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 Fractions and Quality of the Surface Layer of a Constructed and Vegetated Soil After Coal Mining. II - Physical Compartments and Carbon Management Index

Soils constructed after mining often have low carbon (C) stocks and low quality of organic matter (OM). Cover crops are decisive for the recovery process of these stocks, improving the quality of constructed soils. Therefore, the goal of this study was to evaluate the effect of cover crops on total organic C (TOC) stocks, C distribution in physical fractions of OM and the C management index (CMI) of a soil constructed after coal mining. The experiment was initiated in 2003 with six treatments: Hemarthria altissima (T1), Paspalum notatum (T2), Cynodon dactylon (T3), Urochloa brizantha (T4), bare constructed soil (T5), and natural soil (T6). Soil samples were collected in 2009 from the 0.00-0.03 m layer, and the TOC and C stocks in the physical particle size fractions (carbon in the coarse fraction - CCF, and mineral-associated carbon - MAC) and density fractions (free light fraction - FLF; occluded light fraction - OLF, and heavy fraction - HF) of OM were determined. The CMI components: carbon pool index (CPI), lability (L) and lability index (LI) were estimated by both fractionation methods. No differences were observed between TOC, CCF and MAC stocks. The lowest C stocks in FLF and OLF fractions were presented by T2, 0.86 and 0.61 Mg ha-1, respectively. The values of TOC stock, C stock in physical fractions and CMI were intermediate, greater than T5 and lower than T6 in all treatments, indicating the partial recovery of soil quality. As a result of the better adaptation of the species Hemarthria and Brizantha, resulting in greater accumulation of labile organic material, the CPI, L, LI and CMI values were higher in these treatments, suggesting a greater potential of these species for recovery of constructed soils.

ORGANIC MATTER FRACTIONS IN A QUARTZIPSAMMENT UNDER CULTIVATION OF IRRIGATED MANGO IN THE LOWER SÃO FRANCISCO VALLEY REGION, BRAZIL

Improper land use has lead to deterioration and depletion of natural resources, as well as a significant decline in agricultural production, due to decreased soil quality. Removal of native vegetation to make way for agricultural crops, often managed inadequately, results in soil disruption, decreased nutrient availability, and decomposition of soil organic matter, making sustainable agricultural production unviable. Thus, the aim of the present study was to evaluate the impact of growing irrigated mango (over a 20 year period) on the organic carbon (OC) stocks and on the fractions of soil organic matter (SOM) in relation to the native caatinga (xeric shrubland) vegetation in the Lower São Francisco Valley region, Brazil. The study was carried out on the Boa Esperança Farm located in Petrolina, Pernambuco, Brazil. In areas under irrigated mango and native caatinga, soil samples were collected at the 0-10 and 10-20 cm depths. After preparing the soil samples, we determined the OC stocks, carbon of humic substances (fulvic acid fractions, humic acid fractions, and humin fractions), and the light and heavy SOM fractions. Growing irrigated mango resulted in higher OC stocks; higher C stocks in the fulvic acid, humic acid, and humin fractions; and higher C stocks in the heavy and light SOM fraction in comparison to nativecaatinga, especially in the uppermost soil layer.

Carbon in Humic Fractions of Organic Matter in Soil Treated with Organic Composts under Mango Cultivation

