Sorption and desorption of non-ionic herbicides onto particulate organic matter from surface soils under different land uses

In vegetative filter strips used to intercept pesticides present in run‐off, particulate organic matter derived from the vegetation plays an important function in pesticide sorption processes, because it accumulates at the soil surface and quickly responds to changes in land use. Two herbicides with contrasted properties: isoproturon, moderately hydrophobic (log K_ow= 2.5), diflufenican, strongly hydrophobic (log K_ow= 4.9), and isopropylaniline, a metabolite of isoproturon, were used to characterize the sorption and desorption properties of POM originating from soils under three different land uses: a cropped plot under conventional wheat/maize rotation, an adjacent 10‐year‐old grassed strip and a nearby 80‐year‐old oak/chestnut forest. Chemical structural composition information obtained from solid‐state ¹³C CPMAS NMR and estimation of hydrophobicity from contact angle measurements were used to explain the different sorption capacities of POM according to their size and origins. Sorption of isoproturon and diflufenican increased with hydrophobicity of POM, which was greater in the forest soil. Aromaticity of POM was positively correlated to sorption coefficients (K_oc). Desorption of the more hydrophobic compounds, diflufenican and isopropylaniline was weak for all POM fractions, regardless of their origin and size. On the other hand, desorption of isoproturon depended on land use and POM characteristics. The sorption capacities of POM were not only controlled by their chemical composition, but also by their size, due to a greater number of sorptive sites related to a greater surface area with decreasing particle‐size.     

Carbon storage in loess derived surface soils from Central Germany: Influence of mineral phase variables

The influence of the soil mineral phase on organic matter storage was studied in loess derived surface soils of Central Germany. The seven soils were developed to different genetic stages. The carbon content of the bulk soils ranged from 8.7 to 19.7 g kg^—1. Clay mineralogy was confirmed to be constant, with illite contents > 80 %. Both, specific surface area (SSA, BET‐N₂‐method) and cation exchange capacity (CEC) of bulk soils after carbon removal were better predictors of carbon content than clay content or dithionite‐extractable iron. SSA explained 55 % and CEC 54 % of the variation in carbon content. The carbon loadings of the soils were between 0.57 and 1.06 mg C m^—2, and therefore in the ”︁monolayer equivalent” (ME) level. The increase in SSA after carbon removal (ΔSSA) was significantly and positively related to carbon content (r² = 0.77). Together with CEC of carbon‐free samples, ΔSSA explained 90 % of the variation in carbon content. Clay (< 2 μm) and fine silt fractions (2—6.3 μm) contained 68—82 % of the bulk soil organic carbon. A significantly positive relationship between carbon content in the clay fraction and in the bulk soil was observed (r² = 0.95). The carbon pools of the clay and fine silt fractions were characterized by differences in C/N ratio, δ¹³C ratio, and enrichment factors for carbon and nitrogen. Organic matter in clay fractions seems to be more altered by microbes than organic matter in fine silt fractions. The results imply that organic matter accumulates in the fractions of smallest size and highest surface area, apparently intimately associated with the mineral phase. The amount of cations adhering to the mineral surface and the size of a certain and specific part of the surface area (ΔSSA) are the mineral phase properties which affect the content of the organic carbon in loess derived arable surface soils in Central Germany most. There is no monolayer of organic matter on the soil surfaces even if carbon loadings are in the ME level.     

