Application of scanning calorimetry to estimate soil organic matter loss after fires

The severe heating of soil during wildfires and prescribed burns may result in adverse effects on soil fertility due to organic matter loss. No rapid and reliable procedure exists to evaluate soil organic matter (SOM) losses due to heating. Enthalpy of SOM combustion correlates with organic matter content. Quartz is a ubiquitous mineral in soils and has a remarkably constant composition and reversible α–β phase transition at 575 °C. We suggest that SOM content in heated and unheated soils can be compared using the ratio of SOM combustion enthalpy on heating to the β–α quartz transition enthalpy measured on cooling of the same sample. This eliminates the need to dry and weigh the samples, making possible field applications of the proposed method. The feasibility of using the (ΔH _{comb SOM})/(ΔH _β–α Qz) ratio was established with experiments on soil samples heated in the laboratory and the method was then used for evaluation of SOM loss on two pile burn sites at UC Berkeley’s Blodgett Forest Research Station in Georgetown, California.     

Changes induced in the thermal properties of Galizian soils by the heating in laboratory conditions

The soil properties can be strongly affected by wildfires, causing direct effects on ecosystem productivity and sustainability. These effects depend, among other things, on the soil type and on the temperature reached during the fire. The variations of thermal properties of several Galizian soils heated in an oven in laboratory conditions at different temperatures (200–500 °C) during 15 min have been examined in this study. The measured properties are heat of combustion of soil organic matter, ignition temperature, specific heat and mass loss, determined using DSC 2920 TA Instruments and a TGA 7 Perkin Elmer under dry air gas flow. In agreement with other authors, this study establishes three temperature intervals with different effects on the soil: up to 200 °C, low intensity heating, with no significant changes in thermal properties; between 200 and 350 °C, medium intensity heating, with losses of organic matter up to 50%; and high intensity heating to temperature higher than 350 °C, with harmful effects on the soil organic matter. On the other hand and taking into account that the sampled soils had been affected by forest fires, the variations of thermal soil properties with the laboratory heating temperatures allowed for an estimation of the temperature reached by the soil in the real fire.     

The effect of firesorb as a fire retardant on the thermal properties of a heated soil

The DSC technique was used to characterise under laboratory conditions, the effect of a polymer substance, Firesorb, that tries to be used as a flame retardant in forest fires, over two different Galician soils (NW Spain). Samples of these soils with different doses of this retardant were heated in an oven at 230 and 350°C to simulate medium and high intensity fires, respectively. The effect of the retardant was determined as a result of the comparison between the enthalpy of combustion of the organic matter and the ignition temperature of these subsamples and the corresponding unheated and untreated ones. Both parameters, enthalpy of combustion and ignition temperature, were determined directly from the DSC experiments. The results showed that the effect of the retardant remains clear in heating at 230°C and the content of organic matter of the soil was a determining factor in its quantification. However the effect of the retardant in heating at high temperatures is almost null in both soils.     

Practical application of thermogravimetry in soil science

Properties and compositions of soils originating from different sources usually vary, depending largely on the conditions of soil forming processes and parent materials. Our previous investigations of soils from contrasting localities showed linear correlations between carbon dioxide produced by soil microorganisms and thermal mass losses of air-dried soils recorded using thermogravimetry. The correlations were observed at temperatures corresponding both to moisture evaporation and thermal degradation of soil organic matter. In this work, those soils were combined into one group and the correlation analysis was repeated using both linear and power functions. Whereas the linear dependency between respiration and water evaporation was confirmed; the connection between respiration and thermal decay of organic matter appeared to follow power function. These findings indicate the existence of fundamental unifying principles in soil forming processes, in terms of water binding and clay-dependent organic carbon sequestration, notwithstanding the fact, that soils develop under contrasting conditions. Additional soils were analyzed in order to test the applicability of obtained models for prediction of soil respiration using thermogravimetry. The results indicate a promising potential of this method mainly for soils originating from areas undisturbed by anthropogenic activity.     

