Occurrence and prevalence of antibiotics in wastewater treatment plants and effluent receiving rivers in South Africa using UHPLC-MS determination.

The increased usage of antibiotics over the recent years has led to an increased interest in monitoring their presence in wastewater all over the world. In this study the occurrence of sixteen (16) selected antibiotics (amoxicillin, ampicillin, azithromycin, ciprofloxacin, doxycycline, erythromycin, gentamicin, metronidazole, norfloxacin, ofloxacin, penicillin, sulfamethoxazole, sulfapyridine, sulfamethizole, tetracycline and trimethoprim) were determined in two wastewater treatment plants and two effluent receiving rivers in Northern part of Pretoria, South Africa. Targeted screening and identification of antibiotics was done using ultra high-performance liquid chromatography coupled with mass spectrometry after sample clean-up and pre-concentration using solid phase extraction. The concentrations of the targeted antibiotics detected in influent samples ranged between 0.78 and 96.8 ng mL-1 and those in effluent were between 0.12 and 9.89 ng mL-1. The highest recorded concentrations in all samples were those of doxycycline (30.9-120 ng mL-1) and sulfamethoxazole (2.52-96.8 ng mL-1) in effluent and influent samples, respectively. The concentrations of antibiotics in the rivers receiving effluents were between 0.03 and 72.8 ng mL-1 in upstream samples and 0.008-76.8 ng mL-1 in downstream samples, indicating that there is other source of contaminate to these rivers other than the treatment plants. Risk assessment using the hazard quotients ranged between 0.24 and 889 indicating that the presence of these antibiotics and antibiotic mixtures posed higher ecological risks to aquatic organisms. From the study, it could be concluded that wastewater treatment plants were releasing antibiotics to the environment and posing a risk to the aquatic ecosystem and public health. Therefore, there is a need to research into developing more efficient conventional wastewater treatment technologies that can completely remove antibiotics from wastewater.

Determination of antibiotics during treatment of hospital wastewater using automated solid-phase extraction followed by UHPLC-MS: occurrence, removal and environmental risks.

The extent of removal of pharmaceuticals by African-based wastewater treatment plants (WWTPs) is relatively unknown with various studies observing high concentrations in effluents. This is mainly due to WWTPs still utilising the traditional treatment methods which are known to be less effective. In this study, 15 selected antibiotics (amoxicillin, ampicillin, azithromycin, ciprofloxacin, doxycycline, erythromycin, gentamicin, metronidazole, norfloxacin, ofloxacin, penicillin, sulfamethoxazole, sulfapyridine, tetracycline and trimethoprim) were monitored in wastewater as it goes through sedimentation (primary and secondary), aeration and chlorination stages of a WWTP. Analytical method involved solid-phase extraction followed by liquid chromatographic determination. Removal efficiencies during sedimentation were generally positive with doxycycline achieving 80-95.8%, while negative removal efficiencies were observed for penicillin V (-46.4 to -17.1%) and trimethoprim (-26.2 to -18.9%). The aeration and agitation stage resulted in concentration enhancement for several antibiotics with seven of them ranging between -273 and -15.5%. This stage was responsible for the relatively low overall removal efficiencies in which only 4 antibiotics (doxycycline, tetracycline, ciprofloxacin, and erythromycin) experienced overall removal efficiencies above 50%. The recorded effluent concentrations ranging between 0.0130 and 0.383 ng/mL were translated to low potential for development of antibiotic resistance genes in the receiving environments while ecotoxicity risk was high for only amoxicillin, ampicillin and sulfapyridine. The study has provided an overview of the performance of common wastewater treatment processes in South Africa and hopes that more monitoring and environmental risk data can be made available towards drafting of antibiotic priority lists that cater for Africa.

Trace Metals, Crude Protein, and TGA-FTIR Analysis of Evolved Gas Products in the Thermal Decomposition of Roasted Mopane Worms, Sweet Corn, and Peanuts.