Mineral surfaces and soil organic matter

The organic carbon content of soil is positively related to the specific surface area (SSA), but large amounts of organic matter in soil result in reduced SSA as determined by applying the Brunauer–Emmett–Teller (BET) equation to the adsorption of N₂. To elucidate some of the controlling mechanisms of this relation, we determined the SSA and the enthalpy of N₂ adsorption of separates with a density > 1.6 g cm^?3 from 196 mineral horizons of forest soils before and after removal of organic matter with NaOCl. Likewise, we investigated these characteristics before and after sorption of increasing amounts of organic matter to four mineral soil samples, oxides (amorphous Al(OH)₃, gibbsite, ferrihydrite, goethite, haematite), and phyllosilicates (kaolinite, illite). Sorption of organic matter reduced the SSA, depending on the amount sorbed and the type of mineral. The reduction in SSA decreased at larger organic matter loadings. The SSA of the mineral soils was positively related to the content of Fe oxyhydroxides and negatively related to the content of organic C. The strong reduction in SSA at small loadings was due primarily to the decrease in the micropores to which N₂ was accessible. This suggests preferential sorption of organic matter at reactive sites in or at the mouths of micropores during the initial sorption and attachment to less reactive sites at increasing loadings. The exponential decrease of the heat of gas adsorption with the surface loading points also to a filling or clogging of micropores at early stages of organic matter accumulation. Desorption induced a small recovery of the total SSA but not of the micropore surface area. Destruction of organic matter increased the SSA of all soil samples. The SSA of the uncovered mineral matrix related strongly to the amounts of Fe oxyhydroxides and the clay. Normalized to C removed, the increase in SSA was small in topsoils and illuvial horizons of Podzols rich in C and large for the subsoils containing little C. This suggests that micropores preferentially associate with organic matter, especially at small loadings. The coverage of the surface of the soil mineral matrix as calculated from the SSA before and after destruction of organic matter was correlated only with depth, and the relation appeared to be linear. We conclude that mineralogy is the primary control of the relation between surface area and sorption of organic matter within same soil compartments (i.e. horizons). But at the scale of complete profiles, the surface accumulation and stabilization of organic matter is additionally determined by its input.     

Sorption of copper (II) and sulphate to different biochars before and after composting with farmyard manure

Biochar application has been suggested for reducing toxic levels of metals in contaminated soils and enhancing nutrient retention in agro‐ecosystems. We studied sorption of copper (Cu(II)) and sulphate‐sulphur (SO₄‐S) to charcoal, gasification coke and flash‐pyrolysis biochar in order to relate sorption to char properties. Furthermore, we investigated the effect of composting of charcoal and gasification coke on sorptive properties. Langmuir sorption affinity coefficients for Cu(II) for non‐composted biochars increased in the order flash‐pyrolysis char < charcoal < gasification coke. The sorption capacity for Cu(II) of the chars decreased in the order gasification coke (629 mg kg^?1) > flash‐pyrolysis char (196 mg kg^?1) > charcoal (56 mg kg^?1). Composting significantly increased the sorption affinity coefficient approximately by a factor of 5 for charcoal (up to 1.1 l mg^?1) and by a factor of 3–4 for gasification coke (up to 3.2 l mg^?1). Whereas Cu(II) sorption to gasification coke (composted or not) was largely irreversible, sorption to flash‐pyrolysis char and charcoal showed higher reversibility. Relationships between Cu(II) sorption and biochar properties such as cation exchange capacity, specific surface area or aromaticity suggest that sorption was largely determined by complexation with organic matter. Sorption of SO₄‐S was negligible by non‐composted and composted biochars. Composted gasification coke might be suited to reducing toxic Cu(II) concentrations in contaminated soils. Composted charcoal can potentially improve Cu(II) retention in a plant available form in acidic, sandy soils with small organic matter contents. Transient effects of biochars on soil pH can over‐ride the influence of sorption to biochars on concentrations of trace elements in soil solution and their availability to plants.     

Sorptive stabilization of organic matter by microporous goethite: sorption into small pores vs. surface complexation

