Identifying organic micropollutants' transformation products from the soil dissipation experiment by non-targeted high-resolution mass spectrometry approach: Can we gain more than transformation product identity?

Risk assessment of environmental hazards originating from xenobiotics extensively used worldwide (e.g., pharmaceuticals, bisphenols, or preservatives) requires a combined study of their effects, mobility, dissipation mechanisms, and subsequent transformation product identification and evaluation. We have developed an efficient accelerated solvent extraction method for a broad range of micropollutants of variable physical-chemical properties in soils to enable more accurate hazard characterisation. Micropollutant recoveries from freeze-dried soils were 60-120%, with the exception of atorvastatin, fexofenadine, and telmisartan, which had reduced recoveries (40-66%). The observed matrix effect ranged from -26% to 17% and was corrected by the matrix matching standard for quantitative analysis. The method allows sensitive and reliable determination of a wide range of analytes in soil samples and, consequently, qualitative analysis of transformation products (TP) with variable physicochemical properties. We identified TPs of five compounds (venlafaxine, telmisartan, valsartan, atorvastatin, and sertraline) by applying suspect and non-targeted data analyses. To our knowledge, the transformation product of atorvastatin was reported for the first time. All others were found in soil or other matrices. Valsartan (formed valsartan acid) and atorvastatin (transformed probably by oxidative decarboxylation of beta, delta dihydroxy heptanoic acid chain to propionic acid) were modified to a relatively large extent. All other compounds identified were only hydroxylated (sertraline and telmisartan) or demethylated (venlafaxine). We estimated the stability and presence of the identified TPs based on the constructed time trends and the ratio between TP formation and degradation rates. We demonstrated how valuable a non-targeted approach can be for complex evaluation of the fate and effect of soil pollutants.

LC-HRMS method for study of pharmaceutical uptake in plants: effect of pH under aeroponic condition.

Global climate changes cause water scarcity in many regions, and the sustainable use of recycled water appears crucial, especially in agriculture. However, potentially hazardous compounds such as pharmaceuticals can enter the food chain and pose severe risks. This paper aims to study the presence of selected pharmaceutical active compounds (PhACs) and their metabolites in crops grown in aeroponic conditions and evaluate the potential of PhAC plant uptake. A solvent extraction with an acidified mixture of acetonitrile and water followed by LC-HRMS was developed and validated for quantifying nine pharmaceuticals and their nine metabolites in three plants. We aimed for a robust method with a wide linear range because an extensive concentration range in different matrices was expected. The developed method proved rapid and reliable determination of selected pharmaceuticals in plants in the wide concentration range of 10 to 20,000 ng g-1 and limit of detection range 0.4 to 9.0 ng g-1. The developed method was used to study the uptake and translocation of pharmaceuticals and their metabolites in plant tissues from an aeroponic experiment at three different pH levels. Carbamazepine accumulated more in the leaves of spinach than in arugula. On the other hand, sulfamethoxazole and clindamycin evinced higher accumulation in roots than in leaves, comparable in both plants. The expected effect of pH on plants' uptake was not significant.

Dissipation of twelve organic micropollutants in three different soils: Effect of soil characteristics and microbial composition.

The dissipation kinetics and half-lives of selected organic micropollutants, including pharmaceuticals and others, were systematically investigated and compared among different soil types. While some pollutants (e.g., atorvastatin, valsartan, and bisphenol S) disappeared rapidly in all the tested soils, many of them (e.g., telmisartan, memantine, venlafaxine, and azithromycin) remained persistent. Irrespective of the soil characteristics, venlafaxine showed the lowest dissipation kinetics and the longest half-lives (250 to approximately 500 days) among the stable compounds. The highest first and second-order kinetics were, however, recorded for valsartan (k1; 0.262 day-1) and atorvastatin (k2; 33.8 g µg-1 day-1) respectively. Nevertheless, more than 90% (i.e., DT90) of all the rapidly dissipated compounds (i.e., atorvastatin, bisphenol S, and valsartan) disappeared from the tested soils within a short timescale (i.e., 5-36 days). Dissipation of pollutants that are more susceptible to microbial degradation (e.g., atorvastatin, bisphenol S, and valsartan) seems to be slower for soils possessing the lowest microbial biomass C (Cmic) and total phospholipid fatty acids (PLFAtotal), which also found statistically significant. Our results revealing the persistence of several organic pollutants in agricultural soils, which might impact the quality of these soils, the groundwater, and eventually on the related biota, is of high environmental significance.

