Dissipation of oxytetracycline in soils under different redox conditions

This study investigated the dissipation kinetics of oxytetracycline in soils under aerobic and anoxic conditions. Laboratory experiments showed that the dissipation of oxytetracycline in soil followed first-order reaction kinetics and its dissipation rates decreased with increasing concentration. Oxytetracycline dissipated faster in soil under aerobic conditions than under anoxic conditions. The half-lives for oxytetracycline in soil under aerobic conditions ranged between 29 and 56 days for non-sterile treatments and 99-120 days for sterile treatments, while under anoxic conditions the half-lives of oxytetracycline ranged between 43 and 62 days in the non-sterile soil and between 69 and 104 days in the sterile soil. This suggests microbes can degrade oxytetracycline in agricultural soil. Abiotic factors such as strong sorption onto soil components also played a role in the dissipation of oxytetracycline in soil.     

Assessment of phenylurea herbicides sorption on various Mediterranean soils affected by irrigation with wastewater

The retention values of two herbicides, chlorotoluron and isoproturon, in five Mediterranean soils were assessed by two different approaches, a dynamic method, using a batch technique (BT) and a static method, using a soil saturated paste (SP). The SP method led in all cases to lower herbicide sorption when compared with BT, although pesticide distribution constants from both methods were linearly related for the set of used soils (R² ? 0.99) showing that both methods similarly reflected the behaviour of the different soils. Low-quality water, evaluated by employing recycled urban wastewater, did not modify herbicide sorption when compared with high quality water, in any soil and with any method.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Effect of soil ageing on in vivo arsenic bioavailability in two dissimilar soils

Arsenic (As) bioavailability in spiked soils aged for up to 12 months was assessed using in vitro and in vivo methodologies. Ageing (natural attenuation) of spiked soils resulted in a decline in in vivo As bioavailability (swine assay) of over 75% in soil A (Red Ferrosol) but had no significant effect on in vivo As bioavailability even after 12 months of ageing in soil B (Brown Chromosol). Sequential fractionation, however, indicated that there was repartitioning of As within the soil fractions extracted during the time course investigated. In soil A, the As fraction associated with the more weakly bound soil fractions decreased while the residual fraction increased from 12% to 35%. In contrast, little repartitioning of As was observed in soil B indicating that natural attenuation may be only applicable for As in soils containing specific mineralogical properties.     

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.     

Modeling and interpreting bioavailability of organic contaminant mixtures in subsurface environments

Bioavailability often controls the fate of organic contaminants in surface and subsurface aquatic environments. Bioavailability can be limited by sorption, mass transfer, and intrinsic biodegradation potential and can be further altered by the presence of other compounds. This paper reviews current perspectives on the processes influencing subsurface contaminant bioavailability, how these processes are modeled, and how the relative role of the various processes can be assessed through bioavailability indices. Although these processes are increasingly well understood, the use of sophisticated models and indices often are precluded by an inability to estimate the many parameters that are associated with complex models. Nonetheless, the proper representation of sorption, mass transfer, biodegradation, and co-solute effects can be critical in predicting bio-attenuation. The influence of these processes on contaminant fate is illustrated with numerical simulations for the simultaneous degradation of toluene (growth substrate) and trichloroethylene (nongrowth cometabolite) in hypothetical, aerobic, solid-water systems. The results show how the relative impacts on contaminant fate of the model's various component processes depends upon system conditions, including co-solute concentrations. Slow biodegradation rates increase the inhibition effects of a cometabolite and suppress the rate enhancement effects of a growth substrate. Irrespective of co-solute effects, contaminant fate is less sensitive to biodegradation processes in systems with strong sorption and slow desorption rates. Bioavailability indices can be used to relate these findings and to help identify appropriate modeling simplifications. In general, however, there remains a need to redefine such indices in order that bioavailability concepts can be better incorporated into site characterization, remediation design, and regulatory oversight.     

Sequential sorption of lead and cadmium in three tropical soils

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.     

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments.     

Dynamics of PCB removal and detoxification in historically contaminated soils amended with activated carbon

Activated carbon (AC) can help overcome toxicity of pollutants to microbes and facilitate soil bioremediation. We used this approach to treat a Histosol and an Alluvial soil historically contaminated with PCB (4190 and 1585 mg kg⁻¹, respectively; primarily tri-, tetra- and pentachlorinated congeners). Results confirmed PCB persistence; reductions in PCB extractable from control and AC-amended soils were mostly due to a decrease in tri- and to some extent tetrachlorinated congeners as well as formation of a bound fraction. Mechanisms of PCB binding by soil and AC were different. In addition to microbial degradation of less chlorinated congeners, we postulate AC catalyzed dechlorination of higher chlorinated congeners. A large decrease in bioavailable PCB in AC-amended soils was demonstrated by greater clover germination and biomass. Phytotoxicity was low in treated soils but remained high in untreated soils for the duration of a 39-month experiment. These observations indicate the utility of AC for remediation of soils historically contaminated with PCB.     

