Experimental approaches and analytical techniques for determining organic compound bound residues in soil and sediment

Research has shown that many chemicals form persistent and permanently bound residues in soils and sediments that play an important role in soil and sediment detoxification processes, long-term compound partitioning behaviour and compound bioavailability and toxicity in soil and sediment. This article reviews the methodological approaches that have been applied to determine the nature of bound residues in soil and sediment, the application of specific analytical techniques, the type of information they generate, and their relative advantages and disadvantages. It begins by defining bound residues and discussing soil-compound interactions. The application of model compound studies for elucidating specific binding interactions is reviewed along with long-term laboratory and field soil incubation experiments. The use of radiolabelled compounds, isotopically labelled compounds and combinations of both in these experiments are outlined by examples from the literature, along with sequential extraction schemes for releasing bound residues from soil, sediment and humic materials. The importance of spectroscopic methods, and particularly nuclear magnetic resonance techniques for characterising the structure of bound residues in soil and sedimentary humic substances is discussed and illustrated by examples from the literature on the subject. The process of bound residue formation is highly complex and requires further research to establish the mechanisms of bound residue formation and their subsequent environmental and toxicological fate. Much of the uncertainty regarding the elucidation of bound residue formation arises from our poor understanding of the structure of soil and sedimentary organic matter. Significant advances in our understanding of the formation and fate of bound residues will be made when we develop a deeper insight into the complex and heterogeneous structure of soil and sedimentary organic matter.     

Sorption of naphthalene derivatives to soils from a long-term field experiment

The influence of long-term farming practices on the soil's behaviour to adsorb hydrophobic organic compounds (HOCs) over long times was investigated. Adsorption of five naphthalene derivatives (naphthalene, 1-naphthol, 1-naphthylamine, 1-hydroxy-2-naphthoic acid, 1,4-naphthoquinone) was examined on soils with varying amounts and origins of soil organic matter obtained after amendment with different organic materials over more than 40 years. Soil organic matter, pore sizes and aggregate stability were significantly altered influencing the adsorption behaviour of the soils. Samples of soil amended with peat having an organic carbon content of 3.4% sorbed naphthalene derivatives stronger than the soil treated with sewage sludge (2.6% C(org)). All other treatments, calcium nitrate, plots without nitrogen fertilizers, grassland, animal manure, green manure and the fallowed soil sorbed less and no significant difference was found between them although the organic carbon content ranged from 1.0% to 2.6%. Thus, a decrease of the carbon content of a soil does not necessarily imply a reduction of sorption capacities for hydrophobic compounds such as naphthalene derivatives. Furthermore, the importance of protonation of HOCs for the adsorption on soil surfaces was shown. Different polarities of electronic structures of HOCs distinctly influence their adsorption behaviour.     

Characterization of extractable and non-extractable polycyclic aromatic hydrocarbons in soils and sediments from the Pearl River Delta, China

Formation of bound residues of pollutants in soils and sediments is an important process to control the fate of pollutants in the environment. The most of bound residue is not solvent extractable. In this paper, we measured both extractable and non-extractable polycyclic aromatic hydrocarbons (PAHs) in different organic matter fractions of samples from the Pearl River Delta, China. Non-extractable PAHs concentration was 234.45-1424.57 μg/kg and accounted for 33.78-57.44% of total PAHs. 2-3 Ring PAHs were the dominant species and differed in concentration substantially between the samples. The atomic ratio of PAHs over organic-C in the fractions ordered as solvent soluble organic matter > humin > humic acids, matching the content of aliphatic moieties in the fractions of organic matter. The ratio of extractable and non-extractable PAHs may relate to the aging process of PAHs in soil and sediment.     

Bound residues: environmental solution or future problem?

The paper examines the issue of bound residues from the viewpoint of the risk assessment procedures employed for environmental protection. It considers, on one hand, the evidence that such residues are so tightly bound to soil organic matter as to be essentially unavailable; and on the other, the perspective that we should not be loading up the environment with compounds whose future behaviour and release we cannot predict. Existing knowledge of the mechanisms by which residues bind to soil organic matter suggests that release will be closely dependent on soil organic matter breakdown. Simple models of organic matter turnover suggest that the release following single applications of individual compounds will be very slow; but the significance of releases following repeated application over many years of a number of compounds needs to be investigated further. Applying environmental risk assessment techniques is complicated by the difficulty in identifying parent molecules and potential metabolites in the bound residue fraction. The paper concludes that for single additions of individual compounds, bound residues probably do represent an environmental solution. But the long-term significance of bound residues formed from multiple additions of a number of compounds is less clear. The paper recommends that future work should emphasise the biological significance of such residues and their release.     

