Facile solvent-free modified biochar for removal of mixed steroid hormones and heavy metals: isotherm and kinetic studies.

Water contamination has become a global challenge to human survival. Non-biodegradable heavy metal cations and steroid hormones could accumulate in the human body and could result in serious health problems. In this study, we prepared biochar from waste shells of African star apples and modified biochar using a solvent-free ball milling facile method. The X-ray photoelectron spectrometer (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis revealed biochar functional groups in C=C, C-O, and C=O. Brunauer Emmett Teller (BET) was used to determine the surface area, the surface area of ball-milled biochar obtained at 550 °C (BASA550) increased from 174 m2/g to 304 m2/g after modification. The Langmuir and Freundlich adsorption isotherms best described the experimental adsorption data with RL < 1 and 1/n < 1 and a high degree of agreement of R2 data; Langmuir (R2 = 0.9291-0.9992) and Freundlich (R2 = 0.9077-0.9974). The adsorption kinetic studies using pseudo-first-order and pseudo-second-order models revealed that the pseudo-second-order model accurately described the adsorption process). The application of the BASA550 for treating wastewater samples showed a good percentage of removal. The removal percentage for cadmium, nickel, and lead was recorded as 92.96%, 90.89%, and 90.29%, respectively. The percentage removal in the influent and effluent were found to be 85.06%, 83.87%, 84.73%, and 89.37%, 86.48%, and 87.40%, respectively. The maximum percentage removal of steroid hormones from ultrapure water ranged from 84.20 to 89.63%, while from the spiked effluent and influent the percentage removal of 78.91-87.81% and 73.58-84.51% were obtained. The reusability of the ball-milled biochar was investigated and the result showed that the adsorbent (BASA550) had a good reusability potential for the first four cycles.

Simultaneous Determination of Multiple Contaminants in Chicken Liver Using Dispersive Liquid-Liquid Microextraction (DLLME) Detected by LC-HRMS/MS.

Simultaneous determination of a mixture of food contaminants, including pesticides, sulphonamides, fluoroquinolones, anthelmintics, and aflatoxin B1, in solid biological samples (chicken liver) by dispersive liquid-liquid microextraction/liquid chromatography-high resolution mass spectrometry (DLLME/LC-HRMS) is presented. Previous work focused on the application of DLLME to single-class contaminants. In this work, the DLLME extraction method has been extended to complex multiresidues in the biological matrix. The first part of this study was the selection of an appropriate solvent that enabled the dissolution of analytes from the chicken livers. The matrix-matched calibration curves showed good linearity in the range 0.5-50.0 µg kg-1 for aflatoxin B1 and 50-500 µg kg-1 for pesticides, fluoroquinolones, sulphonamides, and anthelmintics, with a coefficient of determination (R2) values of 0.9916-0.9967. The mean recoveries were in the range of 80.4-96.3%, and the relative standard deviation (RSD) values were in the range of 1.53-8.98%. The limit of detection (LOD) and the limit of quantification (LOQ) values were 0.03 µg kg-1 and 0.09 µg kg-1, respectively, for aflatoxin B1, and for pesticides, fluoroquinolones, sulphonamides, and anthelmintics, they were in the range of 0.011-1.197 µg kg-1 and 0.150-2.579 µg kg-1, respectively. The developed method was compared with the standard solid phase extraction (SPE) method, and there was no significant difference between the two methods.

Fast screening method to determine metabolites of nitrofurans in chicken meat using partitioned dispersive liquid-liquid microextraction combined with HPLC/DAD.