Relative bioavailability to laying hens of indicator polychlorobiphenyls present in soil

Transfer of indicator polychlorobiphenyls (PCBs) from soil into hen eggs may occur in hens reared outdoor, which ingest significant amounts of soil. This transfer depends on the bioavailability of the ingested compounds. The impact of soil on the bioavailability of indicator PCBs was assessed by means by a relative bioavailability (RBA) trial, in which their deposition in egg yolk and in abdominal fat, in response to their ingestion through contaminated-soil and through spiked-oil were compared. A sandy soil (709 μg indicator PCBs kg⁻¹ dry matter) was collected in the vicinity of a former fire involving treated wood. Twenty-eight laying hens were individually housed and fed one of the seven experimental diets during 14 d. The seven experimental diets were an uncontaminated control diet, three diets in which contaminated soil was introduced at levels of 3%, 6% and 9% and three diets in which spiked oil was introduced to achieve similar levels and profile of contaminants. Yolk, abdominal fat and liver were collected at the end of exposure. Indicator PCBs were extracted by ASE (Accelerated Solvent Extraction) and analyzed by GC-HMRS. Within each ingested matrix, the concentration of indicator PCBs in yolk and in abdominal fat linearly increased with the amount of indicator PCB ingested (P < 0.001). Except for PCB 28, the slopes of the responses to soil and to oil could not be differentiated (P > 0.1). RBA estimates did not differ from 1 for all indicator PCBs except for PCB 28, for which it was 0.58-0.59. Measurements performed on liver confirm these conclusions.     

Effect of soil and sediment composition on acetochlor sorption and desorption

Background, aim, and scope  Herbicide fate and its transport in soils and sediments greatly depend upon sorption–desorption processes. Quantitative determination of herbicide sorption–desorption is therefore essential for both the understanding of transport and the sorption equilibrium in the soil/sediment–water system; and it is also an important parameter for predicting herbicide fate using mathematical simulation models. The total soil/sediment organic carbon content and its qualitative characteristics are the most important factors affecting sorption–desorption of herbicides in soil or sediment. Since the acetochlor is one of the most frequently used herbicides in Slovakia to control annual grasses and certain annual broad-leaved weeds in maize and potatoes, and posses various negative health effects on human beings, our aim in this study was to investigate acetochlor sorption and desorption in various soil/sediment samples from Slovakia. The main soil/sediment characteristics governing acetochlor sorption–desorption were also identified. Materials and methods  The sorption–desorption of acetochlor, using the batch equilibration method, was studied on eight surface soils, one subsurface soil and five sediments collected from the Laborec River and three water reservoirs. Soils and sediments were characterized by commonly used methods for their total organic carbon content, distribution of humus components, pH, grain-size distribution, and smectite content, and for calcium carbonate content. The effect of soil/sediment characteristics on acetochlor sorption–desorption was examined by simple correlation analysis. Results  Sorption of acetochlor was expressed as the distribution coefficient (K _d). K _d values slightly decreased as the initial acetochlor concentration increased. These values indicated that acetochlor was moderately sorbed by soils and sediments. Highly significant correlations between the K _d values and the organic carbon content were observed at both initial concentrations. However, sorption of acetochlor was most closely correlated to the humic acid carbon, and less to the fulvic acid carbon. The total organic carbon content was found to also significantly influence acetochlor desorption. Discussion  Since the strong linear relationship between the K _d values of acetochlor and the organic carbon content was already released, the corresponding K _oc values were calculated. Considerable variation in the K _oc values suggested that other soil/sediment parameters besides the total soil organic carbon content could be involved in acetochlor sorption. This was revealed by a significant correlation between the K _oc values and the ratio of humic acid carbon to fulvic acid carbon (C_HA/C_FA). Conclusions  When comparing acetochlor sorption in a range of soils and sediments, different K _d values which are strongly correlated to the total organic carbon content were found. Concerning the humus fractions, the humic acid carbon content was strongly correlated to the K _d values, and it is therefore a better predictor of the acetochlor sorption than the total organic carbon content. Variation in the K _oc values was attributed to the differences in distribution of humus components between soils and sediments. Desorption of acetochlor was significantly influenced by total organic carbon content, with a greater organic carbon content reducing desorption. Recommendations and perspectives  This study examined the sorption–desorption processes of acetochlor in soils and sediments. The obtained sorption data are important for qualitative assessment of acetochlor mobility in natural solids, but further studies must be carried out to understand its environmental fate and transport more thoroughly. Although, the total organic carbon content, the humus fractions of the organic matter and the C_HA/C_FA ratio were sufficient predictors of the acetochlor sorption–desorption. Further investigations of the structural and chemical characteristics of humic substances derived from different origins are necessary to more preciously explain differences in acetochlor sorption in the soils and sediments observed in this study.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.     

Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils

This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg⁻¹ and Sector 3: pH 4.2, total Cu = 112 mg Cu kg⁻¹) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg⁻¹ (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils.     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.     

EDTA and HCl leaching of calcareous and acidic soils polluted with potentially toxic metals: remediation efficiency and soil impact

The environmental risk of potentially toxic metals (PTMs) in soil can be diminished by their removal. Among the available remediation techniques, soil leaching with various solutions is one of the most effective but data about the impact on soil chemical and biological properties are still scarce. We studied the effect of two common leaching agents, hydrochloric acid (HCl) and a chelating agent (EDTA) on Pb, Zn, Cd removal and accessibility and on physico-chemical and biological properties in one calcareous, pH neutral soil and one non-calcareous acidic soil. EDTA was a more efficient leachant compared to HCl: up to 133-times lower chelant concentration was needed for the same percentage (35%) of Pb removal. EDTA and HCl concentrations with similar PTM removal efficiency decreased PTM accessibility in both soils but had different impacts on soil properties. As expected, HCl significantly dissolved carbonates from calcareous soil, while EDTA leaching increased the pH of the acidic soil. Enzyme activity assays showed that leaching with HCl had a distinctly negative impact on soil microbial and enzyme activity, while leaching with EDTA had less impact. Our results emphasize the importance of considering the ecological impact of remediation processes on soil in addition to the capacity for PTM removal.     

Impact of woodchip biochar amendment on the sorption and dissipation of pesticide acetamiprid in agricultural soils

Pyrolysis of vegetative biomass into biochar and application of the more stable form of carbon to soil have been shown to be effective in reducing the emission of greenhouse gases, improving soil fertility, and sequestering soil contaminants. However, there is still lack of information about the impact of biochar amendment in agricultural soils on the sorption and environmental fate of pesticides. In this study, we investigated the sorption and dissipation of a neonicotinoid insecticide acetamiprid in three typical Chinese agricultural soils, which were amended by a red gum wood (Eucalyptus spp.) derived biochar. Our results showed that the amendment of biochar (0.5% (w/w)) to the soils could significantly increase the sorption of acetamiprid, but the magnitudes of enhancement were varied. Contributions of 0.5% newly-added biochar to the overall sorption of acetamiprid were 52.3%, 27.4% and 11.6% for red soil, paddy soil and black soil, respectively. The dissipation of acetamiprid in soils amended with biochar was retarded compared to that in soils without biochar amendment. Similar to the sorption experiment, in soil with higher content of organic matter, the retardation of biochar on the dissipation of acetamiprid was lower than that with lower content of organic matter. The different effects of biochar in agricultural soils may attribute to the interaction of soil components with biochar, which would block the pore or compete for binding site of biochar. Aging effect of biochar application in agricultural soils and field experiments need to be further investigated.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Dissolved organic carbon from sewage sludge and manure can affect estrogen sorption and mineralization in soils

In this study, effects of sewage sludge and manure borne dissolved organic carbon (DOC) on 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) sorption and mineralization processes were investigated in three agricultural soils. Batch equilibrium techniques and equilibrium dialysis methods were used to determine sorption mechanisms between DOC, estrogens and the soil solid phase. It was found that that the presence of organic waste borne DOC decreased estrogen sorption in soils which seems to be controlled by DOC/estrogen complexes in solution and by exchange processes between organic waste derived and soil borne DOC. Incubation studies performed with ¹⁴C-estrogens showed that DOC addition decreased estrogen mineralization, probably due to reduced bioavailability of estrogens associated with DOC. This increased persistence combined with higher mobility could increase the risk of estrogen transport to ground and surface waters.     

Sorption isotherms of brominated diphenyl ethers on natural soils with different organic carbon fractions

Sorption isotherms of BDE-28 and BDE-47 on natural soils with different contents of soil organic matter (SOM) were investigated. Due to low water solubility of BDEs and resulted narrow ranges of aqueous equilibrium concentration, the linear distribution model showed similar and good fitting efficiency to the linear portion of nonlinear Freundlich curve. For the same sample, the linear and nonlinear model fitting sorption coefficients were close. At the statistically significant level of 0.05 or 0.1, significant relationships of total organic carbon fraction (fOC) with the fitting sorption coefficients can be observed. As for BDE-28, the relationships of fOC and SOM fractions with the single point partition coefficients at different aqueous concentrations of BDEs were significant; while for BDE-47, the relationships became less significant or insignificant, especially at higher aqueous concentrations. The findings in this study may facilitate more understanding on transport and fate of studied BDEs in soil systems.