Sequential Density Fractionation Research Articles

Dynamics of macroplastics and microplastics formed by biodegradable mulch film in an agricultural field

Conventional plastic mulch brings agronomic and economic benefits to crop production, but a large amount of plastic waste amasses when the mulch is removed from the fields after harvest. Soil-biodegradable plastic mulch (BDM) has emerged as a promising alternative to conventional plastic mulch as it can be tilled into the soil after harvest, thereby alleviating disposal problems. However, direct evidence on complete degradation of biodegradable mulch under natural conditions is still lacking. We quantified the dynamics of macro- (>5 mm) and microplastics (0.1–5 mm in size) in four years after a one-time application of mulch in a field with monoculture maize. The BDM feedstock was polybutyleneadipate-co-terephthalate (PBAT) and polylactic acid (PLA)-based, and both a clear and black BDM were tested. The BDM plastic mulch films degraded into macro- and micoplastics. Macroplastics disappeared 2.5 years after mulch incorporation. We developed a new extraction method for biodegradable microplastics using a sequential density fractionation approach with a H2O and a ZnCl2 solution. Microplastic concentrations in the soil ranged from 350 to 525 particles/kg after 2.5 years, 175 to 250 particles/kg after 3 years, and 50 to 125 particles/kg after 3.5 year following mulch incorporation. This continuous decrease of detectable plastic particle concentrations in soil suggests that BDMs fragment degrade into smaller and smaller particles, which eventually may biodegrade completely. While we cannot ascertain whether persistent and undetectable nanoplastics may form, macro- and microplastics formed from BDM seem to disappear with time.

Accumulation of 137Cs in aggregated organomineral assemblage in pasture soils 8 years after the accident at the Fukushima Daiichi nuclear power plant

Despite the presence of minerals that allow Cs fixation in soils, 137Cs remains available to crops for several years after its deposition, particularly in pasture soils. Larger amounts of organic matter derived from herbage residues are accumulated in pasture soils than in tilled farmland soils. As the above-ground part of herbage crops initially received airborne 137Cs during the accident at Fukushima Daiich nuclear power plant (FDNPP), the organic matter originated from the contaminated herbage should play an important role in the fate of 137Cs in soils. To evaluate the role of organic matter on 137Cs distribution between potentially mobile and immobile fractions, we compared the distribution of 137Cs and stable 133Cs, which are differently associated with organic matter, by sequential extraction and density fractionation. Soil samples were collected 8 years after the accident from Andosols in pasture fields located about 160 km southwest of FDNPP. More than 90% of 137Cs was not extracted even after oxidative digestion of organic matter, suggesting that most 137Cs was strongly associated with soil minerals. Density fractionation results showed that the 137Cs/133Cs ratio was highest in the density fraction of 1.6–1.8 g cm−3, in which organic matter —including fragmented and decomposed plant detritus —was associated with minerals. Mineral-free organic matter, mostly composed of fresh plant detritus (<1.6 g cm−3), had a higher 137Cs/133Cs ratio than that of crops harvested in the same year of soil sampling. Thus, the transfer of 137Cs from soil to plants decreased with cultivation cycles. Our results demonstrate that plant-available 137Cs in pasture soil decreased with aging time, not only through increased 137Cs fixation in mineral-dominated fractions but also through its physical sequestration in aggregates.

Bioenergy production effects on SOM with depth of loblolly pine forests on Paleaquults in southeastern USA

