RESUMEN
Bisphenol A alternatives are manufactured as potentially less harmful substitutes of bisphenol A (BPA) that offer similar functionality. These alternatives are already in the market, entering the environment and thus raising ecological concerns. However, it can be expected that levels of BPA alternatives will dominate in the future, they are limited information on their environmental safety. The EU PARC project highlights BPA alternatives as priority chemicals and consolidates information on BPA alternatives, with a focus on environmental relevance and on the identification of the research gaps. The review highlighted aspects and future perspectives. In brief, an extension of environmental monitoring is crucial, extending it to cover BPA alternatives to track their levels and facilitate the timely implementation of mitigation measures. The biological activity has been studied for BPA alternatives, but in a non-systematic way and prioritized a limited number of chemicals. For several BPA alternatives, the data has already provided substantial evidence regarding their potential harm to the environment. We stress the importance of conducting more comprehensive assessments that go beyond the traditional reproductive studies and focus on overlooked relevant endpoints. Future research should also consider mixture effects, realistic environmental concentrations, and the long-term consequences on biota and ecosystems.
Asunto(s)
Compuestos de Bencidrilo , Monitoreo del Ambiente , Contaminantes Ambientales , Fenoles , Fenoles/toxicidad , Compuestos de Bencidrilo/toxicidad , Contaminantes Ambientales/toxicidad , Monitoreo del Ambiente/métodos , Animales , Humanos , Disruptores Endocrinos/toxicidadRESUMEN
Ionic liquids (ILs) have recently gained significant attention in both the scientific community and industry, but there is a limited understanding of the potential risks they might pose to the environment and human health, including their potential to accumulate in organisms. While membrane and storage lipids have been considered as primary sorption phases driving bioaccumulation, in this study we used an in vitro tool known as solid-supported lipid membranes (SSLMs) to investigate the affinity of ILs to membrane lipid - phosphatidylcholine and compare the results with an existing in silico model. Our findings indicate that ILs may have a strong affinity for the lipids that form cell membranes, with the key factor being the length of the cation's side chain. For quaternary ammonium cations, increase in membrane affinity (logMA) was observed from 3.45 ± 0.06 at 10 carbon atoms in chain to 4.79 ± 0.06 at 14 carbon atoms. We also found that the anion can significantly affect the membrane partitioning of the cation, even though the anions themselves tend to have weaker interactions with phospholipids than the cations of ILs. For 1-methyl-3-octylimidazolium cation the presence of tricyanomethanide anion caused increase in logMA to 4.23 ± 0.06. Although some of our data proved to be consistent with predictions made by the COSMOmic model, there are also significant discrepancies. These results suggest that further research is needed to improve our understanding of the mechanisms and structure-activity relationships involved in ILs bioconcentration and to develop more accurate predictive models.
Asunto(s)
Líquidos Iónicos , Líquidos Iónicos/química , Fosfatidilcolinas/química , Fosfatidilcolinas/metabolismo , Membrana Celular/metabolismo , Membrana Celular/química , Membrana Celular/efectos de los fármacos , Lípidos de la Membrana/química , Lípidos de la Membrana/metabolismo , Compuestos de Amonio Cuaternario/química , Compuestos de Amonio Cuaternario/metabolismo , Membrana Dobles de Lípidos/química , Membrana Dobles de Lípidos/metabolismo , HumanosRESUMEN
Water pollution has become a critical global concern requiring effective monitoring techniques and robust protection strategies. Contaminants of emerging concern (CECs) are increasingly detected in various water sources, with their harmful effects on humans and ecosystems continually evolving. Based on literature reports highlighting the promising sorption properties of metal-organic frameworks (MOFs), the aim of this study was to evaluate the suitability of NH2-MIL-125 (Ti) and UiO-66 (Ce) as sorbents in passive sampling devices (MOFs-PSDs) for the collection and extraction of a wide group of CECs. Solvothermal methods were used to synthesize MOFs, and the characterization of the obtained materials was performed using field-emission scanning electron microscopy (FE-SEM), powder X-ray diffractometry (pXRD) and Fourier-transform infrared (FTIR) spectroscopy. The research demonstrated the sorption capabilities of the tested MOFs, the