ABSTRACT Soil organic matter (SOM) plays a key role in maintaining the productivity of tropical soils, providing energy and substrate for the biological activity and modifying the physical and chemical characteristics that ensure the maintenance of soil quality and the sustainability of ecosystems. This study assessed the medium-term effect (six years) of the application of five organic composts, produced by combining different agro-industrial residues, on accumulation and chemical characteristics of soil organic matter. Treatments were applied in a long-term experiment of organic management of mango (OMM) initiated in 2005 with a randomized block design with four replications. Two external areas, one with conventional mango cultivation (CMM) and the other a fragment of regenerating Caatinga vegetation (RCF), were used as reference areas. Soil samples were collected in the three management systems from the 0.00-0.05, 0.05-0.10, and 0.10-0.20 m layers, and the total organic carbon content and chemical fractions of organic matter were evaluated by determining the C contents of humin and humic and fulvic acids. Organic compost application significantly increased the contents of total C and C in humic substances in the experimental plots, mainly in the surface layer. However, compost 3 (50 % coconut bagasse, 40 % goat manure, 10 % castor bean residues) significantly increased the level of the non-humic fraction, probably due to the higher contents of recalcitrant material in the initial composition. The highest increases from application of the composts were in the humin, followed by the fulvic fraction. Compost application increased the proportion of higher molecular weight components, indicating higher stability of the organic matter.

Carbon Stocks in Compartments of Soil Organic Matter 31 Years after Substitution of Native Cerrado Vegetation by Agroecosystems

ABSTRACT Changes in carbon stocks in different compartments of soil organic matter of a clayey Latossolo Vermelho Distrófico (Typic Haplustox), caused by the substitution of native savanna vegetation (cerrado sensu stricto) by agroecosystems, were assessed after 31 years of cultivation. Under native vegetation, a stock of 164.5 Mg ha-1 C was estimated in the 0.00-1.00 m layer. After 31 years of cultivation, these changes in soil C stocks were detected to a depth of 0.60 m. In the case of substitution of cerrado sensu stricto by no-tillage soybean-corn rotation, a reduction of at least 11 % of the soil C pools was observed. However, the adoption of no-tillage as an alternative to tillage with a moldboard plow (conventional system) reduced CO2 emissions by up to 12 %.

Fifth-order cyclicity and organic matter contents relationship (Lower Eocene, Pyrenees)

The Upper Limestone Member of the Corones Formation of the Spanish Pyrenees consists of various units (Lower and Upper Foraminifera Units, Shale Unit, Cherty-ostracode Unit, Ostracode Unit and Chara-ostracode Unit) and offers strong facies and lateral thickness (20 to 80 m) variations. Detailed facies analyses, fifth-order cycles and organic geochemical determinations in the central domain of the Corones platform carbonates (Cherty-ostracode Unit), lower Eocene in age, were carried out to establish a case of close relationship between variations in organic matter productivity and cyclicity with annual period. The Cherty-ostracode Unit displays a continuous and pervasive fifth-order cyclicity, represented by 5 cycles. Each cycle consists of a lower part (mollusc facies) and an upper part (laminated ostracode facies). The calculated fifth-order cycle period ranges from about 17,000 to 28,000 years, which falls within the Milankovitch Band. Variations in organic matter content related to these carbonate cycles have been established. The lower mollusc facies members show a low organic carbon content and Hydrogen Index (HI) below 0.6% in weight and 261, respectively. By contrast, the upper laminated ostracode facies members show high organic carbon contents (up to 2% in weight) and high HI (between 164 and 373), and are also characterized by important silicification processes (the content in chert is up to 30%). The organic geochemistry resulting from these organic rich levels reflects a contribution of algal marine input.

Reconstruction of the recent history of a large deep prealpine lake (Lake Bourget, France) using subfossil chironomids, diatoms, and organic matter analysis: towards the definition of a lake-specific reference state