Selective accumulation of pharmaceutical residues from 6 different soils by plants: a comparative study on onion, radish, and spinach.

The accumulation of six pharmaceuticals of different therapeutic uses has been thoroughly investigated and compared between onion, spinach, and radish plants grown in six soil types. While neutral molecules (e.g., carbamazepine (CAR) and some of its metabolites) were efficiently accumulated and easily translocated to the plant leaves (onion > radish > spinach), the same for ionic (both anionic and cationic) molecules seems to be minor to moderate. The maximum accumulation of CAR crosses 38,000 (onion), 42,000 (radish), and 7000 (spinach) ng g-1 (dry weight) respectively, in which the most majority of them happened within the plant leaves. Among the metabolites, the accumulation of carbamazepine 10,11-epoxide (EPC - a primary CAR metabolite) was approximately 19,000 (onion), 7000 (radish), and 6000 (spinach) ng g-1 (dry weight) respectively. This trend was considerably similar even when all these pharmaceuticals applied together. The accumulation of most other molecules (e.g., citalopram, clindamycin, clindamycin sulfoxide, fexofenadine, irbesartan, and sulfamethoxazole) was restricted to plant roots, except for certain cases (e.g., clindamycin and clindamycin sulfoxide in onion leaves). Our results clearly demonstrated the potential role of this accumulation process on the entrance of pharmaceuticals/metabolites into the food chain, which eventually becomes a threat to associated living biota.

Assessment of potential mobility of selected micropollutants in agricultural soils of the Czech Republic using their sorption predicted from soil properties.

The sorption of organic contaminants in soils and sediment is a crucial factor affecting their mobility in the vadose zone environment. The Freundlich sorption isotherms were evaluated for eleven micropollutants and eight soils. The highest Freundlich sorption coefficients, KF, were obtained for triclosan (324 ± 153 cm3/nµg1-1/ng-1) followed by sertraline (120 ± 74), venlafaxine (74.3 ± 41.2), telmisartan (33.3 ± 13.6), atorvastatin (8.66 ± 4.78), bisphenol S (8.03 ± 4.87), lamotrigine (6.92 ± 3.02), 2-phenylbenzimidazole-5-sulfonic acid (3.77 ± 2.25), memantine (3.42 ± 1.64), 1-methyl-1H-benzotriazole (2.05 ± 0.99), and valsartan (0.88 ± 0.89). The KF values for the individual compounds were correlated with soil properties. Multiple linear regressions were used to derive equations for predicting the KF values using the soil properties. The first set of equations contained mainly properties with the strongest correlations with the KF values, e.g., a base cation saturation for positively charged compounds or a hydrolytic acidity for negatively charged compounds. The second set of equations contained properties included in the map of agricultural soils of the Czech Republic. These equations always indicated positive correlations with oxidizable organic carbon and clay content. They also included either a negative or positive correlation with pHKCl. A positive correlation with pHKCl was obtained for venlafaxine, memantine, and sertraline, which were mostly positively charged. A negative correlation with pHKCl was obtained for the remaining compounds. The second set of equations, the soil map, and the database of soil properties were used to predict the KF value distributions within the Czech agricultural soils. It resulted in similar KF distributions' patterns for valsartan, lamotrigine, atorvastatin, and telmisartan (with a positive correlation between KF and hydrolytic acidity), which considerably differed from the KF patterns for the other compounds. These maps were used to delineate areas with a leaching potential of the compounds toward groundwater that will serve as a tool for assessing a potential groundwater vulnerability.

Desorption of pharmaceuticals and illicit drugs from different stabilized sludge types across pH.