ease and rapidity of their chemical regeneration and the possibility of reuse as sorbents. Using chemometric analysis, the structural properties of CECs determining the sorption efficiency on the surface of NH2-MIL-125 (Ti) were identified. The MOFs-PSDs were lab-calibrated to examine the kinetics of analytes sorption and determine the sampling rates (Rs). MOFs-PSDs and CNTs-PSDs (PSDs containing carbon nanotubes as a sorbent) were then placed in the Elblag River and the Vistula Lagoon to sampling and extraction of the target compounds from the water. CNTs-PSDs were selected, based on our previous research, for the comparison of the effectiveness of the MOFs-PSDs in environmental monitoring. MOFs-PSDs were successfully used in monitoring of CECs in water. The time-weighted average concentrations (CTWA) of 2-hydroxycarbamazepine, carbamazepine-10,11-epoxide, p-nitrophenol, 3,5-dichlorophenol and caffeine were determined in the Elblag River and CTWA of metoprolol, diclofenac, 2-hydroxycarbamazepine, carbamazepine-10,11-epoxide, p-nitrophenol, 3,5-dichlorophenol and caffeine were determine in the Vistula Lagoon using MOFs-PSDs and a high-performance liquid chromatography coupled with triple quadrupole mass spectrometer.
RESUMEN
Human serum albumin (HSA) effectively binds different types of low-molecular-weight compounds and thus enables their distribution in living organisms. Recently, it has been reported that the protein-ligand interactions play a crucial role in bioaccumulation processes and provide an important sorption phase, especially for ionogenic compounds. Therefore, the binding interactions of such compounds with proteins are the subject of an ongoing interest in environmental and life sciences. In this paper, the influence of some counter-ions, namely [B(CN)4]- and [C(CN)3]- on the affinity of the [IM1-12]+ towards HSA has been investigated and discussed based on experimental methods (isothermal titration calorimetry and steady-state fluorescence spectroscopy) and molecular dynamics-based computational approaches. Furthermore, the thermal stability of the resulting HSA/ligand complexes was assessed using DSC and CD spectroscopy. As an outcome of the work, it has been ascertained that the protein is able to bind simultaneously the ligands under study but in different regions of HSA. Thus, the presence in the system of [IM1-12]+ does not disturb the binding of [C(CN)3]- and [B(CN)4]-. The presented results provide important information on the presence of globular proteins and some ionogenic compounds in the distribution and bioaccumulation of ILs in the environment and living organisms.
Asunto(s)
Líquidos Iónicos , Albúmina Sérica Humana , Humanos , Albúmina Sérica Humana/química , Líquidos Iónicos/química , Ligandos , Sitios de Unión , Dicroismo Circular , Simulación del Acoplamiento Molecular , Espectrometría de Fluorescencia , Termodinámica , Unión ProteicaRESUMEN
Imidazolium ionic liquids (ILs) are chemical compounds beginning to be used on a mass scale. Although their presence in the environment is usually treated as only potential threat, there are already first evidences that this has become a real case. Taking into account their increasing use it might be expected that this problem will also increase in the nearest future. Given that some of the imidazolium cations exhibit high potential for bioconcentration, it is likely that they will accumulate in the tissues of wild organisms. Thus, there is no doubt that monitoring the presence of these compounds in organisms from potentially contaminated waters will be needed. Therefore, the aim of our study was to develop and fully validate a novel and reliable analytical procedure for the determination of the mixture of imidazolium ILs in Mytilus trossulus mussels. For this purpose, different extraction techniques were tested such as: microwave-assisted extraction (MAE), accelerated-solvent extraction (ASE) and bullet-blender homogenization (HOMO). Finally, the proposed procedure is based on the application of MAE technique for the extraction of imidazolium cations and SPE technique using Oasis HLB cartridges for the purification of the obtained extracts and LC-MS/MS technique with QqQ analyzer for their final determination. Absolute recoveries of the proposed analytical procedure reached 71-90%. The developed procedure is characterized with low limits of quantification, at 50-100 ng g-1 dry tissue and allows for reliable determination of trace amounts of the tested compounds in complex biological matrix. Matrix effects obtained for the optimized procedure ranged from 7.8 to 37.5%. As a result, this is the first study presenting the analytical procedure for the analysis of imidazolium ILs in aquatic animal tissues.
