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Intensive livestock farming has increased the use of veterinary pharmaceuticals in many developing countries, and this is considered a significant concern to the freshwater ecosystem. However, the information on the potential acute toxicity of piggery effluent waste and the veterinary pharmaceutical effluent discharged into the aquatic environment is limited. This study assessed the adverse effect of a piggery effluent and the cocktail mixtures of high- and low-level doses of three frequently occurring veterinary pharmaceuticals (tetracycline (TETR), ivermectin (IVER), and salicylic acid (SALA)) on freshwater organisms using three representative freshwater biotests organisms: Pseudokirchneriella subcapitata (P. subcapitata), Daphnia magna (D. magna), and Tetrahymena thermophila (T. thermophila). The freshwater organism test results showed that the 24-h and 48-h EC50 algal toxicity to P. subcapitata exposed to 10% unfiltered piggery effluent were 25.6 and 49.3% respectively while the 24-h LC50 value to Cladocera, D. magna exposed to unfiltered piggery effluent was 23.2 (17.7-30.4)%. The 24-h EC50 protozoan toxicity to T. thermophila exposed to 1% HLD veterinary pharmaceuticals was 0.014 µg/L. Thus, the study established the different sensitivities of freshwater organisms to various percentage levels of piggery effluent and high- and low-level doses of veterinary pharmaceutical. The piggery effluent and the pharmaceutical cocktail mixtures have potential toxicological effects on the freshwater ecosystem.

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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.

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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.

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This study assessed the concentrations of polybrominated diphenylethers (PBDEs) in stream water obtained from Asunle stream, an adjoining stream of the Obafemi Awolowo University dumpsite. Water samples were collected for a period of eight months from six different locations comprising of a spot upstream in an uphill area relative to the refuse dumpsite and five others downstream along the stream course. The sampled waters were extracted with dicholoromethane using liquid-liquid extraction method and cleanup was carried out with silica gel. The final extracts after concentration were analyzed using GC-MS/MS. The recovery experiments were adequate (105%-110%). The mean levels of Æ©6PBDEs compounds analyzed ranged from 0.03 to 0.45 ng/mL. Seasonal variability of PBDEs indicated that higher levels were found during the wet season. The levels of PBDEs recorded in this work were relatively lower compared to the values reported in the literature from other developed nations.

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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.

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Assessment of levels of polybrominated diphenyl ethers (PBDEs) from the sediment of Asunle stream, an adjourning stream of the Obafemi Awolowo University dumpsite, has been carried out. Sediment samples were collected from the stream at six locations for a period of 8 months, composed of 4 months each of wet (May-Aug) and dry (Nov-Feb) seasons. Soxhlet extraction was employed for the isolation of all the target compounds from the sediment samples. Extracts were further subjected to multi-layer column chromatography employing different forms of silica gel. The prepared samples were analyzed using GC-MS. The overall mean concentrations of the total PBDEs ranged from 1.80 to 9.46 ng/g. The results showed that the concentrations of the PBDEs were slightly higher during the wet season than those during the dry season. In all the studied locations, BDE28, BDE47, BDE99, BDE100, BDE153, and BDE154 were detected in all the sediment samples at concentrations that ranged from 0.73 to 10.43 ng/g. Results of this study indicated that BDE153 was the major pollutant of the Asunle stream sediments.

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The effect of tributyltin (TBT) on the stability of hemocytic lysosome membranes of the mussel, Mytilus galloprovincialis, and the use thereof as a biomarker of TBT-induced stress, was investigated. Mussels were exposed to 0.1 and 1.0 µg/L tributyltin respectively for 4 weeks. Lysosomal membrane stability of hemocytes was tested weekly by means of the neutral red retention time (NRRT) assay, after which the mussel samples were analyzed for TBT content. The two exposed groups exhibited significantly increased (p < 0.05) whole body TBT concentrations with concomitant significant decreases (p < 0.05) in NRRT (R(2) values of 0.85 and 0.971 for lower and higher exposure groups, respectively). The higher exposure group showed a typical dose-response curve. For the control, no TBT was detected and NRRT remained stable. It was concluded that the NRRT assay could be considered as a useful technique, and lysosomal membrane destabilization a useful early warning and cellular biomarker of stress due to TBT exposure in M. galloprovincialis.

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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.

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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.

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The removal of triphenyltin chloride from contaminated simulated seawater with adsorption method was discussed. The adsorbents used are fly ash, nSiO2, and nSiO2/fly ash composite. The results showed that the adsorption of the adsorbents increases with increase in the adsorbent dose, contact time, pH, stirring speed, initial TPT concentration, and decreased with increase in temperature. The adsorption fitted well with the Freundlich isotherm, showing that the adsorbent and TPT combined with function groups and the adsorption kinetics followed the pseudo-second-order kinetic model. The thermodynamic parameters were also evaluated. Optimal conditions for the adsorption of TPT from simulated seawater were applied to TPT removal from natural seawater. A higher removal efficiency of TPT (>99%) was obtained for the nSiO2/fly ash composite but not for fly ash and nSiO2.

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The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO.