Pharmaceutical and illicit drug residues in sewage sludge may present important risks following direct application to agricultural soils, potentially resulting in uptake by plants. Leaching/desorption tests were performed on different types of stabilized sewage sludge originating from multiple treatment technologies in the Slovak Republic. Acid rain and base-rich condition of soil with different pH conditions were simulated to model the effect of widely varying pH (pH 2, 4, 7, 9, and 12) on the leaching/desorption of pharmaceuticals and illicit drugs. Twenty-nine of 93 target analytes were found above the limit of quantification in sludge or associated leachates. Total desorbed amounts of pharmaceuticals and illicit drugs ranged from 810 to 4000 µg/kg, and 110 to 3600 µg/kg of the dry mass of anaerobic and aerobic sludge, respectively. Desorbed fractions were calculated as these values are normalized to initial sludge concentration and, therefore, were more suitable for qualitative description of the behavior of individual compounds. Using principal component analysis, qualitative analysis of the desorbed fraction confirmed the differences among sludge types, pharmaceuticals, and desorption pH. Desorbed fractions could not be related to the octanol/water distribution coefficient. Desorbed fractions also did not reflect the expected ionization of studied molecules unless converted into their relative values. Generally, the lowest mobility was observed within the environmentally relevant pH range of 4-9, and high pH generally resulted in high desorption, especially in anaerobically stabilized sludges.

A novel multiscale biophysical model to predict the fate of ionizable compounds in the soil-plant continuum.

Soil pollution from emerging contaminants poses a significant threat to water resources management and food production. The development of numerical models to describe the reactive transport of chemicals in both soil and plant is of paramount importance to elaborate mitigation strategies. To this aim, in the present study, a multiscale biophysical model is developed to predict the fate of ionizable compound in the soil-plant continuum. The modeling framework connects a multi-organelles model to describe processes at the cell level with a semi-mechanistic soil-plant model, which includes the widely used Richards-based solver, HYDRUS. A Bayesian probabilistic framework is used to calibrate and assess the capability of the model in reproducing the observations from an experiment on the translocation of five pharmaceuticals in green pea plants. Results show satisfactory fitting performance and limited predictive uncertainty. The subsequent validation with the cell model indicates that the estimated soil-plant parameters preserve a physically realistic meaning, and their calibrated values are comparable with the existing literature values, thus confirming the overall reliability of the analysis. Model results further suggest that pH conditions in both soil and xylem play a crucial role in the uptake and translocation of ionizable compounds.

On the Use of Mechanistic Soil-Plant Uptake Models: A Comprehensive Experimental and Numerical Analysis on the Translocation of Carbamazepine in Green Pea Plants.

Food contamination is a major worldwide risk for human health. Dynamic plant uptake of pollutants from contaminated environments is the preferred pathway into the human and animal food chain. Mechanistic models represent a fundamental tool for risk assessment and the development of mitigation strategies. However, difficulty in obtaining comprehensive observations in the soil-plant continuum hinders their calibration, undermining their generalizability and raising doubts about their widespread applicability. To address these issues, a Bayesian probabilistic framework is used, for the first time, to calibrate and assess the predictive uncertainty of a mechanistic soil-plant model against comprehensive observations from an experiment on the translocation of carbamazepine in green pea plants. Results demonstrate that the model can reproduce the dynamics of water flow and solute reactive transport in the soil-plant domain accurately and with limited uncertainty. The role of different physicochemical processes in bioaccumulation of carbamazepine in fruits is investigated through Global Sensitivity Analysis, which shows how soil hydraulic properties and soil solute sorption regulate transpiration streams and bioavailability of carbamazepine. Overall, the analysis demonstrates the usefulness of mechanistic models and proposes a comprehensive numerical framework for their assessment and use.

How microbial community composition, sorption and simultaneous application of six pharmaceuticals affect their dissipation in soils.

Pharmaceuticals may enter soils due to the application of treated wastewater or biosolids. Their leakage from soils towards the groundwater, and their uptake by plants is largely controlled by sorption and degradation of those compounds in soils. Standard laboratory batch degradation and sorption experiments were performed using soil samples obtained from the top horizons of seven different soil types and 6 pharmaceuticals (carbamazepine, irbesartan, fexofenadine, clindamycin and sulfamethoxazole), which were applied either as single-solute solutions or as mixtures (not for sorption). The highest dissipation half-lives were observed for citalopram (average DT50,S for a single compound of 152 ±â€¯53.5 days) followed by carbamazepine (106.0 ±â€¯17.5 days), irbesartan (24.4 ±â€¯3.5 days), fexofenadine (23.5 ±â€¯20.9 days), clindamycin (10.8 ±â€¯4.2 days) and sulfamethoxazole (9.6 ±â€¯2.0 days). The simultaneous application of all compounds increased the half-lives (DT50,M) of all compounds (particularly carbamazepine, citalopram, fexofenadine and irbesartan), which is likely explained by the negative impact of antibiotics (sulfamethoxazole and clindamycin) on soil microbial community. However, this trend was not consistent in all soils. In several cases, the DT50,S values were even higher than the DT50,M values. Principal component analyses showed that while knowledge of basic soil properties determines grouping of soils according sorption behavior, knowledge of the microbial community structure could be used to group soils according to the dissipation behavior of tested compounds in these soils. The derived multiple linear regression models for estimating dissipation half-lives (DT50,S) for citalopram, clindamycin, fexofenadine, irbesartan and sulfamethoxazole always included at least one microbial factor (either amount of phosphorus in microbial biomass or microbial biomarkers derived from phospholipid fatty acids) that deceased half-lives (i.e., enhanced dissipations). Equations for citalopram, clindamycin, fexofenadine and sulfamethoxazole included the Freundlich sorption coefficient, which likely increased half-lives (i.e., prolonged dissipations).