Managed loblolly pine (P. taeda L.) forests comprise a major land-use across the “wood basket” of the southeastern US. Lower coastal plain loblolly pine forests can enhance carbon (C) storage in fast-growing vegetation and soils, representing a significant opportunity to manage these forests for improved soil health through an understanding of soil C and nitrogen (N) storage. Furthermore, these forests have unrealized potential to produce biomass for emerging bioenergy markets. Despite this, very little is known about how intensified management (herbaceous bioenergy production) of these forests influences short-term soil organic C (SOC) and soil organic N (SON) pools in surface and subsurface soil horizons. The field site was located in the Lower Coastal Plain of North Carolina, USA in which trees were planted in bedded (e.g., raised) rows (bed) and intercropped with or without switchgrass (P. virgatum L.) between the bedded rows of trees (interbed). Soils were collected from four depths (0–5, 5–15, 15–30, and 30–45 cm) and two locations (bed and interbed regions) and fractionated into light and heavy mineral-associated SOC and SON pools using a sequential density fractionation technique. Bulk soil SOC and SON concentration as well as C:N ratio decreased with depth for both treatments, while 15N became enriched. Free and occluded lighter fractions (< 1.65 g cm−3) had higher SOC and SON concentration (~45% C and ~ 1.15% N) compared to medium (1.65–2.00 g cm−3) and heavy (> 2.00 g cm−3) fractions. At the 0–5 cm depth in interbeds, SOC and SON were concentrated in the free light fraction (~45%), but transitioned to being concentrated in the heaviest mineral-associated fraction at the 15–30 (~55%) and 30–45 (~70%) cm depth. The 15N analysis of density fractions indicated progressive enrichment with increasing density, suggesting increasing incorporation of microbially-derived products into stable mineral-associated soil organic matter (SOM) pools. In the pine-switchgrass treatment, SOC and SON concentrations were higher in the light and medium fractions in beds and interbeds compared to the pine only treatment, particularly at the 30–45 cm depth. The C:N ratio in the pine-switchgrass treatment was higher compared to the pine only treatment indicating inputs of new plant-derived organic matter. Furthermore, the δ13C stable isotope signature was enriched in both the occluded light fraction (1.65 g cm−3) and the mineral-associated fraction (1.65–1.85 g cm−3). Our results suggest that switchgrass intercropping is contributing to the early buildup of SOM in particulate and mineral-associated SOM pools possibly through additions of new root-derived organic matter and the positive effect on soil microbial activity through priming of microbes.

Evidence linking calcium to increased organo-mineral association in soils

Geochemical indicators are emerging as important predictors of soil organic carbon (SOC) dynamics, but evidence concerning the role of calcium (Ca) is scarce. This study investigates the role of Ca prevalence in SOC accumulation by comparing otherwise similar sites with (CaCO3-bearing) or without carbonates (CaCO3-free). We measured the SOC content and indicators of organic matter quality (C stable isotope composition, expressed as δ13C values, and thermal stability) in bulk soil samples. We then used sequential sonication and density fractionation (DF) to separate two occluded pools from free and mineral-associated SOC. The SOC content, mass, and δ13C values were determined in all the fractions. X-ray photoelectron spectroscopy was used to investigate the surface chemistry of selected fractions. Our hypothesis was that occlusion would be more prevalent at the CaCO3-bearing site due to the influence of Ca on aggregation, inhibiting oxidative transformation, and preserving lower δ13C values. Bulk SOC content was twice as high in the CaCO3-bearing profiles, which also had lower bulk δ13C values, and more occluded SOC. Yet, contrary to our hypothesis, occlusion only accounted for a small proportion of total SOC (< 10%). Instead, it was the heavy fraction (HF), containing mineral-associated organic C, which accounted for the majority of total SOC and for the lower bulk δ13C values. Overall, an increased Ca prevalence was associated with a near-doubling of mineral-associated SOC content. Future investigations should now aim to isolate Ca-mediated complexation processes that increase organo-mineral association and preserve organic matter with lower δ13C values.

Distribution and chemical species of phosphorus across density fractions in Andisols of contrasting mineralogy

Strong control of iron (Fe) and aluminum (Al) phases on soil phosphorus (P) dynamics is well established. How organic and inorganic P forms are associated with Fe and Al phases remains poorly understood, and sequential density fractionation thus allows one to assess the soil continuum from organic-rich particles (< 1.8 g cm−3) to organo-mineral particles (1.8–2.25 g cm−3), and finally to mineral rich particles (> 2.25 g cm−3). We combined the density fractionation approach with wet extraction techniques, 31P NMR spectroscopy and X-ray absorption near-edge structure (XANES) spectroscopy to investigate the distribution and chemical species of P in relation to Fe and Al phases for two Andisols: an allophanic Andisol rich in short-range-order aluminosilicates (silandic) and a non-allophanic Andisol rich in organic matter (OM) and organo-aluminum complexes (aluandic). We fractionated the soils to the density classes of 1.6–1.8, 1.8–2.0, 2.0–2.25, 2.25–2.5, and > 2.5 g cm−3 using the sodium polytungstate solutions. Across five density fractions, inorganic and total P were distributed in low to meso-density fractions (1.6–2.25 g cm−3) where major portions of extractable Fe and Al were found. The major P pool was found in the NaOH extraction step for low- to meso-density ranges (< 2.25 g cm−3), suggesting that Al and Fe (oxyhydr)oxides and aluminosilicates have significant roles in P sorption in allophanic and non-allophanic Andisols. In contrast, the residual P remaining after the sequential extraction was predominant in heavier-density fractions (> 2.25 g cm−3). Molybdate-reactive and total P extracted by NaOH in the density fractions were positively correlated with oxalate extractable Al (Alox) in the allophanic Andisol (r > 0.91) and with pyrophosphate extractable Al (Alp) in the non-allophanic Andisol (r > 0.97), suggesting stronger control of Al phases to P over Fe phases. The non-destructive XANES analysis confirmed that P in both Andisols was associated primarily with Al, not Fe, and suggested the presence of P bound to organo-Al complexes in the non-allophanic Andisol (up to 76% of P in the 1.6–1.8 g cm−3 fraction where Alp is enriched). Solution 31P NMR spectra of NaOH-EDTA soil extracts showed that the primary organic P group was phosphomonoesters that decreased with increasing density in allophanic and non-allophanic Andisols. Myo-inositol hexakisphosphate (IHP) and scyllo-IHP were identified in a density fraction between 1.8 and 2.25 g cm−3 of non-allophanic Andisol. Our study highlights the importance of low- to meso-density fractions in organic and inorganic P reservoirs in Andisols.