Methods have been developed for the hydrolysis and derivatisation of protein-bound metabolites of nitrofurans and for the extraction of 2-nitrobenzaldehyde derivatives of the metabolites from chicken meat. In this work, the time needed for hydrolysis and derivatisation was reduced from the conventional 16 h to 90 min. Based on partitioned dispersed liquid-liquid microextraction, a method for extracting 2-nitrobenzaldehyde derivatives of metabolites from crude chicken meat has been developed. Under the optimised experimental conditions, enrichment factors (EFs) ranging from 92.8 to 208.9 were obtained. The method was linear over the range of 10-600 µg kg-1 with determination coefficients (r2) between 0.9979 and 0.9996. Intraday and interday repeatability expressed as a percentage RSD, ranged from 2.2% to 11.2%, and 2.7% to 12.4%, respectively. LOD of 1.07-2.25 µg kg-1 and LOQ of 3.09-6.2 µg kg-1 were obtained. The proposed method was applied in the analysis of metabolites of nitrofurans in chicken meat obtained from farmers using them for their domestic consumption and proved free of the analytes. A recovery of 85.2-109.4% with a %RSD ranging between 3.4% and 13.7% was obtained at three spiking levels. The proposed method was successfully further applied for the analysis of target analytes in chicken meat samples purchased from different supermarkets around Roodeport, Gauteng (South Africa). There was no target analyte detected in the analysed samples. Therefore, the developed methods can be used for monitoring the corresponding metabolites of nitrofurans in chicken meat.

Evaluating the Performance of Ball-Milled Silk Fibroin Films for Simultaneous Adsorption of Eight Pharmaceuticals from Water.

Pollutants mainly exist as multicomponent mixtures in the environment. Therefore, it is necessary to synthesize low-cost adsorbents that can simultaneously adsorb multiple compounds. This work presents the prospect of the adsorption of multiclass pharmaceuticals from the aqueous environment using an adsorbent derived from silk fibroin of the wild silkworm Argema mimosae. The adsorbent was prepared by dissolving degummed silk fibroin and the resultant solution was cast to obtain films that were ball-milled to powder. FTIR results revealed bands corresponding to N-H and C=O stretching vibrations. Particle size distribution data generally showed two size groups in the range of 50-90 nm and 250-625 nm. The study focused on the adsorptive removal of multiple compounds consisting of eight pharmaceuticals representing various classes including a ß-blocker (pindolol), anesthetic (lidocaine), stimulant (caffeine), antiviral (nevirapine), steroid (estriol), anti-epileptic (carbamazepine), and a non-steroidal anti-inflammatory drug (naproxen). The adsorption process was best fitted to the pseudo-second-order isotherm and an overall match to the Freundlich model. Thermodynamic parameters suggested that the process was mainly exothermic and more spontaneous at lower temperatures. The performance of the adsorbent was further evaluated using environmental waters and the adsorbent demonstrated good potential for simultaneous adsorption of multicomponent pharmaceuticals.

Fabrication of electrospun Mondia whitei/PVA nanofibres: application in the removal of acidic drugs.

Novel electrospun Mondia whitei/PVA blend nanofibres were fabricated for potential water treatment applications by blending a natural polymer extracted from Mondia whitei (MW) roots with poly (vinyl alcohol) (PVA). The fabricated nanofibres were shown to have a smooth and uniform morphology with an average diameter of 99 ± 0.025 nm. The FTIR, XPS, XRD, and TGA characterisation results indicated changes in functional groups, crystallinity, and thermal stability of the Mondia whitei/PVA blend nanofibres, as compared to the original material. This finding confirmed that the polymers interacted through hydrogen bonding of MW and hydroxyl groups of PVA. The performance of the fabricated nanofibres was investigated for the removal of acidic drugs from spiked water samples. Factors (concentration of acidic drugs, dosage of the nanofibers and contact time) which affect the removal efficiency of the nanofibres were optimised using ultrapure water. Using the nanofibres, 100% removal efficiency for acidic drugs (aspirin, ketoprofen, fenoprofen, diclofenac, and ibuprofen) was achieved. The removal efficiency of the influent wastewater was 76, 89, 97, 93 and 94% for aspirin, ketoprofen, fenoprofen, diclofenac and ibuprofen, respectively, while the removal efficiency of the effluent was 86, 96, 97, 97 and 95% for aspirin, ketoprofen, fenoprofen, diclofenac and ibuprofen, respectively.

Fabrication and Characterization of Sericin-PVA Composite Films from Gonometa postica, Gonometa rufobrunnea, and Argema mimosae: Potentially Applicable in Biomaterials.

