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.

Soil carbon saturation : evaluation and corroboration by long-term incubations

Although current assessments of agricultural management practices on soil organic C (SOC) dynamics are usually conducted without any explicit consideration of limits to soil C storage, it has been hypothesized that the SOC pool has an upper, or saturation limit with respect to C input levels at steady state. Agricultural management practices that increase C input levels over time produce a new equilibrium soil C content. However, multiple C input level treatments that produce no increase in SOC stocks at equilibrium show that soils have become saturated with respect to C inputs. SOC storage of added C input is a function of how far a soil is from saturation level (saturation deficit) as well as C input level. We tested experimentally if C saturation deficit and varying C input levels influenced soil C stabilization of added C-13 in soils varying in SOC content and physiochemical characteristics. We incubated for 2.5 years soil samples from seven agricultural sites that were closer to (i.e., A-horizon) or further from (i.e., C-horizon) their C saturation limit. At the initiation of the incubations, samples received low or high C input levels of 13 C-labeled wheat straw. We also tested the effect of Ca addition and residue quality on a subset of these soils. We hypothesized that the proportion of C stabilized would be greater in samples with larger C Saturation deficits (i.e., the C- versus A-horizon samples) and that the relative stabilization efficiency (i.e., Delta SCC/Delta C input) would decrease as C input level increased. We found that C saturation deficit influenced the stabilization of added residue at six out of the seven sites and C addition level affected the stabilization of added residue in four sites, corroborating both hypotheses. Increasing Ca availability or decreasing residue quality had no effect on the stabilization of added residue. The amount of new C stabilized was significantly related to C saturation deficit, supporting the hypothesis that C saturation influenced C stabilization at all our sites. Our results suggest that soils with low C contents and degraded lands may have the greatest potential and efficiency to store added C because they are further from their saturation level. (c) 2008 Elsevier Ltd. All rights reserved.

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.

Acid hydrolysis of easily dispersed and microaggregate-derived silt- and clay-sized fractions to isolate resistant soil organic matter

The current paradigm in soil organic matter (SOM) dynamics is that the proportion of biologically resistant SOM will increase when total SOM decreases. Recently, several studies have focused on identifying functional pools of resistant SOM consistent with expected behaviours. Our objective was to combine physical and chemical approaches to isolate and quantify biologically resistant SOM by applying acid hydrolysis treatments to physically isolated silt- and clay-sized soil fractions. Microaggegrate-derived and easily dispersed silt- and clay-sized fractions were isolated from surface soil samples collected from six long-term agricultural experiment sites across North America. These fractions were hydrolysed to quantify the non-hydrolysable fraction, which was hypothesized to represent a functional pool of resistant SOM. Organic C and total N concentrations in the four isolated fractions decreased in the order: native > no-till > conventional-till at all sites. Concentrations of non-hydrolysable C (NHC) and N (NHN) were strongly correlated with initial concentrations, and C hydrolysability was found to be invariant with management treatment. Organic C was less hydrolysable than N, and overall, resistance to acid hydrolysis was greater in the silt-sized fractions compared with the clay-sized fractions. The acid hydrolysis results are inconsistent with the current behaviour of increasing recalcitrance with decreasing SOM content: while %NHN was greater in cultivated soils compared with their native analogues, %NHC did not increase with decreasing total organic C concentrations. The analyses revealed an interaction between biochemical and physical protection mechanisms that acts to preserve SOM in fine mineral fractions, but the inconsistency of the pool size with expected behaviour remains to be fully explained.

Does the acid hydrolysis-incubation method measure meaningful soil organic carbon pools?

