Pharmaceuticals In Sediments Research Articles

Spatial trends and ecotoxic risk assessment of selected pharmaceuticals in sediments from Lake Victoria, Uganda, East Africa

Pharmaceutical residues in the aquatic environment are an emerging issue of global concern because of their effects on ecosystems including; antibacterial resistance development and endocrine disruption. Lake Victoria is the largest freshwater lake in Africa, and the second largest lake in the world. It is also the main source of the White Nile River, arguably the longest river in the world, flowing through South Sudan, Sudan, Ethiopia and Egypt, discharging into the Mediterranean Sea. However, its ecology is threatened by rapid industrialisation, urbanization, and increased agricultural activities, which have led to increased pollution via polluted runoffs. In this study, the occurrence of twenty-five pharmaceutical compounds (14 antibiotics, four anti-epileptic and antidepressant drugs, three analgesic and anti-inflammatory drugs, three beta-blockers, and one lipid regulator) was studied in 55 sediment samples obtained from the Ugandan sector of Lake Victoria, and their ecotoxic risk assessed. All the target compounds were quantifiable with levofloxacin (2–120 ng g−1 dm; dry mass), ciprofloxacin (3–130 ng g−1 dm) enoxacin (9–75 ng g−1 dm), ibuprofen (6–50 ng g−1 dm), metoprolol (1–92 ng g−1 dm) and propranolol (1–52 ng g−1 dm) being predominant. Murchison Bay, being the chief recipient of sewage effluents, municipal and industrial waste from Kampala city and its suburbs, had the highest levels. Ecotoxic risk assessment revealed that ciprofloxacin, levofloxacin, sulfamethoxazole, sulfamethazine, oxytetracycline, tetracycline, erythromycin, norfloxacin, ibuprofen, diclofenac, carbamazepine, atenolol, and metoprolol posed high toxic risks to sediment-dwelling organisms (risk quotients, RQ >1). This is the first study reporting concentrations and ecotoxic risks of pharmaceuticals in sediments of Lake Victoria, Uganda, and the whole of East Africa. Detection, identification and quantification of pharmaceuticals in Lake Victoria sediments is essential for gaining knowledge on their occurrence and fate which can ultimately be used to assist in constructing relevant policy and management recommendations.

Sorption and Degradation Potential of Pharmaceuticals in Sediments from a Stormwater Retention Pond

Stormwater retention ponds commonly receive some wastewater through misconnections, sewer leaks, and sewer overloads, all of which leads to unintended loads of organic micropollutants, including pharmaceuticals. This study explores the role of pond sediment in removing pharmaceuticals (naproxen, carbamazepine, sulfamethoxazole, furosemide, and fenofibrate). It quantifies their sorption potential to the sediments and how it depends on pH. Then it addresses the degradability of the pharmaceuticals in microcosms holding sediment beds and pond water. The sediment-water partitioning coefficient of fenofibrate varied little with pH and was the highest (average log Kd: 4.42 L kg−1). Sulfamethoxazole had the lowest (average log Kd: 0.80 L kg−1), varying unsystematically with pH. The coefficients of naproxen, furosemide and carbamazepine were in between. The degradation by the sediments was most pronounced for sulfamethoxazole, followed by naproxen, fenofibrate, furosemide, and carbamazepine. The first three were all removed from the water phase with half-life of 2–8 days. Over the 38 days the experiment lasted, they were all degraded to near completion. The latter two were more resistant, with half-lives between 1 and 2 months. Overall, the study indicated that stormwater retention ponds have the potential to remove some but not all pharmaceuticals contained in wastewater contributions.

