Evaluation of the probable synergistic toxicity of selected potentiated antiretroviral and antibiotics on some aquatic biomarker organisms.

Environmental effects of active pharmaceutical compounds (APCs) in the environment are not well characterized, hence the need for comprehensive evaluation. This study employed three bioassays using three organisms, namely, Allium cepa, Daphnia magna, and Salmonella typhimurium, in the ecotoxicity study of lone and a mixture of selected APCs, namely, lamivudine (L), an antiretroviral, and ciprofloxacin (C) and sulfamethoxazole (S), antibiotics, at a concentration range between 10 and 100 ppb, in order to evaluate the potential of the lone and ternary mixture to exert synergistic toxicity. Study results from exposure to lone APCs showed that the L, C, and S trio individually had fatal impacts on daphnids, with mortality rates of 100, 75, and 95%, respectively, after 48 h. Sulfamethoxazole showed a mutagenic tendency, with a mutation ratio (background/sample ratio) of 2.0. Lamivudine showed a lethal impact on the root length of A. cepa (p > 0.05, p = 3.60E-3). Further microscopic examination of the A. cepa root tip revealed chromosomal aberrations on exposure to each compound. The LCS-mix ecotoxicology bioassays indicated a synergistic effect on the daphnids, probably due to potentiation. Although the LCS mix had a cytotoxic effect (evidenced by the absence of bacteria colonies) on exposed TA 98 P450 Salmonella typhimurium strain, this effect was not observed in other bacterial strains. Microscopic examination of A. cepa exposed to the LCS-mix revealed an aberration in the mitotic stage of the cell. The impact of combination of the pharmaceuticals in aqueous ecosystems was greater than when exposed to the tested individual pharmaceutical compounds. Study result showed that these compounds have tendencies to pose a higher risk to exposed living entities when in combined/potentiated forms, and this could lead to distortion of the regular functioning of the ecosystem, particularly bacterial and other microbial populations that are listed among primary producers of the aquatic food web.

Occurrence and risk assessment of fullerene colloidal nanoparticles by ultrasonic-assisted dispersive liquid-liquid extraction and high-performance liquid chromatography in surface waters.

This paper presents a developed analytical technique for risk assessment of colloidal fullerene in surface waters by ultrasonic-assisted dispersive liquid-liquid extraction (UADLLE) and high-performance liquid chromatography ultraviolet-visible detector (HPLC-UV). Fullerene colloidal nanoparticles were synthesised and characterized by high-resolution transmission electron microscopy (HRTEM) and ultraviolet-visible spectroscopy (UV-Vis). Ultrasonication step, disperser solvent, and sodium chloride salt enhance the surface area of fullerene derivative aggregates for better contact and lowers the solubility of fullerene derivative to the aqueous solution, respectively promoting mass transfer of fullerene from aqueous into the organic phase. Several extraction parameters were optimized, and the optimal conditions were established: 5 mL toluene as extraction solvent (2 cycles); 200 mL water sample; 1% sodium chloride salt; 15 min ultrasonication, and 400 µL methanol as disperser solvent. The mean absolute recoveries established in drinking water, wastewater, and river water were 117%, 103%, and 93%, respectively. The proposed analytical technique was linear in the ranges between 0.25 µg L-1 - 250 µg L-1 with an r-squared of 0.9958. The limit of detection (LOD) determined from the signal-to-noise ratio of 3 was 0.11 µg L-1 and the limit of quantification (LOQ) from a signal-to-noise ratio of 10 was 0.38 µg L-1. The precision ranges from 2% to 11% and accuracy percent error ranged from 7%-14% for spiked concentration levels of 0.25 µg L-1, 50 µg L-1, and 250 µg L-1. The measured environmental concentration (MECs) for the fullerene in water samples ranged from not detected to 10.54 µg L-1 and ecological assessment showed the concentration level of the fullerene can pose risk. Overall, according to the author's knowledge, this is the earlier work on the occurrence and risk assessment of fullerene colloidal nanoparticles (C61-PCBM) in potable and wastewater on the African continent.

