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.     

Distribution coefficients (Kd) and desorption rates of 137Cs and 241Am in Black Sea sediments

The distribution coefficients (K_d) and desorption rates of ¹³⁷Cs and ²⁴¹Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The K_d values were found to be 500 for ¹³⁷Cs and 3800 for ²⁴¹Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for ¹³⁷Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of ¹³⁷Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of ²⁴¹Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the ²⁴¹Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than ¹³⁷Cs under Black Sea conditions.     

The binding of three PCB congeners to dissolved organic carbon in freshwaters

The binding of three polychlorinated biphenyl (PCB) congeners to natural levels of dissolved organic carbon (DOC) was measured in 12 lakes and streams using Sep-Pak C₁₈ columns. The association coefficients calculated on the basis of DOC (i.e. K_DOC mL/g C), varied by over an order of magnitude among the different freshwaters and ranged between 2.05 × 10² and 8.86 × 10³ mL/g C for PCB 52 and 1.03 × 10⁴ and 1.70 × 10⁵ mL/g C for PCB 153. In general, there were no significant correlations (p > 0.05) between the K_DOC values and various chemical parameters in the study lakes and streams.

A relationship was derived between the fraction of bound PCB and the octanol-water partition coefficient. While this relationship explained almost 50% of the variation in the observed data, it is apparent that other factors influence K_DOC values and that in natural freshwaters, only a small fraction of the DOC is involved in the binding of PCBs and other hydrophobic pollutants.     

Determination of 99Tc deposited on the ground within the 30-km zone around the Chernobyl reactor and estimation of 99Tc released into atmosphere by the accident

Technetium-99 was determined in samples from the 30-km zone around the Chernobyl reactor. Concentrations of ⁹⁹Tc in soil samples taken from three forest sites ranged from 1.1 to 14.1 Bq kg⁻¹ dry weight for the organic soil layers, and from 0.13 to 0.83 Bq kg⁻¹ dry weight for the mineral soil layers. In particular, for the organic layers, the measured ⁹⁹Tc concentrations were one or two orders of magnitude higher than those due to global fallout ⁹⁹Tc. The ⁹⁹Tc depositions (Bq m⁻²), based on the sum of the depositions measured in organic and mineral layers, ranged from 130 Bq m⁻² within the 10-km zone to about 20 Bq m⁻² close to the border of the 30-km zone. Taking the corresponding measured ¹³⁷Cs depositions into account, it was found that the activity ratio of ⁹⁹TW/¹³⁷Cs ranged from 6 × 10⁻⁵ to 1.2 × 10⁻⁴. It was estimated that about 970 GBq of ⁹⁹Tc had been released by the Chernobyl accident. This figure corresponded to 2%–3% of the total ⁹⁹Tc inventory in the core.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.     

Phytoremediation of radiostrontium ((90)Sr) and radiocesium ((137)Cs) using giant milky weed (Calotropis gigantea R.Br.) plants

Potential of plants to remove radionuclides/toxic elements from soils and solutions can be successfully applied for removal of important radionuclides such as strontium-90 (⁹⁰Sr) and cesium-137 (¹³⁷Cs). When uptake of ¹³⁷Cs and ⁹⁰Sr by Calotropis gigantea plants incubated in distilled water spiked with the radionuclides either alone or in combination was studied, it was found to have a high efficiency for the removal of ⁹⁰Sr, with 90% being removed from solutions (5 × 10³ kBq l⁻¹) within 24 h of incubation. However, in case of ¹³⁷Cs, about 44% could be removed from solutions (5 × 10³ kBq l⁻¹) at the end of 168 h of incubation. Accumulation of ⁹⁰Sr and ¹³⁷Cs was higher in roots compared to shoots. The plants could remediate both ⁹⁰Sr and ¹³⁷Cs when they were added together to the solution. When two months old plants were incubated in low level nuclear waste, 99% of activity disappeared at the end of 15 days. The present study suggests that C. gigantea could be used as a potential candidate plant for phytoremediation of ⁹⁰Sr and ¹³⁷Cs.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Relationship between electron donor and microorganism on the dechlorination of carbon tetrachloride by an anaerobic enrichment culture