Organic carbon preservation promoted by aromatic compound-iron complexes through manure fertilization in red soil

This study was aimed at evaluating the effect of manure fertilization on organo-mineral complexes based on unfertilized (CK) and 5-year manure fertilization (M) in red soils (ultisols). Sequential density fractionation was adopted to obtain particular organic matter (POM, 2.6 (MOM> 2.6)), which were demineralized by hydrofluoric acid (HF). The HF-dissolved organic carbon (OC) was identified as mineral bound OC, and was characterized by comparing the band area of Fourier transform infrared spectroscopy before and after 10% HF demineralization. Manure fertilization significantly increased the OC and nitrogen contents of bulk soil, POM, MOM1.8–2.2, and MOM2.2–2.6, but did not affect MOM> 2.6. About 82.9–86.1% soil OC was retained by MOM1.8–2.2 and MOM2.2–2.6 dominated with iron (Fe) and aluminum oxides and phyllosilicates, in which HF-dissolved OC was significantly positively correlated with poorly crystalline (Feo) (R2 = 0.61, P 2.6 was composed of aromatic C, amide N, and polysaccharides, not being affected by fertilization. Our results suggested that manure fertilization promotes organo-mineral association, particularly for aromatic compound-Fe complexes, contributing to OC preservation in red soils.

Organo-Mineral Interactions Are More Important for Organic Matter Retention in Subsoil Than Topsoil

Decomposing crop residues contribute to soil organic matter (SOM) accrual; however, the factors driving the fate of carbon (C) and nitrogen (N) in soil fractions are still largely unknown, especially the influence of soil mineralogy and autochthonous organic matter concentration. The objectives of this work were (1) to evaluate the retention of C and N from crop residue in the form of occluded and mineral-associated SOM in topsoil (0–20 cm) and subsoil (30–70 cm) previously incubated for 51 days with 13C-15N-labelled corn residues, and (2) to explore if specific minerals preferentially control the retention of residue-derived C and N in topsoil and subsoil. We used topsoil and subsoil having similar texture and mineralogy as proxies for soils being rich (i.e., topsoil) and poor (i.e., subsoil) in autochthonous organic matter. We performed a sequential density fractionation procedure and measured residue-derived C and N in occluded and mineral-associated SOM fractions, and used X-ray diffraction analysis of soil density fractions to investigate their mineralogy. In accordance with our hypothesis, the retention of C and N from crop residue through organo-mineral interactions was greater in subsoil than topsoil. The same minerals were involved in the retention of residue-derived organic matter in topsoil and subsoil, but the residue-derived organic matter was associated with a denser fraction in the subsoil (i.e., 2.5–2.6 g cm−3) than in the topsoil (i.e., 2.3–2.5 g cm−3). In soils and soil horizons with high clay content and reactive minerals, we find that a low SOM concentration leads to the rapid stabilization of C and N from newly added crop residues.