Asunto(s)
Líquidos Iónicos , Mytilus , Animales , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos , Mytilus/química , Microondas , Extracción en Fase Sólida/métodosRESUMEN
Although imidazolium ionic liquids (ILs) are beginning to be used more widely in many industrial fields e.g., as reaction media, electrolytes, stationary phases in gas chromatography), there is still little information about their potential environmental fate. Among the uncertainties regarding the risks associated with these compounds, bioconcentration is one of the key issues, about which many doubts have been raised in recent years. While in vitro data suggest that permanently charged compounds can also bioconcentrate, conclusive evidence in the form of studies on organisms, at least for selected compounds, is needed. Therefore, the main objective of this work was to determine whether imidazolium cations of ILs, namely 1-methyl-3-octylimidazolium ([IM18]+) and 1-methyl-3-dodecylimidazolium ([IM1-12]+), can bioconcentrate in marine invertebrates tissues. During 21-day experiments, Mytilus trossulus mussels were exposed to these cations individually, at a concentration of 10 µg/L. In our study, it has been demonstrated for the first time during in vivo study, that long-chain imidazolium ionic liquids can bioconcentrate. The determined BCF value for [IM1-12]+ of 21,901 ± 3400 L/kg makes this compound to be considered highly bioaccumulative according to commonly accepted criteria. However, the obtained BCF for [IM18]+ (with the value below 100) suggests that this cation has little potential for bioconcentration. On the other hand, no salinity or anion influence on the bioconcentration of the tested cations was observed. Our tests also confirm that imidazolium ILs exhibit acute toxicity only at relatively high concentration levels, as LC50 reached 0.68 mg/L for [IM1-12][Br], and 11.66 mg/L for [IM18][C(CN)3]. This further confirms that the risks associated with the potential presence of these compounds in the environment should be attributed to their high persistence and potential bioconcentration, rather than acute toxicity.
Asunto(s)
Líquidos Iónicos , Mytilus , Animales , Líquidos Iónicos/química , Bioacumulación , Alimentos Marinos , CationesRESUMEN
Ionic liquids (ILs) are considered to be very promising group of chemicals and the number of their potential applications is growing rapidly. However, while these compounds were originally proposed as a green alternative to classical solvents, there are certain doubts as to whether this classification is correct. Although in recent years there have been first reports published proving the presence of some ILs in the environment and even in human blood, at this point the scale of this possible problem is not yet fully understood. However, there is no doubt that as the number of ILs applications increases, analytical capabilities for rapid detection of possible environmental contamination should be also considered. Therefore, in this review paper, recent evidences for the ILs environmental contamination as well as analytical achievements related to the extraction of ILs from various environmental matrices have been summarized and important gaps and future perspectives have been pointed out. Based on the presented data it might be concluded that there is the urgent need for further development towards risk assessment of these potential environmental contaminants.
Asunto(s)
Contaminantes Ambientales , Líquidos Iónicos , Contaminantes Ambientales/análisis , Humanos , Líquidos Iónicos/química , Líquidos Iónicos/toxicidad , Solventes/químicaRESUMEN
In recent years, the growing interest in applying photoelectrocatalysis (PEC) to decompose organic pollutants has resulted in the need to search for new photoelectrode materials with high activity under visible light radiation. The presented research showed an increased photoelectrocatalytic activity under sunlight of Ti/TiO2 sensitized with SnS quantum dots, obtained by the successive ionic layer adsorption and reaction (SILAR) method. The presence of SnS caused the enhanced absorption of visible irradiation and the reduction of recombination of generated charges by a p-n heterojunction created with the TiO2. The highest efficiency of photoelectrocatalytic degradation of anticancer drugs (ifosfamide, 5-fluorouracil, imatinib) was achieved for the SnS-Ti/TiO2 photoelectrode with a SnS quantum dot size from 4 to 10 nm. In addition, a decrease of IF PEC degradation efficiency was observed with increasing pH and with the presence of Cl-, NO3-, HCO3- and organic matter in the treated solution. Studies of the PEC mechanism have shown that drug degradation occurs mainly as a result of the direct and indirect action of photogenerated holes on the SnS-Ti/TiO2 photoelectrode, and the identified degradation products allowed for the presentation of the degradation pathway of IF, 5-FU and IMB. Duckweed (Lemna minor) growth inhibition tests showed no toxicity of the drug solutions after treatment.
