Effects of ozonation on soil organic matter of contaminated soil containing residual oil

Purpose  

Ozonation has been shown to be a feasible method for removal of organic pollutants resistant to biodegradation in contaminated soils. However, little is known about the impact of ozonation on soil organic matter (SOM). This study was conducted to investigate the change in SOM characteristics and the consequent change in sequestration of contaminants in soil during ozonation.     

Fractionation of copper and cadmium and their binding with soil organic matter in a contaminated soil amended with organic materials

Purpose  

The contamination of agricultural soils by heavy metals is a worldwide problem. Organic amendments can be used for the immobilization and binding of heavy metal ions in soils by complexation, adsorption, and precipitation. A field trial was carried out to evaluate the influence of some low-cost organic materials such as rice straw (RS), green manure (GM), and pig manure (PM) on the distribution of Cu and Cd and the retention of these metals by organic matter fractions in heavy metal-polluted soils.     

Kinetics of added organic matter decomposition in a Mediterranean sandy soil

Carbon mineralization kinetics of 17 organic materials were studied in a Mediterranean sandy soil. These added organic matters (AOM) used in the organic fertilizer industry differed in their origin and composition: plant residues from the agri-food industry, animal wastes, manures (plant and animal origin), composts at different composting times and organic fertilizers. The mixtures AOM-soils were incubated under aerobic conditions at 28°C during 6 months. Soil moisture was maintained at 75% water holding capacity and respired-CO₂ was regularly trapped into alkali media in closed chambers, then checked by HCl titration. Analyses of CO₂ were performed in triplicate at 17 sampling occasions. The mineralized AOM fraction (MAOMF) varied according to the AOM origin: from 12–33% of added C for composts, to 65–90% for animal-originated AOM, with many intermediate patterns for plant-originated AOM.Seven decomposition models from the literature were fitted to actual MAOMF: (a) three consecutive models with two 1st-order-kinetic compartments and three parameters (m1, humification; m2, exchange; m3, decomposition), (b) three parallel models (m4, with two compartments and three parameters; m8, a 1st-order plus 0-order model with three parameters; m5, a three-compartment model with four parameters), and (c) m7, a model with one 2nd-order-kinetic compartment and two parameters. Additionally, m6, a simplified version of m5 was proposed. Models m2 and m7 did not match with actual data or gave a poor fit. By the correlation parameters, the most simple model m4 was chosen instead of the consecutive models m1 and m3. Residual sums of squares were always greater—but not significantly—in m8 than in m4, which confirmed the superiority of the models with two 1st-order compartments against 1st-order plus 0-order models for incubation times higher than 100 days. Model m5 (most of its parameters being not correlated) gave the best predictions of our data. The proposed m6 version gave predictions with similar precision as m4 and appeared powerful with only two parameters (very labile and stable fractions of the AOM). A compromise between the precision of the predictions and the simplicity of the formulae allowed the recommendation of the well-known m4 model, and above all the simpler m6 model.     

Abiotic solubilization of soil organic matter,a less-seen aspect of dissolved organic matter production

Dissolved organic matter (DOM) is a small but reactive pool of the soil organic matter (SOM) that contributes to soil dynamics including the intermediary pool spanning labile to resistant SOM fractions. The solubilization of SOM (DOM production) is commonly attributed to both microbially driven and physico-chemically mediated processes, yet the extent to which these processes control DOM production is highly debated. We conducted a series of experiments using ¹³C-ryegrass residue or its extract (¹³C-ryegrass-DOM) separately under sterile and non-sterile conditions to demonstrate the importance of DOM production from microbial and physico-chemical processes. Soils with similar properties but differing in parent material were used to test the influence of mineralogy on DOM production. To test the role of the source of C for DOM production, one set of soils was leached frequently with ¹³C-ryegrass-DOM and in the other set of soils ¹³C-ryegrass residue was incorporated at the beginning of the experiment into the soil and soils were leached frequently with 0.01 mol L⁻¹ CaCl₂ solution. Leaching events for both treatments occurred at 12-d intervals over a 90-day period. The amount of dissolved organic C and N (DOC and DON) leached from residue-amended soils were consistently more than 3 times higher in sterile than non-sterile soils, decreasing with the time. Despite changes in the concentration of DOC and DON and the production of CO₂, the proportion of DOC derived from the ¹³C-ryegrass residue was largely constant during the experiment (regardless of microbial activity), with the majority (about 70%) of the DOM originating from native SOM. In ¹³C-residue-DOM treatments, after successive leaching events and regardless of the sterility conditions i) the native SOM consistently supplied at least 10% of the total leached DOM, and ii) the contribution of native SOM to DOM was 2–2.9 times greater in ¹³C-residue-DOM amended soils than control soils, suggesting the role of desorption and exchange reactions in DOM production in presence of fresh DOM input. The contribution of the native SOM to DOM resulted in higher aromaticity and humification index. Our results suggest that physico-chemical processes (e.g. exchange or dissolution reactions) can primarily control DOM production. However, microbial activity affects SOM solubilization indirectly through DOM turnover.     