The thermal behavior of mopane worms (Imbrasia belina), roasted peanuts (Arachis hypogaea L.), and sweet corn (Zea mays L. saccharata) was investigated under inert conditions using the TGA-FTIR analytical technique heated from 64 to 844°C at a heating rate of 20°C/min. The degradation patterns of the food samples differed as sweet corn and peanuts exhibited four degradation stages 188, 248, 315, and 432°C and 145, 249, 322, and 435°C, respectively. Mopane worms displayed three (106, 398, and 403°C). The different decomposition patterns together with the types of evolved gases shown by FTIR analysis justified the varied biochemical and chemical composition of foods. The common evolved gas species between the food samples were H2O, CO2, P=O, CO, and CH4 but mopane worms showed two extra different bands of C-N and N-H. Higher volumes of evolved gases were recorded at temperatures between 276 and 450°C, which are higher than the usual cooking temperature of 150°C. This means that the food maintained its nutritional value at the cooking temperature. Mopane worms were found to contain twice and four times crude protein content than peanuts and corn, respectively. Only total arsenic metal was reported to be above threshold limits.

Development and application of a membrane assisted solvent extraction-molecularly imprinted polymer based passive sampler for monitoring of selected pharmaceuticals in surface water.

In this work, we demonstrate the development, evaluation and pre-liminary application of a novel passive sampler for monitoring of selected pharmaceuticals in environmental waters. The samplers were calibrated in laboratory-based experiments to obtain sampling rates (Rs) for carbamazepine, methocarbamol, etilefrine, venlafaxine and nevirapine. Passive sampling was based on the diffusion of the target pharmaceuticals from surface water through a membrane bag which housed an ionic liquid as a green receiving solvent and a molecularly imprinted polymer. Effects of biofouling, deployment time and solvent type for the receiver phase were optimized for selective uptake of analytes in surface water. Notably, there was a decrease in the uptake of selected pharmaceuticals and consequently a decrease in their sampling rates in the presence of biofouling. The optimum matrix-matched sampling rates ranged from 0.0007 - 0.0018 L d-1 whilst the method detection and quantification limits ranged from 2.45 - 3.26 ng L-1 and 8.06 - 10.81 ng L-1, respectively. The optimized passive sampler was deployed in a dam situated in the heart of a typical highly populated township in the Gauteng Province of South Africa. Only etilefrine and methocarbamol were detected and quantified at maximum time weighted average concentrations of 12.88 and 72.29 ng L-1, respectively.

Health effects and risks associated with the occurrence of pharmaceuticals and their metabolites in marine organisms and seafood.

Pharmaceuticals and their metabolites are continuously invading the marine environment due to their input from the land such as their disposal into the drains and sewers which is mostly followed by their transfer into wastewater treatment plants (WWTPs). Their incomplete removal in WWTPs introduces pharmaceuticals into oceans and surface water. To date, various pharmaceuticals and their metabolites have been detected in marine environment. Their occurrence in marine organisms raises concerns regarding toxic effects and development of drug resistant genes. Therefore, it is crucial to review the health effects and risks associated with the presence of pharmaceuticals and their metabolites in marine organisms and seafood. This is an important study area which is related to the availability of seafood and its quality. Hence, this study provides a critical review of the information available in literature which relates to the occurrence and toxic effects of pharmaceuticals in marine organisms and seafood. This was initiated through conducting a literature search focussing on articles investigating the occurrence and effects of pharmaceuticals and their metabolites in marine organisms and seafood. In general, most studies on the monitoring of pharmaceuticals and their metabolites in marine environment are conducted in well developed countries such as Europe while research in developing countries is still limited. Pharmaceuticals present in freshwater are mostly found in seawater and marine organisms. Furthermore, the toxicity caused by different pharmaceutical mixtures was observed to be more severe than that of individual compounds.

Determination of furanic compounds in Mopane worms, corn, and peanuts using headspace solid-phase microextraction with gas chromatography-flame ionisation detector.