This study deals with the fabrication and characterization of sericin-poly(vinyl alcohol) (PVA) composite films from three southern African silkworm cocoons. The sericin-PVA films were achieved by chemically cross-linking poly(vinyl alcohol) (PVA) with pure silk sericin protein using glutaraldehyde (GA) as a cross-linking agent. Fourier transform infrared (FTIR) results confirmed the overall cross-linking of pure silk sericin into PVA-GA networks to form cross-linked sericin-PVA films. This incident was shown by the incorporation of distinct major amide I (ν = 1640-1650 cm-1), amide II (ν = 1538-1540 cm-1), and amide III (ν = 1238-1244 cm-1) peaks. X-ray diffraction (XRD) showed sericin-PVA films to have two features, one representing amorphous and crystalline regions of silk sericin and the other representing sharp high-intensity PVA peaks at around 2θ = 20.2°, demonstrating a high crystallinity in the films as a result of the hydroxyl groups in its side chain. The swelling capacity of the three sericin-PVA films was influenced by the glutaraldehyde content used during the cross-linking process and pH of the aqueous medium into which the films were immersed after a period of time. The water contact angles of the sericin-PVA films were low, at 56.6 ± 0.56 and 60.2 ± 0.86, indicating further their hydrophilic nature. The scanning electron microscopy (SEM) images of the sericin-PVA films showed a rough texture with a granular network pattern on their surface. From the preliminary results, it was observed that the cytotoxicity of three sericin strains (Gonometa rufobrunnea, Argema mimosae, and Gonometa postica) had a cell viability percentage of 103, 90, and 80% respectively, demonstrating their biocompatibility in providing a favorable natural microenvironment for cell culture. The characterization results of the three silk sericin-PVA films demonstrated their potential for application in biomedical and biomaterial fields.

Optimization of an Ultra-Sonication Extraction Method for Major Compounds Found in Mondia whitei Using Design of Experiment.

Optimum extraction conditions are vital in quality control methods to enable accurate quantification of the compounds of interest. An ultra-sonication method was developed for the extraction of seven major compounds found in Mondia whitei. Extraction temperature, time, power, frequency, percentage of ethanol in water and solvent to sample ratio were screened to access their significance on the percentage recovery of the compounds of interest. These parameters were screened using Descriptive screening design. Extraction temperature, solvent to sample ratio and the interaction between temperature and percentage ethanol in water were found to have a significant effect on the response. These parameters were then optimized using central composite design. The optimum conditions were found to be 66.1% ethanol in water, 70 °C temperature and 3 mL: 5 mg solvent to sample ratio. This method was successfully applied in the development of a quality control method for the seven compounds in Mondia whitei samples.

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.

Profiling of Silk Sericin from Cocoons of Three Southern African Wild Silk Moths with a Focus on Their Antimicrobial and Antioxidant Properties.

Silk sericin was extracted from the cocoons of three Southern African wild silk moth species, namely Gonometapostica, G. rufobrunnae (Lepidoptera: Lasiocampidae), and Argema mimosae (Lepidoptera: Saturniidae); these three sericin extracts were analysed to determine the relationship that exists between their chemical structures and their functional properties. The relationship was investigated by utilising several methods that include the determination of the amino acid composition, and characterisation of the secondary structures with Fourier transformation infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The antibacterial properties of these three sericin extracts were evaluated by an agar well diffusion assay with three Gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus, and Staphylococcus epidermidis) as test microorganisms; and, lastly, the antioxidant properties of the three sericin extracts were determined using several scavenging methods that include the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS˙+), and the ferric reducing antioxidant power (FRAP) assay. The amino acid composition in the silk sericin extracts from G. postica, G. rufobrunnea, and Argema mimosa in terms of the polar/non-polar ratio (P/NP) was found to be 65:35, 56:44, and 59:41, respectively. The FTIR spectra of these three silk sericin extracts showed distinct major bands such as amide A (3265 cm-1), amide B (3062 cm-1), amide I (1644 cm-1), amide II (1538 cm-1), and amide III (1244 cm-1). The XRD patterns of the silk sericin extracts revealed both amorphous and α-helical structures, with small crystalline regions. All three silk sericin extracts presented potent antibacterial efficacy against the three Gram-positive bacteria and were found to have excellent antioxidant activities against the tested free radicals.

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.

Development of an HPLC-DAD Method for the Quantification of Ten Compounds from Moringa oleifera Lam. and Its Application in Quality Control of Commercial Products.