Competitive and synergic sorption of carbamazepine, citalopram, clindamycin, fexofenadine, irbesartan and sulfamethoxazole in seven soils.

Sorption of pharmaceuticals, which can occur in soils, may differ when present in a soil solution as a single compound or in a solution with other pharmaceuticals. Therefore, the sorption isotherms described by the Freundlich equations were evaluated for 6 compounds, which were applied in solutions of a single pharmaceutical, two pharmaceuticals or all pharmaceuticals to seven soils. Study mainly focused on a behavior of fexofenadine and irbesartan that occurred in soils in 3 forms (cationic, zwitter-ionic or neutral, anionic). Sorption of both compounds slightly increased (in some soils) when applied together, largely increased when applied with carbamazepine (neutral), and extremely increased when applied in solutions with citalopram (strongly sorbed cation), which could be explained by a cooperative multilayer sorption on soil constituents. On the other hand, sorption of both compounds moderately decreased when applied with clindamycin (cation and neutral) or sulfamethoxazole (neutral or anion). The magnitude of an increase or decrease in the Freundlich sorption coefficient (KF) for a particular compound depended on soil conditions, a form of compound's molecule and its interaction with molecules of other compounds. Despite sorption being influenced by other compound(s) in solution, the KF coefficients evaluated for a particular compound under the different conditions were mostly correlated with the same soil properties: KF,CAR with an organic carbon content, KF,CIT and KF,CLI with a base cation saturation, KF,SUL with hydrolytic acidity, and KF,FEX and KF,IRB with sorption complex saturation.

Soil influences on uptake and transfer of pharmaceuticals from sewage sludge amended soils to spinach.

Sewage sludge from wastewater treatment plants, which may contain various contaminants including pharmaceuticals, is often used as a soil amendment. These contaminants may subsequently be taken up by plants. In the present study we examined uptake of select pharmaceuticals from sewage sludge applied to soils by spinach plants. Seven soils were amended with sewage sludge from two wastewater treatment plants (A and B). Concentrations of compounds in plant tissues (roots and leaves) of spinach planted 45 days in these soils under greenhouse conditions were evaluated after harvest. The largest bioaccumulation in the roots and leaves was observed for sertraline (bioaccumulation factors (BAF) of 3.3-37.9 and 1-13.4, respectively), tramadol (1.3-10.0 and 4.8-30.0), and carbamazepine (2.2-17.2 and 6.1-48.8) and its metabolite carbamazepine 10,11-epoxide (not-quantified to 7.3 and 9.3-96.7). Elevated bioaccumulation in spinach roots was also identified for telmisartan (3.0-20.3) and miconazole (4.3-15.1), and leaves for metoprolol acid (not-quantified to 24.3). BAF values resulting from application of sludge B were similar to or moderately higher than BAFs from sludge A. The BAF values of carbamazepine and carbamazepine 10,11-epoxide in all tissues were negatively correlated with soil cation exchange capacity (CEC). This negative correlation between BAF and CEC was also observed for tramadol (A-roots and B-leaves), citalopram (B-roots), and telmisartan (B-roots) or between BAF and clay content for metoprolol acid (A-leaves and B-roots), tramadol (B-roots and A-leaves) and venlafaxine (B-roots). However, in the case of some other compounds (i.e. sertraline, amitriptyline, mirtazapine, metoprolol), uptake and the subsequent translocation and transformation from 3 soils of a higher pH and base cation saturation (Stagnic Chernozem Siltic, Haplic Chernozem and Greyic Phaeozem) significantly differed from 4 soils with a lower pH and base cation saturation (Haplic Luvisol, Haplic Cambisol, Dystric Cambisol and Arenosol Epieutric). Such observations proved strong compound dependent influences of soil conditions on various compounds bioaccumulations in plants and necessity of studying these processes always in diverse soils.

