put to agricultural use. In this context, the objective of this study was to determine the chemical composition, nitrogen, phosphorus, potassium, calcium, magnesium and carbon content, as well as the qualitative characteristics through Fourier transform infrared spectroscopy of four samples of poultry litter and one sample of cattle manure, from the southwestern region of Paraná, Brazil. Results revealed that, in general, the poultry litter presented higher amount of nutrients and carbon than the cattle manure. The infrared spectra allowed identification of the functional groups present and the differences in degree of sample humification. The statistical treatment confirmed the quantitative and qualitative differences revealed.

Effect of drainage and wildfire on peat hydrophysical properties

Consecutive multiple disturbances to northern peatlands can dramatically impact peat hydrophysical properties. We examine the impact of a double disturbance (drainage and wildfire) on the hydrophysical and moisture retention properties of peat, a key regulator of peatland ecohydrological resilience, and compare this with the impact to each individual disturbance (drainage and wildfire). The compound effect of drainage and wildfire resulted in a shift of the surface datum down the peat profile, revealing denser peat. Less-dense near-surface peats that regulate water-table position and near-surface moisture content, both favourable to Sphagnum recolonization, were lost. At a drained peatland that was then subject to wildfire, peat bulk density increased by 14.1%, von Post humification class increased by two categories and water retention increased by 15.6%, compared with an adjacent burned but undrained (single disturbance) portion of the fen. We discuss the key hydrophysical metrics of peatland vulnerability and outline how they are affected by the isolated impacts of drainage and wildfire, as well as their combined effects. We demonstrate that multiple peatland disturbances have likely led to an increase in hydrological limitations to Sphagnum recovery, which may impact peatland ecohydrological resilience.

Evaluation of optical techniques for characterising soil organic matter quality in agricultural soils

Soil organic matter (SOM) is one of the main global carbon pools. It is a measure of soil quality as its presence increases carbon sequestration and improves physical and chemical soil properties. The determination and characterisation of humic substances gives essential information of the maturity and stresses of soils as well as of their health. However, the determination of the exact nature and molecular structure of these substances has been proven difficult. Several complex techniques exist to characterise SOM and mineralisation and humification processes. One of the more widely accepted for its accuracy is nuclear magnetic resonance (NMR) spectroscopy. Despite its efficacy, NMR needs significant economic resources, equipment, material and time. Proxy measures like the fluorescence index (FI), cold and hot-water extractable carbon (CWC and HWC) and SUVA-254 have the potential to characterise SOM and, in combination, provide qualitative and quantitative data of SOM and its processes. Spanish and British agricultural cambisols were used to measure SOM quality and determine whether similarities were found between optical techniques and 1H NMR results in these two regions with contrasting climatic conditions. High correlations (p < 0.001) were found between the specific aromatic fraction measured with 1H NMR and SUVA-254 (Rs = 0.95) and HWC (Rs = 0.90), which could be described using a linear model. A high correlation between FI and the aromatics fraction measured with 1H NMR (Rs = −0.976) was also observed. In view of our results, optical measures have a potential, in combination, to predict the aromatic fraction of SOM without the need of expensive and time consuming techniques.