Stabilization of organic matter (OM) by sorption to minerals is thought to be due to (i) sorption into small pores (Ø < 50 nm) that prevents hydrolytic enzymes approaching and decomposing the organic substrate or (ii) reduced availability of organic molecules after formation of strong multiple bonds by complexation of organic ligands at mineral surfaces. We tested these two potential mechanisms by studying the binding of dissolved OM to microporous goethite (α‐FeOOH). The size of organic molecules dissolved prior to and after equilibration with goethite was determined using atomic force microscopy (AFM). The goethite–OM complexes were analysed for bulk and surface elemental composition (by X‐ray photoelectron spectroscopy, XPS), specific surface area (SSA) and mesopore and micropore volumes (by N₂ adsorption/desorption), by scanning electron microscopy (SEM), and by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The absolute density of goethite–OM complexes was determined by gas pycnometry and the sorbed OM’s apparent density was calculated by assuming no major changes in the volumes of the goethite upon sorption of OM. The stability of the OM–mineral interactions was tested in desorption experiments and by treatment with NaOCl. Surface accumulation of OM by sorption decreased the N₂‐accessible SSA of the goethite, mostly because micropores (Ø < 2 nm) were rendered inaccessible to N₂. The decrease in accessibility of micropores was most pronounced at small surface OM concentrations. The majority of dissolved organic molecules detected with AFM prior to interaction with goethite were globular with a diameter of 4–10 nm, the rest were mainly linear, 20–100 nm long and 4–8 nm thick. After contact with goethite, the latter type of molecules dominated, which suggests preferential sorption of globular molecules. Their size exceeded or equalled the size of micropores and small mesopores (Ø < 10 nm) and so sorption therein is unlikely. Also, the changes in volumes of pores with a size of 2–50 nm were smaller than the estimated volume of the OM sorbed. The apparent density of sorbed OM always exceeded that of the freeze‐dried OM and was largest at small surface concentrations. DRIFT spectroscopy showed that most carboxyl groups at the goethite surface were in their complexed form. The proportion of complexed carboxyl groups dropped at larger surface concentrations, parallel to the decrease in micropore volume. Thus, micropores seem to favour the formation of multiple complex bonds per molecule. Scanning electron microscopy showed that at small surface concentrations, OM coated the goethite crystals and crystallites tightly, while at larger surface concentrations bulky accumulations of OM were more abundant. Even strongly desorbing reagents such as NaOH and Na pyrophosphate released only part of the sorbed OM. Treatment with NaOCl removed mainly bulky accumulations of OM; the OM tightly bound to goethite crystals was hardly affected by NaOCl. We conclude that molecules tightly bound via multiple complex bonds, probably at the mouths of small pores, are barely desorbable and resist the attack of chemical reagents and probably also of enzymes.     

Millimetre‐scale distribution of organic matter composition at intact biopore and crack surfaces

Structured subsoil horizons are characterized by biopores and shrinkage cracks, which may serve as preferential flow paths. The surfaces of cracks and biopores may be coated by clay‐organic material. The spatially‐distributed organic matter (OM) composition at such structural surfaces was studied at the millimetre scale using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in the mid‐infrared range (MIR). Intact biopores such as earthworm burrows and root channels, and crack surfaces of nine subsoil horizons were analysed. The samples were from arable and forest Luvisols, one Regosol, one Stagnosol and Cambisols developed from loess, till, mudstone and limestone. For better comparison between soils, the DRIFT signal intensities were corrected for the particle‐size effects. The OM was characterized by the ratio between alkyl‐ (C–H) and carbonyl (C=O) functional groups (C–H/C=O), which represent an index of the potential wettability (PWI) of the OM. The PWI was larger for biopores than for crack surfaces and the soil matrix, indicating a smaller potential wettability of OM at biopore surfaces. The millimetre‐scale spatial variability of OM was especially large for the surfaces of root channels. Samples from till‐derived Luvisols had smaller PWI (with greater potential wettability than surfaces from loess‐derived Luvisols) than other soil types. The mean PWI of the arable Luvisol crack surfaces was less than that of the forest Luvisol samples. The results suggest that the spatial distribution of OM properties at intact structural surfaces may be important for describing sorption and mass transfer processes during preferential flow.     

