Oxidation of chlorophenols in soil at natural pH by catalyzed hydrogen peroxide: the effect of soil organic matter.

This investigation reports on the effects of soil organic matter (SOM) during the oxidation of chlorophenols with Fe2+-catalyzed H2O2 (Fenton oxidation) system. The soil pH was 7.1 and was not altered. Sorption experiments of soil pre-treated under various oxidation conditions were performed. Concentrations of organic matter in the liquid phase and soil before and after oxidation were analyzed. The results were correlated to the observation in batch Fenton oxidation tests. They showed that the oxidation of chlorophenols at natural soil pH depended on the dose of H2O2 and Fe2+. The soil organic content did not vary significantly after various Fenton treatments, while the sorption of chlorophenols was 10-25% less by the oxidation. The concentration of chlorophenols in the liquid phase exhibited a "decrease and rebound" phenomenon in the batch Fenton oxidation tests. It appeared that the oxidation of SOM resulted in the release of sorbed chlorophenols which were then oxidized by the excess H2O2. An "oxidation-desorption-oxidation" scheme was proposed to describe one of the interaction mechanisms among the oxidant, SOM, and chlorophenols during oxidation.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Role of extractable and residual organic matter fractions on sorption of phenanthrene in sediments

Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents were much higher than reported values. Phen sorption for the extracted fractions was almost linear, whereas that for the residual fractions was nonlinear, especially for LGF with n 0.56–0.63. As the different organic fractions were removed sequentially, sorption energy distribution on the residual sediment organic matter (SOM) became more heterogeneous. In addition, increasing sorption capacity for the residual fractions, except for BLF with its high polarity, suggested that more sorption sites on the SOM matrix became accessible to Phen. The sorption capacity for LGF was comparable to that of condensed SOM. The residual fraction LGF generally controlled the overall sorption at low Phen concentration, but the extractable fraction FL surpassed the former fraction at high Phen concentration, demonstrating the importance of condensed SOM in the sorption of hydrophobic organic compounds (HOCs) in sediments.     

Soil organic matter from pioneer species and its implications to phytostabilization of mined sites in the Sierra de Cartagena (Spain)

Pioneer plant species were observed growing on mined areas despite unfavourable conditions such as extreme pH, high salinity and phytotoxic levels of several elements. This study evaluated the contribution of pioneer species to the accumulation of soil organic matter (SOM). We collected 51 samples from 17 non-vegetated, natural and pioneer-vegetated sites in five highly saline mined areas in the Sierra de Cartagena (Spain). The composition of SOM was determined using total C, N and S elemental anlayzer, pyrolysis and solid state (13)C NMR spectroscopy. Results showed that pioneer species like Lygeum spartum had contributed approximately 11 kg SOM kg(-1) soil into the Balsa Rosa sites since 1991; it will take approximately 120 years of continuous growth for this plant to increase the SOM level comparable to natural site. In the Portman Bay area, Sarconia ramosissima and Phragmites australis can contribute SOM equivalent to present day SOM in natural sites in the next 30 years. Low quality SOM (C/N>20) deposited by pioneer plants was dominated by lignin-derived organic compounds such as phenols, guaiacols, syringols and aromatics while polyssacharides and alkyls were the major components in high quality SOM (C/N<20). The addition of SOM to mine wastes is similar to early stages of soil formation and with time, we expect the formation of well-developed Ah horizon on the surface of mine wastes. The presence of P. australis on several sites makes it a very good candidate for successful revegetation of hostile conditions found in many mined sites.     

Artificial and enhanced humification of soil organic matter using microwave irradiation

Microwave (MW) irradiation, a less energy-intensive irradiation technique, was employed to promote the changes in physicochemical properties of soil organic matter (SOM). MW was irradiated to forest soils for 10 min. Then, the physical and chemical properties of the SOM were analyzed with UV absorbance spectroscopy, Fourier transform infrared spectroscopy, elemental analysis, and size exclusion chromatography. Also, the SOM was fractionated into biopolymer, fulvic acid, and humic acid, and each fraction was analyzed quantitatively. These analyses revealed that the SOM became more aromatic and nonpolar, highly condensed, and macromolecular organic substances that possess a higher amount of functional groups found in highly humified substances than the original SOM as a result of the MW irradiation. The humification-like alteration of SOM property was attributable to the thermal cracking and to the radical reaction, particularly when the MW was irradiated along with activated carbon under the aerobic condition. The results of this study suggest that the artificial and enhanced property changes of SOM can be accomplished by MW irradiation on an engineering time scale, which can contribute to the successful soil and groundwater remediation practice.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Changes in soil organic matter chemical properties after organic amendments