An investigation involving the supplement of different concentrations of substrates and microorganisms was carried out under anaerobic condition to assess the feasibility of bioremediation of carbon tetrachloride (CCl₄) with the amendment of low concentrations of auxiliary substrate and microorganisms. The concentrations of substrate and microorganisms ranged from 10 to 100 mg/l and from 3.7 × 10⁴ to 3.7 × 10⁶ cell/ml, respectively. The biotransformation rate of CCl₄ increased progressively with the increase in the concentrations of the substrate and microorganisms. In the low biomass-amended system (3.7 × 10⁴cells/ml), 28–71% and 57–96% of CCl₄ removals were exhibited when 10–100 mg/l of acetate or glucose was supplemented, respectively, whereas nearly complete degradation of CCl₄ was observed in the heavily inoculated systems (3.7 × 10⁶ cells/ml). An addition of electron donor in the low microbial activity batches enhanced greater efficiency in dechlorination than in the high microbial activity batches. The second-order rate constants ranged from 0.0059 to 0.0092 l/mg/day in high biomass input system, while a two- to four-fold increase in rate constant was obtained in the low microbial activity system. This study indicates that biomass was the more important environmental parameter than substrate affecting the fate of CCl₄. The addition of auxiliary substrates was effective only in low biomass-amended batches (0.56 mg-VSS/l) and diminished inversely with the increase of microbial concentration.     

Changes in the chemical composition of water-extractable organic matter during composting: distribution between stable and labile organic matter pools

Aerobic decomposition and stabilization of organic matter during the composting of waste materials is primarily due to the biochemical transformation of water-soluble compounds in the liquid phase by the microbial biomass. For this reason water-soluble organic matter represents the most active fraction of compost, both biologically and chemically, and thus should directly reflect the biochemical alteration of organic matter. This work aims to elucidate the microbial-mediated processes responsible for the distribution of soluble organic matter between stable and labile pools with composting time. Accordingly, chemical analysis as well as UV absorption, and ¹H and ¹³C-NMR spectroscopy of samples collected during the industrial composting of urban waste revealed microbial induced transformation of water-extractable organic matter over time. The chemical composition changed from labile, hydrophilic, plant-derived organic compounds in the beginning to predominately stable, hydrophobic moieties comprising lignin-derived phenols and microbially-derived carbohydrates at later stages of composting.     

Physico-chemical versus microbial release of c-atrazine bound residues from a loamy clay soil incubated in laboratory microcosms

A loamy clay soil containing unextractable ¹⁴C-ring labeled atrazine residues was incubated in microcosms under abiotic and biotic conditions. The mineralization activity of the soil microflora was evaluated by the release of total CO₂ and ¹⁴C0₂. After 63 days of sample incubation the total organic carbon mineralization was of 1.71%, that of ¹⁴C-residues was of 0.72% of the initial radioactivity. No direct relationship was established between the mineralization of atrazine residues and the global mineralization. The contribution of soil microorganisms in the release of ¹⁴C-residues was weak. The availability of non-extractable residues was mainly controlled by physico-chemical factors. The low value of the reextractability rate and the distribution of bound residues during the soil sample incubation shown the active role of organic matter in detoxification procedure. Ninety percent of the residues remained bound after 63 days of incubation and were thus, potentially available without biocide activity.

The fractionation of soil organic matter allowed to specify the distribution of bound residues within the organic compartments. After a long-stay of pesticides in soils, approximately 65% of bound residues were associated with humin.     

Role of dissolved humic acids in the biodegradation of a single isomer of nonylphenol by Sphingomonas sp

This study shows the important role of humic acids in the degradation of ¹⁴C and ¹³C labeled isomer of NP by Sphingomonas sp. strain TTNP3 and the detoxification of the resulting metabolites. Due to the association of NP with humic acids, its solubility in the medium was enhanced and the extent of mineralization of nonylphenol increased from 20% to above 35%. This was accompanied by the formation of significant amounts of NP residues bound to the humic acids, which also occurred via abiotic reactions of the major NP metabolite hydroquinone with the humic acids. Gel permeation chromatography showed a non-homogenous distribution of NP residues with humic acids molecules, with preference towards molecules with high-molecular-weight. Solid state ¹³C nuclear magnetic resonance spectroscopy indicated that the nonextractable residues resulted exclusively from the metabolites. The chemical shifts of the labeled carbon indicated the possible covalent binding of hydroquinone to the humic acids via ester and possibly ether bonds, and the incorporation of degradation products of hydroquinone into the humic acids. This study provided evidences for the mediatory role of humic acids in the fate of NP as a sink for bacterial degradation intermediates of this compound.     