The literature was reviewed and analyzed to determine the feasibility of using a combination of acid hydrolysis and CO2-C release during long-term incubation to determine soil organic carbon (SOC) pool sizes and mean residence times (MRTs). Analysis of 1100 data points showed the SOC remaining after hydrolysis with 6 M HCI ranged from 30 to 80% of the total SOC depending on soil type, depth, texture, and management. Nonhydrolyzable carbon (NHC) in conventional till soils represented 48% of SOC; no-till averaged 56%, forest 55%, and grassland 56%. Carbon dates showed an average of 1200 yr greater MRT for the NHC fraction than total SOC. Longterm incubation, involving measurement of CO2 evolution and curve fitting, measured active and slow pools. Active-pool C comprised 2 to 8% of the SOC with MRTs of days to months; the slow pool comprised 45 to 65% of the SOC and had MRTs of 10 to 80 yr. Comparison of field C-14 and (13) C data with hydrolysis-incubation data showed a high correlation between independent techniques across soil types and experiments. There were large differences in MRTs depending on the length of the experiment. Insertion of hydrolysis-incubation derived estimates of active (C-a), slow (C-s), and resistant Pools (C-r) into the DAYCENT model provided estimates of daily field CO2 evolution rates. These were well correlated with field CO2 measurements. Although not without some interpretation problems, acid hydrolysis-laboratory incubation is useful for determining SOC pools and fluxes especially when used in combination with associated measurements.

Spatial variability of soil organic carbon in grasslands: implications for detecting change at different scales

Extensive data used to quantify broad soil C changes (without information about causation), coupled with intensive data used for attribution of changes to specific management practices, could form the basis of an efficient national grassland soil C monitoring network. Based on variability of extensive (USDA/NRCS pedon database) and intensive field-level soil C data, we evaluated the efficacy of future sample collection to detect changes in soil C in grasslands. Potential soil C changes at a range of spatial scales related to changes in grassland management can be verified (alpha=0.1) after 5 years with collection of 34, 224, 501 samples at the county, state, or national scales, respectively. Farm-level analysis indicates that equivalent numbers of cores and distinct groups of cores (microplots) results in lowest soil C coefficients of variation for a variety of ecosystems. Our results suggest that grassland soil C changes can be precisely quantified using current technology at scales ranging from farms to the entire nation. (C) 2001 Elsevier Science Ltd. All rights reserved.

Environmental factors controlling soil respiration in three semiarid ecosystems

Previous research suggests that soil organic C pools may be a feature of semiarid regions that are particularly sensitive to climatic changes. We instituted an 18-mo experiment along an elevation gradient in northern Arizona to evaluate the influence of temperature, moisture, and soil C pool size on soil respiration. Soils, from underneath different free canopy types and interspaces of three semiarid ecosystems, were moved upslope and/or downslope to modify soil climate. Soils moved downslope experienced increased temperature and decreased precipitation, resulting in decreased soil moisture and soil respiration las much as 23 acid 20%, respectively). Soils moved upslope to more mesic, cooler sites had greater soil water content and increased rates of soil respiration las much as 40%), despite decreased temperature. Soil respiration rates normalized for total C were not significantly different within any of the three incubation sites, indicating that under identical climatic conditions, soil respiration is directly related to soil C pool size for the incubated soils. Normalized soil respiration rates between sites differed significantly for all soil types and were always greater for soils incubated under more mesic, but cooler, conditions. Total soil C did not change significantly during the experiment, but estimates suggest that significant portions of the rapidly cycling C pool were lost. While long-term decreases in aboveground and belowground detrital inputs may ultimately be greater than decreased soil respiration, the initial response to increased temperature and decreased precipitation in these systems is a decrease in annual soil C efflux.

The role of sulphates and organic vapours in growth of newly formed particles in a eucalypt forest

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photooxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.

The organic fraction of bubble-generated, accumulation mode Sea Spray Aerosol (SSA)