Asunto(s)
Antineoplásicos , Nanotubos , Puntos Cuánticos , Antineoplásicos/farmacología , Fluorouracilo/farmacología , Luz Solar , TitanioRESUMEN
As the knowledge on the joint effects of pharmaceuticals towards different non-target organisms is still limited, the aim of our study was to evaluate the toxicity of mixtures of pharmaceuticals, as well as their baseline toxicity towards three selected organisms, namely the bioluminescent bacteria Aliivibrio fischeri, the crustacean Daphnia magna, and the duckweed Lemna minor. Different mixtures composed of three up to five pharmaceuticals having the same or different mechanisms of action in terms of their therapeutic activity (non-steroidal anti-inflammatory drugs, opioid analgesic, antibacterial and anti-epileptic drugs) were investigated. The observed EC50s were compared with those predicted using the concentration addition (CA) and independent action (IA) models. In general, the EC50 values for mixtures predicted with the CA model were lower than those obtained with the IA model, although, in some cases, test predictions of these two models were almost identical. Most of the experimentally determined EC50 values for the specific mixtures were slightly higher than those predicted with the CA model; hence, a less than additive effect was noted. Based on the obtained results, it might be concluded that the CA model assumes the worst-case scenario and gives overall closer predictions; therefore, it should be recommended also for modeling the mixture toxicity of pharmaceuticals with different modes of action.
Asunto(s)
Araceae , Contaminantes Químicos del Agua , Aliivibrio fischeri , Animales , Daphnia , Preparaciones Farmacéuticas , Contaminantes Químicos del Agua/toxicidadRESUMEN
One of the challenges in research into photoelectrocatalytic (PEC) degradation of pollutants is finding the appropriate photoanode material, which has a significant impact on the process efficiency. Among all others, photoelectrodes based on an ordered TiO2 nanotube arrays are a promising material due to well-developed surface area and efficient charge separation. To increase the PEC activity of this material, the SILAR method was used to decorate Ti/TiO2 nanotubes by PbS quantum dots (QD). The ifosfamide (IF) degradation rate constants was twice as higher for PbS-Ti/TiO2 (0.0148 min-1) than for Ti/TiO2 (0.0072 min-1). Our research showed the highest efficiency of PEC degradation of drugs using IIIPbS-Ti/TiO2 made with 3 SILAR cycles (PbS QD size mainly 2-4 nm). The 4 and 6 of SILAR cycles resulted in the aggregation of PbS nanoparticles on the Ti/TiO2 surface and decreased IF PEC degradation rate to 0.0043 and 0.0033 min-1, respectively. Research on PEC mechanism has shown that the drugs are degraded mainly by the activity of photogenerated holes and hydroxyl radicals. In addition, the identified drug intermediates made possible to propose a degradation pathways of anticancer drugs and the ecotoxicity test show no inhibition of Lemna minor growth of treated solutions.
