Impact of soil texture on the distribution of soil organic matter in physical and chemical fractions

Previous research on the protection of soil organic C from decomposition suggests that soil texture affects soil C stocks. However, different pools of soil organic matter (SOM) might be differently related to soil texture. Our objective was to examine how soil texture differentially alters the distribution of organic C within physically and chemically defined pools of unprotected and protected SOM. We collected samples from two soil texture gradients where other variables influencing soil organic C content were held constant. One texture gradient (16-60% clay) was located near Stewart Valley, Saskatchewan, Canada and the other (25-50% clay) near Cygnet, OH. Soils were physically fractionated into coarse- and fine-particulate organic matter (POM), silt- and clay-sized particles within microaggregates, and easily dispersed silt-and clay-sized particles outside of microaggregates. Whole-soil organic C concentration was positively related to silt plus clay content at both sites. We found no relationship between soil texture and unprotected C (coarse- and fine-POM C). Biochemically protected C (nonhydrolyzable C) increased with increasing clay content in whole-soil samples, but the proportion of nonhydrolyzable C within silt- and clay-sized fractions was unchanged. As the amount of silt or clay increased, the amount of C stabilized within easily dispersed and microaggregate-associated silt or clay fractions decreased. Our results suggest that for a given level of C inputs, the relationship between mineral surface area and soil organic matter varies with soil texture for physically and biochemically protected C fractions. Because soil texture acts directly and indirectly on various protection mechanisms, it may not be a universal predictor of whole-soil C content.

Stabilization mechanisms of soil organic matter: Implications for C-saturation of soils

The relationship between soil structure and the ability of soil to stabilize soil organic matter (SOM) is a key element in soil C dynamics that has either been overlooked or treated in a cursory fashion when developing SOM models. The purpose of this paper is to review current knowledge of SOM dynamics within the framework of a newly proposed soil C saturation concept. Initially, we distinguish SOM that is protected against decomposition by various mechanisms from that which is not protected from decomposition. Methods of quantification and characteristics of three SOM pools defined as protected are discussed. Soil organic matter can be: (1) physically stabilized, or protected from decomposition, through microaggregation, or (2) intimate association with silt and clay particles, and (3) can be biochemically stabilized through the formation of recalcitrant SOM compounds. In addition to behavior of each SOM pool, we discuss implications of changes in land management on processes by which SOM compounds undergo protection and release. The characteristics and responses to changes in land use or land management are described for the light fraction (LF) and particulate organic matter (POM). We defined the LF and POM not occluded within microaggregates (53-250 mum sized aggregates as unprotected. Our conclusions are illustrated in a new conceptual SOM model that differs from most SOM models in that the model state variables are measurable SOM pools. We suggest that physicochemical characteristics inherent to soils define the maximum protective capacity of these pools, which limits increases in SOM (i.e. C sequestration) with increased organic residue inputs.

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.

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.

Manipulating double-decker molecules at the liquid-solid interface

We have used a scanning tunneling microscope to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, porphyrinato double-decker molecules at the liquid/solid interface between 1-phenyloctane solvent and graphite. We employed nano-grafting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic double-decker molecules; the overlayer structure is epitaxial on graphite. We have also used nano-grafting to place double-decker molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a scanning tunneling microscope at low bias voltage resulted in the removal of the adsorbed doubledecker molecular layer and substituted the double-decker molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic double-decker molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the double-decker molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular “sliding block puzzle” with cascades of double-decker molecules on the graphite surface.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

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.

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

Halogen bonding between an isoindoline nitroxide and 1,4-diiodotetrafluorobenzene: new tools and tectons for self-assembling organic spin systems

Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which NO.⋅⋅⋅I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems...

Exploiting the 1,2,3-triazolium motif in anion-templated formation of a bromide-selective rotaxane host assembly

Stimulated by the efficacy of copper (I) catalysed Huisgen-type 1,3-dipolar cycloaddition of terminal alkynes and organic azides to generate 1,4-disubstituted 1,2,3-triazole derivatives, the importance of ‘click’ chemistry in the synthesis of organic and biological molecular systems is ever increasing.[1] The mild reaction conditions have also led to this reaction gaining favour in the construction of interlocked molecular architectures.[2-4] In the majority of cases however, the triazole group simply serves as a covalent linkage with no function in the resulting organic molecular framework. More recently a renewed interest has been shown in the transition metal coordination chemistry of triazole ligands.[3, 5, 6] In addition novel aryl macrocyclic and acyclic triazole based oligomers have been shown to recognise halide anions via cooperative triazole C5-H….anion hydrogen bonds.[7] In light of this it is surprising the potential anion binding affinity of the positively charged triazolium motif has not, with one notable exception,[8] been investigated. With the objective of manipulating the unique topological cavities of mechanically bonded molecules for anion recognition purposes, we have developed general methods of using anions to template the formation of interpenetrated and interlocked structures.[9-13] Herein we report the first examples of exploiting the 1,2,3-triazolium group in the anion templated formation of pseudorotaxane and rotaxane assemblies. In an unprecedented discovery the bromide anion is shown to be a superior templating reagent to chloride in the synthesis of a novel triazolium axle containing [2]rotaxane. Furthermore the resulting rotaxane interlocked host system exhibits the rare selectivity preference for bromide over chloride...