Radionuclide content of Las Vegas Wash sediments

The Las Vegas Wash is an excavated waterway channel which drains all surface water and effluent discharge from sewage-treatment facilitates from the greater Las Vegas Metropolitan Area to Lake Mead. Fine and course sediment samples were collected at 100-m intervals and analyzed to determine the distribution of gamma-emitting radionuclides in the lower 5,500 m of the Las Vegas Wash. Results indicate depletion of long-lived fission products in upstream Wash sediments. However, trace levels of ¹³⁷Cs measured in downstream sediments suggest the resuspension and transport of radioactive fallout within the Wash. Levels of ⁴⁰K, ²³²Th, ²³⁵U, and ²³⁸U found in Wash sediments were consistent with levels typically found in southeast Nevada soils.     

湖北省能源消费CO2与大气污染物协同减排研究

以2015年为基准年,基于拓展的STIRPAT模型预测2025年湖北省能源消费CO2和主要大气污染物排放量.通过设置基准(记为BAU)情景、低碳(记为LC)情景和强化低碳(记为ELC)情景3种控制情景,测算CO2和主要大气污染物的减排量,并运用污染物减排量交叉弹性法评价了CO2减排对主要大气污染物的协同效应.结果表明,...     

Phenotypical dissection of immunoregulatory T cell subsets in human after furan exposure

Phenotypical dissection of helper (T4⁺) and suppressor cytotoxic (T8⁺) T lymphocytes using Leu 8 reagent reveal a significant increase of T8⁺ Leu 8⁻ subset in human after furan exposure.     

Micro-scale bromination procedure for synthesis of “2,3,7,8-substituted” brominated dibenzo-p-dioxins and dibenzofurans from [C]-labeled precursors

Brominated dibenzo-p-dioxin and dibenzofuran (BDD/BDF) isomers, specifically having from one to three halogens located in the 2,3,7,8-substituent positions, that are [¹³C]-labeled for use as analytical internal standards in mass spectrometric methods are not yet commercially available. Based upon the current availability of [¹³C]-labeled dibenzo-p-dioxin and dibenzofuran (DD/DF) precursors, we have developed a simple and efficient synthetic procedure which produces brominated congeners that are predominantly substituted in the 2,3,7, and 8-positions. The gas/solid reaction of vaporized precursor and surface-supported iron (III) bromide occurs rapidly (seconds) at temperatures ≥ 240°C and can provide total product yields in the range of 30 to 50 mole % for initial precursor amounts between 1 μg and 10 mg. In this paper we shall describe the utility of this approach to produce 5 μg quantities of [¹³C₁₂]-2,7-dibromodibenzo-p-dioxin (27-DBDD) and [¹³C₁₂]-2,8-dibromodibenzo-p-dioxin (28-DBDD).     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.     

Transformation products distribution of atrazine in corn plants treated with radiolabelled herbicide

Roots of whole plants at four leaf stage grown in specialized soil treatment vessels were treated with ¹⁴C-atrazine. Plant tissues were exhaustively extracted with methanol and extracts were separated by preparative thin layer chromatography (TLC). The extracted material was separated in two TLC bands at Rf0.00 and Rf0.18 containing 33% and 67% of plant ¹⁴C-residues, respectively. Methanol extracts of these bands subjected to derivatization, hydrolysis and analysis by TLC, revealed the presence of a number of transformation products consisting of hydroxy analogues of atrazine and their dealkylated metabolites. The transformation products had variable distribution patterns amongst leaf, stalk and root tissues. Diaminohydroxyatrazine, hydroxyatrazine, and deethylhydroxyatrazine were the main ¹⁴C-residues. Stalk tissue contained more ¹⁴C-residues which were largely located at and just below the ligule. The significance of ¹⁴C-residue accumulation at the ligule and the transformation product compartmentalization are discussed.