Root uptake of atenolol, sulfamethoxazole and carbamazepine, and their transformation in three soils and four plants.

Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb's lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb's lettuce and spinach, respectively. Compounds' transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb's lettuce, and spinach.

Effect of adjuvant on pendimethalin and dimethenamid-P behaviour in soil.

Adjuvants are used to improve pesticides' performance. It is expected that adjuvants should increase sorption and persistence, as well as decrease mobility of pesticides in soils. Impact of the "Grounded" brand adjuvant on the behaviour of two herbicides, pendimethalin and dimethenamid-P, was investigated in a Haplic Chernozem. Both herbicides were tested in a laboratory batch sorption experiment with and without adjuvant. The sorption experiment showed that adjuvant negligibly increased dimethenamid-P sorption (KF = 2.12 and 2.15 cm3/n µg1 - 1/n g-1) but significantly increased pendimethalin sorption (KF = 270.1 and 3096.4 cm3/n µg1 - 1/n g-1). In field conditions, both herbicides were retained mainly in the topsoil layer (0-5 cm). The pendimethalin dissipation half-lives were similar for all treatments (ranging from 43.0 to 44.6 days) and were not influenced by either irrigation (p = 0.86) or adjuvant (p = 0.9). The dimethenamid-P dissipation half-lives ranged from 8.8 days for irrigated treatment without adjuvant to 12.9 days for non-irrigated treatment with adjuvant. Dimethenamid-P dissipation half-life in treatments with adjuvant was significantly longer (p = 0.049) than was half-life in a treatment without adjuvant. Significantly longer dissipation half-life was observed also in non-irrigated treatments than in irrigated treatments (p = 0.044).

Sorption of citalopram, irbesartan and fexofenadine in soils: Estimation of sorption coefficients from soil properties.

The sorption of 3 pharmaceuticals, which may exist in 4 different forms depending on the solution pH (irbesartan in cationic, neutral and anionic, fexofenadine in cationic, zwitter-ionic and anionic, and citalopram cationic and neutral), in seven different soils was studied. The measured sorption isotherms were described by Freundlich equations, and the sorption coefficients, KF (for the fixed n exponent for each compound), were related to the soil properties to derive relationships for estimating the sorption coefficients from the soil properties (i.e., pedotransfer rules). The largest sorption was obtained for citalopram (average KF value for n = 1 was 1838 cm3 g-1) followed by fexofenadine (KF = 35.1 cm3/n µg1-1/n g-1, n = 1.19) and irbesartan (KF = 3.96 cm3/n µg1-1/n g-1, n = 1.10). The behavior of citalopram (CIT) in soils was different than the behaviors of irbesartan (IRB) and fexofenadine (FEX). Different trends were documented according to the correlation coefficients between the KF values for different compounds (RIRB,FEX = 0.895, p-value<0.01; RIRB,CIT = -0.835, p-value<0.05; RFEX,CIT = -0.759, p-value<0.05) and by the reverse relationships between the KF values and soil properties in the pedotransfer functions. While the KF value for citalopram was positively related to base cation saturation (BCS) or sorption complex saturation (SCS) and negatively correlated to the organic carbon content (Cox), the KF values of irbesartan and fexofenadine were negatively related to BCS, SCS or the clay content and positively related to Cox. The best estimates were obtained by combining BCS and Cox for citalopram (R2 = 93.4), SCS and Cox for irbesartan (R2 = 96.3), and clay content and Cox for fexofenadine (R2 = 82.9).

Antibiotics degradation in soil: A case of clindamycin, trimethoprim, sulfamethoxazole and their transformation products.