Effect of physical forms of soil organic matter on phenanthrene sorption

The sorption coefficient, K(OC), of phenanthrene (PHE) has been reported to vary with different types of organic matter, leading to uncertainties in predicting the environmental behavior of PHE. Among the studies that relate organic matter properties to their sorption characteristics, physical conformation of organic matter is often neglected. In this work, organic matter samples of different physical forms were examined for their sorption characteristics. Dissolved humic acids (DHA) showed significantly higher K(OC) than the corresponding solid humic acids (SHA) from which the DHAs were made. The K(OC) of DHAs was found to be related to polarity, whereas K(OC) of SHAs increased with aliphatic carbon content. Soil particles were treated with H(2)O(2) to remove organic matter, and humic acid was coated on H(2)O(2)-treated soil particles to make organo-mineral complexes at pH 4, 7 and 10. Although the nonlinear sorption was apparent for SHAs and H(2)O(2)-treated soil particles, the organo-mineral complexes formed using these two components at pH 4, 7 and 10 exhibited relatively linear sorption at organic carbon content, f(OC)>0.5%. These results indicate that organic matter of the same composition may have different sorption properties due to different physical forms (or conformations). Nonlinear sorption for the complexes formed at pH 4 with lower f(OC) (<0.5%) was also discussed.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of ¹⁴C labeled isoproturon have been determined in two Moroccan soils by β -counting–liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.     

Environmental fate of amitrole: influence of dissolved organic matter

In this study the environmental fate of amitrole in terrestrial and aquatic model ecosystems was investigated. Under aerobic conditions mineralization of amitrole is the main degradation pathway. The experiments revealed that the leaching behaviour is low in the presence or the absence of dissolved organic matter (DOM) despite the high water solubility due to a strong binding of amitrole to soil constituents. Under anaerobic conditions the addition of DOM increases the transport of amitrole in soil columns. The tests with water/sediment model ecosystems showed that the mineralization of amitrole is lower in comparison to aerobic soil experiments. Up to 80.6% of the applied 14C-labelled amitrole transfer into the sediment and about 1/3 of this amount formed bound residues, which are not extractable.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of (14)C labeled isoproturon have been determined in two Moroccan soils by beta -counting-liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.     

Persistence, degradation and leaching of coumaphos in soil

Dissipation, degradation and leaching of fresh 14C coumaphos, alkylated 14C coumaphos and aged residues of 14C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4-methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Tracing the transformation of labelled [1-13C]phenanthrene in a soil bioreactor

[1-(13)C]-labelled phenanthrene was incubated in a closed bioreactor to study the flux and biotransformation of polycyclic aromatic hydrocarbon (PAH) in contaminated soils on a bulk and molecular level. The degradation of extractable phenanthrene was observed by GC-MS measurements and the mineralisation was monitored by (13)CO(2) production. The transformation of the (13)C-label into non-extractable soil-bound residues was determined by carbon isotopic measurements. With these data we were able to calculate a carbon budget of the (13)C-label. Moreover, the chemical structure of non-extractable bound residues was characterised by applying selective chemical degradation reactions to cleave xenobiotic subunits from the macromolecular organic soil matrix. The obtained low molecular weight products yielded (13)C-labelled compounds which were identified using IRM (isotope ratio monitoring)-GC-MS and structurally characterised with GC-MS. Most of the (13)C-labelled products obtained by chemical degradation of non-extractable bound residues are well-known metabolites of phenanthrene. Thus, metabolites of [1-(13)C]phenanthrene formed during biodegradation appear to be reactive components which are subsequently involved in the bound residue formation. Hydrolysable amino acids of the soil residues were significantly labelled with (13)C as confirmed by IRM-GC-MS measurements. Therefore, phenanthrene-derived carbon was transformed by anabolic microbial processes into typical biologically derived compounds. These substances are likely to be incorporated into humic-like material after cell death.     

Formation and long-term fate of non-extractable residues in outdoor lysimeter studies

Long-term outdoor lysimeter studies using (14)C-labelled compounds allow the quantification of the 'non-extractable residue fraction'. More than 20 lysimeter studies under realistic environmental conditions showed that more than 80% of residual carbon of the molecule is retained in the topsoil layer even after several years. Generally, 50-90% of this residual radiocarbon is regarded as 'soil bound residue'. Microbial biomass is present in large quantities in topsoil and continuously influences chemical and biochemical alteration of pesticide molecules that may interact directly with the total soil organic matter. Labelling techniques using radioactive isotopes like (14)C have been used to characterize these residues in the humus matrix. Our studies have been directed to the investigation of extractability and/or bioavailability of these residues in long-term investigations.     

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.     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.     

Persistence,degradation and leaching of coumaphos in soil

Abstract

Dissipation, degradation and leaching of fresh ¹⁴C coumaphos, alkylated ¹⁴C coumaphos and aged residues of ¹⁴C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4 ‐ methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Water extractable organic carbon in untreated and chemical treated biochars

