Pharmaceuticals In Natural Waters Research Articles

Validation and Application of the Diffusive Gradients in Thin-Films Technique for In Situ Measurement of β-Blocker Drugs in Waters and Sediments

The occurrence of β-blocker drugs in aquatic environments worldwide has caused increasing attention to their threat to human health in recent years. It is essential to monitor these widely prescribed pharmaceuticals in natural waters and sediments, helping us investigate their potential risk to humans and ecosystems. In this study, a passive sampling technique, diffusive gradients in thin-films (DGT), was systematically developed for eight frequently detected β-blockers. The effective capacities of target compounds were large enough for the devices to deploy for several weeks. The uptake of all compounds was linearly correlated with deployment times during the 7-day laboratory experiment and agreed well with the theoretical line, except for several compounds (e.g., ATL) due to their relatively slow uptake rate. The performance of most compounds was independent of varying pH values and organic matter contents; only a few compounds were affected, while the application in high-salinity environments needs to be conducted with caution. Field deployments of DGT to detect β-blockers in situ in rivers and sediments proved that DGT is an effective tool to monitor β-blocker drugs and their fate in the natural aquatic environment, while DGT probes can provide information for us to investigate the biogeochemical processes occurred in sediment, especially at the sediment–water interface. This novel approach will help us understand the behaviour of β-blocker drugs in the aquatic environment, assess their risks, finally protect human health and maintain the sustainable development of the ecosystem.

Emerging pharmaceutical contaminants in key aquatic environments of the Philippines

Pharmaceuticals in natural waters are considered emerging pollutants due to their low concentrations and the negative effects they pose to the environment. Common sources of such pollutants include untreated wastewater from hospitals, residential, industrial, and agricultural sources. Many wastewater treatment methods only remove a subset of all pharmaceuticals from the wastewater; remaining pharmaceuticals are discharged into natural waters, and ultimately drain into coastal areas. Regions without proper wastewater treatment are especially susceptible to such contamination. This study deals with the distribution, sources, and seasonal variability of pharmaceuticals in key aquatic systems in the Philippines. Two watershed continuums (Davao Gulf, Davao City; Macajalar Bay, Cagayan de Oro City); two tourist areas (Boracay Island, Aklan; Mabini, Batangas); and one pristine atoll (Tubbataha Reefs, Palawan)—all with varied prevailing human population pressures—were studied. Samples of hospital wastewater as well as groundwater, surface and bottom water samples from rivers and coastal seas collected during dry and wet seasons were analyzed using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Thirty-four target pharmaceutical residues and antibiotics were extracted and quantified. Acetaminophen was detected at concentrations of up to 289.17 ppb in freshwater samples, and at concentrations of up to 253.39 ppb in seawater samples. Ubiquitous to all the sites was caffeine, reaching 1848.57 ppb. Sulfamethazine, a commonly used veterinary antibiotic, was detected at 764.91 ppb in a river site in Cagayan de Oro. Untreated hospital wastewater contained metformin, iopamidol, sulfamethoxazole, acetylsulfamethoxazole, ciprofloxacin, and azithromycin, but these pharmaceuticals were not detected in other river and coastal waters. Samples collected during the dry season exhibited higher concentrations than those from the wet season, which appears to be related to increase in transient populations from tourism activities as well as dilution. The presence of pharmaceutical residues and antibiotics in these areas and the potential impact on the environment indicate the need for stricter wastewater management measures, particularly in communities located near water bodies. As the results of this study show, such measures might be most beneficial and effective if imposed during dry season and in areas open to tourism.

Montmorillonite-Based Natural Adsorbent from Colombia for the Removal of Organic Pollutants from Water: Isotherms, Kinetics, Nature of Pollutants, and Matrix Effects

