Influences of preparative methods of humic acids on the sorption of 2,4,6-trichlorophenol

Humic acids (HAs) are a major component of soil organic matter which strongly affects the sorption behavior of organic contaminants in soils. To assess the sorption-desorption characteristics of organic compounds on HAs, the organic adsorbent is usually isolated using an acid-base extraction method followed by air-drying or freeze-drying. In this study, a peat soil from the Yangming mountain area of Taiwan was sampled and repeatedly extracted followed by either air-drying or a non-drying treatment (denoted DHAs and NDHAs, respectively). The sorption of 2,4,6-TCP on HAs was evaluated using the batch method. Kinetic sorption results indicated that DHAs exhibited a two-step first-order sorption behavior, involving a rapid sorption followed by a slow sorption. The slow sorption may be attributed to the diffusion of 2,4,6-TCP through the condensed aromatic domains of HAs. On the contrary, the sorption of 2,4,6-TCP on NDHAs was extremely rapid, and the sorption data did not fit existing kinetic models. Each HA sample exhibited a nonlinear sorption isotherm. Sorption nonlinearity (represented by Freundlich N values) and K(oc) had a positive relationship with aliphaticity for DHAs; however, nonlinearity and K(oc) correlated positively with aromaticity when NDHAs adsorbents were used. We conclude that the air-drying technique may artificially create a more condensed area, which strongly affects the sorption characteristics of HAs. Thus, an incorrect evaluation of the sorption capacity and its relationship with the chemical composition of HAs would arise following use of the air-drying method.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Long-term effects of amendment with liquid swine manure on proton binding behavior of soil humic substances

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from liquid swine manure (LSM), soils amended with either 90 or 150 m(3)ha(-1)year(-1) of LSM for 7 years, and the corresponding unamended control soil were investigated by a current potentiometric titration method. The non-ideal competitive adsorption (NICA)-Donnan model for proton binding by two classes of binding sites (i.e., carboxylic- and phenolic-type groups) was fit to titration data, and a set of fitting parameters was obtained for each HA and FA sample. The NICA-Donnan model was shown to describe with a great degree of accuracy the behavior of experimental titration datasets, and highlighted important differences in the acid-base properties of the HAs and FAs examined. When compared to the unamended soil HA and FA, LSM-HA and LSM-FA, had smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, smaller heterogeneity of carboxylic-type groups, and smaller, in the case of HA, or similar, in the case of FA, heterogeneity of phenolic-type groups. Amendment with LSM caused a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. Further, LSM application induced a decrease of the heterogeneity of carboxylic-type groups, whereas appeared not to affect substantially the heterogeneity of phenolic-type groups of LSM-amended soil HAs and FAs. These effects were more evident for HAs than for FAs and tended to slightly increase with increasing LSM amendment rate.     

Effect of soil properties on degradation and sorption of methyl bromide in soil

Methyl bromide (CH₃Br) is currently the most widely used soil fumigant, and its emission into the atmosphere after application reportedly contributes to ozone depletion in the stratosphere. Irreversible degradation and partially reversible sorption reactions affect the quantity of this furnigant reaching the soil surface and escaping into the atmosphere. Incubation studies in closed headspace vials under controlled conditions showed that degradation of CH₃Br was highly dependent on soil organic matter content, and to a lesser extent, on the moisture level in the soil. Methylation of CH₃Br on organic matter was suggested to be the major reaction that CH₃Br undergoes in the soil environment. Other soil constituents such as clay did not contribute to the degradation under moist or air-dried conditions, though enhanced degradation was observed on oven-dried montmorillonite and kaolinite clays. Within soil profiles, degradation of CH₃Br decreased with soil depth mainly due to the reduction of soil organic matter content with depth. In both Greenfield and Wasco sandy loams, the degradation rate of CH₃Br in soil layers from 0 to 270 cm could be estimated from soil organic matter content. Sorption of CH₃Br on moist soils was generally limited, and varied with soil depth. The degree of sorption could be predicted from soil moisture alone or soil moisture and organic matter content.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Carbon nanotubes (CNTs), as a type of superior adsorbents for both organic and inorganic contaminants, are increasingly introduced into the environment. Ubiquitous natural organic matter (NOM) would coat on the released CNTs and change their physicochemical properties and sorption of contaminants. The effects of four sequentially extracted humic acids (HAs, as a model NOM) from a peat soil on the physicochemical properties and Cd(II) sorption of three multiwalled CNTs (MWNTs) with different surface areas were investigated. The MWNTs as purchased with very few oxygen-containing functional groups had relatively low sorption capacities (0.93–1.49 mg g⁻¹) for Cd(II) and the sorption capacity increased with increasing surface area of the MWNTs. Surface-coating with the HAs lowered surface areas of the MWNTs but greatly increased their sorption capacities (5.42–18.4 mg g⁻¹). The MWNT-bound HAs introduced oxygen-containing functional groups and negative charges to the MWNT surfaces, which could thus increase the apparent sorption of Cd(II) through chemical complexation and electrostatic attraction, respectively. The later-extracted HAs with lower polarity were more favorable for the surface-coating but increased less Cd(II) sorption by the MWNTs. The results are expected to shed light on understanding the underlying mechanism of the effect of NOM on the sorption of heavy metal ions by CNTs.     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.     