Thermochemical Study of 1-Methylhydantoin

Using static bomb combustion calorimetry, the combustion energy of 1-methylhydantoin was obtained, from which the standard molar enthalpy of formation of the crystalline phase at T = 298.15 K of the compound studied was calculated. Through thermogravimetry, mass loss rates were measured as a function of temperature, from which the enthalpy of vaporization was calculated. Additionally, some properties of fusion were determined by differential scanning calorimetry, such as enthalpy and temperature. Adding the enthalpy of fusion to the enthalpy of vaporization, the enthalpy of sublimation of the compound was obtained at T = 298.15 K. By combining the enthalpy of formation of the compound in crystalline phase with its enthalpy of sublimation, the respective standard molar enthalpy of formation in the gas phase was calculated. On the other hand, the results obtained in the present work were compared with those of other derivatives of hydantoin, with which the effect of the change of some substituents in the base heterocyclic ring was evaluated.     

Effect of the soil uses on their thermal stability

Differential scanning calorimetry was applied to assess on seasonally soil organic matter changes. Soils were collected in two sites located in Viveiro (Galicia, Spain). One of them has been used as arable land and the other one was under pinewood. Soil samples were seasonally collected during a year. The heat of combustion and the ignition temperature of the soil organic matter were calculated by analyzing the thermograms obtained by differential scanning calorimetry. The shape and the maximum and end temperatures of the two exothermic peaks observed in the thermograms, yielded information about the relations between the labile and recalcitrant pools, and hence information about carbon stabilization degree in both soils.     

Sublimation measurements of pharmaceutical compounds by isothermal thermogravivletry

Procedures for measuring sublimation rates of pharmaceutical compounds by isothermal thermogravimetry are discussed. Experimental data was obtained using the Mettler TA4000 thermogravimetric system. The sublimation rate is measured directly from the mean weight loss per unit time in the linear region of the monitored TG profile at a set isothermal temperature. This data when fitted to the Arrhenius equation yields the sublimation enthalpy. For the benzoic acid reference, the enthalpy so calculated is 99% of the value obtained from direct vacuum TG measurements. Thermal degradation in the solid state or pre-melting can effect a departure from the characteristic linear mass loss-time sublimative profile. Data pertaining to several established Merck drugs is discussed. Examples where loss of residual solvent, onset of thermal degradation and pre-melting phenomena affect the measurement, are presented.     

Fractionated combustion analysis of carbon in forest soils — new possibilities for the analysis and characterization of different soils

The fractionated combustion analysis of carbon allows the sequential analysis of the total organic carbon (TOC), total inorganic carbon (TIC) and total carbon (TC) fractions in forest soils. Magnesium carbonate and calcium carbonate of the inorganic carbon fraction can also be detected separately. Soils from various forest stands cause different combustion characteristics of the organic carbon fraction, also depending on the soil profile depth. This automatic combustion technique is suitable to characterize the organic carbon fraction of different soil types.     

Interrelations between soil respiration and its thermal stability

Biological transformation of organic matter in soil is a crucial factor affecting the global carbon cycle. In order to understand these complex processes, soils must be investigated by a combination of various methods. This study compares the dynamics of biological mineralization of soil organic matter (SOM) determined via CO₂ evolution during an 80-day laboratory incubation with their thermo-oxidative stability determined by thermogravimetry (TG). Thirty-three soil samples, originating from a wide range of geological and vegetation conditions from various German national parks were studied. The results showed a correlation between the amount and rate of respired CO₂ and thermal mass losses of air-dried, conditioned soils occurring around 100?°C with linear coefficients of determination up to R ²?=?0.85. Further, correlation of soil respiration with thermal mass losses around 260?°C confirmed previous observations. The comparison of TG profiles from incubated and non-incubated soils underlined the importance of thermal mass losses in these two temperature intervals. Incubated soils had reduced thermal mass losses above 240?°C and conversely an increased mass loss at 100?C120?°C. Furthermore, the accurate determination of soil properties by TG such as soil organic carbon content was confirmed, and it was shown that it can be applied to a wider range of carbon contents as was previously thought. It was concluded that results of thermal analysis could be a helpful starting point for estimation of soil respiration and for development of methods revealing processes in soils.     