An HPLC-DAD separation method for the simultaneous quantification of ten compounds from Moringa oleifera plant was developed. The method was validated with pure solvent and different matrices of M. oleifera products. This method was found to be linear in the concentration range of 1 to 10 mg L-1 for all the compounds in the solvent and from 3 to 10 mg kg-1 in the different matrices. The correlation coefficients ranged between 0.9900 and 0.9999. Intra-day and inter-day variability showed that the developed method is both repeatable and precise with percent relative standard deviation values less than 10% and 20%, respectively. Limits of detection ranged between 0.06 and 0.8 mg L-1 for the solvent and 0.1-1.5 mg kg-1 for the matrices, while the limit of quantification ranged between 0.2 and 2.8 mg L-1 and 0.4-4.8 mg kg-1, respectively. The validated method was applied successfully to thirty-two different M. oleifera products, whereby all ten compounds were detected in one of the samples. Principal component analysis was used to assess the correlation and variance between the products. Variations were observed in products from different regions and from different manufacturers.

Application of mesoporous nanofibers as sorbent for removal of veterinary drugs from water systems.

A novel environmentally benign method was developed for the simultaneous removal of sulphonamides and multiclass class of veterinary drugs using mesoporous nanofibers. Processing parameters which affect the removal efficiency, such as pH, initial analyte concentration, adsorbent dosage and contact time were studied. An optimised method was applied to a real wastewater samples collected from Daspoort Wastewater Treatment Plant (WWTP), South Africa. Under optimum conditions, the removal efficiency of veterinary drugs from effluent and influent ranged from 35.24-94.57 ± 0.24 and 31.71-76.91 ± 0.65 mg g-1, respectively. The surface area, cumulative volume of pores and average pore diameter of the nanofibers were determined as 2402.62 ± 13.62 m2 g-1, 2.04 cm3 g-1 and 3.39 nm, respectively. The maximum adsorption capacity was ranged from 166 to 1000 mg g-1. The adsorption kinetics obeyed the pseudo-second-order rate equation suggesting that particle diffusion was the rate-limiting mechanism for adsorption of veterinary drugs on electrospun nanofibers.

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.

Characterisation of water-soluble protein powder and optimisation of process parameters for the removal of sulphonamides from wastewater.

A valuable method for the efficient removal of sulphonamides from wastewater using protein powder extracted from the seeds of Moringa stenopetala is presented in this study. The surface morphology, crystallinity and functional groups of protein powder were characterised by SEM, XRD, FTIR and Raman spectrometry. Parameters that affect the removal of sulphonamides, such as concentration, the adsorbent dosage and pH, were optimised. The method was applied to a real wastewater sample collected from the Daspoort Wastewater Treatment Plant located in Pretoria, South Africa. The percentage removal under optimum conditions was observed to be 86.4 to 95.1% for the aqueous solution of a mixture of standards and from 83.0 to 90.5% and 75.2 to 87.7 % for the effluent and influent wastewater samples respectively. Therefore, proteins extracted from Moringa stenopetala seeds demonstrated to be effective and environmentally friendly material for possible application in water treatment in general and wastewater treatment in particular.

Chemical, structural and thermal properties of Gonometa postica silk fibroin, a potential biomaterial.

In the present study, chemical, structural and thermal properties of fibroin from Gonometa postica, a wild silkmoth species were investigated. Silk from Gonometa rufobrunnea and Bombyx mori species were included in this study for comparison. The results indicated that G. postica and G. rufobrunnea silk exhibited similar properties whereas distinct differences were observed with B. mori silk. Amino acid analysis showed that glycine, alanine and serine accounted for more than 70% of the total amino acid content in all species. The amount of polar amino acids in Gonometa fibroin was significantly higher than for B. mori fibroin suggesting increased chemical reactivity of the former. The abundance of basic amino acids in Gonometa fibroin makes it a promising biomaterial in cell and tissue culture. Structural analysis revealed a unique ß-sheet structure of Gonometa fibroin which is comprised of both poly-alanine and poly-glycine-alanine sequences. The maximum decomposition temperatures for Gonometa and B. mori fibroin were 350°C and 320°C respectively. The influence of amino acid composition on structural and thermal properties of the silks is also discussed.

The use of liquid membranes in the multi-residue extraction of stilbenes in a variety of biological matrices and their detection with LC-ES-MS.

