This study assessed the distribution of five heavy metals (Cd, Pb, Cu, Zn, and Fe) across the various stages of treatment in three selected sewage treatment facilities and their receiving waterbodies in the Eastern Cape Province, South Africa. Aqueous and solid (sludge) samples were collected monthly from September 2015 to February 2016. Quantitation was achieved by atomic absorption spectrometry after necessary sample preparations. Concentrations of heavy metal cations in the sludge generally varied from <DL (below detection limit) to 1.17 mg kg−1, <DL to 0.14 mg kg−1, 27.588 to 69.789 mg kg−1, and <DL to 0.099 mg kg−1 for Cu, Cd, Fe and Pb; while Zn was below detection all through. Similarly, the levels of Cu, Cd, and Fe in the influents, effluents, upstream and downstream across the three plants ranged from <DL–6.588 mg L−1, <DL–0.636 mg L−1, <DL–0.878 mg L−1 and <DL–0.711 mg L−1, respectively; Zn and Pb were less than DL in all the matrices and study locations. All the contaminants were below hazardous levels in all the sludge and aqueous samples except Cd which was higher in effluents and surface waters across the board. Wastewater Treatment Plant (WWTP)-A exhibited better removal capacity for Fe (86.6%), compared to WWTP-B (34.7%) and WWTP-C (56.9%). However, the removal of Cu and Zn was very poor in all the treatment facilities studied. Carcinogenic and non-carcinogenic risks evaluated were sufficiently low. This suggests that the levels of contamination, even with respect to Cd, was minimal. Nevertheless, efforts should be made to keep the concentrations of these contaminants at levels safe for humans and aquatic organisms. Furthermore, the use of the effluents from these facilities for irrigation should be discouraged to prevent unnecessary build-up of metals in the soil and plants grown with such, as well as subsequent bioaccumulation and biomagnification in the food chain.
The incidence and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in the Buffalo River Estuary in the Eastern Cape Province of South Africa were assessed in this study. A total of 60 surface water and 19 sediment samples were collected from 5 sites of the estuary over a period of 6 months (December 2015 to May 2016). Extraction of PAHs from the water and sediment samples was achieved by using liquid–liquid and soxhlet extraction methods respectively, followed by column clean up with silica gel and quantification by gas chromatography–flame ionization detection. Individual PAH levels in the water and sediment samples ranged from not detected (ND) to 24.91 μg/L and ND to 7792 μg/kg, respectively. Total concentrations of the PAHs in the water and sediment samples varied as 14.91–206 μg/L and 1107–22,310 μg/kg in that order. Total levels of the contaminants were above the target values in the two matrices and were higher in summer than autumn. Although the noncarcinogenic risk of PAHs estimated in the water column through dermal absorption was very low compared with the target value, the carcinogenic risk determined was high for both adults and children. Similarly, benzo(a)pyrene and dibenzo(a,h)anthracene were found to be of higher carcinogenic and mutagenic risks in the sediments collected from the study area. Diagnostic ratios suggest that the target hydrocarbons are predominantly from pyrolytic sources. It therefore could be inferred that the water body is conspicuously polluted; hence, efforts should be made to control all the activities contributing to such magnitude of pollution at the sites.
Several methods of extraction and analytical determination for total petroleum hydrocarbons (TPHCs) in aqueous and solid samples are reviewed. Infrared spectroscopy is one of the efficient methods that are being replaced today pursuant to getting rid of some halogenated solvents classified as ozone-depleting substances. The gravimetric method which uses n-hexane as an extraction solvent for the determination of oil and grease, as well as the nonpolar materials, has become a preferred choice, despite being not suitable for volatiles because of the mandatory evaporation step. Other frequently used methods include gas chromatography with a flame ionization detector (FID) or mass spectrometric detector (MSD) which has the capacity to reveal the type of hydrocarbons present and is applicable to both volatile and semivolatile samples. Ultraviolet fluorescence is another method that is available both as a portable field device and as off-site laboratory equipment. Each of the methods has its own advantages and disadvantages; hence, the choice of method is guided by the type of data needed as discussed in detail in this review. The distribution of TPHC in water and sediments across the globe and the factors influencing the distribution were also reviewed.