Airflow dispersion in unsaturated soil

Dispersion data is abundant for water flow in the saturated zone but is lacking for airflow in unsaturated soil. However, for remediation processes such as soil vapour extraction, characterization of airflow dispersion is necessary for improved modelling and prediction capabilities. Accordingly, gas-phase tracer experiments were conducted in five soils ranging from uniform sand to clay at air-dried and wetted conditions. The disturbed soils were placed in one-dimensional stainless steel columns, with sulfur hexafluoride used as the inert tracer. The tested interstitial velocities were typical of those present in the vicinity of a soil vapour extraction well, while wetting varied according to the water-holding capacity of the soils. Results gave dispersivities that varied between 0.42 and 2.6 cm, which are typical of values in the literature. In air-dried soils, dispersion was found to increase with the pore size variability of the soil. For wetted soils, particle shape was an important factor at low water contents, while at high water contents, the proportion of macroporous space filled with water was important. The relative importance of diffusion decreased with increasing interstitial velocity and water content and was, in general, found to be minor compared to mechanical mixing across all conditions studied.     

Sorption of tebuconazole onto selected soil minerals and humic acids

The aim of the present study was to investigate tebuconazole sorption on common soil minerals (birnessite, ferrihydrite, goethite, calcite and illite) and humic acids (representing soil organic matter). Tebuconazole was used (i) in the commercial form Horizon 250 EW and (ii) as an analytical grade pure chemical. In the experiment with the commercially available tebuconazole, a significant pH-dependent sorption onto the oxides was observed (decreasing sorption with increasing pH). The highest sorption was found for ferrihydrite due to its high specific surface area, followed by humic acids, birnessite, goethite and illite. No detectable sorption was found for calcite. The sorption of analytical grade tebuconazole on all selected minerals was significantly lower compared to the commercial product. The sorption was the highest for humic acids, followed by ferrihydrite and illite and almost negligible for goethite and birnessite without any pH dependence. Again, no sorption was observed for calcite. The differences in sorption of the commercially available and analytical grade tebuconazole can be attributed to the additives (e.g., solvents) present in the commercial product. This work proved the importance of soil mineralogy and composition of the commercially available pesticides on the behavior of tebuconazole in soils.     

毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

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.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Transport of rimsulfuron and its metabolites in soil columns

This paper presents a study on degradation, sorption and transport of the sulfonylurea herbicide rimsulfuron and its major metabolites in alluvial soil columns. The formulation of rimsulfuron was found to strongly affect its degradability. Hydrolysis of pure rimsulfuron takes place rapidly in distilled water (t(1/2)=2.2 days) or indeed instantaneously in alkaline solution. The formulated rimsulfuron (Titus, 25% rimsulfuron, Du Pont De Nemours) is more persistent in alluvial soil suspensions (t(1/2)=7.5 days). The study of sorption of Titus and its two major metabolites (1 and 2) revealed that these three chemicals are potentially highly mobile in the studied soil: in suspension distribution coefficients of 0.0028, 0.125 and 0.149 cm3 g(-1) were obtained respectively. Given the instability of rimsulfuron in alkaline solutions, the pH effect was evaluated with metabolite 2 in water saturated Fontainebleau sand columns at pH 6, 8 and 10. Transport was found to be strongly dependent on pH; a linear relationship was obtained between pH and the retardation factor or the dispersion coefficient. In alluvial soil columns, rimsulfuron from Titus was found to be very mobile (R=1.2) and rapidly degraded into metabolites 1 and 2, which were transported at a similar velocity. Nevertheless, the risks of groundwater contamination by rimsulfuron seem very low, as it is rapidly degraded under dynamic conditions (t(1,2)=1.4 days). On the other hand the relatively stable metabolite 2 seems likely to persist in the soil and to be transported to the groundwater. Special attention should thus be given to this compound at least as long as its harmlessness is not demonstrated.     

Leaching of trifluralin,metolachlor, and metribuzin in a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied in field plots located on a Commerce clay loam soil near Baton Rouge, Louisiana at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The half-lives of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth were found to be 54.7 days, 35.8 days and 29.8 days, respectively. The proportion of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth was 94.7%, 86.6%, and 75.4%, respectively of that found in the top 0-60 cm soil depth 30 days after application. Trifluralin concentrations were within a range of 0.026 ng/mL to 0.058 ng/mL in 1 m deep well water, and between 0.007 ng/mL and 0.039 ng/mL in 2 m deep well water over a 62 day period after application. Metolachlor concentrations in the 1 m and 2 m wells ranged from 3.62 ng/mL to 82.32 ng/mL and 8.44 ng/mL to 15.53 ng/mL, respectively. Whereas metribuzin concentrations in the 1 m and 2 m wells ranged from 0.70 ng/mL to 27.75 ng/mL and 1.71 ng/mL to 3.83 ng/mL, respectively. Accordingly, trifluralin was found to be strongly adsorbed on the soil and showed negligible leaching. Although metolachlor and metribuzin were also both readily adsorbed on the soil, their leaching potential was high. As a result, in the clay loam soil studied, metribuzin concentration in groundwater with shallow aquifers is likely to exceed the 10 mg/L US Environmental Protection Agency (EPA) advisory level for drinking water early in the application season, whereas trifluralin and metolachlor concentrations are expected to remain substantially lower than their respective 2 ng/mL and 175 ng/mL EPA advisory levels.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Effect of clays, metal oxides, and organic matter on rhamnolipid biosurfactant sorption by soil