A Simple Model to Estimate the Number of Metal Engineered Nanoparticles in Samples Using Inductively Coupled Plasma Optical Emission Spectrometry.

Accurate determination of the size and the number of nanoparticles plays an important role in many different environmental studies of nanomaterials, such as fate, toxicity, and occurrence in general. This work presents an accurate model that estimates the number of nanoparticles from the mass and molar concentration of gold nanoparticles (AuNPs) in water. Citrate-capped AuNPs were synthesized and characterized using transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy (UV-vis). A mimic of environmental matrices was achieved by spiking sediments with AuNPs, extracted with leachate, and separated from the bulk matrix using centrifuge and phase transfer separation techniques. The quantification of AuNPs' molar concentration on the extracted residues was achieved by inductively coupled plasma optical emission spectroscopy (ICP-OES). The molar concentrations, an average diameter of 27 nm, and the colloidal suspension volumes of AuNPs enable the calculation of the number of nanoparticles in separated residues. The plot of the number of AuNPs against the mass of AuNPs yielded a simple linear model that was used to estimate the number of nanoparticles in the sample using ICP-OES. According to the authors' knowledge, this is the first adaptation of the gravimetric method to ICP-OES for estimating the number of nanoparticles after separation with phase transfer.

Occurrence, detection and ecotoxicity studies of selected pharmaceuticals in aqueous ecosystems- a systematic appraisal.

Pharmaceutical compounds (PCs) have globally emerged as a significant group of environmental contaminants due to the constant detection of their residues in the environment. The main scope of this review is to fill the void of information on the knowledge on the African occurrence of selected PCs in environmental matrices in comparison with those outside Africa and their respective toxic actions on both aquatic and non-aquatic biota through ecotoxicity bioassays. To achieve this objective, the study focused on commonly used and detected pharmaceutical drugs (residues). Based on the conducted literature survey, Africa has the highest levels of ciprofloxacin, sulfamethoxazole, lamivudine, acetaminophen, and diclofenac while Europe has the lowest of all these PC residues in her physical environments. For ecotoxicity bioassays, the few data available are mostly on individual groups of pharmaceuticals whereas there is sparsely available data on their combined forms.

Quantification and Ecological Risk Assessment of Colloidal Fullerenes Nanoparticles in Sediments by Ultrasonic-Assisted Pressurized Liquid Extraction and High Performance Liquid Chromatography.

Fullerenes engineered nanomaterials are regarded as emerging environmental contaminants. This is as their widespread application in many consumer products, as well as natural release, increases their environmental concentration. In this work, an ultrasonic-assisted pressurized liquid extraction (UAPLE) method followed by high performance liquid chromatography with ultraviolet-visible detector (HPLC-UV-vis) was developed for extraction and determination of fullerene in sediments. The method was validated and found to be suitable for environmental risk assessment. Thereafter, the method was used for the determination of fullerene (C61-PCBM) in sediment samples collected from Umgeni River, South Africa. The current method allows for adequate sensitivity within the linear range of 0.01-4 µg g-1, method limit detection of 0.0094 µg g-1 and recoveries ranged between 67-84%. All the parameters were determined from fortified sediments samples. The measured environmental concentration (MEC) of fullerene in the sediment samples ranged from not detected to 30.55 µg g-1. To the best of our knowledge, this is the first report on the occurrence and ecological risk assessment of carbonaceous fullerene nanoparticles in African sediments and biosolids.

Environmental Risk Characterization of an Antiretroviral (ARV) Lamivudine in Ecosystems.