A headspace-solid phase microextraction - gas chromatography-flame ionisation detector (HS-SPME-GC/FID) method was developed for the simultaneous determination of furan, 2-methylfuran and 2-furaldehyde in thermally processed Mopane worms, corn, and peanuts. The optimal HS-SPME conditions with polydimethylsiloxane/carboxen/divinylbenzene (PDMS/CAR/DVB) fiber were 30 °C, 40 min and 600 rpm stirring speed. The recoveries, detection and quantification limits for the analytes in food samples were 67-106%, 0.54-3.5 µg kg-1, and 1.8-12 µg kg-1, respectively. These results showed that the developed method was accurate, reproducible, and sensitive for the determination of furan, 2-methylfuran and 2-furaldehyde in complex food matrices with limited interference from other components. The optimised analytical method was applied for monitoring the presence of the furanic compounds in heat-processed South African foods. Although 2-furaldehyde was not detected in food samples, the maximum concentrations of 24 and 95 µg kg-1 were found for furan and 2-methylfuran, respectively.

Multivariate optimization of a two-way technique for extraction of pharmaceuticals in surface water using a combination of membrane assisted solvent extraction and a molecularly imprinted polymer.

This work demonstrates development and evaluation of a two-way technique based on the combination of membrane assisted solvent extraction and a molecularly imprinted polymer (MASE-MIP) for selective and efficient extraction of five selected pharmaceuticals belonging to five different therapeutic classes. The pharmaceuticals were extracted from surface water samples followed by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-qTOF/MS) determination. A central composite design was applied to optimize the influence of the sample salt content, the stirring rate, the stirring time and the amount of MIP on the extraction of an anticonvulsant (carbamazepine), a cardiac stimulant (etilefrine), a muscle relaxant (methocarbamol), an antiretroviral (nevirapine) and an antidepressant (venlafaxine) from surface water. Optimization of the analytical method was performed by spiking water with a mixture of all five pharmaceuticals at 500 ng mL-1. Optimum extraction conditions for a sample volume of 18 mL were found to be 5 g of salt content, a stirring rate of 400 rpm, an extraction time of 60 min and 50 mg of MIP. The MASE-MIP-LC-qTOF/MS method gave detection and quantification limits ranging from 0.09 to 0.20 ng mL-1 and 0.31-0.69 ng mL-1, respectively. The spiked river water samples yielded recoveries ranging from 38 to 91% for the selected model compounds belonging to the five classes of pharmaceuticals. Upon the application of the developed analytical method in water analysis, all selected pharmaceuticals were detected in South African river water with nevirapine and venlafaxine being more prominent attaining the maximum concentrations of 1.64 and 2.48 ng mL-1, respectively.

Target and Suspect Screening of Pharmaceuticals and their Transformation Products in the Klip River, South Africa, using Ultra-High-Performance Liquid Chromatography-Mass Spectrometry.

In spite of recent reports about the presence of pharmaceuticals in African water bodies, their prevalence has still not been sufficiently quantified. The few available studies have mostly focused on a limited number of pharmaceuticals. In the present study, a suspect screening of 92 compounds (mainly pharmaceuticals and their transformation products) along the Klip River, South Africa was conducted, followed by target monitoring of 21 of the detected pharmaceuticals. The experimental approach was based on solid-phase extraction followed by analysis with ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (UHPLC-QTOF-MS). The results revealed 47 pharmaceuticals, 31 of which were detected for the first time in South African waters. Seven detected pharmaceuticals (propyphenazole, sulfamerazine, levamisole, tryptophan, dibucaine, albuterol, and fenpropimorph) are not approved medications in South Africa. Six pharmaceutical metabolites were detected for the first time in South Africa. Pharmaceuticals with the highest concentrations in river water were flumequine (0.257 µg L-1 ), oxolinic acid (0.355 µg L-1 ), and acetaminophen (0.432 µg L-1 ). Oxolinic acid presented the highest hazard quotient, 48.6, indicating a risk of toxicity to aquatic organisms. Hazard quotients for other pharmaceuticals were below 1, except that of flumequine, which reached 1.285. These results suggest a need for further research into the fate of pharmaceuticals in surface waters, and a quantification of the risks associated with the identified drugs because they are likely to accumulate in the tissues of fish/aquatic organisms, thus affecting humans. Environ Toxicol Chem 2022;41:437-447. © 2021 SETAC.