Remediation of a sandy soil artificially contaminated with copper using a polyacrylate polymer

Abstract. We investigated whether a Na-K polyacrylate polymer could be used to remediate a sandy soil artificially contaminated with copper. An experiment, carried out in solution culture, showed that ionic copper was rapidly trapped within the polymer to a maximum content of c. 190mg Cu g ^-1 dry polymer, the proportion needed for chelation of each copper ion by four carboxylic groups present in the polymer chains. Cu-EDTA was not retained by the polymer. Growth of perennial rygrass in 10 kg pots was stimulated in the gel-amended soil, and even in the pots with the highest levels of copper, growth was much less impaired than in pots without polymer. Copper concentrations of the shoot.; were smaller in the plants cultivated in the amended soil. Water extractable copper was considerably reduced in the contaminated gel-amended soil and polymer particles removed from the soil were shown to contain high levels of copper.     

Impact of surfactant and dissolved organic matter on uptake of atrazine in maize and its mobility in soil

Journal of Soils and Sediments - The purposes of this study were to investigate the activation and transport of atrazine in the presence of dissolved organic matter (DOM) and the surfactant (Triton...     

有机物质种类对污染土壤铜形态及活性的影响

本文试验研究了几种有机物质对冶炼厂附近污染土壤中铜形态及其活性的影响 .结果表明 ,有机物质添加后对土壤铜化学形态与活性的影响进程较为迅速 ,半个月内就有明显的表现 :不同类型有机物质都对土壤铜的化学活性有控制作用 ,但控制效果因有机物质种类而异 ,且与有机物质在土壤中腐解转化有关 .     

Effect of CaCl2 on the kinetics of dissolved organic matter release from a sandy soil�

The dissolution of organic matter in soil is of fundamental relevance for the fate of organic contaminants associated with organic matter and for the microbial availability of organic matter. In this study, the kinetics of soil organic matter (SOM) dissolution from a sandy forest soil was investigated under different electrolyte conditions, using a continuous extraction method. The mathematical analysis of the concentration signal obtained from extractions with constant flow rates and after sudden flow rate changes showed that the dissolution of SOM is diffusion limited. The dissolution rate was lower during extraction with 0.01 M CaCl₂. The reaction on sudden flow rate changes was slower when extracting with 0.01 M CaCl₂ as compared to water, and the mechanism was different. These observations were explained by a gel phase developing in the swelling SOM. The lower dissolution rates found for extractions with 0.01 M CaCl₂ could indicate a more stable gel structure in the presence Ca²⁺. The development of the gel phase may be influenced by mechanical strain due to increased flow rates.     

水溶性有机物在土壤中的化学行为及其对环境的影响

水溶性有机物(Dissolved organic matter,DOM)是能够溶解于水的有机化合物的统称。尽管目前对于陆地生态系统中DOM的研究尚不完善,对其性质、组成和分类方法等问题的看法还没有达成一致,但现有研究结果已经表明DOM是一种十分活跃的重要化学组分。DOM进入土壤后将发生吸附、解吸、迁移、转化等一系列化学过程,进而对土壤及环境产生一系列重要影响:一方面,DOM可以与土壤胶体结合,形成有机无机结合体,从而改善土壤性质,DOM还可以通过其自身的分解产生养分离子,从而提高土壤肥力;另一方面,DOM也可能亲合土壤中原来与土壤胶体结合的养分,使之与DOM一起进入土壤溶液,从而增加土壤中养分离子被淋失的风险,并造成土壤养分的损失以及水体的富营养化,DOM还有可能活化土壤中重金属离子,增加土壤中重金属离子的毒性,并使土壤中的重金属离子向地下水迁移。由于其对土壤和环境的多种效应,水溶性有机物近年来已经逐渐成为土壤学、环境科学、生态学等学科的研究热点之一。     

不同氮肥处理对污染红壤中铜有效性的影响

通过室内培养试验,发现不同氮肥处理对污染红壤中铜有效性有显著影响。在培养前期(0~15 d),施用尿素显著降低了红壤水溶态铜和有效态铜含量,而施用硫酸铵和硝酸钙则显著提高了水溶态铜含量,且硝酸钙的作用显著大于硫酸铵,但这两种氮肥对红壤有效态铜含量影响较小;培养60 d后,尿素对该红壤两种形态铜的抑制效应逐渐转为正效应,且硫酸铵的促进作用更为显著;硝酸钙对红壤两种形态铜的促进作用不如尿素。氮肥的施用量对两种形态铜也具有显著影响。同一施氮水平下,水溶态铜含量和有效态铜含量在不同氮肥处理间均达显著差异(硫酸铵>尿素>硝酸钙)。不同氮肥影响红壤铜有效性的主要机制是土壤pH的变化,红壤水溶态铜和有效态铜含量均与pH呈极显著负相关。     

