Determination of per- and polyfluoroalkyl compounds in paper recycling grades using ultra-high-performance liquid chromatography-high-resolution mass spectrometry.

Globally, per- and polyfluoroalkyl substances (PFAS)-related research on paper products has focused on food packaging with less consideration on the presence of PFAS at different stages of the paper recycling chain. This study analysed the prevalence of PFAS in paper grades used for the manufacture of recycled paperboard. The presence of PFAS was attributed to the use of PFAS-containing additives, consumer usage, exposure to packed goods as well as contamination during mingling, sorting, collection, and recovery of paper recycling material. Q Orbitrap mass spectrometry was used to analyse the paper samples after accelerated solvent extraction and solid phase extraction. The distribution and possible propagation of 22 PFAS were determined in pre-consumer, retail and post-consumer paper products. Post-consumer samples had the highest combined average concentration (ΣPFAS) at 213 ng/g, while the ΣPFAS in retail (159 ng/g) and pre-consumer samples (121 ng/g) was detected at lower concentrations. This study showed that waste collection and recycling protocols may influence PFAS propagation and that measures must be developed to minimise and possibly eliminate exposure opportunities.

Uptake, translocation, and metabolization of amitriptyline, lidocaine, orphenadrine, and tramadol by cress and pea.

The uptake, translocation, and metabolization of four widely used drugs, amitriptyline, orphenadrine, lidocaine, and tramadol, were investigated in a laboratory study. Cress (Lepidium sativum L.) and pea (Pisum sativum L.) were employed as model plants. These plants were grown in tap water containing the selected pharmaceuticals at concentrations ranging from 0.010 to 10 mg L-1, whereby the latter concentration was employed for the (tentative) identification of drug-related metabolites formed within the plant. Thereby, mainly phase I metabolites were detected. Time-resolved uptake studies, with sampling after 1, 2, 4, 8, and 16 days, revealed that all four pharmaceuticals were taken up by the roots and further relocated to plant stem and leaves. Also in these studies, the corresponding phase I metabolites could be detected, and their translocation from root to stem (pea only) and finally leaves could be investigated.

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.

Trends in removal of pharmaceuticals in contaminated water using waste coffee and tea-based materials with their derivatives.

The introduction of large amounts of pharmaceuticals into the environmental waters is well-documented in literature with their occurrence reported in all different water matrices accessible to humans and animals. At the same time, the increasing consumption of coffee and tea-based beverages results in the generation of solid waste, which is mostly disposed-off in the environment. To minimize environmental pollution, coffee and tea-based materials have been proposed as suitable options to remove pharmaceuticals in environmental waters. Therefore, this article provides a critical review on the preparation and applications of coffee and tea-based materials in removing pharmaceuticals from contaminated water. In this context, most studies in literature focused on the applications of these materials as adsorbents, while only limited work on their role in degradation of pharmaceuticals is discussed. The successful application in adsorption studies is attributed to high surface areas of adsorbents and the ability to easily modify the adsorbent surfaces by incorporating functional groups that provide additional oxygen atoms, which promote easy interactions with pharmaceuticals. Hence, the adsorption mechanisms are mostly described by hydrogen bonding, electrostatic and π-π interactions with sample pH playing a dominant role in the adsorption process. Overall, the present article focused on the developments, trends and future research direction on the preparations and applications of coffee and tea-based materials for efficient removal of pharmaceuticals in water. PRACTITIONER POINTS: Review of tea and coffee wastes application for removal of pharmaceuticals in water Key applications in adsorption and degradation of pharmaceuticals in water Removal mostly explained by hydrogen bonding, electrostatic, and π-π interactions Trends, gaps, and future research to be explored are reviewed and highlighted.

Trends in Innovations and Recent Advances in Membrane Protected Extraction Techniques for Organics in Complex Samples.

Membrane protected extraction is an ongoing innovation for isolation and pre-concentration of analytes from complex samples. The extraction process, clean-up and pre-concentration of analytes occur in a single step. The inclusion of solid sorbents such as molecularly imprinted polymers (MIPs) after membrane extraction ensures that selective double extraction occurs in a single step. The first step involves selective extraction using the membrane and diffused analytes are trapped on the solid sorbent enclosed in the membrane. No further clean-up is required even for very dirty samples like plant extracts and wastewaters samples. Sample clean-up occurs during extraction in the first process and not as additional step since matrix components are prevented from trapping on the sorbent. This can be referred to as prevention is better than cure approach. In this work, the analytical methods that employed membrane protected extraction for various organics such as pesticides, polycyclic aromatic hydrocarbons, and pharmaceuticals are reviewed. The designs of these analytical methods, their applications, advantages and drawbacks are discussed in this review. Literature suggests that the introduction of solid sorbents in membrane creates the much-needed synergy in selectivity. Previous reviews focused on membrane combinations with MIPs while discussing micro-solid-phase extraction. The scope of this review was broadened to include other sample preparation aspects such as membrane protected stir bar solvent extraction and membrane protected solid-phase microextraction. In addition, novel sample preparation methods for solid samples which include Soxhlet membrane protected molecular imprinted solid phase extraction and membrane protected ultra sound assisted extracted are discussed.