The presence of dyes and pharmaceuticals in natural waters is a growing concern worldwide. To address this issue, the potential of montmorillonite (MMT), an abundant clay in Colombia, was assessed for the first time for the removal of various dyes (indigo carmine (IC), congo red (CR), methylene blue (MB) and crystal violet (CV)) and pharmaceuticals (levofloxacin and diclofenac) from water. Initially, the MMT was characterized. TGA and FTIR showed OH groups and water adsorbed onto MMT. XRD showed an interlayer spacing of 11.09 Å and a BET surface area of 82.5 m2g−1. SEM/EDS revealed a typical flake surface composed mainly of Si and O. Subsequently, the adsorbent capacity of MMT was evaluated for the removal of the pollutants. Adsorption isotherms showed a fit to the Langmuir model, which was confirmed by the Redlich–Peterson isotherm, indicating a monolayer-type adsorption. Furthermore, adsorption kinetics were best described by the pseudo-second-order model. Adsorption capacity (for dyes CV > MB > CR > IC) was associated with the attractive forces between the contaminants and MMT (PZC 2.6). Moreover, the findings evidenced that MMT can remove MB, CR, CV, and levofloxacin by electrostatic attractions and hydrogen bonding, while for IC and diclofenac only hydrogen bonding takes place. It was shown that MMT was most cost-effective at removing CV. Additionally, the material was able to be reused. Finally, the MMT efficiently removed CV in textile wastewater and levofloxacin in urine due to the positive charge of the pollutants and the low PZC of MMT.

Early Biological Modulations Resulting from 1-Week Venlafaxine Exposure of Marine Mussels Mytilus galloprovincialis Determined by a Metabolomic Approach.

There is growing evidence of the presence of pharmaceuticals in natural waters and their accumulation in aquatic organisms. While their mode of action on non-target organisms is still not clearly understood, their effects warrant assessment. The present study assessed the metabolome of the Mediterranean mussel (Mytilus galloprovincialis) exposed to a 10 µg/L nominal concentration of the antidepressant venlafaxine (VLF) at 3 time-points (1, 3, and 7 days). Over the exposure period, we observed up- or down-modulations of 113 metabolites, belonging to several metabolisms, e.g., amino acids (phenylalanine, tyrosine, tryptophan, etc.), purine and pyrimidine metabolisms (adenosine, cyclic AMP, thymidine, etc.), and several other metabolites involved in diverse functions. Serotonin showed the same time-course modulation pattern in both male and female mussels, which was consistent with its mode of action in humans, i.e., after a slight decrease on the first day of exposure, its levels increased at day 7 in exposed mussels. We found that the modulation pattern of impacted metabolites was not constant over time and it was gender-specific, as male and female mussels responded differently to VLF exposure.

Impact of Artificial Infiltration on the Removal of Nonsteroidal Anti-Inflammatory Drugs during Treatment of Surface Water

The content of pharmaceuticals in natural waters is steadily increasing. Especially nonsteroidal anti-inflammatory drugs (NSAIDs) are often detected in natural waters due to their widespread use. This group of compounds includes commonly used representatives, such as paracetamol and ketoprofen. The quality of natural waters determines the processes applied for the treatment of drinking water. The methods used in order to remove pharmaceuticals from treated water include adsorption and biologically active filtration. Both processes also occur during artificial infiltration (forced flow of intake surface water through the ground to the collecting wells) at surface water intakes. The processes, which occur in the soil, change the water quality characteristics to a great extent. The goal of the study was to evaluate the removal efficiency of paracetamol and ketoprofen in the process of artificial infiltration used as a pre-treatment of surface water. The studies were conducted at a field experimental installation located at the technical artificial infiltration intake. The experimental installation consisted of three metering wells (piezometers) which were located on the way between the bank of the infiltration pond and the collecting well. The collected water samples allowed to evaluate the change of selected NSAIDs concentrations during the passage of water through the ground. The analysis procedure included solid phase extraction (SPE) and high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Removal of the studied NSAIDs in the infiltration process occurred with variable effectiveness throughout the year. Paracetamol was removed with annual efficiency equal to 42%, although no significant removal of ketoprofen was observed.