Evolution of surface properties and organic matter stabilisation in podzolic B horizons as assessed by nitrogen and phosphate sorption

In podzolic B horizons illuviated Al, Fe and organic matter (OM) increase with the ongoing of the pedogenic process. Depending on OM load on mineral surfaces, modifications of the soil surface properties are expected and may influence OM stabilisation. The proportion of labile organic pools should thus vary depending on the type of podzolic horizon. In this work, we selected B horizons at increasing intensity of podzolisation, evaluated the labile OM pools through oxidation with 2 % NaClO and characterised surface properties with N₂ and phosphate sorption. Before and after oxidation, we assessed the NaOH-extractable OM fractions. Oxidation was more effective on the least polar organic compounds and led to an increase in the fulvic to humic acid ratio. Specific surface area (SSA) increased after oxidation only in the least podzolised horizons, while selectively preserved OM induced a decrease in SSA in the more developed Bs, Bsm and Bhs. Phosphate sorption induced a release of OM and always decreased after oxidation, although variations in P affinity for the surfaces were observed. The effect of oxidation on surface parameters pointed to a specific association between organics and minerals that changed during soil development. At the very beginning of podzolisation, the dominant forms seemed related to organo-metallic complexes with little interaction with surfaces. With Bs development, weak interactions between mineral surfaces and OM appeared, while at a later stage OM differentiated into bulky structures and tightly bound, rigid ones, with extremely low N₂ accessibility. The latter were not sensitive to low concentration NaClO while the former were easily oxidised.     

Effect of Ionic Strength and Index Cation on the Sorption of Phenanthrene

Sorption characteristics of phenanthrene were studied in batch equilibrium experiments with 32 Australian soils that varied widely in physicochemical properties. Sorption of phenanthrene varied widely among the soils and was generally nonlinear, with the nonlinearity index (n) of the Freundlich isotherm varying from 0.62 to 1.01. Simple regression analyses revealed that total organic carbon (TOC) accounts for about 68 % of the variation in the partition coefficient (K′ _f ) for sorption among the soils at an equilibrium concentration (C _e ) of 0.05 mg/L. The organic carbon normalized distribution coefficient (K _OC ), varied considerably between soils with >70 % of the variance of logK _OC being accounted for by logTOC, clay and log dissolved organic carbon (DOC). These results show that the phenanthrene C _e is influenced by both TOC as well as the DOC in soil suspensions. The effects of ionic strength (IS) and index cation were investigated using four contrasting soils. Results show that with an increase in IS from 0.03 to 0.15 M sorption of phenanthrene generally increased in CaCl₂ background solutions, whereas the effect was less significant and variable in NaCl background solutions. Sorption of phenanthrene was slightly higher at low IS (0.03 M) with Na⁺ as index cation compared with that of Ca²⁺, whereas an opposite trend was observed at higher IS (0.15 M). For two soils high in TOC, the flocculation of endogenous DOC in the presence of Ca²⁺ reduced the influence of background electrolyte and resulted in a more linear sorption isotherm as well as higher sorption capacity. This trend was more significant with Ca²⁺ relative to Na⁺.     

Soil organic carbon and its sorptive preservation in central Germany

Soils are increasingly viewed as a potential sink for atmospheric carbon. However, their use to meet CO₂ emission reductions is problematic for there are knowledge gaps regarding the mechanisms involved in the sequestration of organic carbon (OC). There is evidence which suggests that OC concentrations are controlled by the mineralogy and related specific surface area (SSA) of a given soil. The goal of this study was to examine the importance of sorptive mechanisms on OC stabilization. The objectives were (i) to determine the SSA, clay mineralogy and dithionite‐ and oxalate‐extractable Fe and Al concentrations of several soils, and (ii) to analyse how these variables are related to OC concentrations. Five soils were sampled and analysed: two Umbrisols, a Stagnic Acrisol, an Anthrosol/Vertisol/Gleysol‐Chernozem and a Gleysol (FAO terminology), all located in Hesse, Germany. Oxalate‐extractable Fe and Al were found to be the best predictors of OC concentrations in the soils examined. Specific surface area correlated significantly with the OC content of the B and C horizons of one Umbrisol and the entire profile of the Anthrosol/Vertisol/Gleysol‐Chernozem. The relationship between SSA and OC concentrations is likely to be restricted to certain soils and might be a product of the sorptive capacity of Fe and Al oxides. We can assume that the available mineral surface area on oxides is a limiting factor in terms of a soil's capacity to sequester organic carbon. As such, attention should be paid to soil mineralogy and how this might limit the use of soils as a sink for atmospheric CO₂.     