Organic inputs are used to improve soil physical and chemical properties, but the corresponding changes in soil organic matter (SOM) chemical properties are not well known. In this study, we compared some characteristics of the SOM of a soil receiving either no organic inputs, or two different amendments during 15 years (straw or conifer compost). Quantities of organic carbon and C/N values were determined on particle size fractions after physical soil fractionation to localize changes due to amendments. Contents in reactive functional groups, acid-base properties and copper binding affinities were determined by titration experiments for the soluble fraction of SOM: the fulvic acid fraction (FA). Data of FA extracted from the bulk soil were compared to data of FA extracted from the <20 microm size fraction with the help of either a discrete or a continuous model (fit of data with FITEQL or NICA, respectively). Copper binding characteristics of FA extracted from the <20 microm size fraction did not change significantly after organic inputs, while those of FA extracted from the bulk organic-amended soils were found different from the ones with no amendment. Minor effects observed in the finer soil fractions were ascribed to their low turn-over of organic carbon and/or to a greater homogeneity in the nature of the organic carbon entering these fractions. Our results show major chemical changes in coarser soil organic fractions after organic amendments.     

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.     

Alteration of sediment organic matter in sediment microbial fuel cells

The alteration of physico-chemical properties of sediment organic matter (SOM) incubated under current-harvesting conditions as well as no-current producing conditions over 120 days using sediment microbial fuel cell systems was examined. The SOM was microbially oxidized under anaerobic conditions with an electrode serving as a terminal electron acceptor. It was found that SOM around the electrochemically-active electrodes became more humified, aromatic, and polydispersed, and had a higher average molecular weight, along with its partial degradation and electricity generation compared to that for the original sediment. These changes in SOM properties were analogous to those commonly observed in the early stages of the SOM diagenetic process (i.e. humification). Such a humification-like process was evidently more stimulated when electrical current was produced than no-current condition. These new findings associated with microbially-catalyzed electricity generation may present a potential for the energy-efficient remediation, monitoring, and/or management of the geo-environment.     

On the use of a freeze-dried versus an air-dried soil humic acid as a surrogate of soil organic matter for contaminant sorption

The sorption of phenanthrene (PHN) to relatively pure soil humic acids (HAs) was investigated to assess the suitability of the soil HA as a surrogate sorbent for the soil organic matter (SOM). The HAs were prepared in both freeze-dried and air-dried forms. The two forms of HAs from the same source are similar in composition but the freeze-dried HAs exhibit a significantly higher initial surface area (SA) (3.86-4.59 m(2)/g); the SAs of air-dried HAs are below 0.1 m(2)/g. However, the SAs of freeze-dried HAs are not stable upon contact with water; the samples lose practically all the SA after 4 days of immersion in water. The PHN sorption to both forms of HAs is practically linear, whether a co-solute is present or not. The sorption linearity observed with the present freeze-dried HAs is in sharp contrast with the allegedly nonlinear PHN sorption on similar freeze-dried HAs as presented by others.     

The impact of vegetation on sedimentary organic matter composition and PAH desorption

Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C₃-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax^® beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k_slow and k_{very slow}. After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

土壤有机质对铊在土壤中吸附-解吸行为的影响

研究了土壤有机质对Tl＋在红壤和黄土2种土壤中的吸附-解吸行为的影响。结果表明,去除土壤有机质后红壤和黄土对Tl＋的吸附量均明显下降,下降幅度最高分别达到24.7%和28.2%,黄土的下降幅度大于红壤;黄土对Tl＋吸附率最高下降幅度约为20%,也高于红壤的15%。土壤有机质对Tl＋吸附的贡献率平均值分别是黄土39.2%、红壤32.8%。2种土壤对Tl＋的解吸量在去除有机质之后都明显增大,在初始Tl＋浓度较高的情况下,增大幅度明显;并且Tl＋的初始浓度越高,土壤在去有机质前后的解吸率相差就越大,在Tl＋最大处理浓度为20 mg/L时,红壤和黄土的解吸率增加分别达到60.8%和65.5%。     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Effects of natural organic matter on the microporous sorption sites of black carbon in a Yangtze River sediment

Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N₂ and CO₂ adsorption. The results suggest that the adsorption of N₂ was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO₂ was not. Instead, the uptake of CO₂ was higher in the presence of AOC, likely due to the partition of CO₂ molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene.     

Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity

¹³C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of ¹³C (1.1 % of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on ¹³CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance.

After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using ¹³CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of ¹³CP-MAS NMR scans was increased in order to obtain satisfactory spectra.

Results show that chemical pre-treatment of soils with C/Fe > 1 caused high C losses. Bulk soils were therefore studied by increasing the number of ¹³CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K = 1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe < 1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9–25.4%), a pre-treatment of at least 1.39 mol l⁻¹ HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra.     

Impacts of microbial redox conditions on the phase distribution of pyrene in soil-water systems

Variations in the soil/sediment organic matter (SOM)-hydrophobic organic contaminant (HOC) bindings upon microbially mediated redox conditions were examined. While the extractability of pyrene associated with soil declined after its biodegradation began during aerobic incubation, its variations were almost constant (±3.0-4.4%) during anoxic/anaerobic incubations. The dissolved organic matter released from the soil incubated under highly reduced conditions became more humified and aromatic, had a higher average molecular weight, and was more polydispersed compared to that obtained from oxic incubation, similar to the SOM alterations in the early stage of diagenesis (humification). The concentrations of pyrene in the aqueous phase increased significantly during the soil incubations under highly reduced conditions due to its favorable interaction with the altered DOM. Our results suggest that the microbially mediated redox conditions have significant impacts on SOM and should be considered for the transport, fate, bioavailability, and exposure risk of HOCs in the geo-environments.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Impact of soil organic matter on the distribution of polycyclic aromatic hydrocarbons (PAHs) in soils

The knowledge on the distribution of hydrophobic organic contaminants in soils can provide better understanding for their fate in the environment. In the present study, the n-butanol extraction and humic fractionation were applied to investigate the impact of SOM on the distribution of polycyclic aromatic hydrocarbons (PAHs). The results indicated that 80.5%-94.8% of the target PAHs could be extracted by n-butanol and 63.1%-94.6% of PAHs were associated with fulvic acid (FA). Concentrations of un-extracted PAHs increased significantly with the increasing soil organic matter (SOM), however, such an association was absent for the extractable fractions. The results suggested that the sequestration played a critical role in the accumulation of PAHs in soils. SOM also retarded the diffusion of PAHs into the humin fractions. It implied that sequestration in SOM was critical for PAH distribution in soils, while the properties of PAH compounds also had great influences.     

Spatial distribution of organic geochemical record in the core sediments along the prominent zones of Central Kerala,India

The study investigated the origin, quality, composition, and trophic state of sedimentary organic matter (SOM) in core samples collected from three zones (Munambam, Vypin, Chettuva) of Central Kerala, India. The SOM exhibited enhanced levels for carbohydrate (CHO) followed by protein (PRT) and lipid (LPD); and phytopigment in the sediment followed the trend: Pheophytin (Pheo) > Carotenoid (carotend) > Chlorophyll-a (Chl-a) > Chlorophyll-b (Chl-b) > Chlorophyll-c (Chl-c). The low PRT: CHO ratio indicated a large amount of nonliving or aged organic matter in the sedimentary environment. Whereas the low Chl-a: Pheo ratio interprets the abundance of dead plant materials in the sediments. Correlation matrix showed strong association between organic matter and clay fraction of sediment. Furthermore, the strong interrelationships between biochemical components and chloropigments in all the zones suggested that SOM is strictly connected to phytodetritus deposition. Vypin zone near Vallarpadam Container Terminal revealed the presence of high biopolymeric carbon content. Besides, the PRT: CHO > 1 reflected the eutrophic condition at the same site but the low PRT: CHO ratio in the remaining stations displays the oligotrophic nature.