Distinctive Roles of Two Aggregate Binding Agents in Allophanic Andisols: Young Carbon and Poorly-Crystalline Metal Phases with Old Carbon

Interaction of organic matter (OM) with soil mineral components plays a critical role in biophysical organization (aggregate structure) as well as in biogeochemical cycling of major elements. Of the mineral components, poorly-crystalline phases rich in iron (Fe) and aluminum (Al) are highly reactive and thus contribute to both OM stabilization and aggregation. However, the functional relationship among the reactive metal phases, C stability, and aggregation remains elusive. We hypothesized that relatively young C acts as a binding agent to form the aggregates of weak physical stability, whereas the reactive metal phases and older C bound to them contribute to stronger aggregation. Using four surface horizons of Andisols having a gradient of soil C concentration due to decadal OM management, we conducted sequential density fractionation to isolate six fractions (from &lt;1.6 to &gt;2.5 g cm−3) with mechanical shaking, followed by selective dissolution and radiocarbon analysis. After 28 years of no-till with litter compost addition, not only C and N but inorganic materials including the reactive metal phases (pyrophosphate-, oxalate-, and dithionite-extractable metals) showed clear shifts in their concentrations towards lower-density fractions (especially &lt;2.0 g cm−3) on a ground-area basis. This result was explained by the binding of compost-derived OM with soil particles. Major portions of the reactive metal phases in bulk samples were distributed in mid-density fractions (2.0–2.5 g cm−3) largely as sonication-resistant aggregates. Theoretical density calculations, together with depletion in radiocarbon (Δ14C: −82 to −170‰) and lower C:N ratio, implied that the sorptive capacity of the reactive metal phases in these fractions were roughly saturated with pre-existing OM. However, the influx of the compost-derived, modern C into the mid-density fractions detected by the paired-plot comparison suggests decadal C sink in association with the reactive metal phase. Our results supported the concept of aggregate hierarchy and further provided the following new insights. At the high hierarchy level where shaking-resistant aggregates form, soil organo-mineral particles appeared to be under a dynamic equilibrium and the changes in OM input regime controlled (dis)aggregation behavior due to the binding effect of relatively young C. At a lower hierarchy level, the reactive metal phases were bound to N-rich, 14C-depleted OM and together functioned as persistent binding agent. Our study suggests that the recognition of binding agents and aggregate hierarchy level would help to untangle the complex organo-mineral interactions and to better understand soil C stability.

Depth trends of soil organic matter C:N and 15N natural abundance controlled by association with minerals

Plant residues show carbon:nitrogen (C:N) decreases, 15N isotopic enrichment and preferential loss of labile substrates during microbial decay. In soil profiles, strikingly similar patterns of decreasing C:N and 15N isotopic enrichment with increasing depth are well documented. The parallel trend in organic matter composition with soil depth and during plant residue decay has been used as evidence to suggest that organic products accumulate or develop in the subsoil due to increasing intensity of microbially-driven processing, although no studies to date have verified this. Here, by applying sequential density fractionation, specific surface area, oxalate extractable Fe and Al, C:N and δ15N measures with depth to soils with relatively uniform soil mineralogy (Oxisols), climates and vegetation we show that changes in organo-mineral associations drive subsoil C:N and δ15N and C:N depth patterns more than in situ organic matter decay. Our results provide the first direct evidence that soil depth trends could be driven by mineral association instead of in situ processing.

Organic carbon characteristics in density fractions of soils with contrasting mineralogies

This study was aimed to evaluate the role of minerals in the preservation of organic carbon (OC) in different soil types. Sequential density fractionation was done to isolate particulate organic matter (POM, <1.8gcm−3) and mineral associated OM (MOM: 1.8–2.2, 2.2–2.6 and >2.6gcm−3) from four soils, i.e., a Ferralsol, a Luvisol, a Vertisol and a Solonetz. Organic matter (OM) in the density fractions was characterised using diffuse reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and mass spectroscopy in the original states (i.e., without any chemical pre-treatment), and after 6% sodium hypochlorite (NaOCl) and 10% hydrofluoric acid (HF) treatments. The NaOCl oxidation resistant fraction was considered asa relatively stable pool of OC and the HF soluble fraction was presumed as the mineral bound OC. Phyllosilicate-dominated soils, i.e., Vertisol, Luvisol and Solonetz, contained a greater proportion of POM than Fe and Al oxide-dominated Ferralsol. Wider C:N ratio and lower δ13C and δ15N in POM suggest the dominance of labile OC in this fraction and this was also supported by a greater proportion of NaOCl oxidised OC in the same fraction that was enriched with aliphatic C. The sequential density fractionation method effectively isolated OM into three distinct groups in the soils: (i) OM associated with Fe and Al oxides (>1.8gcm−3 in the Ferralsol); (ii) OM associated with phyllosilicates (1.8–2.6gcm−3) and (iii) OM associated with quartz and feldspar (>2.6gcm−3) in the other three soils. Greater oxidation resistance, and more dissolution of OC during the HF treatment in the Fe and Al oxides dominated fractions suggest a greater potential of these minerals to protect OC from oxidative degradation as compared to the phyllosilicates, and quartz and feldspar matrices. OM associated with Fe and Al oxides was predominantly aromatic and carboxylate C. Decreased C:N ratio in the NaOCl oxidation resistant OM and HF soluble OM of phyllosilicates, and quartz and feldspars dominant fractions compared to their untreated fractions indicate a preferred retention of N rich organic compounds by these minerals. OM associated with phyllosilicates was enriched with protonated amide N and aromatic C. Quartz and feldspars associated OM comprised of N containing organic compounds and polysaccharides, although we don’t expect any role of these minerals in their preservation. Our results imply that the abundance and surface properties of minerals in the soil largely control the dynamics of OC and subsequently protect OC from microbial cycling.