Twelve different soil types that represent the soil compartments of the Czech Republic were fortified with three antibiotics (clindamycin (CLI), sulfamethoxazole (SUL), and trimethoprim (TRI)) to investigate their fate. Five metabolites (clindamycin sulfoxide (CSO), hydroxy clindamycin sulfoxide (HCSO), S-(SDC) and N-demethyl clindamycin (NDC), N4-acetyl sulfamethoxazole (N4AS), and hydroxy trimethoprim (HTR)) were detected and identified using HPLC/HRMS and HRPS in the soil matrix in this study. The identities of CSO and N4AS were confirmed using commercially available reference standards. The parent compounds degraded in all soils. Almost all of the metabolites have been shown to be persistent in soils, with the exception of N4AS, which was formed and degraded completely within 23 days of exposure. The rate of degradation mainly depended on the soil properties. The PCA results showed a high dependence between the soil type and behaviour of the pharmaceutical metabolites. The mentioned metabolites can be formed in soils, and the most persistent ones may be transported to the ground water and environmental water bodies. Because no information on the effects of those metabolites on living organism are available, more studies should be performed in the future to predict the risk to the environment.

Influence of Elevation Data Resolution on Spatial Prediction of Colluvial Soils in a Luvisol Region.

The development of a soil cover is a dynamic process. Soil cover can be altered within a few decades, which requires updating of the legacy soil maps. Soil erosion is one of the most important processes quickly altering soil cover on agriculture land. Colluvial soils develop in concave parts of the landscape as a consequence of sedimentation of eroded material. Colluvial soils are recognised as important soil units because they are a vast sink of soil organic carbon. Terrain derivatives became an important tool in digital soil mapping and are among the most popular auxiliary data used for quantitative spatial prediction. Prediction success rates are often directly dependent on raster resolution. In our study, we tested how raster resolution (1, 2, 3, 5, 10, 20 and 30 meters) influences spatial prediction of colluvial soils. Terrain derivatives (altitude, slope, plane curvature, topographic position index, LS factor and convergence index) were calculated for the given raster resolutions. Four models were applied (boosted tree, neural network, random forest and Classification/Regression Tree) to spatially predict the soil cover over a 77 ha large study plot. Models training and validation was based on 111 soil profiles surveyed on a regular sampling grid. Moreover, the predicted real extent and shape of the colluvial soil area was examined. In general, no clear trend in the accuracy prediction was found without the given raster resolution range. Higher maximum prediction accuracy for colluvial soil, compared to prediction accuracy of total soil cover of the study plot, can be explained by the choice of terrain derivatives that were best for Colluvial soils differentiation from other soil units. Regarding the character of the predicted Colluvial soils area, maps of 2 to 10 m resolution provided reasonable delineation of the colluvial soil as part of the cover over the study area.

Transformation of atenolol, metoprolol, and carbamazepine in soils: The identification, quantification, and stability of the transformation products and further implications for the environment.

Pharmaceuticals are a large group of substances that have been recognized as environmental contaminants in recent years. Research on the pharmaceutical fate in soils is currently limited or missing. In this study, three pharmaceuticals (atenolol (ATE), carbamazepine (CAR), and metoprolol (MET)) were introduced to soils and exposed for 61 day under aerobic conditions. Thirteen different soils were used in the study to increase the understanding of pharmaceutical behaviour in the soil matrix. Ten metabolites were detected and tentatively identified. Some of them, such as atenolol acid (AAC), carbamazepine 10,11-epoxide (EPC), 10,11-dihydrocarbamazepine (DHC), trans-10,11-Dihydro-10,11-dihydroxy carbamazepine (RTC), and metoprolol acid (MAC), were consequently confirmed using commercial reference standards. It was concluded that the aerobic conditions of the experiment determined the pharmaceutical degradation pathway of studied compounds in the soils. The different amounts/rates and degradation of the transformation products can be attributed to differences in the soil properties. ATE degraded relatively quickly compared with CAR, whereas MET degradation in the soils was unclear. The persistence of CAR and its metabolites, in combination with low CAR sorption, enable the transportation of CAR and its metabolites within soils and into the ground water. Thus, CAR may cause adverse effects on the environment and humans.

Simultaneous sorption of four ionizable pharmaceuticals in different horizons of three soil types.