Effect of polar-dissolved organic matter fractions on the mobility of prometryne in soil

Purpose  

Using two fractions of dissolved organic matter (DOM) with different polarity, we carried out the experiments with standard batch equilibration, soil column leaching, and soil thin layer chromatography to investigate the behavior of the herbicide prometryne in soils. The purpose of the study was to: (1) separate DOM into hydrophilic matter and hydrophobic acid forms and characterize their chemical properties; (2) analyze interaction between the DOM fractions and prometryne in soils.     

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.     

沙地土壤有机质与土壤水动力学参数的关系

试验测定了不同有机质含量的沙地土壤饱和导水率、水分特征曲线及一些水分常数,研究分析了沙地土壤有机质含量与水动力学参数的关系以及有机质影响沙地土壤水分运动的机理。结果表明沙地土壤有机质含量与几个水分常数均呈极显著线性相关,土壤水吸力相同时有机质含量越高,土壤含水量也越大;土壤有机质含量和<0.01mm物理性粘粒与土壤饱和导水率呈极显著线性负相关,沙地土壤有机质是影响水分动力学参数最重要的因子之一。     

Effect of dissolved organic matter on the precipitation and mobility of the lead compound chloropyromorphite in solution

Chloropyromorphite, CPM, Pb₅(PO₄)₃Cl, is one of the most insoluble lead minerals. Inducing the formation of CPM by application of phosphate to soil has been suggested for immobilizing Pb at contaminated sites. We have examined the effect of organic matter on the completeness and the rate of CPM precipitation and on the particle size and the mobility of CPM crystals. We did experiments at pH 3–7 and with varying content of dissolved organic C, 0–72 mg C l^?1, mixing Pb(NO₃)₂ (0.5 mmol l^?1) and phosphate (2 mmol l^?1) solutions. The organic matter was extracted from samples of a forest floor. The precipitates were identified by X‐ray diffraction, and their size and shape were analysed by scanning electron microscopy and by photon correlation spectroscopy. The presence of organic matter in the solutions did not affect the mass of CPM that precipitated within 30 minutes at pH 5, 6 and 7. At pH 3 and 4, however, organic matter strongly inhibited the precipitation. The particles were markedly smaller in solutions containing organic matter than without at all pHs and passed through water‐saturated columns filled with calcareous sand, whereas the precipitates from the carbon‐free solutions did not. We suggest that the organic matter blocked the surfaces of crystal seeds and impaired crystal growth. At high pH, organic matter may additionally decrease the crystal size of the individual crystals by increasing the number of crystal seeds. We conclude that organic matter in the solution might limit the potential of phosphate to immobilize Pb in soil because it favours the formation of mobile colloids.     

Optimizing soil dissolved organic matter extraction by grey relational analysis

Dissolved organic matter(DOM) in soil plays an important role in the fate and transport of contaminants.It is typically composed of many compounds,but the effect of different extraction factors on the abundance of different DOM components is unknown.In this study,DOM was extracted from three soils(paddy field,vegetable field and forest soils) with various extraction time,liquid to solid ratios(LSRs),extractant types,and extractant concentrations.The LSR had a significant effect on DOM content,which increased by 0.5–4.0 times among the three soils when LSR increased from 2:1 to 10:1(P 0.05).Dissolved organic matter content increased by 4%–53% when extraction time increased from 10 to 300 min(P 0.05).Extractant concentration had different effects on DOM content depending on the extractant.Higher concentrations of KCl promoted DOM extraction,while higher concentrations of KH_2PO_4 inhibited DOM extraction.Therefore,grey relational analysis was used to further quantitatively evaluate the effect of extraction time,LSR,and extractant concentration on DOM,using KCl as an extractant.For the paddy field and forest soils,the impact of these three factors on DOM extraction efficiency was in the following order:KCl concentration LSR extraction time.However,the effect was different for the vegetable field soil:LSR extraction time KCl concentration.Taking all these factors into account,1.50 mol L~(-1) KCl and an LSR of 10:1 with a shaking time of 300 min was recommended as the most appropriate method for soil DOM extraction.     