Development and Application of the Diffusive Gradients in Thin-Films Technique for Measuring Psychiatric Pharmaceuticals in Natural Waters

Psychiatric pharmaceuticals are widely distributed in the aquatic environment and have attracted recent attention due to their potential for environmental effects. A robust and reliable in situ passive sampling approach, the diffusive gradients in thin-films (DGT) technique, is developed here to measure 14 psychiatric pharmaceuticals. A new binding material, mixed-mode cation exchange resin (Poly-Sery MCX, 40 μm, CNW, Germany), was used for the first time in DGT and compared to XAD and HLB. Reliable elution efficiencies of the pharmaceuticals from the binding gels were obtained in methanol/ammonia, and diffusion coefficients for all the compounds were determined. The influence of diffusive layer thickness (0.515-2.015 mm), deployment time (3-168 h), and important environmental conditions-pH (3.02-9.45), ionic strength (0.0001-0.5 M), and dissolved organic matter (0-20 mg L-1)-were evaluated. The capacity of XAD, HLB, and MCX gels for binding all the test pharmaceuticals was ∼335 μg per disc, meaning that DGT could theoretically be deployed for over 30 months if there are no competitive effects or confounding factors. The uptake kinetics of psychiatric pharmaceuticals onto MCX gel were much faster than those onto XAD and HLB gels in the first hour. DGT measured concentrations of test pharmaceuticals at two sample points in a river (over 6 days) were comparable to those obtained by grab sampling. This study demonstrates the accuracy and reliability of DGT for measuring psychiatric pharmaceuticals across a wide range of freshwater conditions found in the natural environment.

Phototransformation of three selected pharmaceuticals, naproxen, 17α-Ethinylestradiol and tetracycline in water: Identification of photoproducts and transformation pathways

Transformation products (TPs) may be formed during various processes, however, it was proved that one of the main mechanisms responsible for degradation of pharmaceuticals in natural waters is photolysis. Three compounds were selected, tetracycline (TC), 17-α-ethinylestradiol (EE2) and naproxen (NAP), for degradation experiments which were performed using a xenon lamp emitting light with a spectrum closely approximating that of natural sunlight. Identification of photodegradation products was achieved via liquid chromatography coupled with high resolution quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) providing accurate mass measurements and MS/MS experiments for structural elucidation. Results indicate that degradation of compounds under the study follows pseudo-first-order kinetics. Photolysis rate constants (k) were determined and half-lifes (t1/2) calculated to be 11, 120, and 13 min for TC, EE2 and NAP, respectively. Xenon lamp irradiation led to the formation of several photoproducts. Many of them have been identified for the first time. LC-QTOF-MS analysis allowed for the identification of seven, four, and eight TPs of TC, EE2 and NAP, respectively. Finally, the presence of parent compounds and identified TPs was investigated in various real-world water samples. Only three degradation products of 17-α-ethinylestradiol and naproxen were detected in wastewater effluent and treated water samples. Quantitative structure-activity relationship (QSAR) approach was applied in order to estimate physical-chemical properties of selected pharmaceuticals and their TPs. This allowed predicting the fate of all analytes in the aqueous environment.

Impact of the wastewater-mixing zone on attenuation of pharmaceuticals in natural waters: Implications for an impact zone inclusive environmental risk assessment

The direct discharge of untreated wastewater has been identified as an important source of environmental contamination by active pharmaceutical ingredients and other ‘down-the-drain’ chemicals in developing countries. It necessitates the development of an environmental risk assessment approach for the resulting impact zone. This study was designed to investigate the impact of low level of dilution (<10) on the natural attenuation processes of distribution and degradation within the impact zone. Dilution of the untreated wastewater resulted in increased desorption and corresponding environmental concentrations. The presence/absence of the microbial population in the batches affected the degree of sorption depending on the compound charge (i.e. positive or negative), highlighting an experimental technical bias. The degradation half-lives of acebutolol and diclofenac increased with increasing dilution and resulted in higher environmental persistence. The modelling of the biochemical oxygen demand (BOD) allowed an estimate of the temporal end boundary of the impact zone to be predicted as 24h. Therefore, it was concluded that most of the investigated compounds would persist beyond the end of the impact zone as defined by the return to environmental BOD concentrations. It is proposed that, within environmental risk assessment protocols, the impact zone should be considered as a semi-natural wastewater treatment area in such a way to allow the estimate of environmental concentrations of pharmaceuticals beyond its end.