Soils may be contaminated by human or veterinary pharmaceuticals. Their behaviour in soil environment is largely controlled by sorption of different compounds in a soil solution onto soil constituents. Here we studied the sorption affinities of 4 pharmaceuticals (atenolol, trimethoprim, carbamazepine and sulfamethoxazole) applied in solute mixtures to soils taken from different horizons of 3 soil types (Greyic Phaeozem on loess, Haplic Luvisol on loess and Haplic Cambisol on gneiss). In the case of the carbamazepine (neutral form) and sulfamethoxazole (partly negatively charged and neutral), sorption affinity of compounds decreased with soil depth, i.e. decreased with soil organic matter content. On the other hand, in the case of atenolol (positively charged) and trimethoprim (partly positively charged and neutral) compound sorption affinity was not depth dependent. Compound sorption affinities in the four-solute systems were compared with those experimentally assessed in topsoils, and were estimated using the pedotransfer rules proposed in our previous study for single-solute systems. While sorption affinities of trimethoprim and carbamazepine in topsoils decreased slightly, sorption affinity of sulfamethoxazole increased. Decreases in sorption of the two compounds could be attributed to their competition between each other and competition with atenolol. Differences between carbamazepine and atenolol behaviour in the one- and four-solute systems could also be explained by the slightly different soil properties in this and our previous study. A great increase of sulfamethoxazole sorption in the Greyic Phaeozem and Haplic Luvisol was observed, which was attributed to elimination of repulsion between negatively charged molecules and particle surfaces due to cation sorption (atenolol and trimethoprim) on soil particles. Thus, our results proved not only an antagonistic but also a synergic affect of differently charged organic molecules on their sorption to soil constituents.

Development of fast and robust multiresidual LC-MS/MS method for determination of pharmaceuticals in soils.

The aim of this study was to develop a simple extraction procedure and a multiresidual liquid chromatography-tandem mass spectrometry method for determination of a wide range of pharmaceuticals from various soil types. An extraction procedure for 91 pharmaceuticals from 13 soil types, followed by liquid chromatography-tandem mass spectrometry analysis, was optimized. The extraction efficiencies of three solvent mixtures for ultrasonic extraction were evaluated for 91 pharmaceuticals. The best results were obtained using acetonitrile/water (1/1 v/v with 0.1 % formic acid) followed by acetonitrile/2-propanol/water (3/3/4 v/v/v with 0.1 % formic acid) for extracting 63 pharmaceuticals. The method was validated at three fortification levels (10, 100, and 1000 ng/g) in all types of representative soils; recovery of 44 pharmaceuticals ranged between 55 and 135 % across all tested soils. The method was applied to analyze actual environmental samples of sediments, soils, and sludge, and 24 pharmaceuticals were found above limit of quantification with concentrations ranging between 0.83 ng/g (fexofenadine) and 223 ng/g (citalopram).

An analysis of the dissipation of pharmaceuticals under thirteen different soil conditions.

The presence of human and veterinary pharmaceuticals in the environment is recognized as a potential threat. Pharmaceuticals have the potential to contaminate soils and consequently surface and groundwater. Knowledge of contaminant behavior (e.g., sorption onto soil particles and degradation) is essential when assessing contaminant migration in the soil and groundwater environment. We evaluated the dissipation half-lives of 7 pharmaceuticals in 13 soils. The data were evaluated relative to the soil properties and the Freundlich sorption coefficients reported in our previous study. Of the tested pharmaceuticals, carbamazepine had the greatest persistence (which was mostly stable), followed by clarithromycin, trimethoprim, metoprolol, clindamycin, sulfamethoxazole and atenolol. Pharmaceutical persistence in soils was mostly dependent on the soil-type conditions. In general, lower average dissipation half-lives and variability (i.e., trimethoprim, sulfamethoxazole, clindamycin, metoprolol and atenolol) were found in soils of better quality (well-developed structure, high nutrition content etc.), and thus, probably better microbial conditions (i.e., Chernozems), than in lower quality soil (Cambisols). The impact of the compound sorption affinity onto soil particles on their dissipation rate was mostly negligible. Although there was a positive correlation between compound dissipation half-life and Freundlich sorption coefficient for clindamycin (R=0.604, p<0.05) and sulfamethoxazole (R=0.822, p<0.01), the half-life of sulfamethoxazole also decreased under better soil-type conditions. Based on the calculated dissipation and sorption data, carbamazepine would be expected to have the greatest potential to migrate in the soil water environment, followed by sulfamethoxazole, trimethoprim and metoprolol. The transport of clindamycin, clarithromycin and atenolol through the vadose zone seems less probable.