Adsorption of phosphate and organic matter on metal (hydr)oxides in arable and forest soil: a mechanistic modelling study

Phosphate (PO₄) and organic matter (OM) compete for adsorption to metal (hydr)oxides. Our objective was to quantify the effect of OM on PO₄ solubility in forest and arable soil by desorption experiments and surface complexation (SC) modelling. We sampled different types of soil along an age gradient (≈50–2500 years) and from different depths (0–80 cm). The soil types are calcareous and cover a range of soil organic carbon (SOC) contents (5.6–43.5 g kg^?1), PO₄ contents (0.2–5.9 mmol kg^?1) and water‐soluble PO₄ concentrations (0.03–13.4 µm ). Assuming that PO₄ concentrations are controlled by desorption, PO₄ concentrations were expected to correlate with the PO₄ loading on metal‐(hydr)oxide surfaces. However, we show that the PO₄ loading alone is a poor predictor of PO₄ solubility because its solubility increases with increasing SOC content. These data were explained by SC modelling, which shows a decrease in the apparent adsorption affinity of PO₄ with increasing OM loading on to the metal (hydr)oxides. As a consequence, if the competition with OM is disregarded in SC modelling, it results in underestimation of the PO₄ concentration by several orders of magnitude. For forest soil, predicted OM loadings increase slightly with increasing soil age. For arable soil, however, OM loadings were much smaller, which we explain by the replacement of PO₄ with OM. Overall, adsorption interactions strongly affect PO₄ solubility and levels of OM and PO₄ stabilization in soil.     

Influence of organic matter on selenite sorption by Andosols

Abstract

The influence of soil organic matter on selenite sorption was investigated in the selenite adsorption capacity and the surface particle charge change by ligand exchange reaction using the hydrogen peroxide (H₂O₂) treatment and the ignition treatment of two Andosols. The removal of organic carbon (C) in soils accelerated selenite sorption, implying that organic matter of soils had negative influence on the selenite adsorption on the soils. Positive charge decrease on soil particles, concomitant proton consumption, and release of silicon (Si), sulfate (SO₄ ^2‐), and organic C were observed in selenite sorption by the soils. The development of surface particle negative charge with selenite sorption was smaller in the H₂O₂‐treated soil than in the original soils and was scarcely observed in the ignition‐treated soil. It can be assumed that the increase of negative charge by selenite sorption was attributed to new negative sites borne by released insoluble organic matter and negative charge development directly by selenite sorption was small.     

Sorption of cadmium by complexes of kaolinite with humic acid

Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.     

活化过硫酸钠氧化土壤对挥发性有机污染物吸附特性的影响

活化过硫酸钠(Sodium persulfate,SPS)氧化技术是一种新型的土壤修复技术。为了更科学地评价化学氧化处理后土壤的环境风险,本文通过亚铁离子活化过硫酸钠法对有机质(Organic matter,OM)含量存在显著差别的两种土壤进行氧化处理,比较了活化过硫酸钠氧化前后两种土壤样品对3种挥发性有机污染物的吸附特性。结果表明,亚铁活化的SPS能够氧化土壤中腐殖酸和胡敏素类的有机质。对OM含量较高的1号土,SPS氧化对有机质的去除率为71.9%。而对OM含量较低的2号土,SPS氧化对有机质的去除率为49.9%。1号土样对3种挥发性有机物的吸附以分配作用为主,氧化后的1号土样对3种物质的吸附机制不变,但吸附量有所增加;2号土样对3种挥发性有机污染物的吸附有一定的非线性,而氧化后的2号土样对3种物质的吸附线性特征增强。吸附数据用对数形式的Freundlich方程拟合得到分配系数lg Kf值,比较有机碳标化后的分配系数lg Kfoc,氧化后的土壤有机质对3种挥发性有机污染物的吸附特性有所提高。分析表明,SPS氧化了有机质中较多的极性组分(如羧基及羟基等),从而使处理后的土壤中有机质的非极性增强,强化了对非极性化合物的吸附。     