Recent studies have detected a dominant accumulation mode (~100 nm) in the Sea Spray Aerosol (SSA) number distribution. There is evidence to suggest that particles in this mode are composed primarily of organics. To investigate this hypothesis we conducted experiments on NaCl, artificial SSA and natural SSA particles with a Volatility-Hygroscopicity-Tandem-Differential-Mobility-Analyser (VH-TDMA). NaCl particles were atomiser generated and a bubble generator was constructed to produce artificial and natural SSA particles. Natural seawater samples for use in the bubble generator were collected from biologically active, terrestrially-affected coastal water in Moreton Bay, Australia. Differences in the VH-TDMA-measured volatility curves of artificial and natural SSA particles were used to investigate and quantify the organic fraction of natural SSA particles. Hygroscopic Growth Factor (HGF) data, also obtained by the VH-TDMA, were used to confirm the conclusions drawn from the volatility data. Both datasets indicated that the organic fraction of our natural SSA particles evaporated in the VH-TDMA over the temperature range 170–200°C. The organic volume fraction for 71–77 nm natural SSA particles was 8±6%. Organic volume fraction did not vary significantly with varying water residence time (40 secs to 24 hrs) in the bubble generator or SSA particle diameter in the range 38–173 nm. At room temperature we measured shape- and Kelvin-corrected HGF at 90% RH of 2.46±0.02 for NaCl, 2.35±0.02 for artifical SSA and 2.26±0.02 for natural SSA particles. Overall, these results suggest that the natural accumulation mode SSA particles produced in these experiments contained only a minor organic fraction, which had little effect on hygroscopic growth. Our measurement of 8±6% is an order of magnitude below two previous measurements of the organic fraction in SSA particles of comparable sizes. We stress that our results were obtained using coastal seawater and they can’t necessarily be applied on a regional or global ocean scale. Nevertheless, considering the order of magnitude discrepancy between this and previous studies, further research with independent measurement techniques and a variety of different seawaters is required to better quantify how much organic material is present in accumulation mode SSA.

Widening the gap between measurement and modelling of secondary organic aerosol properties?

The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the subsaturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

Robust tracking control of autonomous underwater vehicles in the presence of disturbance inputs

An autonomous underwater vehicle (AUV) is expected to operate in an ocean in the presence of poorly known disturbance forces and moments. The uncertainties of the environment makes it difficult to apply open-loop control scheme for the motion planning of the vehicle. The objective of this paper is to develop a robust feedback trajectory tracking control scheme for an AUV that can track a prescribed trajectory amidst such disturbances. We solve a general problem of feedback trajectory tracking of an AUV in SE(3). The feedback control scheme is derived using Lyapunov-type analysis. The results obtained from numerical simulations confirm the asymptotic tracking properties of the feedback control law. We apply the feedback control scheme to different mission scenarios, with the disturbances being initial errors in the state of the AUV.

Analysis of the build-up of semi and non volatile organic compounds on urban roads

Vehicular traffic in urban areas may adversely affect urban water quality through the build-up of traffic generated semi and non volatile organic compounds (SVOCs and NVOCs) on road surfaces. The characterisation of the build-up processes is the key to developing mitigation measures for the removal of such pollutants from urban stormwater. An in-depth analysis of the build-up of SVOCs and NVOCs was undertaken in the Gold Coast region in Australia. Principal Component Analysis (PCA) and Multicriteria Decision tools such as PROMETHEE and GAIA were employed to understand the SVOC and NVOC build-up under combined traffic scenarios of low, moderate, and high traffic in different land uses. It was found that congestion in the commercial areas and use of lubricants and motor oils in the industrial areas were the main sources of SVOCs and NVOCs on urban roads, respectively. The contribution from residential areas to the build-up of such pollutants was hardly noticeable. It was also revealed through this investigation that the target SVOCs and NVOCs were mainly attached to particulate fractions of 75 to 300 µm whilst the redistribution of coarse fractions due to vehicle activity mainly occurred in the >300 µm size range. Lastly, under combined traffic scenario, moderate traffic with average daily traffic ranging from 2300 to 5900 and average congestion of 0.47 was found to dominate SVOC and NVOC build-up on roads.

Prediction model of the buildup of volatile organic compounds on urban roads

A model to predict the buildup of mainly traffic-generated volatile organic compounds or VOCs (toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene) on urban road surfaces is presented. The model required three traffic parameters, namely average daily traffic (ADT), volume to capacity ratio (V/C), and surface texture depth (STD), and two chemical parameters, namely total suspended solid (TSS) and total organic carbon (TOC), as predictor variables. Principal component analysis and two phase factor analysis were performed to characterize the model calibration parameters. Traffic congestion was found to be the underlying cause of traffic-related VOC buildup on urban roads. The model calibration was optimized using orthogonal experimental design. Partial least squares regression was used for model prediction. It was found that a better optimized orthogonal design could be achieved by including the latent factors of the data matrix into the design. The model performed fairly accurately for three different land uses as well as five different particle size fractions. The relative prediction errors were 10–40% for the different size fractions and 28–40% for the different land uses while the coefficients of variation of the predicted intersite VOC concentrations were in the range of 25–45% for the different size fractions. Considering the sizes of the data matrices, these coefficients of variation were within the acceptable interlaboratory range for analytes at ppb concentration levels.