Asunto(s)
Antineoplásicos , Nanotubos , Puntos Cuánticos , Energía Solar , TitanioRESUMEN
Nowadays, a huge scientific attention is being paid to the chemicals of emerging concern, which may pose a significant risk to the human and whole ecosystems. Among them, residues of pharmaceuticals are a widely investigated group of chemicals. In recent years it has been repeatedly demonstrated that pharmaceuticals are present in the environment and that some of them can be toxic to organisms as well as accumulate in their tissues. However, even though the knowledge of the presence, fate and possible threats posed by the parent forms of pharmaceuticals is quite extensive, their transformation products (TPs) have been disregarded for long time. Since last few years, this aspect has gained more scientific attention and recently published papers proved their common presence in the environment. Also the interest in terms of their toxicity, bioconcentration and stability in the environment has increased. Therefore, the aim of our paper was to revise and assess the current state of knowledge on the fate and effects resulting from the presence of the pharmaceuticals' transformation drugs in the environment. This review discusses the metabolites of compounds belonging to six major pharmaceutical groups: SSRIs, anticancer drugs, antibiotics, antihistamines, NSAIDs and opioids, additionally discussing other individual compounds for which literature data exist. The data presented in this paper prove that some TPs may be as harmful as their native forms, however for many groups of drugs this data is still insufficient to assess the risk posed by their presence in the environment.
Asunto(s)
Preparaciones Farmacéuticas , Contaminantes Químicos del Agua , Antiinflamatorios no Esteroideos , Bioacumulación , Ecosistema , Humanos , Contaminantes Químicos del Agua/análisisRESUMEN
Due to the genotoxic, carcinogenic and teratogenic mechanism of action, anticancer drugs are highly hazardous compounds. Their occurrence, fate, and effects in the environment have not been systematically studied as compared to other medicaments. Therefore, reliable data, including their stability and persistency, is required in order to assess it. Taking into account, that hydrolysis is one of the most important factors regarding stability of chemicals in water, the aim of our study was to investigate the hydrolytic stability of five commonly used anticancer drugs (ifosfamide, cyclophosphamide, 5-fluorouracil, imatinib, and methotrexate) and one metabolite (7-hydroxymethotrexate), as the systematized and coherent data available is limited. The hydrolysis studies have been prepared according to the OECD 111 procedure to obtain standardized and comparable results. The preliminary tests at pH 4, 7, and 9 and 50 °C show that only cyclophosphamide and ifosfamide are unstable, whereas the estimated t1/2 at 25 °C is >1 year for other investigated compounds. Moreover, much more detailed experiments were performed and indicate that at environmentally relevant temperatures, cyclophosphamide, and ifosfamide would be quite persistent in the terms of hydrolytic stability. Moreover, the preliminary investigation on the hydrolysis products was performed.
Asunto(s)
Antineoplásicos , Ciclofosfamida , Hidrólisis , Ifosfamida , Mesilato de ImatinibRESUMEN
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.
Asunto(s)
Monitoreo del Ambiente/métodos , Contaminantes Ambientales/química , Fluorouracilo/química , Metotrexato/química , Extractos Vegetales/química , Contaminantes del Suelo/química , Suelo/química , Adsorción , Cadmio/química , Monitoreo del Ambiente/instrumentación , Contaminantes Ambientales/análisis , Concentración de Iones de Hidrógeno , Metoprolol/química , Concentración OsmolarRESUMEN
The presence of both pollutants: microplastics and pharmaceutical residues in various environmental compartments is an issue of increasing concern. Available literature data indicates that microplastics can affect the environmental distribution and transport of e.g. persistent organic pollutants (POPs) through sorption interactions, concentrating them at a given point and thus influencing the environmental risks represented by the sorbent and sorbate pair. Therefore, their potential to change the fate of other contaminants in the environment, such as pharmaceuticals, is worth investigating. The aim of this study was to evaluate the sorption capacity of nine pharmaceuticals, commonly used in human and veterinary medicine, which constitute known ubiquitous water pollutants: enrofloxacin (ENR), ciprofloxacin (CIP), norfloxacin (NOR), 5-fluorouracil (5-FU), methotrexate (MET), flubendazole (FLU), fenbendazole (FEN), propranolol (PRO) and nadolol (NAD), on the surface of the most often identified microscopic plastic particles in the aquatic environment, i.e. polypropylene (PP), low density polyethylene (LD-PE), high density polyethylene (HD-PE) and polyvinyl chloride (PVC). The obtained results suggest a complex nature of sorption, including both hydrophobic and electrostatic interactions. However, since the ionic strength of the medium was found to be a significant factor influencing the sorption potential, minute interactions are observed in conditions common for the natural environment.