Assessing the impact of afforestation on soil organic C sequestration by means of sequential density fractionation.

Afforestation is a prevalent practice carried out for soil recovery and carbon sequestration. Improved understanding of the effects of afforestation on soil organic carbon (SOC) content and dynamics is necessary to identify the particular processes of soil organic matter (SOM) formation and/or decomposition that result from afforestation. To elucidate these mechanisms, we have used a sequential density fractionation technique to identify the transfer mechanisms of forest derived C to soil fractions and investigate the impact of afforestation on SOC sequestration. Surface soil samples from continuous maize crop land (C4) and forest land (C3), which had been established 5, 12 and 25 yr, respectively, on the Northeast China Plain were separated into five density fractions. SOC, nitrogen (N) concentration and δ13C data from the three forests and adjacent cropland were compared. Afforestation decreased SOC concentration in the < 2.5 g cm-3 fractions from 5 yr forest sites, but increased SOC content in the < 2.0 g cm-3 fractions from 25 yr forest sites. Afforestation did not affect soil mass distribution, SOC and N proportional weight distributions across the density fractions. The < 1.8 g cm-3 fractions from 12 and 25 yr forests showed higher C/N and lower δ13C as compared to other fractions. Incorporation of forest litter-derived C occurred from low density (< 1.8 g cm-3) fractions to aggregates of higher density (1.8-2.5 g cm-3) through aggregate recombination and C transport in the pore system of the aggregates. Some forest litter-derived C could transfer from the light fractions or directly diffuse and adsorb onto mineral particles. Results from this study indicate that microaggregate protection and association between organic material and minerals provide major contribution to the SOC sequestration in the afforested soil system.

Nature of soil organo-mineral assemblage examined by sequential density fractionation with and without sonication: Is allophanic soil different?

Organic matter (OM) bound to soil mineral particles (higher-density particles) tends to be more stabilized, enriched in 13C and 15N, and has a lower C:N ratio. Yet how these variations in OM chemistry are linked to the nature of organo-mineral assemblage remains poorly understood, especially in allophanic soils where high amounts of OM are stabilized by interactions with reactive inorganic phases such as short-range-order (SRO) minerals. We thus assessed the extent to which the degree of aggregation and its disruption during fractionation control the distribution and chemistry of the soil organo-mineral particles across six density fractions using a volcanic soil (allophanic Andisol) based on selective dissolution, microscopy (SEM), solid-state 13C NMR spectroscopy and δ13C and δ15N analyses. Intermediate-density fractions (2.0–2.5gcm−3) accounted for 63–86% of organic C and N, 73–93% of pyrophosphate-extractable iron and aluminum (Fep, Alp), and 78–95% of oxalate-extractable metals (Feo, Alo) in the bulk soil sample. While air-drying pretreatment had little effect, sonication during fractionation led to (i) fragmentation of both plant detritus and some of the aggregates of 30–100mm sizes, (ii) release of occluded low-density fraction (<1.6gcm−3) which largely originated from the aggregates of 1.6–2.0gcm−3 density range, and (iii) redistribution of organo-mineral particles (15–16% of total OM and 7–19% of the extractable metals) within the intermediate density fractions. Positive correlation of Alp with C:N ratio and negative correlation of Alp with δ15N among the fractions suggest preferential binding of Alp phase (e.g., organo-Al complexes) to decaying plant detritus. Positive correlation of Alo and Feo with δ15N, together with theoretical density calculations of idealistic organo-mineral association modes, suggests that 15N enrichment may be coupled with OM binding to SRO minerals and with the formation of physically-stable aggregates of micron/submicron sizes in accord with our conceptual model (Asano and Wagai, 2014). The general pattern of 13C and 15N enrichment and C:N decline with increasing particle density remained largely unchanged despite the sonication effects detected, indicating that sonication-resistant organo-mineral assemblages largely control the observed patterns. The similarity in the density-dependent changes of OM chemistry between the studied Andisol and the soils with crystalline clay and metal oxide mineralogies in previous studies strongly suggests a common biogeochemical control which deserves further investigation.