Evaluation of organochlorine pesticide residues in Beta vulgaris, Brassica oleracea, and Solanum tuberosum in Bloemfontein markets, South Africa.

This study evaluated the level of selected pesticide residues in the staple vegetables; Brassica oleracea var. capitata (cabbage), Beta vulgaris var. cicla (Swiss chard), and Solanum tuberosum (potato) from fresh produce markets in the city of Bloemfontein, South Africa. A QuEChERS extraction method was used followed by quantitation using GC-HRT/MS. The pesticide residues were detected in levels lower than the recommended Maximum Residue Levels ranging from not detected to 121.6 ng/kg recorded for heptachlor in cabbage samples. Cabbage was generally susceptible to pesticide residue accumulation with the average total concentration for different markets at 222 mg/kg. The pesticide residues were predicted to be from recent applications but their existence within guideline limits indicated that their use in vegetable farming was within the FAO/WHO recommended good agricultural practices. While the current situation points that consumption of the vegetables in the province poses limited health concerns due to organochlorine pesticides, the unmonitored use of products containing these compounds may result in elevated levels. Continued monitoring and a call for the South African legislature to revise its regulations of the Fertilizers Act to reflect the current international laws on pesticides management is recommended.

Occurrence and ecotoxicological risk assessment of non-steroidal anti-inflammatory drugs in South African aquatic environment: What is known and the missing information?

Non-steroidal anti-inflammatory drugs (NSAIDs) are medications used individually or as mixtures with other pharmaceuticals for the treatment of various illnesses. Their easy accessibility and high human consumption have resulted to their detection at high concentrations in South African water resources. In the present work, an extensive review of the occurrence and ecotoxicological risk assessment of NSAIDs in South African aquatic environment is provided. Reviewed literature suggested ibuprofen, naproxen, diclofenac, ketoprofen and fenoprofen as the most prominent NSAIDs in the South African aquatic environment. Among these NSAIDs, higher concentrations of ibuprofen are common in South African waters. As a result, this drug was found to pose high ecotoxicological risks towards the aquatic organisms with the highest risk quotients of 14.9 and 11.9 found for algae in surface water and wastewater, respectively. Like in other parts of the world, NSAIDs are not completely removed in wastewater treatment plants. Removal efficiencies below 0% due to higher concentrations of NSAIDs in wastewater effluents rather than influents were observed in certain instances. The detection of NSAIDs in sediments and aquatic plants could serve as the important starting step to investigate other means of NSAIDs removal from water. In conclusion, recommendations regarding future studies that could paint a clearer picture regarding the occurrence and ecotoxicological risks posed by NSAIDs in South African aquatic environment are provided.

A Comparative Study on the Dissolution of Argema mimosae Silk Fibroin and Fabrication of Films and Nanofibers.

Limited studies have been done on silk fibroins of wild silkworm species owing to their relative insolubility in many solvents. In this study, the solubility of Argema mimosae wild silk fibroin in different salts (LiBr, LiCl, Ca(NO3)2, and CaCl2) dissolved in formic acid under varying temperatures was investigated. The dissolution conditions under which the solubility was optimum were optimized using a central composite design approach. The optimum range for solvation of the fibroin were visualized using contour plots. The influence of temperature and salt concentration were found to significantly influence the solvation of the fibroin. Following the successful dissolution of the fibroin, the regenerated silk fibroin solutions were cast to obtain water insoluble films which were used in investigating optimum electrospinning conditions. Average nanofiber diameters in the 110-141 nm range were obtained under optimum electrospinning conditions. The silk forms were characterized using the FTIR, TGA, XRD, and SEM to understand their properties. The investigations revealed that formic acid-salt solvents were effective in the solvation of the wild silk fibroin. Some of the dissolution conditions induced mild effects on the silk fibroin while others were harsh. Furthermore, processing to nanofibers resulted in the degradation of the ß-sheets producing nanofibers rich in α-helices. However, post-treatment using methanol and water vapor were effective in restoring ß-sheet crystallinity.