Practical application of thermogravimetry in soil science

Soil samples collected in South America, North America and West Siberia were measured by thermogravimetry to verify the connection between mass losses and soil respiration represented by the rate and amount of carbon dioxide measured under laboratory conditions. It was demonstrated that linear correlation between those parameters is a common feature for soils originating from different climatic and geographic regions. Significant coefficients of determination were observed in temperature areas corresponding to the moisture evaporation and degradation of soil organic matter (SOM). It was concluded that the correlations are the consequences of soil-forming processes mediated by microorganisms over a long time period. The comparison of experimental data with earlier results showed that disturbance of those processes causes the decrease in observed correlations. The subtraction of thermal mass losses of incubated and non-incubated soils revealed the change in water holding character in all samples, which was ascribed to the transformation of SOM and its water-holding properties during the incubation. In contrast, the changes in thermal mass losses above 200 °C showed that this area reflects the specificity of biological transformation of each soil sample. Further, applied approach and obtained results indicate the necessity of very gentle soil sample preparation and especially gentle air drying to get comparable results about intrinsic soils’ features in different regions.     

Application of pyrolysis-gas chromatography/mass spectrometry to study changes in the organic matter of macro- and microaggregates of a Mediterranean soil upon heating

The heating effect on the soil organic matter (SOM) of a Mediterranean soil was studied in two fractions (macro- and microaggregates) and in two environments (soil under canopy of Quercus coccifera and bare soil between plants). Samples were heated under laboratory conditions at different temperatures (220, 380 and 500°C) to establish their effects on the SOM quality and quantity by comparison with unheated control samples (25°C). The SOM content in the soil under canopy was higher than in the bare one and in the microaggregate fractions than in the macroaggregate ones. Increasing temperatures caused, in general, the decrease of SOM content in both soils as well as in both aggregate classes. The quality of SOM was determined after extraction with 0.1 M NaOH and analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Obtained pyrolysates were characterized by the presence of polyphenols and other aromatic pyrolysis products (lipids, polysaccharides, proteins and lignin derivatives). Some of the products in these control samples, and furthermore the presence of black carbon (BC) markers (e.g. benzene, pyridine and toluene), confirmed the occurrence of past wildfires in the study zone. The composition of the SOM extracted from the soils heated at 220°C, was quite similar to that obtained from unheated soils. The products derived from polysaccharides and lignin, and some coming from polyphenols, were not detected in the pyrolysates of the soil heated at 380 and 500°C.     

Oxidation kinetics of timahdit and tarfaya moroccan oil shales

Organic matter evolution and kinetics of combustion of Tarfaya and Timahdit oil shales have been examined by thermogravimetry (TG) and by differential thermal analysis (DTA). An agreement is observed between both techniques where it was found that combustion of organic matter occurs in two steps. Kissinger's method applied on experimental results gives an activation energy of the same magnitude for the first step of both oil shales (103 kJ mol^–1) whereas the second is 148 kJ mol^–1 for Timahdit and 118 kJ mol^–1 for Tarfaya.The changes in specific surface area during thermal combustion of Timahdit and Tarfaya oil shales have been studied by thermogravimetric gas sorption balance and correlated with experimental results obtained on TG/DTA in air. For Timahdit oil shale oxidation products, specific surface areas calculated from nitrogen adsorption data shows a slight increase during the temperature domain of 280 to 430°C and after this temperature, they increase sharply. However, data obtained with Tarfaya oil shales shows a significant increase at the temperature of maximum oxidation of the first stage of combustion of organic matter.This revised version was published online in November 2005 with corrections to the Cover Date.     