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Until recently, studies reporting the concentrations of polybrominated diphenyl ethers (PBDEs) as well as polybrominated biphenyls (PBBs) are generally scarce in the literature. Consequently, this study was aimed to investigate the occurrence and concentrations of certain PBDE congeners (BDE 28, 47, 100, 99, 154, 153, 183 and 209) and BB 153 in river water samples collected bi-monthly from the Diep River. The routine analyses of the target compounds were performed using a high-capillary GC-microelectron capture detection, while their structural elucidation was assessed using GC-TOF-MS technique. The overall mean concentrations of the sum of the eight PBDE congeners were 2.60, 4.83 and 4.29 ng/L for the upstream, point of discharge and downstream sampling points, respectively. Similarly, the overall mean concentrations of BB 153 were 0.25, 4.85 and 1.56 ng/L for the upstream, point of discharge and downstream sampling points, respectively. BDE 47 was the dominant congener found in these samples contributing between 19 and 26 % to the total PBDEs across the sampling points. The statistical analyses performed on the results obtained showed that all the congeners, except BDE 209 in certain instances, had strong positive correlations with one another, thus suggesting that these contaminants could be emanating from the same source. In this study, potential sources of these pollutants other than WWTP discharges into the investigated river were also identified. However, the relatively high concentrations of the target compounds found at the point of discharge sampling point coupled with the large volume of treated effluent being discharged suggested that the contributions from this source could be very significant over time.

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An assessment of the concentrations of selected polybrominated diphenyl ether (PBDE) congeners as well as BB 153 in leachate samples collected from three landfill sites within the city of Cape Town was conducted. A liquid-liquid extraction technique was employed for the isolation of all the target compounds from the leachate samples. Extracts obtained were further subjected to multi-layer column chromatography employing different forms of silica gel. The prepared samples were analysed using a high capillary gas chromatograph equipped with a micro-electron capture detector (GC-µECD). The overall mean concentrations of the total PBDEs, including BDE 209 ranged between 5.65 and 2,240, 0.28-20.5 and 1.66-1,170 ng/l for Bellville, Coastal Park, and Vissershok landfill sites, respectively. The mean concentrations of BB 153, which were generally low in most of the samples analysed, were 70.4, 7.14 and 8.16 ng/l for Bellville, Coastal Park and Vissershok sites, respectively. The influence of precipitation on the characteristics and quantity of leachate produced from the landfill sites investigated was most pronounced during the August/September sampling regime. Generally, the trend observed in this study clearly indicated a wide variation in the levels of these contaminants in all the landfill sites studied from one sampling period to the other. However, the principal component analysis revealed that the release of these contaminants might be associated with two or three possible sources. This study further confirmed the relevance of landfill leachate as an important source of PBDE contamination of the environment, especially the groundwater and surface water sources.

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The reuse of treated effluent from wastewater treatment plants (WWTPs) as alternative water source for sport-field or landscape irrigation, agricultural, and other industrial purposes is growing significantly. Similarly, the application of treated sludge (biosolid) to agricultural soils is now being considered globally as the most economic means of sludge disposal. However, the presence of emerging organic contaminants in these matrices, including polybrominated diphenyl ethers (PBDEs), which are potential endocrine disruptors, portends a high health risk to humans and the environment in general. In this study, effluent and sewage sludge samples collected from a WWTP were analysed for some selected PBDE congeners (BDE congeners 28, 47, 99 100 153 154 183, and 209) as well as BB-153 using a high-capillary gas chromatograph equipped with an electron capture detector. The sum of the eight PBDE congeners ranged from 369 to 4370, 19.2 to 2640, and 90.4 to 15,100 ng/l for raw water, secondary effluent, and final effluent, respectively. A similar result was observed for sewage sludge samples, which ranged between 13.1 and 652 ng/g dry weight (dw). The results obtained for BB-153 were generally lower compared with those found for most PBDE congeners. These ranged from ND to 18.4 ng/l and ND to 9.97 ng/g dw for effluents and sewage sludge, respectively. In both matrices, BDE 47 and 209 congeners were found to contribute significantly to the overall sum of PBDEs. The reuse of the treated effluent, particularly for agricultural purposes, could enhance the possibility of these contaminants entering into the food chain, thus causing undesirable health problems in exposed subjects.

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Organotin compounds result from the addition of organic moieties to inorganic tin.Thus, one or more tin-carbon bonds exist in each organotin molecule. The organo-tin compounds are ubiquitous in the environment. Organotin compounds have many uses, including those as fungicides and stabilizers in plastics, among others in industry. The widespread use of organotins as antifouling agents in boat paints has resulted in pollution of freshwater and marine ecosystems. The presence of organotin compounds in freshwater and marine ecosystems is now understood to be a threat, because of the amounts found in water and the toxicity of some organotin compounds to aquatic organisms, and perhaps to humans as well. Organotin com-pounds are regarded by many to be global pollutants of a stature similar to biphenyl,mercury, and the polychlorinated dibenzodioxins. This stature results from the high toxicity, persistence, bioaccumulation, and endocrine disruptive features of even very low levels of selected organotin compounds.Efforts by selected governmental agencies and others have been undertaken to find a global solution to organotin pollution. France was the first country to ban the use of the organotins in 1980. This occurred before the international maritime organization (IMO) called for a global treaty to ban the application of tributyltin (TBT)-based paints. In this chapter, we review the organotin compounds with emphasis on the human exposure, fate, and distribution of them in the environment. The widespread use of the organotins and their high stability have led to contamination of some aquatic ecosystems. As a result, residues of the organotins may reach humans via food consumption. Notwithstanding the risk of human exposure, only limited data are available on the levels at which the organotins exist in foodstuffs consumed by humans. Moreover, the response of marine species to the organotins, such as TBT, has not been thoroughly investigated. Therefore, more data on the organotins and the consequences of exposure to them are needed. In particular, we believe the following areas need attention: expanded toxicity testing in aquatic species, human exposure, human body burdens, and the research to identify biomarkers for testing the toxicity of the organotins to marine invertebrates.

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