Supported liquid membrane (SLM) has been used as a sample preparation method in the simultaneous extraction of a mixture of three stilbene compounds in cow's milk, urine, bovine kidney and liver tissues matrices. The stilbene compounds analysed included, dienestrol, diethylstilbestrol and hexestrol. The liquid membrane used for trapping these compounds consisted of 5% tri-n-octylphosphine oxide (TOPO) dissolved in di-n-hexylether/n-undecane (1:1). The extraction efficiencies obtained after enrichment of 1 ng/L stilbenes in variety of biological matrices of milk, urine, liver, kidney and water, ranged from 60 - 70%, 71 - 86%, 69 - 80%, 63 - 7A% and 72 - 93% respectively. The detection limits obtained from urine extraction were 2.1 ng/L, 1.3 ng/L and 3.0 ng/L; from liver and kidney tissues were 2.9 ng/L, 1.6 ng/L and 3.8 ng/L and from milk was 3.2 ng/L, 2.5 ng/L and 4.3 ng/L for hexestrol, dienestrol and diethylstilbestrol respectively.

Comparative study of sample preparation methods; supported liquid membrane and solid phase extraction in the determination of benzimidazole anthelmintics in biological matrices by liquid chromatography-electrospray-mass spectrometry.

Supported liquid membrane (SLM) and solid phase extraction (SPE) have been applied as clean-up and/or enrichment techniques for a mixture of five benzimidazole anthelmintics compounds, namely albendazole, fenbendazole, mebendazole, oxibendazole, and thiabendazole. Two biological matrices, mainly urine and milk, and ultra high purity (UHP) water were spiked with a mixture of these five compounds. Waters Oasis MCX and International Sorbent Technology (IST) HCX SPE sorbents were used. The liquid membrane used for clean-up and/or enrichment of these compounds was 5% tri-n-octylphosphine oxide (TOPO) dissolved in n-undecane/di-n-hexyl ether (1:1). The SLM extraction efficiencies and SPE percentage recoveries ranged between 60 and 100%. The detection limits (DLs) for different benzimidazole compounds by SPE/LC-ES-MS for thiabendazole, oxibendazole, and albendazole was 0.1 ng/L, for fenbendazole and mebendazole was 1 and 10 ng/L, respectively. Similarly, the detection limits of SLM/LC-ES-MS for thiabendazole, oxibendazole, and albendazole was 0.1 ng/L and for fenbendazole and mebendazole was 1 ng/L. The results of optimization of various parameters of the SLM method are reported.

Multiresidue determination of sulfonamides in a variety of biological matrices by supported liquid membrane with high pressure liquid chromatography-electrospray mass spectrometry detection.

A high performance liquid chromatography (HPLC) coupled to a mass spectrometer (MS) was used for a simultaneous determination of 16 sulfonamide compounds spiked in water, urine, milk, and bovine liver and kidney tissues. Supported liquid membrane (SLM) made up of 5% tri-n-octylphosphine oxide (TOPO) dissolved in hexyl amine was used as a sample clean-up and/or enrichment technique. The sulfonamides mixture was made up of 5-sulfaminouracil, sulfaguanidine, sulfamethoxazole, sulfamerazine, sulfamethizole, sulfamethazine (sulfadimidine), sulfacetamide, sulfapyridine, sulfabenzamide, sulfamethoxypyridazine, sulfamonomethoxine, sulfadimethoxine sulfasalazine, sulfaquinoxaline, sulfadiazine, and sulfathiazole. Some of these compounds, such as, sulfaquinoxaline, sulfadiazine, sulfabenzamide, sulfathiazole and sulfapyridine failed to be trapped efficiently by the same liquid membrane (5% TOPO in hexylamine). The detection limits (DL) obtained were 1.8ppb for sulfaguanidine and sulfamerazine and between 3.3 and 10ppb in bovine liver and kidney tissues for the other sulfonamides that were successfully enriched with SLM; 2.1ppb for sulfaguanidine and sulfamerazine and between 7.5 and 15ppb in cow's urine, whereas the DL values in milk were 12.4ppb for sulfaguanidine and sulfamerazine and between 16.8 and 24.3 for the other compounds that were successfully enriched by the membrane. Several factors affecting the extraction efficiency during SLM enrichment, such as donor pH, acceptor pH, enrichment time and the membrane solvent were studied.