Interpretation of the Metabolic Enthalpy Change, ΔHmet,Calculated for Microbial Growth Reactions in Soils

The microcalorimetric method was used to calculate the metabolic enthalpy change per mol of glucose degraded by soil microorganisms, ΔH _met. This parameter has been calculated by microcalorimetry for many organic, inorganic and biochemical reactions, but there is only some information about its quantification for microbial growth reactions in soils. Values of ΔH _met were calculated for different soil samples collected in Galicia (Spain) and Campinas (Săo Paolo, Brazil). Exponential microbial growth was stimulated in all soil samples by the addition of glucose and power-time curves were recorded. Results showed changes in the values of ΔH _met calculated for all the soil samples, suggesting a dependence of this value with the microbial growth rate constant, with the percentage of growth, with the initial number of microorganisms of soil samples, with the quantity of glucose added and with the strain of bacteria growing in soil. The interpretation of variations of ΔH _met provides important qualitative and quantitative information. It reports data that allow to interpret from a qualitative point of view, the increase in biomass as a consequence of the degradation of the organic matter in soil, to understand changes in the percentages of soil organic matter and to know if the microbial population growing in differential soil samples is homogeneous. Therefore, to report that value would be very important in ecological studies, but beforehand, it is necessary to solve some problems that can appear in the experiments done to make the quantification . This revised version was published online in August 2006 with corrections to the Cover Date.     

Applications of stable isotope ratio mass spectrometry in cattle dung carbon cycling studies

Understanding the fate of dung carbon (C) in soils is challenging due to the ubiquitous presence of the plant‐derived organic matter (OM), the source material from which both dung‐derived OM and soil organic matter (SOM) predominantly originate. A better understanding of the fate of specific components of this substantial source of OM, and thereby its contribution to C cycling in terrestrial ecosystems, can only be achieved through the use of labelled dung treatments. In this short review, we consider analytical approaches using bulk and compound‐specific stable carbon isotope analysis that have been utilised to explore the fate of dung‐derived C in soils. Bulk stable carbon isotope analyses are now used routinely to explore OM matter cycling in soils, and have shown that up to 20% of applied dung C may be incorporated into the surface soil horizons several weeks after application, with up to 8% remaining in the soil profile after one year. However, whole soil δ¹³C values represent the average of a wide range of organic components with varying δ¹³C values and mean residence times in soils. Several stable ¹³C isotope ratio mass spectrometric methods have been developed to qualify and quantify different fractions of OM in soils and other complex matrices. In particular, thermogravimetry‐differential scanning calorimetry‐isotope ratio mass spectrometry (TG‐DSC‐IRMS) and gas chromatography‐combustion‐IRMS (GC‐C‐IRMS) analyses have been applied to determine the incorporation and turnover of polymeric plant cell wall materials from C₄ dung into C₃ grassland soils using natural abundance ¹³C isotope labelling. Both approaches showed that fluxes of C derived from polysaccharides, i.e. as cellulose or monosaccharide components, were more similar to the behaviour of bulk dung C in soil than lignin. However, lignin and its 4‐hydroxypropanoid monomers were unexpectedly dynamic in soil. These findings provide further evidence for emerging themes in biogeochemical investigations of soil OM dynamics that challenge perceived concepts of recalcitrance of C pools in soils, which may have profound implications for the assessment of the potential of agricultural soils to influence terrestrial C sinks. Copyright © 2010 John Wiley & Sons, Ltd.     

