Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

Bioavailability of soil organic carbon and Fe as influenced by forestry practices in a subtropical coastal catchment

Potential impacts of plantation forestry practices on soil organic carbon and Fe available to microorganisms were investigated in a subtropical coastal catchment. The impacts of harvesting or replanting were largely limited to the soil top layer (0–10 cm depth). The thirty-year-old Pinus plantation showed low soil moisture content (Wc) and relatively high levels of soil total organic carbon (TOC). Harvesting and replanting increased soil Wc but reduced TOC levels. Mean dissolved organic carbon (DOC) and microbial biomass carbon (MBC) increased in harvested or replanted soils, but such changes were not statistically significant (P > 0.05). Total dithionite-citrate and aqua regia-extractable Fe did not respond to forestry practices, but acid ammonium oxalate and pyrophosphate-extractable, bioavailable Fe decreased markedly after harvesting or replanting. Numbers of heterotrophic bacteria were significantly correlated with DOC levels (P < 0.05), whereas Fe-reducing bacteria and S-bacteria detected using laboratory cultivation techniques did not show strong correlation with either soil DOC or Fe content.

Soil Carbon Turnover Measurement by Physical Fractionation at a Forest-to-Pasture Chronosequence in the Brazilian Amazon

The effect of conversion from forest-to-pasture upon soil carbon stocks has been intensively discussed, but few studies focus on how this land-use change affects carbon (C) distribution across soil fractions in the Amazon basin. We investigated this in the 20 cm depth along a chronosequence of sites from native forest to three successively older pastures. We performed a physicochemical fractionation of bulk soil samples to better understand the mechanisms by which soil C is stabilized and evaluate the contribution of each C fraction to total soil C. Additionally, we used a two-pool model to estimate the mean residence time (MRT) for the slow and active pool C in each fraction. Soil C increased with conversion from forest-to-pasture in the particulate organic matter (> 250 mu m), microaggregate (53-250 mu m), and d-clay (< 2 mu m) fractions. The microaggregate comprised the highest soil C content after the conversion from forest-to-pasture. The C content of the d-silt fraction decreased with time since conversion to pasture. Forest-derived C remained in all fractions with the highest concentration in the finest fractions, with the largest proportion of forest-derived soil C associated with clay minerals. Results from this work indicate that microaggregate formation is sensitive to changes in management and might serve as an indicator for management-induced soil carbon changes, and the soil C changes in the fractions are dependent on soil texture.

Does physical protection of soil organic matter attenuate temperature sensitivity?

Global climate change may induce accelerated soil organic matter (SOM) decomposition through increased soil temperature, and thus impact the C balance in soils. We hypothesized that compartmentalization of substrates and decomposers in the soil matrix would decrease SOM sensitivity to temperature. We tested our hypothesis with three short-term laboratory incubations with differing physical protection treatments conducted at different temperatures. Overall, CO2 efflux increased with temperature, but responses among physical protection treatments were not consistently different. Similar respiration quotient (Q(10)) values across physical protection treatments did not support our original hypothesis that the largest Q(10) values would be observed in the treatment with the least physical protection. Compartmentalization of substrates and decomposers is known to reduce the decomposability of otherwise labile material, but the hypothesized attenuation of temperature sensitivity was not detected, and thus the sensitivity is probably driven by the thermodynamics of biochemical reactions as expressed by Arrhenius-type equations.

Soil carbon saturation : implications for measurable carbon pool dynamics in long-term incubations

The efficiency of agricultural management practices to store SOC depends on C input level and how far a soil is from its saturation level (i.e. saturation deficit). The C Saturation hypothesis suggests an ultimate soil C stabilization capacity defined by four SOM pools capable of C saturation: (1) non-protected, (2) physically protected, (3) chemically protected and (4) biochemically protected. We tested if C saturation deficit and the amount of added C influenced SOC storage in measurable soil fractions corresponding to the conceptual chemical, physical, biochemical, and non-protected C pools. We added two levels of C-13- labeled residue to soil samples from seven agricultural sites that were either closer to (i.e., A-horizon) or further from (i.e., C-horizon) their C saturation level and incubated them for 2.5 years. Residue-derived C stabilization was, in most sites, directly related to C saturation deficit but mechanisms of C stabilization differed between the chemically and biochemically protected pools. The physically protected C pool showed a varied effect of C saturation deficit on C-13 stabilization, due to opposite behavior of the POM and mineral fractions. We found distinct behavior between unaggregated and aggregated mineral-associated fractions emphasizing the mechanistic difference between the chemically and physically protected C-pools. To accurately predict SOC dynamics and stabilization, C Saturation of soil C pools, particularly the chemically and biochemically protected pools, should be considered. (C) 2008 Elsevier Ltd. All rights reserved.