Biochar, as a soil amendment, can increase concentrations of soil organic matter, especially water-extractable organic carbon (WEOC). This can affect the adsorption-desorption equilibrium between the dissolved solid phases in soil organic matter. Dissolved organic carbon (DOC) represents a small proportion of soil organic matter, but is of significant importance in the soil ecosystem due to its mobility and reactivity. Here, water extracts obtained from twelve non-herbaceous biochars (before, and after, chemical treatment with either H(3)PO(4) or KOH), were tested by Liquid Chromatography - Organic Carbon Detection (LC-OCD) to identify the effects of both pyrolysis conditions and chemical treatments on WEOC content. LC-OCD has the capacity to provide a fingerprint of WEOC, which allows analysis of the various fractions present. WEOC content was affected by both the pyrolysis temperature and the feedstock used. High mineral ash contents deriving from the feedstock can prompt thermochemical reactions of lignocelluloses to produce a relatively high WEOC content, which includes low molecular weight neutrals and humic acids as dominant components. A significant change in WEOC occurred during pyrolysis due to secondary reactions which resulted in a much lower WEOC in the high temperature biochars where fractions of low molecular weight acids and neutrals are dominant. Chemical treatments with H(3)PO(4) or KOH increased WEOC concentration, possibly by promoting hydrolysis reactions on biochar surfaces. These observations assist in assessing the contribution of biochar additions to the soil ecosystem and demonstrate the utility of LC-OCD in providing an understanding of how biochar additions to soil can alter DOC.     

Separating the effects of organic matter-mineral interactions and organic matter chemistry on the sorption of diuron and phenanthrene

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.     

Application of a mechanistic desorption-biodegradation model to describe the behavior of polycyclic aromatic hydrocarbons in peat soil aggregates

A procedure was developed to obtain three size fractions (2360 < d(p) < 1000, 1000 < d(p) < 710, and 710 < d(p) < 425 microm) of stable aggregates from Koopveen peat soil by application of an intense mixing regime prior to sieving of the soil material. The organic matter content, aggregation structure and the microstructure of these aggregates were determined and the particles were artificially contaminated with naphthalene and phenanthrene via a solvent phase. A nonlinear Freundlich sorption isotherm was determined for the naphthalene contaminated soil aggregates (n = 0.39; K(F) = 1.13 x 10(-2) m(1.17) kg(-0.39)). The applicability of a mathematical model, that describes sorption equilibrium, intraparticle mass-transfer, and nonlinear bacterial degradation kinetics, was tested by fitting results of dynamic desorption and biodegradation experiments, generated in this study and earlier work on the peat soil aggregates. The experimental data were described adequately although strong variations in the values of the fit parameter, the intra-particle porosity (0.30 < epsilon < 0.88), were found. This indicates the necessity of further investigations.     

Bioavailability to rats of bound [14C] pirimiphos-methyl in stored wheat.

Stored wheat treated with radiolabelled pirimiphos-methyl (0-2-diethyl-amino-6-methyl-pyrimidin-4-yl 0,0-dimethyl phosphorothioate) formed bound (nonextractable) 14C residues. Supercritical fluid extraction, gas chromatography and mass spectrometric techniques were used to identify and quantitate the 14C bound residues in wheat grains. The amount of bound 14C residues present after 28 weeks of storage was about 9.9% of the applied radioactivity. Pirimiphos-methyl accounted for 80% of the bound residue. Grain-bound residues were fed to rats for 5 days. After a total period of 8 days a substantially large percentage of the administered bound 14C residues (72.9%) was eliminated in urine while feces contained only 17.9%. Bound pirimiphos-methyl in wheat grain was metabolized in rats by processes involving hydrolysis, N-dealkylation and 0-demethylation. The results indicate that wheat-bound residues of pirimiphos-methyl are highly bioavailable to the rat and may possess a toxicological potential as manifested by a significant reduction in body weight gain.     

The content and contributions of deposited aeolian organic matter in a dry land ecosystem of the Negev Desert,Israel

The northern Negev desert in Israel has a mosaic of two types of plant community patches. One is dominated by vascular plants (shrub patches) and the other by a nonvascular crust community (crust patches) consisting of cyanobacteria, bacteria, algae, mosses and lichens. The crust patches are sources of soil material and sediment – laden runoff water while the shrub patches are the sinks and function as ‘islands of fertility’ in the desert environment. Accumulation of resources is often a limiting factor in this ecosystem. The aim of this study was to investigate the contribution of high nutrient organic residues that are readily decomposable, to the aeolian deposition on the crust patches. During the five years of the study, three dominant groups were found in the organic matter: plant material, insect and snail residue (feces). The average accumulation of the aeolian deposition of the organic matter showed significant spatial and temporal differences. Similar quantities were found on the north and the south-facing slopes of the watershed with a minimum in the wadi. A significant difference in average accumulated organic matter for the five years was found. The maximum was for the third year (1995) and the minimum for the fifth year (1997). This may be due to the variations in the annual rainfall amount. The results showed that the origin of most of the organic matter content is from native sources. The highest and most significant amount was registered during the spring season, which is the flowering season in the northern Negev. This may explain the high quantity of plant material obtained and the great amounts of insect and snail (feces) residue that were also found during this season. Since the crust patches serve as a source of water and nutrients in this ecosystem, the organic residues that are of high nutrient quality and readily decomposable, contribute to the productivity of the shrub patches and thus of the overall ecosystem.     

Clear effects of soil organic matter chemistry, as determined by NMR spectroscopy, on the sorption of diuron

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.