Combined fluorescent measurements, parallel factor analysis and GC-mass spectrometry in evaluating the photodegradation of PAHS in freshwater systems.

To better understand the transformation and photochemical fate of PAHs in aquatic environments, a custom-designed closed-circuit recirculation photodegradation system, combined with inline semi-continuous fluorescence and absorbance measurements, as well as modelling of excitation-emission (EEM) measurements with parallel factor analysis (PARAFAC), and GC-MS analysis, were combined to create a robust tool for holistically assessing the photodegradation of individual PAHs, their mixtures and photoproduct formation. Selected compounds included in the US EPA priority list, representing 2- to 6-ring compounds, were monitored individually and in mixtures, during 24 h photodegradation experiments. Experiments were conducted in solutions simulating ideal (ultrapure water) and environmentally relevant conditions (1.00 mg L-1 Suwannee River Natural Organic Matter (SRNOM)). The fluorescence, primary PARAFAC components and quantification data obtained by GC-MS, indicated that the decline in parent molecule concentration occurred rapidly within 200 min. The degradation rates of parent PAHs increased with aromaticity (6-ring ≫ 2-ring PAHs) and followed pseudo-first order degradation kinetics. The presence and transformation of degradation products, were captured by PARAFAC. NOM influenced the diversity of photoproducts. From the GC-MS results, photoproducts were only detected in Ant, BAnt and the PAH mixture solutions, but optical property analyses indicated that diverse changes occurred with all PAHs. Spectrometric and chromatographic data demonstrated that parent PAHs and photoproducts co-existed at various stages, which is significant for freshwater systems contaminated with these compounds if photoproducts have higher-toxic potential. These results may be used to model the hazard-potential associated with PAHs present in freshwater systems and understanding the mechanisms that govern their environmental fate.

Occurrence, distribution, spatio-temporal variability and source identification of n-alkanes and polycyclic aromatic hydrocarbons in water and sediment from Loskop dam, South Africa.

In this study, the spatial and temporal variations in the levels of C8-C40 n-alkanes and 18 polycyclic aromatic hydrocarbons (PAHs) in water and sediment from Loskop Dam (Mpumalanga Province South Africa), were investigated between 2015 and 2017. In addition, their sources, which have not been well defined, were also studied over the period. This water body is sourced from a historically contaminated water body, the Olifants River, which flows through areas where a range of industrial and agricultural activities take place. Mass crocodile and fish mortalities have been recorded in this aquatic system, and contamination by organic pollutants were highlighted as a contributing factor. The total average n-alkane concentrations in water and sediments ranged from 0.574±00811 to 18.8±1.39 µg/L and 4760±243 to 30700±906 µg/kg, respectively. Similarly, PAHs were detected at total average concentrations of between 0.150±00494 and 49.8±6.86 µg/L in water and 61.6±5.95 to 2618±300 µg/kg. n-Alkane and PAH diagnostic ratios indicated a mixture of sources of these compounds, attributed to terrestrial, submerged and floating plant material, as well as petrogenic and pyrogenic combustion. Inlet, middle and upper segment site clustering was observed with non-metric multidimensional scaling (NMDS) and hierarchical cluster analysis (HCA), mainly driven by the prevalence of PAHs at the inlet sites and n-alkanes in the upper reaches. By using indicator compounds, the sources of contamination could be predicted. The strategy described here can be applied to any water body for continuous long-term monitoring of pollutant levels and to identify sources attributing to water pollution.