Composition and source identification of road deposited pollutants

Road deposited solids are a mix of pollutants originating from a range of anthropogenic sources common to urban land uses and soil inputs from surrounding areas. These particles accumulate potentially toxic pollutants thereby posing a threat to receiving waters. Reliable estimation of sources of particulate pollutants in build-up and quantification of particle composition is important for the development of best management practices for stormwater quality mitigation. The research study analysed build-up pollutants from sixteen different urban road surfaces and soil from four background locations. The road surfaces were selected from residential, industrial and commercial land uses from four suburbs in Gold Coast, Australia. Collected build-up samples were analysed for solids load, organic matter and mineralogy. The soil samples were analysed for mineralogy. Quantitative and qualitative analysis of mineralogical data, along with multivariate data analysis were employed to identify the relative source contributions to road deposited solids. The build-up load on road surfaces in different suburbs showed significant differences due to the nature of anthropogenic activities, road texture depth and antecedent dry period. Analysis revealed that build-up pollutants consists primarily of soil derived minerals (60%) and the remainder is composed of traffic generated pollutants and organic matter. Major mineral components detected were quartz and potential clay forming minerals such as albite, microline, chlorite and muscovite. An average of 40-50% of build-up pollutants by weight was made up of quartz. Comparison of the mineral component of build-up pollutants with background soil samples indicated that the minerals primarily originate from surrounding soils. About 2.2% of build-up pollutants were organic matter which originates largely from plant matter. Traffic related pollutants which are potentially toxic to the receiving water environment represented about 30% of the build-up pollutants at the study sites.

How can soil monitoring networks be used to improve predictions of organic carbon pool dynamics and CO2 fluxes in agricultural soils?

Abstract As regional and continental carbon balances of terrestrial ecosystems become available, it becomes clear that the soils are the largest source of uncertainty. Repeated inventories of soil organic carbon (SOC) organized in soil monitoring networks (SMN) are being implemented in a number of countries. This paper reviews the concepts and design of SMNs in ten countries, and discusses the contribution of such networks to reducing the uncertainty of soil carbon balances. Some SMNs are designed to estimate country-specific land use or management effects on SOC stocks, while others collect soil carbon and ancillary data to provide a nationally consistent assessment of soil carbon condition across the major land-use/soil type combinations. The former use a single sampling campaign of paired sites, while for the latter both systematic (usually grid based) and stratified repeated sampling campaigns (5–10 years interval) are used with densities of one site per 10–1,040 km². For paired sites, multiple samples at each site are taken in order to allow statistical analysis, while for the single sites, composite samples are taken. In both cases, fixed depth increments together with samples for bulk density and stone content are recommended. Samples should be archived to allow for re-measurement purposes using updated techniques. Information on land management, and where possible, land use history should be systematically recorded for each site. A case study of the agricultural frontier in Brazil is presented in which land use effect factors are calculated in order to quantify the CO2 fluxes from national land use/management conversion matrices. Process-based SOC models can be run for the individual points of the SMN, provided detailed land management records are available. These studies are still rare, as most SMNs have been implemented recently or are in progress. Examples from the USA and Belgium show that uncertainties in SOC change range from 1.6–6.5 Mg C ha−1 for the prediction of SOC stock changes on individual sites to 11.72 Mg C ha−1 or 34% of the median SOC change for soil/land use/climate units. For national SOC monitoring, stratified sampling sites appears to be the most straightforward attribution of SOC values to units with similar soil/land use/climate conditions (i.e. a spatially implicit upscaling approach). Keywords Soil monitoring networks - Soil organic carbon - Modeling - Sampling design