Sequential window acquisition of all theoretical fragments versus information dependent acquisition for suspected-screening of pharmaceuticals in sediments and mussels by ultra-high pressure liquid chromatography-quadrupole time-of-flight-mass spectrometry

The aquatic ecosystems are dynamic environments often affected directly or indirectly by a myriad of anthropogenic contaminants that need to be properly identified. In this study, liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS) suspected-screening was applied to mussels and riverine sediment both, non-spiked and spiked with a mixture of 32 pharmaceuticals. Three data acquisition methods sequential window acquisition of all theoretical fragment-ion spectra (SWATH), in fix (FSWATH) and variable (VSWATH) window modes and Information Dependent Acquisition (IDA) were compared to determine the most suitable acquisition technique. The results obtained in the spiked samples showed that the two SWATH modes enable to obtain the MS/MS spectrum of a higher number of compounds (up to 27 with FSWATH and 25 with VSWATH) than IDA (up to 19) in sediment and mussel. The different data acquisition modes were also tested in non-spiked samples to verify the results obtained in the spiked ones. Importantly, all the methods are able to detect the MS/MS spectrum of several contaminants in the samples when analysed against a database of >600 compounds. Up to 7 contaminants were tentatively detected with IDA, 15 with FSWATH and 17 with VSWATH. Most pollutants were pesticides and pharmaceuticals, being of particular interest the presence of ibuprofen and acetaminophen in mussels.

A modified QuEChERS approach for the analysis of pharmaceuticals in sediments by LC-Orbitrap HRMS.

This work reports on a rapid and sensitive analytical method intended to be used for investigation of 25 multiclass pharmaceuticals in sediments. The method comprises a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction, followed by ultra-high-performance liquid chromatography-high-resolution linear ion trap/Orbitrap mass spectrometry, operated in positive ionization mode. The crucial parameters of both extraction and cleanup as well as those related to liquid chromatography and mass spectrometry were optimized and the method was validated in terms of accuracy, method detection and quantification limits, precision, linearity, and matrix effects. A matrix-matched calibration approach and isotopically labeled internal standards were employed for quantification and correction of matrix effects. In the optimized method, recoveries were calculated to be between 64 and 101% in the intermediate spiking level, with a relative standard deviation below 14%. Method quantification limits ranged from 1.3 to 47ngg-1. The linearity, expressed as a correlation coefficient, was over 0.998 in all cases, within a range from each compound's method quantification limit to 250ngg-1. The matrix effect study revealed slight signal suppression that decreased after the cleanup step for 50% of the pharmaceuticals, proving its adequacy to limit matrix interferences, without causing any important loss of relevant analytes. The applicability of the method was successfully tested in sediments from two Greek rivers in northwestern Greece, revealing the presence of paracetamol, risperidone, venlafaxine, citalopram, and carbamazepine and estimating for the first time the potential occurrence of pharmaceuticals in these two aquatic systems.

Methodologies for the analysis of pesticides and pharmaceuticals in sediments and plant tissue

Eco-technologies that utilize natural processes involving wetland vegetation, soil and their associated microbial assemblages are increasingly used for the removal of contaminants of emerging concern (CECs) from polluted water.

Factors affecting the dissipation of pharmaceuticals in freshwater sediments.

Degradation is one of the key processes governing the impact of pharmaceuticals in the aquatic environment. Most studies on the degradation of pharmaceuticals have focused on soil and sludge, with fewer exploring persistence in aquatic sediments. We investigated the dissipation of 6 pharmaceuticals from different therapeutic classes in a range of sediment types. Dissipation of each pharmaceutical was found to follow first-order exponential decay. Half-lives in the sediments ranged from 9.5 (atenolol) to 78.8 (amitriptyline) d. Under sterile conditions, the persistence of pharmaceuticals was considerably longer. Stepwise multiple linear regression analysis was performed to explore the relationships between half-lives of the pharmaceuticals, sediment physicochemical properties, and sorption coefficients for the compounds. Sediment clay, silt, and organic carbon content and microbial activity were the predominant factors related to the degradation rates of diltiazem, cimetidine, and ranitidine. Regression analysis failed to highlight a key property which may be responsible for observed differences in the degradation of the other pharmaceuticals. The present results suggest that the degradation rate of pharmaceuticals in sediments is determined by different factors and processes and does not exclusively depend on a single sediment parameter. Environ Toxicol Chem 2018;37:829-838. © 2017 SETAC.

