Toward the Proactive Design of Sustainable Chemicals: Ionic Liquids as a Prime Example.

The tailorable and often unique properties of ionic liquids (ILs) drive their implementation into a broad variety of seminal technologies. The modular design of ILs allows in this context a proactive selection of structures that favor environmental sustainability─ideally without compromising their technological performance. To achieve this objective, the whole life cycle must be taken into account and various aspects considered simultaneously. In this review, we discuss how the structural design of ILs affects their environmental impacts throughout all stages of their life cycles and scrutinize the available data in order to point out knowledge gaps that need further research activities. The design of more sustainable ILs starts with the selection of the most beneficial precursors and synthesis routes, takes their technical properties and application specific performance into due account, and considers its environmental fate particularly in terms of their (eco)toxicity, biotic and abiotic degradability, mobility, and bioaccumulation potential. Special emphasis is placed on reported structure-activity relationships and suggested mechanisms on a molecular level that might rationalize the empirically found design criteria.

The impact of insecticides containing deltamethrin and cyfluthrin on the composition of surface compounds in the larvae, females and males of Tenebrio molitor.

This paper presents the effect of insecticides on the composition of the surface compounds of one of the most harmful insects, Tenebrio molitor, by analysis using GC-MS. As a result of the use of insecticides, the composition of the chemical compounds on the surface of insects changes, depending on the insecticides used. The most numerous groups of the marked compounds were fatty acids, alkanes, esters and sterols. The content of the identified compounds in the larvae increased at both 24 and 48 h after the application of insecticides, in comparison with the control samples. The content of identified compounds in the samples taken from the females increased 24, 48 and 72 h after the application of insecticides in comparison with the control samples. By contrast, in samples prepared from males, the content of identified compounds decreased 24 h after the application of insecticides, compared with the control samples. The highest content of chemical compounds was for fatty acids and alkanes after the use of insecticides. The content of fatty acids after the application of the insecticide with deltamethrin was 62.1 ± 3.3-466.9 ± 5.9 µg/g, and after the application of the insecticide with cyfluthrin was 49.9 ± 1.9-458.3 ± 4.2 µg/g. However, the content of alkanes after the use of deltamethrin was 115.6 ± 4.2-4672.0 ± 32.1 µg/g, and after the use of cyfluthrin was 189.4 ± 3.8-3975.0 ± 10.2 µg/g.

Insight into the Sorption of 5-Fluorouracil and Methotrexate onto Soil-pH, Ionic Strength, and Co-Contaminant Influence.

Nowadays anticancer drugs (ADs), like other pharmaceuticals, are recognized as new emerging pollutants, meaning that they are not commonly monitored in the environment; however, they have great potential to enter the environment and cause adverse effects there. The current scientific literature highlights the problem of their presence in the aquatic environment by publishing more and more results on their analytics and ecotoxicological evaluation. In order to properly assess the risk associated with the presence of ADs in the environment, it is also necessary to investigate the processes that are important in understanding the environmental fate of these compounds. However, the state of knowledge on mobility of ADs in the environment is still very limited. Therefore, the main aim of our study was to investigate the sorption potential of two anticancer drugs, 5-fluorouracil (5-FU) and methotrexate (MTX), onto different soils. Special attention was paid to the determination of the influence of pH and ionic strength as well as presence of co-contaminants (cadmium (Cd2+) and another pharmaceutical-metoprolol (MET)) on the sorption of 5-FU and MTX onto soil. The obtained distribution coefficient values (Kd) ranged from 2.52 to 6.36 L·kg-1 and from 6.79 to 12.94 L·kg-1 for 5-FU and MTX, respectively. Investigated compounds may be classified as slightly or low mobile in the soil matrix (depending on soil). 5-FU may be recognized as more mobile in comparison to MET. It was proved that presence of other soil contaminants may strongly influence their mobility in soil structures. The investigated co-contaminant (MET) caused around 25-fold increased sorption of 5-FU, whereas diminished sorption of MTX. Moreover, the influence of environmental conditions such as pH and ionic strength on their sorption has been clearly demonstrated.

Evaluation of the Removal of Selected Phthalic Acid Esters (PAEs) in Municipal Wastewater Treatment Plants Supported by Constructed Wetlands.