Challenges in modelling dissolved organic matter dynamics in agricultural soil using DAISY

Because dissolved organic matter (DOM) plays an important role is terrestrial C-, N- and P-balances and transport of these three components to aquatic environments, there is a need to include it in models. This paper presents the concept of the newly developed DOM modules implemented in the DAISY model with focus on the quantification of DOM sorption/desorption and microbial-driven DOM turnover. The kinetics of DOM sorption/desorption is described by the deviation of the actual DOM concentration in solution from the equilibrium concentration, C_eq. The C_eq is soil specific and estimated from pedotransfer functions taking into account the soil content of organic matter, Al and Fe oxides. The turnover of several organic matter pools including one DOM pool are described by first-order kinetics.The DOM module was tested at field scale for three soil treatments applied after cultivating grass–clover swards. Suction cups were installed at depths 30, 60 and 90 cm and soil solution was sampled for quantification of dissolved organic C (DOC) and dissolved organic N (DON). In the topsoil, the observed fluctuations in DOC were successfully simulated when the sorption/desorption rate coefficient k was low. In the subsoil, the observed concentrations of DOC were steadier and the best simulations were obtained using a high k. The model shows that DOC and DON concentrations are levelled out in the subsoils due to soil buffering. The steady concentration levels were based on the C_eq for each horizon and the kinetic concept for sorption/desorption of DOC appeared a viable approach. If C_eq was successfully estimated by the pedotransfer function it was possible to simulate the DOC concentration in the subsoil. In spite of difficulties in describing the DOC dynamics of the topsoil, the DOM module simulates the subsoil concentration level of DOC well, and also—but with more uncertainty—the DON concentration level.     

Electron transfer capacity of soil dissolved organic matter and its potential impact on soil respiration

Purpose

Soil dissolved organic matter (DOM) as the labile fraction of soil organic carbon (SOC) is able to facilitate biogeochemical redox reactions effecting soil respiration and carbon sequestration. In this study, we took soil samples from 20 sites differing in land use (forest and agriculture) to investigate the electron transfer capacity of soil DOM and its potential relationship with soil respiration.

Materials and methods

DOM was extracted from 20 soil samples representing different land uses: forest (nos. 1–12) and agriculture (nos. 13–20) in Guangdong Province, China. Chronoamperometry was employed to quantify the electron transfer capacity (ETC) of the DOM, including electron acceptor capacity (EAC) and electron donor capacity (EDC), by applying fixed positive or negative potentials to a working electrode in a conventional three-electrode cell. The reversibility of electron accepting from or donating to DOM was measured by applying switchable potentials to the working electrode in the electrochemical system with the multiple-step potential technique. Carbon dioxide produced by soil respiration was measured with a gas chromatograph.

Results and discussion

Forest soil DOM samples showed higher ETC and electron reversible rate (ERR) than agricultural soil DOM samples, which may be indicative of higher humification rate and microbial activity in forest soils. The average soil respiration of forest soil (nos. 1–12) and agricultural soil (nos. 13–10) was 26.34 and 18.58 mg C g^?1 SOC, respectively. Both EDC and EAC of soil DOM had close relationship with soil respiration (p?<?0.01). The results implied that soil respiration might be accelerated by the electroactive moieties contained in soil DOM, which serve as electron shuttles and facilitate electron transfer reactions in soil respiration and SOC mineralization.

Conclusions

DOM of forest soils showed higher ETC and ERR than DOM of agricultural soils. As soil represents one of the largest reservoirs of organic carbon, soil respiration affects C cycle and subsequently CO₂ concentration in the atmosphere. As one of the important characteristics of soil DOM related to soil respiration, ETC has a significant impact on greenhouse gas emission and soil carbon sequestration but has not been paid attention to.     

Effects of dissolved organic matter on permethrin bioavailability to Daphnia species

Synthetic pyrethroids are widely used insecticides in both agricultural and urban environments. Recent studies show frequent appearances of pyrethroid residues in runoff effluents and sediments, which stimulated concerns over the potential ecotoxicological implications. Pyrethroids are known to have two contrasting characteristics, high aquatic toxicity and strong affinity for the solid phase, that may negate the actual toxicity in a multiphased system. This study evaluated the effect of dissolved organic matter (DOM) on the pyrethroid uptake by and acute toxicity to water-column invertebrates using permethrin as a model compound. During the bioassays, the freely dissolved permethrin concentration was simultaneously measured using poly(dimethylsiloxane) (PDMS) fibers as a biomimetic surrogate. The presence of DOM consistently decreased permethrin uptake and increased its LC(50). For instance, compared to the DOM-free treatment, the LC(50) of permethrin to Ceriodaphnia dubia in a pond water containing DOM at 10 mg L(-)(1) increased from 0.56 to 1.03 microg L(-)(1), whereas the bioaccumulation factor by Daphnia magna decreased by 56%. Permethrin accumulation on the PDMS fiber closely mimicked permethrin uptake by D. magna. Statistical analyses suggest that permethrin associated with DOM was completely unavailable to D. magna or C. dubia. The effect of DOM on permethrin bioavailability appeared to depend also on the source of the DOM. These results indicate that the inhibitory role of DOM should be considered in the development of toxicologically relevant water quality limits and in monitoring protocols for permethrin and other pyrethroids in runoff effluents and surface streams that ubiquitously contain DOM.