Optimization of method to quantify soil organic matter dynamics and carbon sequestration potential in volcanic ash soils

Volcanic ash-derived soils are important globally for their C sequestration potential and because they are at risk of compaction and degradation due to land use change. Poorly or non-crystalline minerals impart enormous capacity for soils to store and stabilize C, but also unusual chemical and physical properties that make quantifying meaningful soil C pools challenging. Here, we optimize a soil physical fractionation method to effectively assess soil organic matter dynamics in volcanic ash soils by first comparing three common methods for Andisols of the same soil series under three land uses. Components of those methods that (1) effectively isolated C pools of different size and turnover and (2) demonstrated potential sensitivity to land use change were then modified for a final, combined method. The isolation of C pools corresponding to fundamental mechanisms of protection within aggregates and organo-mineral control on the stabilization of C, which often function to the extreme in volcanic ash soils, underlie these modifications. Combined application of ultrasonic energy to disrupt aggregates and the removal of light fractions with sequential high density fractionation successfully isolated multiple C pools that ranged in radiocarbon-based turnover time from 7 to 1,011 year in the surface 0–15 cm of mineral soil in an undisturbed, native forest. Soil C accumulates as a result of high, continuous input that cycles through a transitional (century-scale) organo-mineral pool and then either becomes occluded and protected within aggregates (multiple centuries) or enters a continuum of organo-mineral and non-crystalline mineral-dominated pools (from centuries to millennium-scale). Comparison of relative C pool sizes and C isotope signature among soils from native forest, grazed pasture, and managed Eucalyptus plantation revealed the potential for making accurate, direct measurements of soil C change over time with land use and management change or disturbance regime.

Assimilation and accumulation of C by fungi and bacteria attached to soil density fractions

Soil microorganisms play a key role in soil organic matter (SOM) dynamics, but little is known about the controls affecting the distribution of microbial biomass and their residues in soil. Here, a forested Cambisol topsoil was incubated with 13C-labeled glycine or beech leaves for 12 weeks prior to sequential density fractionation. The incorporation of the 13C label in amino sugars (AS) was used to gain insight into bacterial and fungal assimilation of the substrates. AS derived from glycine or leaves were compared to total AS to investigate how microbial residues and active communities were distributed among soil density fractions.Bacteria slightly dominated leaf C assimilation, while a pronounced fungal dominance was observed for glycine. The glycine-derived AS and original AS were similarly distributed among the soil density fractions, both peaking in microbial aggregates (1.8–2.4 g cm−3). Leaf-derived AS were mostly found in association with the plant debris (<1.65 g cm−3). The ratios of substrate-derived AS C to substrate-derived C increased with soil fraction density for both glycine and leaves. The same pattern was observed with original AS C to soil fraction C ratios. We concluded that bacteria and fungi were most active where the resource was even though their residues accumulate mostly in microbial aggregates (1.8–2.4 g cm−3). We suggest that such accumulation might be attributed to (1) an increasing stabilization efficiency of microbial residues and (2) the progressive SOM transfer, from plant debris to microbial aggregates (1.8–2.4 g cm−3).

Changes to particulate versus mineral-associated soil carbon after 50 years of litter manipulation in forest and prairie experimental ecosystems