Antiretroviral drugs for the treatment of human immunodeficiency virus (HIV) and other viral infections are among the emerging contaminants considered for ecological risk assessment. These compounds have been reported to be widely distributed in water bodies and other aquatic environments, while data concerning the risk they may pose to unintended non-target species in a different ecosystem (environment) is scanty. In South Africa and other developing countries, lamivudine is one of the common antiretrovirals applied. Despite this, little is known about its environmental impacts as an emerging contaminant. The present study employed a battery of ecotoxicity bioassays to assess the environmental threat lamivudine poses to aquatic fauna and flora. Daphnia magna (filter feeders), the Ames bacterial mutagenicity test, Lactuca sativa (lettuce) germination test, and the Allium cepa root tip assay were conducted, testing lamivudine at two concentrations (10 and 100 µg/L), with environmental relevance. The Daphnia magna toxicity test revealed a statistically significant response (p << 0.05) with a mortality rate of 85% on exposure to 100 µg/L lamivudine in freshwater, which increased to 100% at 48-h exposure. At lower concentrations of 10 µg/L lamivudine, 90% and 55% survival rates were observed at 24 h and 48 h, respectively. No potential mutagenic effects were observed from the Ames test at both concentrations of lamivudine. Allium cepa bioassays revealed a noticeable adverse impact on the root lengths on exposure to 100 µg/L lamivudine. This impact was further investigated through microscopic examination, revealing some chromosomal aberration in the exposed Allium cepa root tips. The Lactuca sativa bioassay showed a slight adverse impact on both the germination rate of the seeds and their respective hypocotyl lengths compared to the control. Overall, this indicates that lamivudine poses an ecological health risk at different trophic levels, to both flora and fauna, at concentrations previously found in the environment.

Soil pH, nitrogen, phosphatase and urease activities in response to cover crop species, termination stage and termination method.

The best management options for cover cropping are largely unknown, including the growth patterns of cover crop (CC) species, optimum termination stages and termination methods. A greenhouse experiment was conducted to explore the following: (i) Effect of two termination stages (vegetative and flowering) on the chemical composition (N and C:N) of four CCs; (ii) Short-term impacts of living CCs and residues on soil pH, total N, urease and phosphatase activities at the two termination stages, and under two termination methods (slash and spray). Species tested as CCs were, vetch (Vicia dasycarpa L.), field pea (Pisum sativum L.), oats (Avena sativa L.), rye (Secale cereal L.) and a control (no CC). The experiment was set up in a randomized block design with three replications. Soil was sampled at kill and one year after CC kill. Delaying termination from vegetative till flowering stage decreased N in the tissue of P. sativum, A. sativa, V. dasycarpa and S. cereal by 59%, 65%, 44% and 56%, respectively, while their C:N ratios increased. Cover crop presence had no effect on soil pH. Living CCs had no significant effect on soil N concentration. The activities of urease and phosphatase were stimulated by all the living CC species. Unlike urease, all CC residues had a positive impact on phosphatase activity at one year. Only P. sativum and V. dasycarpa residues increased soil N concentration in the short-term. Compared to flowering, termination at vegetative stage improved soil N concentrations and phosphatase activity at both sampling times. Termination method had no effect on soil N, urease and phosphatase activity at one year. The significant interaction (P < 0.05) of sampling time, CC and termination stage effects on soil N concentration and phosphatase activity observed in this study indicates that these management approaches can optimize CC benefits and improve soil chemical and biological properties.

Pharmaceuticals and personal care products in water and wastewater: a review of treatment processes and use of photocatalyst immobilized on functionalized carbon in AOP degradation.

The presence of emerging contaminants such as pharmaceutical and personal care products in many aqueous matrices have been reported. One of such matrix is streams of wastewater, including wastewater treatment plants inflows and outflows and wastewater flow by-passing wastewater treatment plants. Their persistence arises from their resistant to breakdown, hence they may remain in the environment over long time, with a potential to cause adverse effects including endocrine disruption, gene toxicity, the imposition of sex organs, antibiotic resistance and many others in some aquatic organisms exposed to arrays of residues of pharmaceutical and personal care products. Among the treatment techniques, advanced oxidation processes have been reported to be a better technique through which these PPCPs can be degraded in the WWTPs. Heterogeneous photocatalysis using various photocatalyst immobilized on solid support such as activated carbon, graphene and carbon nanotubes in AOPs have been shown to be a viable and efficient method of PPCPs degradation. This is because, the performance of most WWTPs is limited since they were not designed to degrade toxic and recalcitrant PPCPs. This review highlight the occurrence, concentration of PPCPs in wastewater and the removal efficiency of heterogeneous photocatalysis of TiO2 immobilized on solid supports.