Determination of volatile compounds during deterioration of African opaque beer using a stir bar sorptive extraction technique and gas chromatography-high resolution mass spectrometry.

Opaque beer traditional to African communities undergoes quick deterioration and is consumed within 7 days of its production. The current study has utilized a stir bar sorptive extraction technique followed by GC-HRT determination to trace variations of 84 volatile compounds in four opaque beers commonly brewed in South Africa over the 7-day shelf life period. The major fruity esters were observed to increase up to Day 4 and eventually decreasing until Day 7 where their levels were finally lower than Day 1. Aldehydes reduced drastically and were less than 50% on Day 2 and becoming almost undetectable at Day 7. The common beer alcohols (phenylethyl alcohol and 3-methyl-1-butanol) decreased during beer shelf life while phenolics with undesirable medicinal tastes (creosol and p-cresol) increased up to 24-fold by Day 7. This study might open future research perspectives around opaque beer traditional to African rural communities.

Application of Hollow Fibre-Liquid Phase Microextraction Technique for Isolation and Pre-Concentration of Pharmaceuticals in Water.

In this article, a comprehensive review of applications of the hollow fibre-liquid phase microextraction (HF-LPME) for the isolation and pre-concentration of pharmaceuticals in water samples is presented. HF-LPME is simple, affordable, selective, and sensitive with high enrichment factors of up to 27,000-fold reported for pharmaceutical analysis. Both configurations (two- and three-phase extraction systems) of HF-LPME have been applied in the extraction of pharmaceuticals from water, with the three-phase system being more prominent. When compared to most common sample preparation techniques such as solid phase extraction, HF-LPME is a greener analytical chemistry process due to reduced solvent consumption, miniaturization, and the ability to automate. However, the automation comes at an added cost related to instrumental set-up, but a reduced cost is associated with lower reagent consumption as well as shortened overall workload and time. Currently, many researchers are investigating ionic liquids and deep eutectic solvents as environmentally friendly chemicals that could lead to full classification of HF-LPME as a green analytical procedure.

Optimization and application of hollow fiber liquid-phase microextraction and microwave-assisted extraction for the analysis of non-steroidal anti-inflammatory drugs in aqueous and plant samples.

Human consumption of non-steroidal anti-inflammatory drugs (NSAIDs) is increasing, which poses a great risk of pollution by these pharmaceuticals on the aquatic environment. Therefore, this study reports the optimization of microwave-assisted extraction using water as a green solvent and hollow fiber liquid-phase microextraction (HF-LPME) methods followed by high-performance liquid chromatography-high resolution mass spectrometry analysis of NSAIDs in wastewater and aquatic plant, Eichhornia crassipes. The optimized MAE resulted in efficient transfer of selected NSAIDs from plant samples into the aqueous phase yielding the recoveries ranging from 91 to115%. A multivariate approach based on half fractional factorial and central composite design was used during the optimization of HF-LPME. Under the optimized conditions, the maximum enrichment factors for naproxen, fenoprofen, diclofenac, and ibuprofen were 49, 126, 93 and 156, respectively. The overall analytical method recoveries ranged from 86 to 116% while the limits of quantitation for wastewater and plant samples ranged from 0.09 to 0.59 µg L-1 and from 0.11 to 0.59 µg kg-1, respectively. The precision of the proposed analytical method which was measured in terms of RSD values did not exceed 5%. Naproxen was the most abundant compound in both wastewater and the Eichhornia crassipes plant samples with concentrations of up to 3.30 µg L-1 and 10.97 µg kg-1, respectively. The detection of NSAIDs in Eichhornia crassipes means this plant has the ability to bioaccumulate pharmaceutical load in surface water.