This paper presents the recent history of a large prealpine lake (Lake Bourget) using chironomids, diatoms and organic matter analysis, and deals with the ability of paleolimnological approach to define an ecological reference state for the lake in the sense of the European Framework Directive. The study at low resolution of subfossil chironomids in a 4-m-long core shows the remarkable stability over the last 2.5 kyrs of the profundal community dominated by a Micropsectra-association until the beginning of the twentieth century, when oxyphilous taxa disappeared. Focusing on this key recent period, a high resolution and multiproxy study of two short cores reveals a progressive evolution of the lake's ecological state. Until AD 1880, Lake Bourget showed low organic matter content in the deep sediments (TOC less than 1%) and a well-oxygenated hypolimnion that allowed the development of a profundal oxyphilous chironomid fauna (Micropsectra-association). Diatom communities were characteristic of oligotrophic conditions. Around AD 1880, a slight increase in the TOC was the first sign of changes in lake conditions. This was followed by a first limited decline in oligotrophic diatom taxa and the disappearance of two oxyphilous chironomid taxa at the beginning of the twentieth century. The 1940s were a major turning point in recent lake history. Diatom assemblages and accumulation of well preserved planktonic organic matter in the sediment provide evidence of strong eutrophication. The absence of profundal chironomid communities reveals permanent hypolimnetic anoxia. From AD 1995 to 2006, the diatom assemblages suggest a reduction in nutrients, and a return to mesotrophic conditions, a result of improved wastewater management. However, no change in hypolimnion benthic conditions has been shown by either the organic matter or the subfossil chironomid profundal community. Our results emphasize the relevance of the paleolimnological approach for the assessment of reference conditions for modern lakes. Before AD 1900, the profundal Micropsectra-association and the Cyclotella dominated diatom community can be considered as the Lake Bourget reference community, which reflects the reference ecological state of the lake.

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.

Elemental (C/N ratios) and isotopic (δ15N(org), δ13C(org)) compositions of sedimentary organic matter from a high-altitude mountain lake (Meidsee, 2661 m a.s.l., Switzerland): Implications for Lateglacial and Holocene Alpine landscape evolution

The deposition of Late Pleistocene and Holocene sediments in the high-altitude lake Meidsee (located at an altitude of 2661 m a.s.l. in the Southwestern Alps) strikingly coincided with global ice-sheet and mountain-glacier decay in the Alpine forelands and the formation of perialpine lakes. Radiocarbon ages of bottom-core sediments point out (pre-) Holocene ice retreat below 2700 m a.s.l., at about 16, 13, 10, and 9 cal. kyr BP. The Meidsee sedimentary record therefore provides information about the high-altitude Alpine landscape evolution since the Late Pleistocene/Holocene deglaciation in the Swiss Southwestern Alps. Prior to 5 cal. kyr BP, the C/N ratio and the isotopic composition of sedimentary organic matter (delta N-15(org), delta C-13(org)) indicate the deposition of algal-derived organic matter with limited input of terrestrial organic matter. The early Holocene and the Holocene climatic optimum (between 7.0 and 5.5 cal. kyr BP) were characterized by low erosion (decreasing magnetic susceptibility, chi) and high content of organic matter (C-org > 13 wt.%), enriched in C-13(org) (>-18 parts per thousand) with a low C/N (similar to 10) ratio, typical of modern algal matter derived from in situ production. During the late Holocene, there was a long-term increasing contribution of terrestrial organic matter into the lake (C/N > 11), with maxima between 2.4 and 0.9 cal. kyr BP. A major environmental change took place 800 years ago, with an abrupt decrease in the relative contribution of terrestrial organic material into the lake compared with aquatic organic material which subsequently largely dominated (C/N drop from 16 to 10). Nonetheless, this event was marked by a rise in soil erosion (chi), in nutrients input (N and P contents) and in anthropogenic lead deposition, suggesting a human disturbance of Alpine ecosystems 800 years ago. Indeed, this time period coincided with the migration of the Walser Alemannic people in the region, who settled at relatively high altitude in the Southwestern Alps for farming and maintaining Alpine passes.