Utility of an alternative method (to USEPA Method 1613) for analysis of priority persistent organic pollutants in soil from mixed industrial-suburban areas of Durban, South Africa.

This study evaluates the adequacy of a USEPA Method 1613 alternative analytical method for analysis of persistent organic pollutants (POPs) in soil from the immediate vicinity of industrialized areas in the eThekwini municipal area in South Africa. The objective of this study is in line with the Stockholm Convention Article 11 on research, development, and monitoring. Furthermore, it became imperative to find an alternative analytical procedure to USEPA Method 1613 that could cater to studies conducted in Africa where recent reviews have indicated that most African countries lack the technical and instrumental capacity for performing analysis of dioxin-like compounds according to USEPA Method 1613, which entails the use of high-resolution chromatography and high-resolution mass spectrometry instrumentation. The study aimed to ascertain the utility of an alternative two-dimensional gas chromatography-time of flight mass spectrometry method for analysis of trace-level priority POPs in soil, along with a fast single quadrupole gas chromatography-mass spectrometry method. The analytical methods were applied to the analysis of POPs on soil samples from industrial areas with oil refineries and a pulp and paper manufacturing company, while other samples were collected near the electricity substations and a landfill site. Analytical results showed BDE 209 as the dominant contaminating polybrominated diphenyl ether (concentration ranges from 0.006 to 5.71 ng g-1 ). Polybrominated biphenyls (PBBs) 9, 10, and 49 were the dominant PBBs detected in 78% of the sites tested, although their concentrations were below the limit of quantification (LOQ). Polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls detected could not be quantified above their respective LOQs, indicating that the Durban area has low priority pollutant contamination levels compared to other regions around the world. The methods developed are a starting point that will inform considerations for routine evaluation and management of soil contamination, which plays a vital role in environmental management. Integr Environ Assess Manag 2023;19:749-762. © 2022 SETAC.

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.

Uptake, Occurrence, and Effects of Nonsteroidal Anti-Inflammatory Drugs and Analgesics in Plants and Edible Crops.

The plant uptake of pharmaceuticals that include nonsteroidal anti-inflammatory drugs (NSAIDs) and analgesics from contaminated environment has benefits and drawbacks. These pharmaceuticals enter plants mostly through irrigation with contaminated water and application of sewage sludge as soil fertilizer. Aquatic plants withdraw these pharmaceuticals from water through their roots. Numerous studies have observed the translocation of these pharmaceuticals from the roots into the aerial tissues. Furthermore, the occurrence of the metabolites of NSAIDs in plants has been observed. This article provides an in-depth critical review of the plant uptake of NSAIDs and analgesics, their translocation, and toxic effects on plant species. In addition, the occurrence of metabolites of NSAIDs in plants and the application of constructed wetlands using plants for remediation are reviewed. Factors that affect the plant uptake and translocation of these pharmaceuticals are examined. Gaps and future research are provided to guide forthcoming investigations on important aspects that worth explorations.

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.

Synthesis of molecularly imprinted polymers for extraction of fluoroquinolones in environmental, food and biological samples.

In recent years, fluoroquinolones have been found present in important water resources and food sources which compromises the food quality and availability, thereby, causing risks to the consumer. Despite the recent advancement in the development of analytical instrumentation for routine monitoring of fluoroquinolones in water, food, and biological samples, sample pre-treatment is still a major bottleneck of the analytical methods. Therefore, fast, selective, sensitive, and cost-effective sample preparation methods prior to instrumental analysis for fluoroquinolones residues in environmental, food and biological samples are increasingly important. Solid-phase extraction using different adsorbents is one of the most widely used pre-concentration/clean-up techniques for analysis of fluoroquinolones. Molecularly imprinted polymers (MIPs) serve as excellent effective adsorbent materials for selective extraction, separation, clean-up and preconcentration of various pollutants in different complex matrices. Therefore, synthesis of MIPs remains crucial for their applications in sample preparation as this offers much-needed selectivity in the extraction of compounds in complex samples. In this study, the progress made in the synthesis of MIPs for fluoroquinolones and their applications in water, food and biological samples were reviewed. The present review discusses the selection of all the elements of molecular imprinting for fluoroquinolones, polymerization processes and molecular recognition mechanisms. In conclusion, the related challenges and gaps are given to offer ideas for future research focussing on MIPs for fluoroquinolones.

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.

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.

Removal of organic pollutants in water using water hyacinth (Eichhornia crassipes).

Globally, water hyacinth is recognized as an invasive species that threatens the survival of aquatic organisms. Its removal from water is performed manually or physically to avoid the secondary water pollution that results through the usage of chemically synthesised herbicides for its control, thus generating solid waste. Among other things, scientists have proposed the conversion of this waste into adsorbents that can be utilized for the remediation of water resources. This is essentially significant as the quality of water remains a necessity in all spheres of life. In this paper, the remediation strategies that have been proposed for the remediation of water resources through the removal of organic pollutants using water hyacinth are reviewed. Phytoremediation and removal of organics through adsorption using water hyacinth have been extensively investigated. From this review, it can be observed that the majority of the reviewed work focussed more on the removal of organic dyes from water. In this context, the mechanisms involved during the adsorption processes are discussed. In the end, future research that is likely to assist in the environmental management of water resources through their remediation with water hyacinth is suggested.

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.

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.