Physicochemical characterization of the pelotherapeutic and balneotherapeutic clayey soils and natural spring water at Isinuka traditional healing spa in the Eastern Cape Province of South Africa.

Isinuka Springs at Port St Johns in the Eastern Cape Province of South Africa is a traditional spa sacred to the AmaMpondo tribe of the Xhosa speaking people. The bathing pond is considered to have healing powers both spiritually and therapeutically. Hundreds of people flock into the spiritual pond every weekend for both recreational and its spiritual healing power. In this study, we present the metal concentrations of the bathing pond (sediments and water samples), the hole drinking water as well as sediments from a cave situated at the bottom of the hill harbouring the bathing pond. Our results show that the geophagic clays from the cave and bathing pond has elevated concentrations of earth metals (up to 134,506 mg kg-1 for calcium), trace metals (up to 36,272 mg kg-1 for iron) and toxic metals (up to 25 mg kg-1 for lead). The levels of both essential and toxic metals in the drinking water were above the recommended daily limits except for zinc and copper. Aluminium, a metal with antibacterial activity was as high as 71,792 mg kg-1 in pond sediments. Even though the results show elevated concentrations especially for toxic metals, the study observes that the spa remains limited in potential for metal toxipathy because the frequency of contact with the pond is minimal estimated at once a week by traditional healers and once a month for locals while visitors from other parts of the province rarely come back.

Determination of selected antiretroviral drugs in wastewater, surface water and aquatic plants using hollow fibre liquid phase microextraction and liquid chromatography - tandem mass spectrometry.

This work describes a simple and sensitive method for the simultaneous isolation, enrichment, identification and quantitation of selected antiretroviral drugs; emtricitabine, tenofovir disoproxil and efavirenz in aqueous samples and plants. The analytical method was based on microwave extraction and hollow fibre liquid phase microextraction technique coupled with ultra-high pressure liquid chromatography-high resolution mass spectrometry. A multivariate approach via a half-fractional factorial design was used focusing on six factors; donor phase pH, acceptor phase HCl concentration, extraction time, stirring rate, supported liquid membrane carrier composition and salt content. The optimal enrichment factors for emtricitabine, tenofovir disoproxil and efavirenz from aqueous phase were 78, 111 and 24, respectively. The analytical method yielded recoveries in the range of 86 to 111%, and quantitation limits for emtricitabine, tenofovir disoproxil and efavirenz in wastewater were 0.033, 0.10 and 0.53 µg L-1, respectively. The drugs were detected in most samples with concentrations up to 37.6 µg L-1 recorded for efavirenz in wastewater effluent. Roots of the water hyacinth plant had higher concentrations of the investigated drugs ranging from 7.4 to 29.6 µg kg-1. Overall, hollow fibre liquid phase microextraction proved to be an ideal tool for isolating and pre-concentrating the selected antiretroviral drugs from environmental samples.

Analysis, occurrence and removal of pharmaceuticals in African water resources: A current status.

Pharmaceuticals are organic compounds used in medicines for alleviation of pain. Since 2017, there has been a steady increase on the availability of information on contamination of water resources caused by pharmaceuticals in some African countries. Thus far, most environmental monitoring studies of pharmaceuticals are conducted in South Africa while there is still no available data in majority of the African countries. Therefore, the knowledge on the presence of pharmaceuticals in African water resources is still lacking. In an attempt to provide more information in this aspect, this review article seeks to critically evaluate the progress made thus far by the African scientists in the environmental monitoring and assessment of pharmaceuticals. The most studied groups of pharmaceuticals in Africa are non-steroidal anti-inflammatory drugs, antibiotics, antiretroviral drugs and steroid hormones. Various remediation studies for selected pharmaceuticals in Africa are documented in literature. In the present review, the challenges facing the African researchers or countries on providing more scientific data on the occurrence of pharmaceuticals in water are discussed. Furthermore, the gaps and recommendations for future work are given.

Mercury accumulation and biotransportation in wetland biota affected by gold mining.