Bioavailability of sinking organic matter in the Blanes canyon and the adjacent open slope (NW Mediterranean Sea)

Submarine canyons are sites of intense energy and material exchange between the shelf and the deep adjacent basins. To test the hypothesis that active submarine canyons represent preferential conduits of available food for the deep-sea benthos, two mooring lines were deployed at 1200 m depth from November 2008 to November 2009 inside the Blanes canyon and on the adjacent open slope (Catalan Margin, NW Mediterranean Sea). We investigated the fluxes, biochemical composition and food quality of sinking organic carbon (OC). OC fluxes in the canyon and the open slope varied among sampling periods, though not onsistently in the two sites. In particular, while in the open slope the highest OC fluxes were observed in August 2009, in the canyon the highest OC fluxes occurred in AprilMay 2009. For almost the entire study period, the OC fluxes in the canyon were significantly higher than those in the open slope, whereas OC contents of sinking particles collected in the open slope were consistently higher than those in the canyon. This result confirms that submarine canyons are effective conveyors of OC to the deep sea. Particles transferred to the deep sea floor through the canyons are predominantly of inorganic origin, significantly higher than that reaching the open slope at a similar water depth. Using multivariate statistical tests, two major clusters of sampling periods were identified: one in the canyon that grouped trap samples collected in December 2008, oncurrently with the occurrence of a major storm at the sea surface, and associated with increased fluxes of nutritionally available particles from the upper shelf. Another cluster grouped samples from both the canyon and the open slope collected in March 2009, concurrently with the occurrence of the seasonal phytoplankton bloom at the sea surface, and associated with increased fluxes of total phytopigments. Our results confirm the key ecological role of submarine canyons for the functioning of deep-sea ecosystems, and highlight the importance of canyons in linking episodic storms and primary production occurring at the sea surface to the deep sea floor.

Reproducing the organic matter model of anthropogenic dark earth of Amazonia and testing the ecotoxicity of functionalized charcoal compounds

The objective of this work was to obtain organic compounds similar to the ones found in the organic matter of anthropogenic dark earth of Amazonia (ADE) using a chemical functionalization procedure on activated charcoal, as well as to determine their ecotoxicity. Based on the study of the organic matter from ADE, an organic model was proposed and an attempt to reproduce it was described. Activated charcoal was oxidized with the use of sodium hypochlorite at different concentrations. Nuclear magnetic resonance was performed to verify if the spectra of the obtained products were similar to the ones of humic acids from ADE. The similarity between spectra indicated that the obtained products were polycondensed aromatic structures with carboxyl groups: a soil amendment that can contribute to soil fertility and to its sustainable use. An ecotoxicological test with Daphnia similis was performed on the more soluble fraction (fulvic acids) of the produced soil amendment. Aryl chloride was formed during the synthesis of the organic compounds from activated charcoal functionalization and partially removed through a purification process. However, it is probable that some aryl chloride remained in the final product, since the ecotoxicological test indicated that the chemical functionalized soil amendment is moderately toxic.

Soil organic matter in fire-affected pastures and in an Araucaria forest in South-Brazilian Leptosols

The objective of this work was to evaluate the distribution pattern and composition of soil organic matter (SOM) and its physical pools of Leptosols periodically affected by fire over the last 100 years in South Brazil. Soil samples at 0-5, 5-10, and 10-15 cm depths were collected from the following environments: native pasture without burning in the last year and grazed with 0.5 livestock per hectare per year (1NB); native pasture without burning in the last 23 years and grazed with 2.0 livestock per hectare per year (23NB); and an Araucaria forest (AF). Physical fractionation was performed with the 0-5 and 5-10 cm soil layers. Soil C and N stocks were determined in the three depths and in the physical pools, and organic matter was characterized by infrared spectroscopy and thermogravimetry. The largest C stocks in all depths and physical pools were found under the AF. The 23NB environment showed the lowest soil C and N stocks at the 5-15 cm depth, which was related to the end of burning and to the higher grazing intensity. The SOM of the occluded light fraction showed a greater chemical recalcitrance in 1NB than in 23NB. Annual pasture burning does not affect soil C stocks up to 15 cm of depth.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

Technical Note: Dissolved organic matter fluorescence a finite mixture approach to deconvolve excitation-emission matrices

The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.