Asunto(s)
Microplásticos/química , Preparaciones Farmacéuticas/química , Contaminantes Químicos del Agua/química , Adsorción , Interacciones Hidrofóbicas e Hidrofílicas , Plásticos , Polietileno/química , Polipropilenos/química , Cloruro de Polivinilo/química , Electricidad EstáticaRESUMEN
The intensive development of medical science has led to an increase in the availability and use of pharmaceutical products. However, nowadays, most of scientific attention has been paid to the native forms of pharmaceuticals, while the transformation products (TPs) of these substances, understood herein as metabolites, degradation products, and selected enantiomers, remain largely unexplored in terms of their characterization, presence, fate and effects within the natural environment. Therefore, the main aim of this study was to evaluate the toxicity of seven native compounds belonging to different therapeutic groups (non-steroidal anti-inflammatory drugs, opioid analgesics, beta-blockers, antibacterial and anti-epileptic drugs), along with the toxicity of their 13 most important TPs. For this purpose, an ecotoxicological test battery, consisting of five organisms of different biological organization was used. The obtained data shows that, in general, the toxicity of TPs to the tested organisms was similar or lower compared to their parent compounds. However, for example, significantly higher toxicity of the R form of ibuprofen to algae and duckweed, as well as a higher toxicity of the R form of naproxen to luminescent bacteria, was observed, proving that the risk associated with the presence of drug TPs in the environment should not be neglected.
Asunto(s)
Araceae , Contaminantes Químicos del Agua/análisis , Antiinflamatorios no Esteroideos , Ecotoxicología , Ibuprofeno , NaproxenoRESUMEN
Even though the occurrence of pharmaceuticals in the water environment is thought to be a potential problem for human health and aquatic organisms, the level of knowledge of their sources and presence in the marine ecosystem is still insufficient. Therefore, this study was designed to determine the emergence of sixteen pharmaceuticals and caffeine in groundwater, submarine groundwater discharge (SGD), rivers and coastal seawater in the southern Baltic Sea. It has been recognized that chemical substances load associated with SGD can affect coastal ecosystems equally or even greater than surface runoff. Hence, the Bay of Puck, which is an active groundwater discharge area, has been chosen as a model study site to assess the preliminary risk of pharmaceutical and caffeine residues supply in coastal ecosystem. A special focus was placed on tracing the possible sources of pollution for groundwater and SGD based on the composition of collected samples. Five pharmaceuticals (carbamazepine, sulfapyridine, sulfamethoxazole, ketoprofen and diclofenac) and caffeine were detected in varying concentrations from below the detection limit to 1528.2 ng L-1. Caffeine and diclofenac were the most widespread compounds. Groundwater was mostly enriched in the analysed compounds and consequently SGD has been recognized as an important source of identified pharmaceutical and caffeine residues to the Bay of Puck. A predicted no-effect concentration (PNEC) was determined in order to perform an environmental risk assessment of five pharmaceuticals and caffeine detected in water samples. Finally, future challenges and potential amendments in monitoring strategies are discussed.
Asunto(s)
Ecosistema , Bahías , Cafeína , Monitoreo del Ambiente , Agua Subterránea , Agua de Mar , Contaminantes Químicos del AguaRESUMEN
The fact that pharmaceuticals are present in the environment has been proven in numerous publications. Nevertheless, their transformation products (mainly metabolites) are detected significantly less often, mainly because they are not included in the detecting methods, even though many of them are excreted from organisms at high rates and may be biologically active or have other properties that make them a potential threat to the environment. One of the most common processes that occur in the aqueous environment is hydrolysis, which may be one of the most important factors influencing the persistency of pharmaceuticals. Therefore four pharmaceuticals (carbamazepine, ibuprofen, tramadol and naproxen) as well as ten metabolites (10,11-dihydro-10-hydroxy carbamazepine, 10,11-dihydro-2-hydroxy carbamazepine, carbamazepine epoxide, 2-hydroxy ibuprofen, ibuprofen carboxylic acid, O-desmethyltramadol, hydroxy metronidazole, N-acetylsulfamethoxazole, 4'-hydroxy diclofenac, and O-desmethylnaproxen) were selected for the hydrolytic stability tests in accordance to OECD 111 Guideline. The preliminary test showed that only carbamazepine epoxide at pH 4, hydroxy metronidazole at pH 9 and 4'-hydroxy diclofenac at pH 4 and 9 were unstable and were included in the extended tests, which resulted in calculation of rate constants and half-lives at the temperature of 20, 50 and 70⯰C as well as the activation energy at the pH values in which these compounds were unstable. The obtained results show that carbamazepine epoxide is quite unstable and the half-life at 20⯰C was a little more than 8 days. Nevertheless, hydroxy-metronidazole and 4'-hydroxy diclofenac did not degrade at 20⯰C for 30 days.