Impacts of compound properties and sediment characteristics on the sorption behaviour of pharmaceuticals in aquatic systems

Sorption is a key factor in determining the persistence, attenuation and bioavailability of sediment-associated contaminants. However, our understanding of the sorption behaviour of pharmaceuticals in sediments is poor. In this study, we investigated the sorption behaviour of a diverse set of pharmaceuticals in a range sediment types. Sorption affinity of pharmaceuticals for all sediments was found to increase in the order mefenamic acid<cimetidine<atenolol<amitriptyline<diltiazem. Comparison of the experimental observations with predictions from an existing model for estimating sorption revealed the model worked poorly for the study pharmaceuticals. Multiple linear regression analysis was therefore used to develop new models for estimating sorption of individual pharmaceuticals based on sediment properties. The analyses indicated that sorption is related to properties such as Log Dow of a compound in the sediment (lipophilicity corrected for the sediment pH), cation exchange capacity, clay%, organic carbon content and exchangeable Ca2+, although, with the exception of atenolol, robust relationships between sediment properties and sorption were not obtained. Overall, the results demonstrate how complex the processes are that drive the sorption of pharmaceuticals in sediments and highlight the need for generation of further experimental data and further model development work.

Comparison of Four Extraction Methods for the Determination of Veterinary Pharmaceuticals in Sediment

In this work extraction by agitation (EA), ultrasound solvent extraction (USE), microwave assisted extraction (MAE) and pressurized liquid extraction (PLE) followed by high performance liquid chromatography with diode array detector (HPLC–DAD) for the determination of eight veterinary pharmaceuticals from different structural groups including one macrolide (tylosine), three anthelmintics (albendazole, febantel and levamisole), two anesthetics (lidocaine and procaine) and two steroidal hormones (hydrocortisone and dexamethasone) in sediment is described. Selected pharmaceuticals are widely used in veterinary practice in Croatia and in the whole world. Since they belong to different structure groups the usage of routine methods is not effective for their extraction from a complex sediment sample. Also, until now no article has been published for systematic extraction of named pharmaceuticals from sediment sample by different extraction methods. EA, USE, MAE and PLE have been optimized regarding different characteristic parameters such as sediment mass, extraction solvent, solvent volume, agitation frequency, power of ultrasound bath, extraction duration, extraction temperature and contact time between sediment and solvent. After extraction, pharmaceuticals were analyzed by HPLC–DAD using C18 stationary phase. HPLC–DAD–EA, HPLC-USE, HPLC–DAD-MAE and HPLC–DAD–PLE methods were validated in terms of selectivity, specificity, linearity, sensitivity, method detection limit (MDL) and quantification (MQL), repeatability, recovery and stability of a standard solution. Recoveries of selected pharmaceuticals from spiked sediment samples were generally higher than 50 %. However, dexamethasone and hydrocortisone showed lower recoveries due to their significantly different molecule structure. This paper shows the ability of simultaneous extraction and analysis of all selected pharmaceuticals by four different extraction methods in complex sediment sample followed by relatively affordable and sensitive HPLC–DAD method.

Geochronologies of pharmaceuticals in a sewage-impacted estuarine urban setting (Jamaica Bay, New York).

Pharmaceuticals are active substances found in sewage effluents and can negatively impact aquatic systems even at low concentrations. A fraction of these chemicals can be attached onto suspended solids and end up in sediments. This research shows concentrations of a wide group of pharmaceuticals in sediments from an urban estuarine setting (Jamaica Bay, New York). Highest concentrations (>75 ng g(-1)) were measured in surface sediments from the inner part of the bay, directly affected by sewage discharges and where water circulation is more restricted. Only 16 out of 61 target compounds were detected, and those positively charged (e.g., metoprolol) and/or highly hydrophobic (e.g., tamoxifen) were predominant. Their sediment-pore water partition coefficients were also calculated for the first time and were in a range between 11 and 2041 L/kg depending on the compound. Analysis of dated sediment cores revealed that pharmaceuticals were well preserved along the sedimentary column, a highly reducing environment. There was an increase in the concentration of most target compounds over the last five decades correlated with the increase in their usage, with some exceptions such as sulfamethazine (now used only for veterinary purposes). Thus, overall concentration of pharmaceuticals in sediment cores showed a doubling time of 9.2 years. Vertical distribution profiles for selected compounds also allowed reconstructing the history of contamination at Jamaica Bay by pharmaceuticals. The use of some of these chemicals as sewage molecular markers was also investigated.