Most organochlorine pesticides (OCPs) which are increasingly used in agriculture and industry are not biodegradable and thereby persist in the environment for a very long period of time. They are capable of negatively impacting the health of humans and biota when present in a higher concentration than recommended. This study evaluated the concentrations of 17 OCPs in surface water samples collected from six sampling sites along the course of the Buffalo River in Eastern Cape, South Africa, between December 2015 and May 2016. The samples were subjected to solvent extraction, followed by florisil clean up, and analyzed using gas chromatography coupled with an electron capture detector. The individual concentrations of OCPs detected ranged from
Polycyclic aromatic hydrocarbons are amongst the pollutants of major concern in the terrestrial and aquatic habitats. They are mostly characterised by carcinogenic and non-carcinogenic effects. Distribution and potential health risks of sixteen priority PAHs in the water and sediment samples collected between December 2015 and June 2016 from Algoa Bay, South Africa, were evaluated. Water and sediment samples collected were extracted with liquid–liquid and soxhlet extraction methods, respectively, and then cleaned up using glass column loaded with silica gel. Final concentrations of the target PAHs were determined by gas chromatography interfaced with flame ionization detector. Results indicated that individual PAH concentrations in surface water, bottom water and sediment samples ranged from not detected (ND) to 24.66 µg/L, ND to 22.81 µg/L and ND to 5.23 mg/kg correspondingly. Total PAHs concentrations varied as 12.78–78.94 µg/L, 1.20–90.51 µg/L and 1.17–10.47 mg/kg in the three environmental matrices in that order. The non-carcinogenic risk was generally below 1, whereas risk indices (dermal contact) were above the acceptable limit of 1 × 10 −4 in the water column, suggesting possible carcinogenic effects to humans, with adults being the most vulnerable. Similarly, highest contributions to TEQs and MEQs in the sediments were made by benzo(a)pyrene and dibenzo(a,h)anthracene, the two most toxic congeners, signifying the possibility of carcinogenicity and mutagenicity in humans. Diagnostic ratios of PAHs reflect a prevailing pyrogenic input all through. The pollution was albeit moderate, yet regular check is recommended to ensure safe and healthy environment for human and aquatic lives. Electronic supplementary material The online version of this article (10.1007/s10653-018-0213-x) contains supplementary material, which is available to authorized users.
Polycyclic aromatic hydrocarbons (PAHs) are major organic pollutants in the environment, which are toxic to humans and biota, given their carcinogenic, mutagenic and teratogenic nature. In this chapter, we carried out an overview of the sources and toxicity of PAHs, their common analytical methods of determination in the water and sediment samples, and also their global trend of distribution, with a view to provide baseline guidance for relevant control authorities. The choice methods for determining these contaminants are high-performance liquid chromatography (HPLC) with UV/luorescence detectors and GC/MS. Mass spectrometer coupled with GC is preferred because it ofers robust identiication of the analyte compounds both by retention time and mass spectrum, with additional structural information. Results collated revealed an extensive distribution of PAHs with total mean concentrations ranging from 0.0003 to 42,350 μg/L in water and 0 to 1.266 × 10 9 μg/kg (dw) in the sediment. PAHs in the two environmental matrices were much higher in the regions with intense oil exploration, shipping and industrial activities. It is therefore necessary to regularly monitor their levels in the aquatic environment, so as to provide mitigation options that will prevent risk to humans and aquatic animals.
PPCPs are found almost everywhere in the environment especially at an alarming rate and at very low concentration in the aquatic systems. Many methods—including pressurized hot water extraction (PHWE), pressurized liquid extraction (PLE), ultrasound-assisted extraction (UAE), and micro-assisted extraction (MAE)—have been employed for their extraction from both surface waters and biota. Solid-phase extraction (SPE) proved to be the best extraction method for these polar, non-volatile, and thermally unstable compounds in water. However, ultrasonic extraction works better for their isolation from sediment because it is cheap and consumes less solvent, even though SPE is preferred as a clean-up method for sediment samples. PPCPs are in groups of—acidic (e.g., diclofenac, ibuprofen, naproxen), neutral (e.g., caffeine, carbamazepine, fluoxetine), and basic pharmaceuticals, as well as antibiotics and estrogens amongst others. PPCPs which are present in trace levels (ng/L) are more often determined by liquid chromatography-mass spectrometry (LC-MS), gas chromatography-mass spectrometry (GC-MS), and high-performance liquid chromatography-ultraviolent (HPLC-UV). Of these, LC-MS and LC-MS-MS are mostly employed for the analysis of this class of compounds, though not without a draw-back of matrix effect. GC-MS and GC-MS-MS are considered as alternative cost-effective methods that can also give better results after derivatization.
Petroleum hydrocarbon profiles of water and sediment samples of Algoa Bay in the Eastern Cape Province of South Africa were assessed using standard analytical procedures. Water (from surface and bottom levels) and sediment samples were collected from five locations in the bay from February to June 2016. Extraction of the petroleum hydrocarbons from the water and sediment samples collected was achieved using liquid-liquid and Soxhlet extraction techniques, respectively, followed by column clean up. Target compounds were analytically determined with gas chromatography–flame ionization detector (GC-FID) and quantified by integrating the areas of both the resolved and unresolved components. Physicochemical properties of the water samples were also determined on site using a SeaBird 19plusV2 CTD SBE 55 device. Estimated limit of detection, limit of quantitation and relative standard deviation for the 35 n-alkane standards ranged from 0.06 to 0.13 μg/L, 0.30 to 0.69 μg/L and 3.61 to 8.32%, respectively. Results showed that total petroleum hydrocarbon (TPH) varied from 45.07 to 307 μg/L in the water and 0.72 to 27.03 mg/kg in the sediments. The mean concentrations of TPH in both the water and sediment samples from Algoa Bay revealed a slight level of pollution. The diagnostic indices used showed that the hydrocarbons in the area were from both biogenic and anthropogenic sources. Hence, there is need for adequate regulation and control of all activities contributing to the levels of petroleum hydrocarbon in the marine environment for the safety of human, aquatic and wild lives in the area.
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