Phthalic acid esters (PAEs) have a negative impact on living organisms in the environment, therefore, are among the group of Endocrine Disrupting Compounds (ECDs). Unfortunately, conventional methods used in municipal wastewater treatment plants (MWWTPs) are not designed to eliminate PAEs. For this reason, the development of cheap and simple but very effective techniques for the removal of such residues from wastewater is crucial. The main aim of this study was the evaluation of the removal of six selected PAEs: diethyl phthalate (DEP), di-n-octyl phthalate (DOP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and dimethyl phthalate (DMP), in real MWWTPs supported by constructed wetlands (MWWTP-CW system). For the first time, the possibility of using three new plants for this purpose, Cyperus papyrus (papyrus), Lysimachia nemorum (yellow pimpernel) and Euonymus europaeus (European spindle), has been presented. For determining the target PAEs in wastewater samples, a method of SPE (Solid-Phase Extraction)-GC-MS(SIM) was developed and validated, and for plant materials, a method of UAE (Ultrasound-Assisted Extraction)-SPE-GC-MS(SIM) was proposed. The obtained data showed that the application of the MWWTP-CW system allows a significant increase in the removal of DEP, DBP, BBP and DEHP from the wastewater stream. Euonymus europaeus was the most effective among the tested plant species for the uptake of analytes (8938 ng × g-1 dry weight), thus, this plant was found to be optimal for supporting conventional MWWTPs.

Impact of environmental factors on the sampling rate of ß-blockers and sulfonamides from water by a carbon nanotube-passive sampler.

Passive techniques are a constantly evolving approach to the long-term monitoring of micropollutants, including pharmaceuticals, in the aquatic environment. This paper presents, for the first time, the calibration results of a new CNTs-PSDs (carbon nanotubes used as a sorbent in passive sampling devices) with an examination of the effect of donor phase salinity, water pH and the concentration of dissolved humic acids (DHAs), using both ultrapure and environmental waters. Sampling rates (Rs) were determined for the developed kinetic samplers. It has been observed that the impact of the examined environmental factors on the Rs values strictly depends on the type of the analytes. In the case of ß-blockers, the only environmental parameter affecting their uptake rate was the salinity of water. A certain relationship was noted, namely the higher the salt concentration in water, the lower the Rs values of ß-blockers. In the case of sulfonamides, water salinity, water pH 7-9 and DHAs concentration decreased the uptake rate of these compounds by CNTs-PSDs. The determined Rs values differed in particular when the values obtained from the experiments carried out using ultrapure water and environmental waters were compared. The general conclusion is that the calibration of novel CNTs-PSDs should be carried out under physicochemical conditions of the aquatic phase that are similar to the environmental matrix.

Electron ionization induced fragmentation of fluorinated derivatives of bisphenols.

RATIONALE: Fluorinated derivatization agents allow for the identification and quantification of emerging pollutants with high sensitivity, yet details of their potential applications using electron ionization are lacking. The fluorine atom itself does not effectively participate in electron ionization. Furthermore, limited information exists regarding the effect of fluorine during electron ionization-induced fragmentation. To fill this gap, this report presents the fragmentation pathways of the fluorinated derivatives of ten bisphenol analogues as exemplary emerging pollutants. METHODS: The bisphenols were derivatized by the acetylation reagent trifluoroacetic anhydride and a new silylation reagent, namely dimethyl(3,3,3-trifluoropropyl)silyldiethylamine (DIMETRIS; previously applied for the analysis of selected pharmaceuticals in environmental samples), and analyzed using GC/MS (electron ionization, 70 eV). Deuterated bisphenol A was added to the group of analytes to confirm the proposed fragmentation pathways. RESULTS: The specific chemical structure of bisphenols gives the possibility of several resonance hybrids of C-centered radicals. This, in turn, results in several fragmentation pathways, unique for each resonance hybrid. Sequential losses of radicals and neutral fragments were observed in both types of derivative, with final stable carbenium ions. McLafferty-type rearrangements were observed between the native structure of the analytes and the introduced substituents. The gamma-shift of F onto Si in the Si(CH2 )2 CF3 substituent is proposed to explain the loss of the fragment with a mass of 78 u. CONCLUSIONS: Both types of derivatization reagent used were found to be applicable, although the use of DIMETRIS was limited for high-mass bisphenols. The introduction of fluorine by derivatization brings benefits for the qualitative and quantitative analysis of bisphenol-type compounds using GC/MS because of the presence of characteristic ions in the mass spectra.

Effects of the entomopathogenic fungus Metarhizium flavoviride on the fat body lipid composition of Zophobas morio larvae (Coleoptera: Tenebrionidae).