Pharmaceuticals and organochlorine pesticides in sediments of an urban river in Florida, USA

Sediments from a rural to urban gradient along the Alafia River in Florida, USA, were collected to determine the risk of environmental contamination with legacy (organochlorine pesticides (OCPs)) and new contaminants (pharmaceuticals). Bed sediments (0–10 cm) collected from rural and urban sub-basins of the Alafia River were analyzed for OCPs and pharmaceuticals using standard gas chromatography and liquid chromatography-mass spectrometry techniques. Three most frequently detected pharmaceuticals in sediments were carbamazepine (100 % of samples), trimethoprim (89 % of samples), and pseudoephedrine (63 % of samples). While acetaminophen, diphenhydramine, lidocaine, and nicotine were detected in <30 % of samples. The detection of caffeine in all sediment samples suggests that domestic wastewater from wastewater treatment plants and/or septic systems may be a contributing source at all the sites. Among the OCPs, endosulfan I was most frequently detected (37 % of samples), followed by δ-hexachlorocyclohexane (15 % of samples), γ-chlordane and endosulfan II (both in 11 % of samples), and dichlorodiphenyldichloroethylene and methoxychlor (both in 7 % of samples). The lower concentrations of OCPs (sum 0–16.1 ng g−1) than pharmaceuticals (sum 0.5–61.9 ng g−1) in sediments are probably due to the historic use of OCPs since these were banned for use in the USA in the 1970s, while pharmaceuticals are still used. The variability in detection and concentrations of legacy and new compounds in rural and urban stream sediments is likely due to the different magnitude of input sources, site characteristics, and chemical properties of individual compounds. Significant positive correlations between OCPs and sediment properties (organic matter, silt, and clay) suggest that sediments are a major sink of various contaminants in the Alafia River. We conclude that the concentrations of both pharmaceuticals and OCPs in sediments of this urban river are relatively lower than existing literature; however, these can still be of environmental concern to aquatic organisms.

English

There is no doubt whatsoever that an increasing number of pharmaceuticals are being discharged in the aquatic environment. They may be present at trace levels. However, pharmaceuticals and their metabolites adverse effects on aquatic lives, animals and humans are a growing concern in the worldwide. Pharmaceuticals contamination of aquatic environment has been of major concern in recent years. Many studies have been published occurrence of pharmaceuticals in different parts of the world. Until now, there is little information about the occurrence of pharmaceuticals in sediment system. Therefore, in this review, focuses will be more on recent studies on the occurrence of detected pharmaceuticals in sediments. Key words:&nbsp;Pharmaceuticals, sediment, aquatic environment.

Multi-phase partitioning, ecological risk and fate of acidic pharmaceuticals in a wastewater receiving river: The role of colloids

The occurrence and multi-phase distribution of five pharmaceutical compounds were investigated in an urban wastewater treatment plant (WWTP) receiving river by analysis of pharmaceuticals in sediment, particulate matter, conventional dissolved phase (>0.7μm), colloidal phase (5kDa to 0.7μm), and truly dissolved phase (<5kDa) water. Diclofenac was found in all samples, followed by clofibric acid, ibuprofen, ketoprofen, and naproxen with the decreasing detection frequency. All targets in WWTP outfall site were higher than those in the upstream and downstream, indicating that the WWTP is an important input source of pharmaceuticals in the river. The colloidal phase contributed 10–14% of ketoprofen, 8–26% of naproxen, 17–36% of clofibric acid, 22–33% of diclofenac, and 9–28% of ibuprofen in the aquatic system, suggesting the colloids will play an important role as carrier to contaminants in the aquatic environment. Based on truly dissolved concentrations of pharmaceuticals in water, only the risk quotient (RQ) value for diclofenac towards fish was higher than 1, indicating it poses a potential risk to aquatic organisms. Finally, a Level III fugacity model was used to further assess the environmental fate of the selected pharmaceuticals (exemplified for clofibric acid and diclofenac). Both clofibric acid and diclofenac tend to accumulate in water compartment with the percentage of 99.7% and 60.6%, respectively. Advection in river is a significant loss process for clofibric acid (56.4%) and diclofenac (54.4%).