Occurrence and probabilistic risk assessment of PAHs in water and sediment samples of the Diep River, South Africa.

This study investigated the levels of polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples of the Diep River freshwater system of Western Cape Province, South Africa. A solid-phase extraction - gas chromatography - flame ionisation detection (SPE-GC-FID) method was utilised to simultaneously determine the 16 United States Environmental Protection Agency (US EPA) listed priority PAHs in water and sediment samples. The seasonal averages of individual PAH detected at the studied sites, ranged between not detected (Nd) and 72.38 ± 9.58 µg/L in water samples and between Nd and 16.65 ± 2.63 µg/g in the corresponding sediment samples. The levels of PAHs measured in water and sediment samples were subjected to probabilistic risk assessment to predict the possibility of regulatory values being exceeded. The average percentage exceedence of 63.26 was obtained for PAHs in water samples of the Diep River, while the corresponding average percentage exceedence obtained for sediment sample was 63.71. Sufficient exposure of humans and aquatic organisms to the exceedance levels obtained, would cause adverse health effect.

Quantification of selected pharmaceutical compounds in water using liquid chromatography-electrospray ionisation mass spectrometry (LC-ESI-MS).

The detection and quantitation of pharmaceutical compounds (PCs) in different environmental matrices is still a challenge, due to their extremely low (ng-µg) concentrations and the lack of rapid and sensitive analytical techniques. A number of techniques, such as enzyme-linked immunosorbent assay (ELISA), chromatography, electrophoresis, and electrochemical methods have been explored. These methods are limited by their poor sensitivity. In this study, a hyphenated liquid chromatography-mass spectrometric (LC-MS) method was developed, validated, and tested for the detection and quantification of seven active pharmaceutical compounds, with solid-phase extraction for analytes recovery and separation of interference from the aqueous matrix. The sensitivity achieved for the method allowed for LODs (µg/L) of 0.0439, 0.0684, 0.1219, 0.0710, 0.1129, 0.0447, 0.0837 and LOQs (µg/L) of 0.1462, 0.2281, 0.4065, 0.2367, 0.3763, 0.1492, 0.2792, for lamivudine, acetaminophen, vancomycin, ciprofloxacin, sulfamethoxazole, diclofenac, and ivermectin, respectively, within a linear range of 0.01-0.1 µg/mL. Other ICH validation parameters are also discussed. The different PCs were positive in 61 % of the tested surface waters, with diclofenac present only in two of the sampling points. The concentrations at which they occurred were variable and ranged between ND and 398.98 µg/L.

Evaluation of selected polychlorinated biphenyls (PCBs) congeners and dichlorodiphenyltrichloroethane (DDT) in fresh root and leafy vegetables using GC-MS.

Persistent organic pollutants (POPs) are dangerous and toxic pollutants that may cause adverse effects on human and animal health, including death. POPs such as polychlorinated biphenyls (PCBs) and pesticides are subtly released into the environment from industrial and agricultural use. Global circulation is due to their trans-boundary transport capacity, contingent on aerodynamic and hydrological properties. Plants have capacity to take-up POPs, and these bio-magnify along heterotrophic transfer pathways. In this study, levels of selected 6-PCB congeners and 3- DDTs in some leaf and root vegetables were investigated. Leaf and root vegetables were collected from different horticultural farms areas in Cape Town. The 6-PCBs and 3-DDTs were recovered from the samples using solid phase extraction(SPE), followed by GC-MS analysis. The ΣPCBs and ΣDDT (on-whole basis), were ranged: 90.9-234 ng/g and 38.9-66.1 ng/g respectively. The 3-PCBs and 6-DDTs levels were slightly higher in leaf vegetables compared to root vegetables. The detection of PCBs and DDTs in the vegetables suggest the probable use of PCBs containing pesticides. Although the observed concentrations were below the WHO maximum residue limits, consumption of such contaminated leaf and root vegetables portend a health risk.