Insects employ different defense strategies against fungal infections and chemicals. We aimed to identify the lipid compositions of the fat body of Zophobas morio larvae before and after fungal infection with the entomopathogenic fungus Metarhizium flavoviride. We used gas chromatography-mass spectrometry to analyze lipid extracts of the fat body isolated of Z. morio 2, 5, and 7 days after fungal infection (treatment group) and compared it with the lipid extracts in a control group injected with physiological isotonic saline. In all the samples, fatty acids were the most abundant compound found in the fat body extracts, with hexadecanoic acid/C16:0 being the most abundant lipid. However, the types and concentrations of lipids changed after fungal infection, likely as an immune response. The most considerable changes occurred in the concentrations of long-chain fatty acids, i.e., hexadecanoic acid/C16:0, octadecenoic acid/C18:1, and octadecanoic acid/C18:0. Contents of methyl ester increased significantly after infection, but that of other esters, especially octanoic acid decyl ester/OADE, decreased on the 5th day after infection. To the best of our knowledge, this is the first detailed analysis of the changes in the lipid composition of the fat body of Z. morio larvae as a result of fungal infection. Our results suggest that entomopathogenic fungal infection affects the internal lipid composition of insects, potentially as a way of adjusting to such infection. These results can help understand infection processes and defense strategies of insects against fungal infection. Ultimately, they can contribute to the creation of more effective chemicals against pest insects.

The Identification of Cotton Fibers Dyed with Reactive Dyes for Forensic Purposes.

Some of the most common microtraces that are currently collected at crime scenes are fragments of single fibers. The perpetrator leaves them at a crime scene or takes them away, for example, on their clothing or body. In turn, the microscopic dimensions of such traces mean that the perpetrator does not notice them and therefore usually does not take action to remove them. Cotton and polyester fibers dyed by reactive and dispersion dyes, respectively, are very popular within clothing products, and they are hidden among microtraces at the scene of a crime. In our recently published review paper, we summarized the possibilities for the identification of disperse dyes of polyester fibers for forensic purposes. In this review, we are concerned with cotton fibers dyed with reactive dyes. Cotton fibers are natural ones that cannot easily be distinguished on the basis of morphological features. Consequently, their color and consequently the dye composition are often their only characteristics. The presented methods for the identification of reactive dyes could be very interesting not only for forensic laboratories, but also for scientists working in food, cosmetics or pharmaceutical/medical sciences.

Identification of Selected Antibiotic Resistance Genes in Two Different Wastewater Treatment Plant Systems in Poland: A Preliminary Study.

Antibiotic resistance is a growing problem worldwide. The emergence and rapid spread of antibiotic resistance determinants have led to an increasing concern about the potential environmental and public health endangering. Wastewater treatment plants (WWTPs) play an important role in this phenomenon since antibacterial drugs introduced into wastewater can exert a selection pressure on antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs). Therefore, WWTPs are perceived as the main sources of antibiotics, ARB and ARG spread in various environmental components. Furthermore, technological processes used in WWTPs and its exploitation conditions may influence the effectiveness of antibiotic resistance determinants' elimination. The main aim of the present study was to compare the occurrence of selected tetracycline and sulfonamide resistance genes in raw influent and final effluent samples from two WWTPs different in terms of size and applied biological wastewater treatment processes (conventional activated sludge (AS)-based and combining a conventional AS-based method with constructed wetlands (CWs)). All 13 selected ARGs were detected in raw influent and final effluent samples from both WWTPs. Significant ARG enrichment, especially for tet(B, K, L, O) and sulIII genes, was observed in conventional WWTP. The obtained data did not show a clear trend in seasonal fluctuations in the abundance of selected resistance genes in wastewaters.

Salinity and pH as factors affecting the passive sampling and extraction of pharmaceuticals from water.

Passive sampling is an attractive technique for the long-term monitoring of pharmaceuticals in the water environment. The reliability of the received results depends on the properly performed calibration, namely the determination of analyte sampling rates. This step can be the source of a systematic error, as the sampling rate values are dependent on the water donor phase parameters. This is especially important for pharmaceuticals, since their chemical characteristics and ionic form change with pH. In this study, the cross-effect of pH (3, 7, and 9) and salinity (0, 7, and 35 practical salinity unit, using artificial sea water) on the passive sampling of 21 pharmaceuticals (antiparasitics, beta-blockers, non-steroidal anti-inflammatory drugs, sulfonamides) was tested. The primarily determined parameter was the sampling rate. In addition, the extraction efficiency, partitioning coefficient, and the concentration of the analytes on the sorbent were calculated. Generally, for the non-steroidal anti-inflammatory drugs, beta-blockers, and antiparasitics, the change both in pH and salinity had a negligible impact on the mentioned experimental parameters. In contrast, the extraction of sulfonamides was impacted by both pH and salinity, while lipophilicity was not a decisive parameter.