Risk assessment on the presence of pharmaceuticals in sediments, soils and waters of the Pego–Oliva Marshlands (Valencia, eastern Spain)

This study is focused on the occurrence of 17 pharmaceuticals in waters (34 samples), sediments (16 samples) and soils (23 samples, at two different depths) in a typical Mediterranean coastal wetland (Pego–Oliva marsh, Spain). Soil and sediment samples were extracted by pressurized liquid extraction (PLE). Aqueous extracts from PLE and water samples were concentrated by solid-phase extraction (SPE) and determined by liquid-chromatography tandem mass spectrometry (LC–MS/MS). Pharmaceuticals were detected in concentrations up to 112ng/L in water samples, up to 15.1ng/g sediments and up to 8.4ng/g in soil. In surface waters, ibuprofen and codeine were the compounds more frequently detected (up to 59ng/L and 63ng/L, respectively). Ground and tap water samples analyzed were also contaminated with pharmaceuticals. The 94% of sediments and the 80% of agricultural soils were polluted (mostly by carbamazepine and acetaminophen). Diffusion of codeine and fluoroquinolones to deeper soil horizons was observed. Possible relationships between variables were established by Pearson correlations and principal components analysis (PCA). An environmental risk assessment based on the available long-term data was performed. Results showed actual risk for the lowest trophic level, and for fishes, due to the presence of fluoroquinolones and ibuprofen. Nevertheless, the presence of pharmaceuticals in the environment is not limited only to an ecological problem since contamination also affects drinking water, being a potential risk to human health.

Optimization of matrix solid-phase dispersion for liquid chromatography tandem mass spectrometry analysis of 12 pharmaceuticals in sediments

The matrix solid-phase dispersion (MSPD) technique accompanied with LC–MS/MS detection for the purpose of determination of 12 pharmaceuticals (sulfaguanidine, sulfadiazine, sulfamethazine, sulfamethoxazole, trimethoprim, roxithromycin, praziquantel, febantel, enrofloxacin, ciprofloxacin, norfloxacin and procaine) applied to sediment samples has been described in this paper. Different parameters, such as the type of solid phase, the elution solvent and its volume have been investigated. The analytes were successfully extracted by C18 as an MSPD sorbent with 5mL of acetonitrile:5% of oxalic acid=6:4 (v/v) as an elution solvent. The proposed method provides a linear response over the concentration range of 0.0005–100μg/g, depending on pharmaceuticals with correlation coefficients above 0.9928 in all cases except for trimethoprim (0.9889). Also, the method has revealed low limits of detection (0.125–500ng/g), good precision (intra and inter-day), a relative standard deviation below 15% and recoveries above 80%, except for roxithromycin, febantel and enrofloxacin. The method has been successfully applied to analysis of different sediment samples.

Occurrence and phase distribution of selected pharmaceuticals in the Yangtze Estuary and its coastal zone

The occurrence and geochemical behavior of nine pharmaceutical compounds were investigated along the Yangtze River Estuary and its coastal area, by sampling and analysis of pharmaceuticals in sediment, suspended particulate matter (SPM), colloidal and soluble phases. In addition, the impact of sewage input was examined by sampling from sewage treatment plants (STP) effluent and its upstream and downstream in the Yangtze River. Although at relatively low concentrations in SPM and sediments, several pharmaceuticals were found at elevated concentration in filtered water samples from STP-affected sites. STP is therefore an important input of pharmaceuticals in the study area. Colloidal phase was further separated from bulk water samples using cross-flow ultrafiltration (CFUF), confirming it being an effective sorbent for pharmaceuticals with high sorption capacity which are 2–4 orders of magnitude higher than SPM. Moreover, mass balance calculations showed that significant percentages of selected pharmaceutical compounds were associated with aquatic colloids, indicating colloids as a reservoir for these contaminants in the Yangtze estuarine system.