Phytoremediation is a cost-effective, eco-friendly technology for the removal of metals from polluted areas. In this study, six different plant species (Datura stramonium, Phragmites australis, Persicaria lapathifolia, Melilotus alba, Panicum coloratum, and Cyperus eragrostis) growing in a gold mine contaminated wetland were investigated as potential phytoremediators of mercury. The accumulation of total mercury and methylmercury in plant tissues was determined during the wet and dry seasons to establish the plants' variability in accumulation. The highest accumulation of total mercury was in the tissues of Phragmites australis with recorded concentrations of 806, 495, and 833 µg kg-1 in the roots, stem, and leaves, respectively, during the dry season. The lowest accumulation levels were recorded for Melilotus alba during both seasons. The highest amount of the methylmercury was found in Phragmites australis during the dry season with a value of 618 µg kg-1. The accumulation and biotransportation were not significantly different between the seasons for some plants. The results of this study indicated that plants growing in wetlands can be used for phytoremediation of mercury and suggest the choice of species for constructed wetlands.

Synthesis of a molecularly imprinted polymer and its application in selective extraction of fenoprofen from wastewater.

The presence of various classes of pharmaceutical drugs in different environmental compartments has been reported worldwide. In South Africa, the detection of pharmaceuticals especially the non-steroidal anti-inflammatory drugs is recent, and more studies are being done in order to fully understand their fate in the aquatic environment. With considerations for the need of better sample preparation techniques, this study synthesized a molecularly imprinted polymer for the selective extraction of a non-steroidal anti-inflammatory drug, fenoprofen in aqueous environmental samples. Batch adsorption studies showed that adsorption of fenoprofen onto the cavities of the polymer followed a Langmuir isotherm as well as a pseudo second order model implying formation of a monolayer on the surface through chemisorption. The polymer had a maximum adsorption capacity of 38.8 mg g-1 and a Langmuir surface area of 1607 m2 g-1. The imprinted polymer was then used as the selective sorbent for solid phase extraction in the analysis of fenoprofen from wastewater followed by chromatographic determination. The analytical method gave a detection limit of 0.64 ng mL-1 and recovery of 99.6%. The concentration of fenoprofen detected in influent and effluent samples from two wastewater treatment plants ranged from 24 to 58 ng mL-1. The ability of the treatment plants to remove fenoprofen during wastewater processing based on the difference in concentrations in influent and effluent samples was found to be 41%. This work has shown that there is a possibility of release of fenoprofen from wastewater treatment plants into surface water sources.

Development of a single format membrane assisted solvent extraction-molecularly imprinted polymer technique for extraction of polycyclic aromatic hydrocarbons in wastewater followed by gas chromatography mass spectrometry determination.

A technique that combines membrane assisted solvent extraction and molecularly imprinted polymer into a single step format has been successfully developed and evaluated for the extraction of the 16 US-EPA priority polycyclic aromatic hydrocarbons in wastewater samples followed by determination using gas chromatography coupled with time of flight mass spectrometry. The technique involves placing the polymer particles into a hydrophobic polypropylene membrane bag which is in contact with an aqueous donor phase. The technique was optimized for various parameters that include presence of an organic modifier in the donor phase, stirring rate and extraction time. The optimum conditions were 25% of dimethyl sulfoxide as an organic modifier and stirring at 1000 rpm for 120 min. The limits of detection using the technique were in the 0.01-0.45 ng mL-1 range. Linearity values determined in the 10-1 000 ng mL-1 calibration range were all above 0.9972. Extraction efficiencies of the sixt analytes calculated as averages for three spiking concentrations ranged from 62.8 to 96.8% (RSD = 3.1-12.3%). The optimized method was tested for the extraction of polycyclic aromatic hydrocarbons in wastewater samples in the presence of surrogate standards. The developed method showed great reproducibility with inter day repeatability values ranging from 0.6 to 24.9%. The analytes were quantified in the nanogram level showing that the developed technique is a viable alternative in the analysis of trace organic compounds in complex aqueous samples.