Changes in lipids composition and metabolism in colorectal cancer: a review.

Altered metabolism of lipids is currently considered a hallmark characteristic of many malignancies, including colorectal cancer (CRC). Lipids are a large group of metabolites that differ in terms of their fatty acid composition. This review summarizes recent evidence, documenting many alterations in the content and composition of fatty acids, polar lipids, oxylipins and triacylglycerols in CRC patients' sera, tumor tissues and adipose tissue. Some of altered lipid molecules may be potential biomarkers of CRC risk, development and progression. Owing to a significant role of many lipids in cancer cell metabolism, some of lipid metabolism pathways may also constitute specific targets for anti-CRC therapy.

Cyfluthrin and Deltamethrin Induce Changes in the Fat Body Composition of Tenebrio molitor Larvae, Males and Females.

The purpose of present study was to analyze the chemical composition of the fat body of insects (Tenebrio molitor) and its eventual variation after the application of insecticides. Using the GC/MS technique, the fat body composition of larvae, males and females was analyzed. The insects were stressed with selected insecticides containing cyfluthrin (Cyflok 50EW) and deltamethrin (K-othrine) recommended for this species of insect by insecticides producers and farmers. The effect of these two chemicals on the chemical compounds patterns from fat body of insects was compared. Possible differences in the fat body composition between developmental stages and the sex of insects were also compared. Possible identified compounds included amino acids, carboxylic acids, alcohols, sterols, glycerol and urea. Our results show that the composition of lipids was different depending on the stage of development, the insecticide used and the elapsed time since its application.

Alterations of Fatty Acid Profile May Contribute to Dyslipidemia in Chronic Kidney Disease by Influencing Hepatocyte Metabolism.

Chronic kidney disease (CKD) is associated with atherogenic dyslipidemia. Our aim was firstly to investigate patterns of fatty acids (FA) composition through various stages of CKD, and secondly, to evaluate the effect of CKD-specific FA disturbances on the expression of genes related to lipid metabolism at a cellular level. Serum FA composition was analyzed in 191 patients with consecutive severity stages of CKD, and 30 healthy controls free from CKD. Next, HepG2 human hepatic cells were treated with major representatives of various FA groups, as well as with FA extracted from a mix of serums of controls and of CKD stage 5 patients. Across worsening stages of CKD severity, there was an increasing monounsaturated FA (MUFA) content. It was associated with a concomitant decrease in n-3 and n-6 polyunsaturated FA. The incubation of hepatocytes with FA from CKD patients (compared to that of healthy subjects), resulted in significantly higher mRNA levels of genes involved in FA synthesis (fatty acid synthase (FASN) increased 13.7 ± 3.5 times, stearoyl-CoA desaturase 1 (SCD1) increased 4.26 ± 0.36 times), and very low density lipoprotein (VLDL) formation (apolipoprotein B (ApoB) increased 7.35 ± 1.5 times, microsomal triacylglycerol transfer protein (MTTP) increased 2.74 ± 0.43 times). In conclusion, there were progressive alterations in serum FA composition of patients with CKD. These alterations may partly contribute to CKD hypertriglyceridemia by influencing hepatocyte expression of genes of lipid synthesis and release.

Evaluation of the Possibility of Using Hydroponic Cultivations for the Removal of Pharmaceuticals and Endocrine Disrupting Compounds in Municipal Sewage Treatment Plants.

The problem of the presence of pharmaceuticals and endocrine disrupting compounds (EDCs) in the environment is closely related to municipal wastewater and in consequence to municipal wastewater treatment plants (MWWTPs) because wastewater is the main way in which these compounds are transferred to the ecosystem. For this reason, the development of cheap, simple but very effective techniques for the removal of such residues from wastewater is very important. In this study, the analysis of the potential of using three new plants: Cyperus papyrus (Papyrus), Lysimachia nemorum (Yellow pimpernel), and Euonymus europaeus (European spindle) by hydroponic cultivation for the removal of 15 selected pharmaceuticals and endocrine disrupting compounds (EDCs) in an MWWTP is presented. In order to obtain the most reliable data, this study was performed using real WWTP conditions and with the determination of the selected analytes in untreated sewage, treated sewage, and in plant materials. For determining the target compounds in plant materials, an Accelerated Solvent Extraction (ASE)-Solid-Phase Extraction (SPE)-GC-MS(SIM) method was developed and validated. The obtained data proved that the elimination efficiency of the investigated substances from wastewater was in the range of 35.8% for diflunisal to above 99.9% for paracetamol, terbutaline, and flurbiprofen. Lysimachia nemorum was the most effective for the uptake of target compounds among the tested plant species. Thus, the application of constructed wetlands for supporting conventional MWWTPs allowed a significant increase in their removal from the wastewater stream.