Rhamnolipids produced by Pseudomonas aeruginosa have been proposed as soil washing agents for enhanced removal of metal and organic contaminants from soil. A potential limitation for the application of rhamnolipids is sorption by soil matrix components. The objective of this study is to empirically determine the contribution of representative soil constituents (clays, metal oxides, and organic matter) to sorption of the rhamnolipid form most efficient at metal complexation (monorhamnolipid). Sorption studies show that monorhamnolipid (R1) sorption is concentration dependent. At low R1 concentrations that are relevant for enhancing organic contaminant biodegradation, R1 sorption followed the order: hematite (Fe(2)O(3))>kaolinite>MnO(2) approximately illite approximately Ca-montmorillonite>gibbsite (Al(OH)(3))>humic acid-coated silica. At high R1 concentrations, relevant for use in complexation/removal of metals or organics, R1 sorption followed the order: illite>humic acid-coated silica>Ca-montmorillonite>hematite>MnO(2)>gibbsite approximately kaolinite. These results allowed prediction of R1 sorption by a series of six soils. Finally, a comparison of R1 and R2 (dirhamnolipid) shows that the R1 form sorbs more strongly alone than when in a mixture of both the R1 and R2 forms. The information presented can be used to estimate, on an individual soil basis, the extent of rhamnolipid sorption. This is important for determining: (1) whether rhamnolipid addition is a feasible remediation option and (2) the amount of rhamnolipid required to efficiently remove the contaminant.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Experimental variability in characterization of cyfluthrin sorption to soil

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-alpha -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, Koc, obtained using different experimental methodologies with one soil can be comparable to the variation in Koc values obtained for soils with different physical and chemical properties using one method. Koc values for cyfluthrin ranged from 56,000 to 300,000 L kg-1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.     

Terbuthylazine persistence in an organic amended soil

The aim of this work was to study the effect of the application of a solid waste from olive oil production (alperujo) on the movement and persistence of the herbicide terbuthylazine (N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine). An experimental olive grove was divided in two plots: (i) Plot without organic amendment (blank) and (ii) Plot treated with alperujo during 3 years at a rate of 17920 kg of alperujo ha(- 1). Terbuthylazine was applied to both plots at a rate of 2 kg ha(- 1) a.i. Triplicates from each plot were sampled at 3 depths (0-10, 10-20 and 20-30 cm), air-dried, remains of olive leaves, grass roots, and stones removed and sieved through a 5 mm mesh sieve. Terbuthylazine was extracted with methanol 1:2 weight:volume ratio, the extracts were evaporated to dryness, resuspended in 2 mL of methanol, filtered and anylized by high performance liquid chromatography (HPLC). Higher amounts of terbuthylazine were detected at each sampling depth in plots treated with alperujo. The increase in soil organic matter content upon amendment with alperujo slightly increased sorption, suggesting that other factors beside sorption affect terbuthylazine degradation rate in organic amended soils.     

Sorption and mobility of pharmaceutical compounds in soil irrigated with reclaimed wastewater

Use of reclaimed wastewater for irrigation is an important route for the introduction of pharmaceutical compounds (PCs) into the environment. In this study, the mobility and sorption-desorption behavior of carbamazepine, naproxen and diclofenac were studied in soil layers sampled from a plot irrigated with secondary-treated wastewater (STWW). Carbamazepine and diclofenac were significantly retarded in the 0-5 cm soil sample rich in soil organic matter (SOM): carbamazepine was not affected by the water quality (freshwater versus STWW), whereas diclofenac exhibited a higher retardation factor (RF) in the freshwater system. Naproxen exhibited significantly lower RFs than diclofenac but with a similar trend - higher retardation in the freshwater versus STWW system. In the 5-15 cm soil sample containing low SOM, naproxen was highly mobile while carbamazepine and diclofenac were still retarded. In the 15-25 cm sample, all compounds exhibited their lowest RFs. Sorption data suggested that SOM governs the studied PCs' interactions with the soil samples. However, higher carbon-normalized sorption coefficients were measured for the PCs in the 15-25 cm sample, suggesting that both quantity and the physicochemical nature of SOM affect sorption interactions. While both naproxen and carbamazepine exhibited reversible sorption isotherms, diclofenac exhibited pronounced sorption-desorption hysteresis. This study suggests that carbamazepine and diclofenac can be classified as slow-mobile compounds in SOM-rich soil layers. When these compounds pass this layer and/or introduced into SOM-poor soils, their mobility increases significantly. This emphasizes the potential transport of PCs to groundwater in semiarid zones due to intensive irrigation with reclaimed wastewater in SOM-poor soils.