Use of 13C to monitor soil organic matter transformations caused by a simulated forest fire

Soil organic matter (SOM) transformations caused by heating were analyzed using the stable carbon isotope (13)C as a tracer to follow C mineralization dynamics and C transfers between different organic compartments. A (13)C-labelled soil, obtained by incorporation of (13)C-enriched Lolium perenne phytomass into a pine forest soil, was heated for 10 min at 385 degrees C to reproduce conditions typical of a forest fire and changes in total C content, potential C mineralization activity and C distribution between the different soil organic fractions were determined. Changes caused by heating on the potential soil C mineralization, determined by laboratory aerobic incubation, reveal alterations to the SOM biodegradability; some stabilized SOM showed an increase in biodegradability, whereas less stabilized SOM became more resistant to microorganisms. Chemical fractionations of SOM allowed us to monitor changes in its composition. As a consequence of heating, the less polymerized humic fractions were the most strongly affected, with the total disappearance of fulvic acids. A significant increase in the quantity and degree of polymerization of the humic acids at the expense of other more (13)C-enriched substances was also found. Finally, a large decrease in humin was observed, its solubilizable part disappearing completely, probably as a consequence of the incorporation of the byproducts into the free organic matter fraction.     

Zn adsorption by different fractions of Galician soils

To evaluate the contribution of organic matter, oxides, and clay fraction to Zn adsorption in six soils from Galicia (Spain), after soil characterization, adsorption isotherms were obtained by adding nine solutions containing between 20 and 500 mg L(-1) concentrations of Zn(NO(3))(2). Distribution coefficients were obtained from the data of adsorption isotherms. Zn adsorption isotherms corresponding to untreated soil and to the organic matter removed samples and organic matter and oxides removed samples were compared with curves pattern and adjusted to Langmuir and Freundlich empirical models. Untreated soils described L-curves whereas when soils were deprived of any component, the curves described were S-type. Distribution coefficients allowed knowing the Zn adsorption capacity of the untreated soil, and of the organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Zn adsorption as long as soil pH is near neutrality. At acid pH, the oxides are the main component that affects Zn adsorption, although to a much smaller extent than the organic matter near neutral conditions. So soil pH is the main soil factor that determines Zn adsorption, before any other soil property.     

聚氯乙烯燃烧特性及HCl的生成机理

采用热重法对聚氯乙烯（ＰＶＣ）的燃烧过程进行了研究,探讨阳聚氯乙烯燃烧科技司,并由它们的微分热重曲线计算出的反应动力学参数及影响反应常数的因素进行了研究。同时,考察了恒速升温和快速升温过程ＨＣＩ的生成特性。结果表明,ＰＶＣ的燃烧机理是由三个过程决定的,可用三个一级反应表示。ＰＶＣ的燃烧过程的第一阶段为脱氯阶段。第二阶段的活化能和指前因子明显低于第一和一阶段。此阶段为挥发分释放阶段。升温速率的增加导     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

Standard enthalpies of formation of transition metal (cobalt, nickel, and zinc) complex salts with an organic ligand 5-aminotetrazol-2-ylacetohydrazide (ATH-2) were obtained by combustion and solution calorimetry. The enthalpy of combustion of the ligand was determined using combustion calorimetry and the standard enthalpy of formation of the ligand was calculated. For calculations by reaction calorimetry, a thermochemical cycle was developed that allows determination of the standard enthalpy of formation of complex salts. The enthalpies of solution of the ligand and transition metal complex salts in water and in 0.1 M hydrochloric acid were determined. The data obtained allow calculations of the enthalpies of salts formation and the enthalpies of three new complex ions. The enthalpies of position isomerization in different compounds were analyzed.     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

The combined use of combustion and solution calorimetry was proposed as a method for determining the standard enthalpy of formation of the complex salts of transition metals, viz., cobalt(II), nickel(II), and zinc, with the organic ligand (5-aminotetrazol-1-yl)acethydrazide. The enthalpies of solution in water and in a 0.1 M solution of hydrochloric acid were measured for the complex salts and ligand. The enthalpy of combustion of the ligand was determined by the combustion calorimetry method, and its standard enthalpy of formation was calculated. The thermochemical cycle was developed for determining the standard enthalpy of formation of the complex salts. The reliable values of the enthalpies of formation of the salts in the standard states were obtained, and the enthalpies of formation of the earlier unknown complex ions were determined.