The Identification of Polyester Fibers Dyed with Disperse Dyes for Forensic Purposes.

In forensic laboratories, the most commonly analyzed microtraces are microscopic fragments of single fibers. One of the main goals of the examination of fragments of fibers a few millimeters long is to determine their characteristic physicochemical properties and compare them with fibers originating from a known source (e.g., a suspect's clothes). The color and dyes of fiber microtraces play an important role in their research and evaluation, being analyzed by means of microscopic, spectroscopic, and chromatographic methods. The results of examinations conducted with the use of spectroscopic techniques might be ambiguous due to overlapping bands of absorption and the transmission and dispersion of electromagnetic radiation corresponding to the specific chemical structure of the fibers and their dyes. For this reason, it is very important to improve currently available spectroscopic methods and/or to propose new ones that allow evidential materials to be analyzed in a much more reliable way. In this review, the possibility of the use of chromatographic techniques with different detection systems for such analyses is underlined. This review covers the different analytical methods used in the forensic analysis of polyester fibers dyed with disperse dyes. Polyester fibers occupy the first position among synthetic fibers in their use for a variety of purposes, and disperse dyes are commonly applied for dyeing them.

A new approach for the extraction of tetracyclines from soil matrices: application of the microwave-extraction technique.

The widespread use of tetracyclines (TCs) in animal husbandry is associated with their constant penetration into the environment and the threat they might pose to living organisms. While the literature data on the analysis of these substances in such matrices as food, tissues, or wastewater are quite extensive, there are still only a few methods presented for the determination of these compounds in soil samples. Moreover, among the literature methods for the extraction of TCs from soil samples, microwave-assisted solvent extraction (MAE) was used only once and in combination with liquid chromatography with spectrophotometric detection (LC-UV). However, according to the EU Commission Decision 2002/657/EC, the use of LC-UV for the determination of compounds, including pharmaceuticals, in environmental samples is not sufficient. Therefore, the development and application of a sensitive and selective method using the MAE-SPE-LC-MS/MS(MRM) technique for the isolation and identification of a mixture of oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) in soils is presented in our study. The credibility of this method has been confirmed with good parameters of validation. The optimal extraction conditions of three TCs using MAE techniques were to conduct double extraction for 10 min each, at 60 °C, using a mixture of ACN:McIlvaine buffer:0.1 M EDTA (2:1:1, v/v/v) and an additional cleaning of the extracts by SPE. The effectiveness of the extraction of these compounds was assessed based on two different ways (absolute recovery from 46 to 65.1% and relative recovery from 101.1 to 109.5%). Finally, the validated MAE-SPE-LC-MS/MS(MRM) method was used for the analysis of six samples from agricultural areas of northern Poland. OTC and TC, at concentrations of 11.7 and 14.5 µg kg-1 were determined in two different samples. An assessment of risk quotients was also performed. The presented method was proven to be a useful tool in the analysis of residues of selected TCs in the soil ecosystem. Obtained data on the presence of these drugs in Polish soils is the first report for this country.

Application of headspace solid-phase microextraction followed by gas chromatography coupled with mass spectrometry to determine esters of carboxylic acids and other volatile compounds in Dermestes maculatus and Dermestes ater lipids.

A constant problem in veterinary medicine, human healthcare, agriculture, forestry and horticulture is the large number of pests, and the lack of effective methods to combat them which cause no harm to the rest of the environment. It is recommended and desired to reduce the use of chemicals and increase the use of agents based on knowledge acquired in the fields of biology, chemistry and agrochemicals. To learn the defense mechanisms of insects we should consider not only the site of their physiological ability to protect against external factors (cuticle), but also the possibility of chemical protection, formed by all compounds on the surface and in the body of insects. In this study, a procedure was developed to determine the esters of carboxylic acids in insect lipids. Headspace solid-phase microextraction was followed by gas chromatography coupled with gas spectrometry. First, the best conditions were selected for the analysis to obtain the best chromatographic separation. An RTx-5 column was used for this purpose. Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate fibers were used to isolate acid esters. PDMS/DVB fiber achieved the best conditions for the extraction; the extraction time was 50 min, the extraction temperature was 105°C and the desorption time was 10 min at 230°C. These solid-phase microextraction conditions were used to analyze volatile compounds extracted from insects belonging to the Dermestidae family.