Multi-residue method for the determination of selected veterinary pharmaceutical residues in surface water around Livestock Agricultural farms.

A multi-residue method for the determination of the occurrence and prevalence levels of selected veterinary pharmaceutical residues in surface water was developed on a high performance liquid chromatography coupled to ultraviolet-visible (HPLC-UV) detector, and tested with the intent of profiling their distribution. The limit of detection (LOD) and limit of quantitation (LOQ) achieved for the selected pharmaceuticals; acetaminophen, diclofenac, salicylic acid, tetracycline, chloramphenicol, ciprofloxacin, bisphenol-A, 17ß-estradiol, estriol, and ivermectin ranged between 0.06-3.45 µg L-1 and 0.17-10.35 µg L-1 respectively. Other International Conference on Harmonization (ICH) parameters for validation of analytical procedures were also evaluated and discussed. Pharmaceutical residues were recovered from surface water samples collected from around livestock farms in Cape Town, South Africa by solid phase extraction (SPE), and thereafter separated and quantified using a validated method on a HPLC-UV-detector. Most frequently detected residues were: acetaminophen (56%), diclofenac (53), tetracycline (72%), 17ß-estradiol (73%); chloramphenicol (68%), and salicylic acid (67%), with significantly high (p > 0.05) spatial variability in the concentration distributions of the pharmaceuticals in the surface waters.

Determination of selected steroid hormones in some surface water around animal farms in Cape Town using HPLC-DAD.

In this study, a method for the simultaneous determination of two steroid hormones, 17ß-estradiol (E2) and estriol (E3), and a hormone mimicking polycarbonate, bisphenol-A (BPA), was developed and validated. This was thereafter used for the determination of the levels of the hormones in surface water collected around some livestock farms. The sensitivity of the method allowed the LODs and LOQs of the hormones and mimic hormone in the range 1.14-2.510 and 3.42-7.53 µg/L, respectively. The results revealed wide variability in the concentrations of E2 and E3, while BPA was not detected at any of the sampling stations. The concentration of E3 ranged between <1.14 and 45.5 µg/L (N = 120) in station 2 water. The highest concentration of E2 (15.7 µg/L, N = 80) was observed in water from station 1. The varied concentrations may be connected with the nature and sources of release, inconsistencies in analyte distribution due to dynamics of water flow pattern and the physical/chemical properties of the receiving water bodies.

Removal of PFOA and PFOS from aqueous solutions using activated carbon produced from Vitis vinifera leaf litter.

The removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from aqueous solutions using agro-waste biomass of Vitis vinifera (grape) leaf litter was studied. Activated carbons were produced from the biomass and chemical activation achieved by using phosphoric acid (H3PO4) and potassium hydroxide (KOH) for the modification of the carbons' surface morphology. Activated carbons were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy and Brunauer-Emmett-Teller (BET) in order to understand removal mechanisms of the contaminants by activated carbons. The effect of solution concentration, pH, adsorbent dosage, contact time and temperature was evaluated to optimize the removal efficiency of activated carbons. Adsorption isotherm models were used to analyse the equilibrium data obtained, and kinetic models were applied to study sorption mechanisms. The results fitted well into Freundlich isotherm with both AC-KOH and AC-H3PO4 having high K f values. Maximum adsorption capacities for AC-H3PO4 were 78.90 and 75.13 mg/g for PFOA and PFOS, respectively. Equilibrium was reached before 60 min on both adsorbents, and thermodynamic studies indicated that the process was exothermic and spontaneous. Surface morphology showed the abundance of microspores (>60%) with BET total surface area of 295.488 and 158.67 m2/g for AC-H3PO4 and AC-KOH activated carbons, respectively. Removal efficiencies were 95 and 90% for PFOA using AC-H3PO4 and AC-KOH, respectively; corresponding values for PFOS were 94 and 88%. Adsorbents' removal capacities depended on the physicochemical characteristics of adsorbents.