Microbial respiration activities related to sequentially separated, particulate and water-soluble organic matter fractions from arable and forest topsoils

This study aimed to reveal differences in the relevance of particulate as well as water-soluble organic matter (OM) fractions from topsoils to the easily biodegradable soil organic matter (SOM). We selected eight paired sites with quite different soil types and soil properties. For each of these sites, we took samples from adjacent arable and forest topsoils. Physically uncomplexed, macro-, and micro-aggregate-occluded organic particle, as well as water-soluble OM fractions were sequentially separated by a combination of electrostatic attraction, ultrasonic treatment, density separation, sieving, and water extraction. The easily biodegradable SOM of the topsoil samples was determined by measuring microbial respiration during a short-term incubation experiment (OC_R). The organic carbon (OC) contents separated by i) the physically uncomplexed water-soluble OM, ii) the macro-, and iii) the micro-aggregate-occluded organic particle as well as water-soluble OM fractions were significantly correlated with OC_R. The correlation coefficients vary between 0.54 and 0.65 suggesting differences in the relevance of these OM fractions to the easily biodegradable SOM. The strongest correlation to OC_R was detected for the OC content separated by the physically uncomplexed water-soluble OM indicating the most distinct relation to the easily biodegradable SOM. This was found to be independent from land use or soil properties.     

Micropore characteristics of organic matter pools in cemented and non‐cemented podzolic horizons

In Podzols, organic matter (OM) is stabilized mainly by interaction with minerals, as a direct consequence of pedogenic processes. Metal–organic associations strongly affect OM surface features, particularly microporosity. Cemented ortstein horizons (CM) may form during podzolization, accompanied by a spatial arrangement of OM on mineral surfaces, which differs from that in non‐cemented horizons (N‐CM). To investigate the metal–organic associations and their changes during pedogenesis, we selected both N‐CM and CM podzolic horizons, isolated NaClO‐resistant OM and compared the specific surface area (SSA) before and after OM oxidation. The SSA was assessed by using N₂, to detect the pores in the range of micropores (< 2 nm) and mesopores (2–50 nm), and CO₂, to measure a smaller microporosity (< 0.5 nm), which is not accessible to N₂. Only the N‐CM samples showed the typical increase in N₂‐SSA after the removal of labile OM, while a decrease was found in all CM horizons. The CO₂‐SSA revealed a large number of small micropores characterizing OM, both before and after oxidation. The smallest micropore classes (< 0.5 nm) were, however, more abundant in NaClO‐resistant OM, which had therefore a larger number of N₂‐inaccessible surfaces than the labile pool. The N₂‐SSA data thus indicated a more homogeneous coverage of mineral surfaces by stabilized OM in CM samples. Because of the abundance of small micropores, OM in these podzolic B horizons had extremely large CO₂‐SSA values (about 800 m² g^?1), with sharp differences between the NaClO‐labile OM (290–380 m² g^?1) and the NaClO‐stabilized pool (1380–1860 m² g^?1), thus indicating very reactive illuvial organic materials.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Assessment of three vermicomposts as organic amendments used to enhance diuron sorption in soils with low organic carbon content

Vermicomposts from the wine and distillery industry containing spent grape marc (V1), biosolid vinasse (V2) and alperujo (V3) from the olive‐oil industry were investigated as organic amendments to a sandy and a clay soil with low organic carbon (OC) contents (≤1%). The sorption‐desorption process was studied in batch experiments using diuron as a non‐ionic herbicide model. The effect of soil and vermicompost characteristics, the solution's ionic strength and incubation time of amended soils on the sorption process was studied. The addition of vermicompost changed soil properties and enhanced sorption capacity by two‐ to four‐fold. The K_oc variability showed that exogenous OC composition influenced diuron sorption. Vermicompost V1, which had the largest OC and lignin content, recorded the largest sorption increment. Vermicompost V3, which had the greatest dissolved organic carbon content and a high degree of humification, made the smallest contribution to sorption. Sorption was also dependent on extraneous calcium in the solution. The incubation of amended soils reduced diuron sorption efficiency except with V3. Pyrolysis‐gas chromatography (Py‐GC) analysis was a useful tool to characterize the vermicomposts and to understand the variation of diuron sorption constants after vermicompost incubation. This research encourages the use of vermicompost from agro‐industrial wastes as a sustainable means to minimize the side effects of neutral herbicides.     