Hyper-Elongation in Colorectal Cancer Tissue - Cerotic Acid is a Potential Novel Serum Metabolic Marker of Colorectal Malignancies.

BACKGROUNDS/AIMS: Colorectal cancer (CRC) cells show some alterations of lipid metabolism. Elongation of fatty acids (FA) has not been studied in CRC tissues thus far. The aim of this study was to verify if CRC specimens and normal colon mucosa differ in terms of their levels of very long-chain FAs, a product of FA elongation. Moreover, the expression of elongase genes has been studied in normal tissue and CRC. Finally, we searched for some specific products of FA elongation in serum of CRC patients. METHODS: The specimens of normal colon mucosa and CRC were obtained from nineteen CRC patients differ in terms of FA elongation. We also searched for some specific products of FA elongation in serum of CRC patients and from healthy volunteers. Tissue and serum FA profiles were determined by means of gas chromatography-mass spectrometry (GC/MS), and the tissue expression of elongases (ELOVLs) was analyzed with real-time PCR. RESULTS: Compared to normal colon tissue, CRC specimens showed significantly higher levels of 22-, 24- and 26-carbon FAs, stronger expressions of ELOVL1 and ELOVL6 (4- and 9-fold elevated respectively), and higher values of 18: 0/16: 0 elongation index. We also demonstrated presence of cerotic acid (26: 0) in serum of all CRC patients but in none of the healthy controls. CONCLUSIONS: CRC tissue seems to be characterized by enhanced FA elongation (hyper-elongation). Presence of cerotic acid in CRC patients sera and absence of this FA in healthy subjects points to this compound as a strong candidate for specific metabolic marker of colorectal malignancies.

Impact of Veterinary Pharmaceuticals on the Agricultural Environment: A Re-inspection.

The use of veterinary pharmaceuticals (VPs) is a result of growing animal production. Manure, a great crop fertilizer, contains a significant amount of VPs. The investigation of VPs in manure is prevalent, because of the potential risk for environmental organisms, as well as human health. A re-evaluation of the impact of veterinary pharmaceuticals on the agricultural environment is needed, even though several publications appear every year. The aim of this review was to collate the data from fields investigated for the presence of VPs as an inevitable component of manure. Data on VP concentrations in manure, soils, groundwater and plants were collected from the literature. All of this was connected with biotic and abiotic degradation, leaching and plant uptake. The data showed that the sorption of VPs into soil particles is a process which decreases the negative impact of VPs on the microbial community, the pollution of groundwater, and plant uptake. What was evident was that most of the data came from experiments conducted under conditions different from those in the environment, resulting in an overestimation of data (especially in the case of leaching). The general conclusion is that the application of manure on crop fields leads to a negligible risk for plants, bacteria, and finally humans, but in future every group of compounds needs to be investigated separately, because of the high divergence of properties.

Ionic liquids for the passive sampling of sulfonamides from water-applicability and selectivity study.

Ionic liquids (ILs) are new-generation, non-volatile solvents which are designable, and their structure may be specifically adjusted to the current application needs. Therefore, it is possible to create and apply ILs which efficiently and selectively extract various analytes from different matrices. It has already been examined that ILs may be applied as receiving phases in passive sampling for the long-term water monitoring of PAHs and pharmaceuticals in water. In this paper, the concept of passive sampling with ILs (PASSIL applied as receiving phases) was continued and developed using phosphonium-, imidazolium-, and morpholinium-cation-based ILs. The target group of analytes was pharmaceuticals which represent one of the most common categories of water contaminants. Fourteen-day-long extractions using various ILs were performed in stirred conditions at a constant temperature (20 °C). The best extraction efficiency was achieved for trihexyl(tetradecyl)phosphonium dicyanamide ([P666-14][N(CN)2]). For this preliminary calibration, the sampling rates were calculated for each sulfonamide. Once again, selectivity was observed in passive sampling using [P666-14][N(CN)2]. Therefore, PASSIL is seen as a very promising method for pharmaceutical monitoring in water.