Review on Physicochemical, Chemical, and Biological Processes for Pharmaceutical Wastewater

Due to the needs of human life and health, pharmaceutical industry has made great progress in recent years, but it has also brought about severe environmental problems. The presence of pharmaceuticals in natural waters which might pose potential harm to the ecosystems and humans raised increasing concern worldwide. Pharmaceuticals cannot be effectively removed by conventional wastewater treatment plants (WWTPs) owing to the complex composition, high concentration of organic contaminants, high salinity and biological toxicity of pharmaceutical wastewater. Therefore, the development of efficient methods is needed to improve the removal effect of pharmaceuticals. This review provides an overview on three types of treatment technologies including physicochemical, chemical and biological processes and their advantages and disadvantages respectively. In addition, the future perspectives of pharmaceutical wastewater treatment are given.

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/CoII are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H2O2/FeII) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO4·− with carbamazepine is 1.92·109 M−1 s−1. In laboratory grade water and in real urban wastewater, SO4·− yielded a faster degradation of carbamazepine compared to HO· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.

Persistence of gemfibrozil, naproxen and mefenamic acid in natural waters

The occurrence of pharmaceuticals in natural waters is a potential threat to human nutrition and ecosystem quality. The persistence of the acidic pharmaceuticals gemfibrozil, naproxen and mefenamic acid was studied in surface waters of Maracaibo Lake and Tule reservoir (Venezuela) under laboratory conditions. A quick and easy analytical method was developed for the determination of the acidic drugs at microgram per liter levels using aqueous derivatization, liquid–liquid extraction and gas chromatography–mass spectrometry. Pharmaceuticals degradation followed a pseudo first-order kinetic and their half-lives were calculated for every experimental condition. Under sunlight, naproxen and mefenamic acid were degraded at moderate rates with half-lives from 9.6 ± 0.5 to 27.0 ± 6.6 days, while gemfibrozil had a higher persistence (t1/2 = 119.5 ± 15.6 − 288.8 ± 61.3 days).

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On-line preconcentration of pharmaceutical residues from large volume water samples using short reversed-phase monolithic cartridges coupled to LC-UV-ESI-MS

A simplified preconcentration method for a range of ultra-trace level pharmaceuticals in natural waters has been developed. Solid phase extraction was performed on-line using a micro-reversed-phase monolithic silica column, allowing for very rapid trace enrichment from large volume (500 ml) samples with minimal sample handling. Acceptable recoveries of >70% were obtained for the majority of compounds investigated and the monolithic columns could be washed and conditioned on-line with no sample carryover and used reproducibly for up to eight extractions each. The on-line SPE-LC-UV method was coupled to electrospray ionisation ion trap mass spectrometry (ESI-MS) to increase both selectivity and specificity. Detection limits were determined in spiked river and tap water samples and found to lie in the low ng/l region using sample volumes of 500 ml, loaded at a flow rate of 10 ml/min, and therefore, were suitable for ultra trace analysis.

Oxidation of pharmaceuticals during water treatment with chlorine dioxide

The potential of chlorine dioxide (ClO 2) for the oxidation of pharmaceuticals during water treatment was assessed by determining second-order rate constants for the reaction with selected environmentally relevant pharmaceuticals. Out of 9 pharmaceuticals only the 4 following compounds showed an appreciable reactivity with ClO 2 (in brackets apparent second-order rate constants at pH 7 and T = 20 ° C ): the sulfonamide antibiotic sulfamethoxazole (6.7×10 3 M −1 s −1), the macrolide antibiotic roxithromycin (2.2×10 2 M −1 s −1), the estrogen 17 α-ethinylestradiol (∼2×10 5 M −1 s −1), and the antiphlogistic diclofenac (1.05×10 4 M −1 s −1). Experiments performed using natural water showed that ClO 2 also reacted fast with other sulfonamides and macrolides, the natural hormones estrone and 17 β-estradiol as well as 3 pyrazolone derivatives (phenazone, propylphenazone, and dimethylaminophenazone). However, many compounds in the study were ClO 2 refractive. Experiments with lake water and groundwater that were partly performed at microgram/L to nanogram/L levels proved that the rate constants determined in pure water could be applied to predict the oxidation of pharmaceuticals in natural waters. Compared to ozone, ClO 2 reacted more slowly and with fewer compounds. However, it reacted faster with the investigated compounds than chlorine. Overall, the results indicate that ClO 2 will only be effective to oxidize certain compound classes such as the investigated classes of sulfonamide and macrolide antibiotics, and estrogens.