Stabilization of dissolved organic matter by sorption to the mineral soil

The main process by which dissolved organic matter (DOM) is retained in forest soils is likely to be sorption in the mineral horizons that adds to stabilized organic matter (OM) pools. The objectives of this study were to determine the extent of degradation of sorbed OM and to investigate changes in its composition during degradation. DOM of different origins was sorbed to a subsoil and incubated for 1 year. We quantified mineralized C by frequent CO₂ measurements in the headspace of the incubation vessels and calculated mean residence times by a double exponential model. Mineralization of C of the corresponding DOM in solution was used as a control to estimate the extent of DOM stabilization by sorption. Changes in the composition of sorbed OM during the incubation were studied by spectroscopic (UV, fluorescence) and isotope (¹³C, ¹⁴C) measurements after hot-water extraction of OM.The fraction of sorbed organic C mineralized during the incubation was only one-third to one-sixth of that mineralized in solution. The mean residence time of the most stable OM sample was estimated to increase from 28 years in solution to 91 years after sorption. For highly degradable DOM samples, the portion of stable C calculated by a double exponential model nearly doubled upon sorption. With less degradable DOM the stability increased by only 20% after sorption. Therefore, the increase in stability due to sorption is large for labile DOM high in carbohydrates and relatively small for stable DOM high in aromatic and complex molecules. Nevertheless, in terms of stability the rank order of OM types after sorption was the same as in solution. Furthermore, the extent of sorption of recalcitrant compounds was much larger than sorption of labile compounds. Thus, sorptive stabilization of this stable DOM sample was four times larger than for the labile ones. We conclude that stabilization of OM by sorption depends on the intrinsic stability of organic compounds sorbed. We propose that the main stabilization processes are selective sorption of intrinsically stable compounds and strong chemical bonds to the mineral soil and/or a physical inaccessibility of OM to microorganisms. The UV, fluorescence and ¹³C measurements indicated that aromatic and complex compounds, probably derived from lignin, were preferentially stabilized by sorption of DOM. The ¹³C and ¹⁴C data showed that degradation of the indigenous OM in the mineral soil decreased after sorption of DOM. We estimated DOM sorption stabilizes about 24 Mg C ha⁻¹ highlighting the importance of sorption for accumulation and preservation of OM in soil.     

Interaction of minerals,organic matter,and microorganisms during biogeochemical interface formation as shown by a series of artificial soil experiments

Our understanding of the interactions between minerals, organic matter, and microorganisms at so-called biogeochemical interfaces in soil is still hampered by the inherent complexity of these systems. Artificial soil maturation experiments can help to bridge a gap in complexity between simple abiotic sorption experiments and larger-scale field experiments. By controlling other soil-forming factors, the effect of a particular variable can be identified in a simplified system. Here, we review the findings of a series of artificial soil incubation experiments with the aim of revealing general trends and conclusions. The artificial soils were designed to determine the effect of mineral composition and charcoal presence on the development of abiotic and biotic soil properties during maturation. In particular, the development of soil aggregates, organic matter (OM) composition and turnover, sorption properties, and the establishment of microbial community composition and function were considered. The main objectives of the research were to determine (1) how surface properties and sorption of chemicals modify biogeochemical interfaces; (2) how much time is required to form aggregates from mixtures of pure minerals, OM, and a microbial inoculum; and (3) how the presence of different mineral and charcoal surfaces affects aggregation, OM turnover, and the development of microbial community composition.