Models of ecosystem carbon (C) balance generally assume a strong relationship between NPP, litter inputs, and soil C accumulation, but there is little direct evidence for such a coupled relationship. Using a unique 50-year detrital manipulation experiment in a mixed deciduous forest and in restored prairie grasslands in Wisconsin, combined with sequential density fractionation, isotopic analysis, and short-term incubation, we examined the effects of detrital inputs and removals on soil C stabilization, destabilization, and quality. Both forested sites showed greater decline in bulk soil C content in litter removal plots (55 and 66 %) compared to increases in litter addition plots (27 and 38 % increase in surface soils compared to controls). No accumulation in the mineral fraction C was observed after 50 years of litter addition of the two forested plots, thus increases in the light density fraction pool drove patterns in total C content. Litter removal across both ecosystem types resulted in a decline in both free light fraction and mineral C content, with an overall 51 % decline in mineral-associated carbon in the intermediate (1.85–2.4 g cm−3) density pool; isotopic data suggest that it was preferentially younger C that was lost. In contrast to results from other, but younger litter manipulation sites, there was with no evidence of priming even in soils collected after 28 years of treatment. In prairie soils, aboveground litter exclusion had an effect on C levels similar to that of root exclusion, thus we did not see evidence that root-derived C is more critical to soil C sequestration. There was no clear evidence that soil C quality changed in litter addition plots in the forested sites; δ13C and Δ14C values, and incubation estimates of labile C were similar between control and litter addition soils. C quality appeared to change in litter removal plots; soils with litter excluded had Δ14C values indicative of longer mean residence times, δ13C values indicative of loss of fresh plant-derived C, and decreases in all light fraction C pools, although incubation estimates of labile C did not change. In prairie soils, δ13C values suggest a loss of recent C4-derived soil C in litter removal plots along with significant increases in mean residence time, especially in plots with removal of roots. Our results suggest surface mineral soils may be vulnerable to significant C loss in association with disturbance, land use change, or perhaps even climate change over century–decadal timescales, and also highlight the need for longer-term experimental manipulations to study soil organic matter dynamics.

Organo-mineral interactions in contrasting soils under natural vegetation

Organo-mineral interactions are important for the cycling and preservation of organic carbon (OC) in soils. To understand the role of soil mineral surfaces in organo-mineral interactions, we used a sequential density fractionation procedure to isolate 2.6 g cm-3 density fractions from topsoils (0-10 cm) of contrasting mineralogies. These soils were under natural vegetation of four major Australian soil types - Chromosol, Ferrosol, Sodosol and Vertosol. The soils and their organic matter (OM) contents were found to be partitioned in four distinct pools: i) particulate organic matter 2.6 g cm-3; and iv) Fe oxides dominant >2.0 g cm-3 (in the Ferrosol.) X-ray photoelectron spectroscopy was used to investigate organic C and N bonding environments associated within each density fraction. Mineral pools were shown to be enriched in distinct organic functional groups: phyllosilicate dominant fractions were enriched with oxidized OC species (C-O, C=O, O-C=O) and protonated amide forms; quartz and feldspar dominated fractions were enriched in aliphatic C and protonated amide forms; Fe oxides dominant fractions had the greatest proportions of oxidized OC species and were low in protonated amide forms. The enrichment of different C species was related to the interaction of functional groups with the mineral surfaces. These results demonstrate the potential of mineral surfaces in influencing the chemical composition of OM bound in surfaces reactions and subsequently the stability of OM in organo-mineral interactions.

Study on the influence of crown ether on arsenic behavior during coal pyrolysis

The influence of crown ether on behaviors of arsenic at different temperatures and residence time was investigated during the pyrolysis of Tuanbo (TB) coal. The modes of occurrence of arsenic were determined by sequential chemical extraction, density fractionation and demineralization. The results indicated that at the same temperature and residence time, the arsenic removal adding dibenzo-18-crown-6 was higher than that adding 18-crown-6, and were all higher than that of TB coal during pyrolysis. When temperature was 850 °C and residence time was 30 min, the arsenic removal of TB coal was 30.63%; at the same condition, the arsenic removal while adding 18-crown-6 was 33.21%, higher than that of TB coal; and the arsenic removal while adding dibenzo-18-crown-6 was 67.41%, significantly higher than that of TB coal. From the results, we can see that adding crown ether can improve the arsenic removal during coal pyrolysis, and especially be conducive to the arsenic which is mainly associated with sulfates & monosulfides and that in stable forms.

Organic matter content and features related to associated mineral fractions in an acid, loamy soil

Sorption of soil organic matter on mineral surfaces is now recognized as a major organic carbon (C) stabilization process. To investigate the role of organo‐mineral interactions in carbon‐rich soils, we separated organo‐mineral associations by sequential density fractionation in the top‐ and subsoil of a forest Acrisol (umbrept) from southern France. Fractions were characterized by scanning electron microscopy, X‐ray diffraction, elemental analysis, 13C NMR and δ13C. For each horizon, we isolated five types of association: light organic matter non‐occluded, and occluded in aggregates (&lt;1.9 g cm−3), and microaggregates formed by poorly crystallized mineral phases (1.9–2.2 g cm−3), by phyllosilicates (2.2–2.5 g cm−3) and by primary mineral particles weakly complexed with organic compounds (&gt;2.5 g cm−3). Carbon accumulation in organo‐mineral fractions was correlated with a relative enrichment in hydrophobic compounds (alkyl C or aromatic C). In contrast, the content in nitrogen and carboxylic groups was more constant. Poorly crystalline mineral phases stabilized the largest amount of soil organic matter. We compiled data from previous studies carried out on soils with different mineralogies (n = 20) and found a significant correlation between the δ13C and the C:N ratio of sorbed organic compounds according to the C content of fractions. This general trend is in line with the conceptual model of a zonal structure of soil organic matter sorbed on mineral surfaces. Furthermore, we hypothesized that the accumulation of hydrophilic (O‐alkyl C) and hydrophobic (alkyl C and/or aromatic C) organic compounds on mineral surfaces is favoured by the structural organization of organo‐mineral associations. The same organo‐mineral associations were found in top‐ and subsoils, indicating similar stabilization processes in surface and deeper horizons.