Experimental warming shows that decomposition temperature sensitivity increases with soil organic matter recalcitrance

Soil C decomposition is sensitive to changes in temperature, and even small increases in temperature may prompt large releases of C from soils. But much of what we know about soil C responses to global change is based on short-term incubation data and model output that implicitly assumes soil C pools are composed of organic matter fractions with uniform temperature sensitivities. In contrast, kinetic theory based on chemical reactions suggests that older, more-resistant C fractions may be more temperature sensitive. Recent research on the subject is inconclusive, indicating that the temperature sensitivity of labile soil organic matter (OM) decomposition could either be greater than, less than, or equivalent to that of resistant soil OM. We incubated soils at constant temperature to deplete them of labile soil OM and then successively assessed the CO2-C efflux in response to warming. We found that the decomposition response to experimental warming early during soil incubation (when more labile C remained) was less than that later when labile C was depleted. These results suggest that the temperature sensitivity of resistant soil OM pools is greater than that for labile soil OM and that global change-driven soil C losses may be greater than previously estimated.

Sensitivity of organic matter decomposition to warming varies with its quality

The relationship between organic matter (OM) lability and temperature sensitivity is disputed, with recent observations suggesting that responses of relatively more resistant OM to increased temperature could be greater than, equivalent to, or less than responses of relatively more labile OM. This lack of clear understanding limits the ability to forecast carbon (C) cycle responses to temperature changes. Here, we derive a novel approach (denoted Q(10-q)) that accounts for changes in OM quality during decomposition and use it to analyze data from three independent sources. Results from new laboratory soil incubations (labile Q(10-q)=2.1 +/- 0.2; more resistant Q(10-q)=3.8 +/- 0.3) and reanalysis of data from other soil incubations reported in the literature (labile Q(10-q)=2.3; more resistant Q(10-q)=3.3) demonstrate that temperature sensitivity of soil OM decomposition increases with decreasing soil OM lability. Analysis of data from a cross-site, field litter bag decomposition study (labile Q(10-q)=3.3 +/- 0.2; resistant Q(10-q)=4.9 +/- 0.2) shows that litter OM follows the same pattern, with greater temperature sensitivity for more resistant litter OM. Furthermore, the initial response of cultivated soils, presumably containing less labile soil OM (Q(10-q)=2.4 +/- 0.3) was greater than that for undisturbed grassland soils (Q(10-q)=1.7 +/- 0.1). Soil C losses estimated using this approach will differ from previous estimates as a function of the magnitude of the temperature increase and the proportion of whole soil OM comprised of compounds sensitive to temperature over that temperature range. It is likely that increased temperature has already prompted release of significant amounts of C to the atmosphere as CO2. Our results indicate that future losses of litter and soil C may be even greater than previously supposed.

Soil management effects on organic carbon in isolated fractions of a Gray Luvisol

Agricultural management affects soil organic matter, which is important for sustainable crop production and as a greenhouse gas sink. Our objective was to determine how tillage, residue management and N fertilization affect organic C in unprotected, and physically, chemically and biochemically protected soil C pools. Samples from Breton, Alberta were fractionated and analysed for organic C content. As in previous report, N fertilization had a positive effect, tillage had a minimal effect, and straw management had no effect on whole-soil organic C. Tillage and straw management did not alter organic C concentrations in the isolated C pools, while N fertilization increased C concentrations in all pools. Compared with a woodlot soil, the cultivated plots had lower total organic C, and the C was redistributed among isolated pools. The free light fraction and coarse particulate organic matter responded positively to C inputs, suggesting that much of the accumulated organic C occurred in an unprotected pool. The easily dispersed silt-sized fraction was the mineral-associated pool most responsive to changes in C inputs, whereas the microaggregate-derived silt-sized fraction best preserved C upon cultivation. These findings suggest that the silt-sized fraction is important for the long-term stabilization of organic matter through both physical occlusion in microaggregates and chemical protection by mineral association.