Asunto(s)
Contaminantes Químicos del Agua/química , HidrólisisRESUMEN
In this paper, an analytical method for the simultaneous determination of twenty pharmaceuticals (eight non-steroidal anti-inflammatory drugs, five oestrogenic hormones, two antiepileptic drugs, two ß-blockers, and three antidepressants) in soils was developed. The optimal method included ultrasound-assisted extraction, a clean-up step on a silica gel column, derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1% trimethylchlorosilane (TMCS) in pyridine and ethyl acetate (2:1:1, v/v/v) for 30â¯minâ¯at 60⯰C, and determination by gas chromatography-mass spectrometry working in the selected ion monitoring mode. This affords good resolution, high sensitivity and reproducibility, and freedom from interferences even from complex matrices such as soils. The method detection limits ranged from 0.3 to 1.7â¯ngâ¯g-1, the intra-day precision represented as RSDs ranged from 1.1 to 10.0%, and the intra-day accuracy from 81.3 to 119.7%. The absolute recoveries of the target compounds were above 80%, except for valproic acid and diethylstilbestrol. The developed method was successfully applied in the analysis of the target compounds in soils collected in Poland. Among the 20 pharmaceuticals, 12 compounds were detected at least once in the soils. The determination of antiepileptic drugs, ß-blockers, and antidepressants was also performed for the first time.
Asunto(s)
Fraccionamiento Químico/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Contaminantes del Suelo/análisis , Estrona/análisis , Hormonas/análisis , Espectrometría de Masas , Polonia , Reproducibilidad de los Resultados , Suelo/química , Compuestos de TrimetilsililoRESUMEN
Pharmaceuticals constitute a significant group of emerging pollutants (EPs). The use of pharmaceuticals in animal breeding causes them to reach the soil environment in excrement and fertilizers. Depending on their chemical properties, pharmaceuticals can be sorbed to the soil or be washed out with rainfall and eventually be entered into groundwater. This paper evaluates the mobility of tramadol (TRA) and carbamazepine (CBZ), and two transformation products, O-desmethyltramadol (O-DMTRA) and 10,11-dihydro-10-hydroxycarbamazepine (10-OH-CBZ) in soils. Both pharmaceuticals are applied in human and animal treatment, which makes them enter the environment in native and metabolized form in high doses. Experiments were carried out in accordance with the OECD 106 procedure (batch tests) and DIN 19528:2009-01 procedure (percolation column test). The adsorption coefficients (Kd) for TRA, CBZ, O-DMTRA and 10-OH-CBZ were, respectively, 1.41⯱â¯0.10, 1.87⯱â¯0.06, 0.90⯱â¯0.03 and 0.37⯱â¯0.07 for sandy soil RS04, and 18.09⯱â¯0.78, 2.56⯱â¯0.05, 10.89⯱â¯0.17 and 0.56⯱â¯0.38⯠Lâ¯kg-1 for loamy soil RS06. The percolation column test was carried out for sandy soil RS04. The results obtained for TRA and O-DMTRA under static conditions indicated a high mobility of these compounds in soil, whereas the column leaching experiment showed that these compounds bind strongly to soil particles. A correlation between static and dynamic tests was observed in the case of CBZ and 10-OH-CBZ. These compounds will probably be characterized by a high or moderate mobility in soil.