Pedogenic, mineralogical and land-use controls on organic carbon stabilization in two contrasting soils

Organo-mineral complexation in soils is strongly controlled by pedogenesis, but the mechanisms controlling it and its interaction with cultivation are not yet well understood. We compared the mineralogy and quality of organic carbon (C) among organo-mineral fractions from two soils with contrasting pedogenic origin. Sequential density fractionation (SDF; using 1.6, 1.8, 2.1, 2.4 and 2.6 g mL-1 sodium polytungstate solutions) followed by thermal analysis was applied to a Chernozem from Ellerslie, Alberta, and a Luvisol from Breton, Alberta, each under native and cultivated land uses. Similar clay mineralogy suggested that pedogenic controls on organic C stabilization were related to long-term vegetation cover. In addition to large differences in total organic C quantities, bulk soil and isolated fractions showed significant differences in organic C quality. Samples under native vegetation revealed greater organo-mineral complexation at Ellerslie compared with Breton, as expressed by less solubilisation, more organic C recovered in intermediate-density fractions, and exothermic differential scanning calorimetry peak signals associated with more stable forms of organic C. Long-term cultivation resulted in an overall shift to more stable organo-mineral complexes. The proportion of soil C in the 2.1-2.4 g mL-1 fraction increased under cultivation from 21 to 32% in Breton samples, and from 6 to 16% in Ellerslie samples. The quality of inherited pedogenic soil organic C stored in a soil thus appears to determine its response to long-term cultivation.Key words: Cultivation, sequential density fractionation, organic carbon, organic matter, thermal analysis

Sequential density fractionation across soils of contrasting mineralogy: evidence for both microbial- and mineral-controlled soil organic matter stabilization

Sequential density fractionation separated soil particles into “light” predominantly mineral-free organic matter vs. increasingly “heavy” organo-mineral particles in four soils of widely differing mineralogy. With increasing particle density C concentration decreased, implying that the soil organic matter (OM) accumulations were thinner. With thinner accumulations we saw evidence for both an increase in 14C-based mean residence time (MRT) of the OM and a shift from plant to microbial origin.Evidence for the latter included: (1) a decrease in C/N, (2) a decrease in lignin phenols and an increase in their oxidation state, and (3) an increase in δ13C and δ15N. Although bulk-soil OM levels varied substantially across the four soils, trends in OM composition and MRT across the density fractions were similar. In the intermediate density fractions (~1.8–2.6 g cm−3), most of the reactive sites available for interaction with organic molecules were provided by aluminosilicate clays, and OM characteristics were consistent with a layered mode of OM accumulation. With increasing density (lower OM loading) within this range, OM showed evidence of an increasingly microbial origin. We hypothesize that this microbially derived OM was young at the time of attachment to the mineral surfaces but that it persisted due to both binding with mineral surfaces and protection beneath layers of younger, less microbially processed C. As a result of these processes, the OM increased in MRT, oxidation state, and degree of microbial processing in the sequentially denser intermediate fractions. Thus mineral surface chemistry is assumed to play little role in determining OM composition in these intermediate fractions. As the separation density was increased beyond ~2.6 g cm−3, mineralogy shifted markedly: aluminosilicate clays gave way first to light primary minerals including quartz, then at even higher densities to various Fe-bearing primary minerals. Correspondingly, we observed a marked drop in δ15N, a weaker decrease in extent of microbial processing of lignin phenols, and some evidence of a rise in C/N ratio. At the same time, however, 14C-based MRT time continued its increase. The increase in MRT, despite decreases in degree of microbial alteration, suggests that mineral surface composition (especially Fe concentration) plays a strong role in determining OM composition across these two densest fractions.