Veterinary pharmaceuticals in aqueous systems and associated effects: an update.

Environmental studies have shown that pharmaceuticals can contaminate aqueous matrices, such as groundwater, surface water, sediment as well as aquatic flora and fauna. Effluents from sewage and wastewater treatment plants, pharmaceutical industries and hospitals have been implicated in such contamination. Recent studies have however revealed significant concentrations of pharmaceuticals in wastewater from animal facilities in proximal aquatic habitats. Furthermore, epidemiological studies have shown a consistent positive correlation between exposure to some drugs of veterinary importance and increased adverse effects in aquatic biota largely due to induction of endocrine disruption, antibiotic resistance, neurotoxicity, genotoxicity and oxidative stress. The aquatic habitats and associated biota are important in the maintenance of global ecosystem and food chain. For this reason, anything that compromises the integrity and functions of the aquatic environment may lead to major upset in the world's ecosystems. Therefore, knowledge about this route of exposure cannot be neglected and monitoring of their occurrence in the environment is required. This review focuses on scientific evidence that link the presence of pharmaceuticals in aqueous matrices to animal production facilities and presents means to reduce the occurrence of veterinary pharmaceutical residues in the aquatic habitats.

Benzo[a]pyrene and Benzo[k]fluoranthene in some processed fish and fish products.

In this study, the concentration levels of the probable carcinogenic PAH fractions, benzo[a]pyrene (BaP) and benzo[k]fluoranthrene (BkF) in fillets of some processed fish species were investigated. Fish species comprising Merluccius poli (hake), Tyrsites atun (snoek), Seriola lalandi (yellow-tail) and Brama brama (angel fish) were bought in fish shops at Gordon's Bay, Western Cape, South Africa. The fish were gutted, filleted and prepared for edibility by frying, grilling and boiling. Polycyclic aromatic hydrocarbons were extracted from each homogenized fish sample, cleaned-up using solid phase extraction (SPE), and analysed for the PAH fractions, BaP and BkF using a Gas Chromatograph coupled with a Flame Ionization Detector (GC-FID). The sum of the two PAHs (∑2PAH) i.e., BaP and BkF ranged between 0.56 and 1.46 µg/kg, in all boiled, grilled and fried fish species. The fried fish extracts showed significantly higher (p < 0.05) abundance of ∑2PAH, than grilled and boiled fish. Dietary safety and PAHs toxicity was also discussed.

Determination of polycyclic aromatic hydrocarbons [PAHs] in processed meat products using gas chromatography - flame ionization detector.

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in smoked, grilled and boiled meats were determined using gas chromatography - flame ionization detector (GC-FID). PAHs in the processed meats were extracted in n-hexane after hydrolysis with methanolic KOH. Clean-up was achieved using solid phase extraction in neutral-Si/basic-Si/acidic-Si/neutral-Si frits. The fractions, benzo[k]fluoranthene (BkP), benzo[a]pyrene (BaP), indeno[123-cd]pyrene (IP) and benzo[ghi]perylene (BghiP) were separated and quantified using GC-FID. The method and instrument limits of detections were 0.1, 0.1, 0.2, 0.3µg/kg and 0.5, 0.5, 1.0, 1.5µg/kg, respectively, for BkP, BaP, IP and BghiP. The method's recovery and precision generally varied between 83.69% and 94.25% with relative standard deviation (RSD) of 3.18-15.60%; and 90.38-96.71% with relative standard deviation (RSD) of 1.82-12.87% respectively. The concentration of BkP, BaP, IP and BghiP in smoked, grilled and boiled meat samples were ranged 0.64-31.54µg/kg, 0.07-7.04µg/kg, 0.09-15.03, 0.51-46.67µg/kg and 0.01-5.11µg/kg, respectively.