Optimisation of in-cell accelerated solvent extraction technique for the determination of organochlorine pesticides in river sediments

Organochlorine pesticides (OCPs) are ubiquitous environmental contaminants with adverse impacts on aquatic biota, wildlife and human health even at low concentrations. However, conventional methods for their determination in river sediments are resource intensive. This paper presents an approach that is rapid and also reliable for the detection of OCPs. Accelerated Solvent Extraction (ASE) with in-cell silica gel clean-up followed by Triple Quadrupole Gas Chromatograph Mass Spectrometry (GCMS/MS) was used to recover OCPs from sediment samples. Variables such as temperature, solvent ratio, adsorbent mass and extraction cycle were evaluated and optimised for the extraction. With the exception of Aldrin, which was unaffected by any of the variables evaluated, the recovery of OCPs from sediment samples was largely influenced by solvent ratio and adsorbent mass and, to some extent, the number of cycles and temperature. The optimised conditions for OCPs extraction in sediment with good recoveries were determined to be 4 cycles, 4.5 g of silica gel, 105 ᴼC, and 4:3 v/v DCM: hexane mixture. With the exception of two compounds (α-BHC and Aldrin) whose recoveries were low (59.73 and 47.66 % respectively), the recovery of the other pesticides were in the range 85.35 – 117.97% with precision < 10 % RSD. The method developed significantly reduces sample preparation time, the amount of solvent used, matrix interference, and is highly sensitive and selective.

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.

Characterisation and source apportionment of polycyclic aromatic hydrocarbons in the sediments of Brisbane River

The thesis was a step forward in predicting the levels and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Brisbane river, especially after the Brisbane floods in 2011. It employed different statistical techniques to provide valuable information that may assist source control and formulation of pollution mitigation measures for the river.

Groundwater flow model of the Logan river alluvial aquifer system Josephville, South East Queensland

The study focuses on an alluvial plain situated within a large meander of the Logan River at Josephville near Beaudesert which supports a factory that processes gelatine. The plant draws water from on site bores, as well as the Logan River, for its production processes and produces approximately 1.5 ML per day (Douglas Partners, 2004) of waste water containing high levels of dissolved ions. At present a series of treatment ponds are used to aerate the waste water reducing the level of organic matter; the water is then used to irrigate grazing land around the site. Within the study the hydrogeology is investigated, a conceptual groundwater model is produced and a numerical groundwater flow model is developed from this. On the site are several bores that access groundwater, plus a network of monitoring bores. Assessment of drilling logs shows the area is formed from a mixture of poorly sorted Quaternary alluvial sediments with a laterally continuous aquifer comprised of coarse sands and fine gravels that is in contact with the river. This aquifer occurs at a depth of between 11 and 15 metres and is overlain by a heterogeneous mixture of silts, sands and clays. The study investigates the degree of interaction between the river and the groundwater within the fluvially derived sediments for reasons of both environmental monitoring and sustainability of the potential local groundwater resource. A conceptual hydrogeological model of the site proposes two hydrostratigraphic units, a basal aquifer of coarse-grained materials overlain by a thick semi-confining unit of finer materials. From this, a two-layer groundwater flow model and hydraulic conductivity distribution was developed based on bore monitoring and rainfall data using MODFLOW (McDonald and Harbaugh, 1988) and PEST (Doherty, 2004) based on GMS 6.5 software (EMSI, 2008). A second model was also considered with the alluvium represented as a single hydrogeological unit. Both models were calibrated to steady state conditions and sensitivity analyses of the parameters has demonstrated that both models are very stable for changes in the range of ± 10% for all parameters and still reasonably stable for changes up to ± 20% with RMS errors in the model always less that 10%. The preferred two-layer model was found to give the more realistic representation of the site, where water level variations and the numerical modeling showed that the basal layer of coarse sands and fine gravels is hydraulically connected to the river and the upper layer comprising a poorly sorted mixture of silt-rich clays and sands of very low permeability limits infiltration from the surface to the lower layer. The paucity of historical data has limited the numerical modelling to a steady state one based on groundwater levels during a drought period and forecasts for varying hydrological conditions (e.g. short term as well as prolonged dry and wet conditions) cannot reasonably be made from such a model. If future modelling is to be undertaken it is necessary to establish a regular program of groundwater monitoring and maintain a long term database of water levels to enable a transient model to be developed at a later stage. This will require a valid monitoring network to be designed with additional bores required for adequate coverage of the hydrogeological conditions at the Josephville site. Further investigations would also be enhanced by undertaking pump testing to investigate hydrogeological properties in the aquifer.

The hydrogeology, hydrology and hydrochemistry of the Condamine River Valley alluvium

The Cainozoic alluvium of the Condamine River valley is interpreted to consist of sediments deposited as floodplain and sheetwash deposits in bedrock valleys eroded into Mesozoic sedimentary rocks and tertiary volcanics. A maximum recorded sediment accumulation of 134 m is centred just south of Dalby. The lower section ofboth the flood plain and sheetwash alluvium is composed of variegated sandy and clayey sediments and the upper section of brown and grey sandy and clayey sediments.

Modification and validation of a microwave-assisted digestion method for subsequent ICP-MS determination of selected heavy metals in sediment and fish samples in Agusan River, Philippines

This study investigated, validated, and applied the optimum conditions for a modified microwave assisted digestion method for subsequent ICP-MS determination of mercury, cadmium, and lead in two matrices relevant to water quality, that is, sediment and fish. Three different combinations of power, pressure, and time conditions for microwave-assisted digestion were tested, using two certified reference materials representing the two matrices, to determine the optimum set of conditions. Validation of the optimized method indicated better recovery of the studied metals compared to standard methods. The validated method was applied to sediment and fish samples collected from Agusan River and one of its tributaries, located in Eastern Mindanao, Philippines. The metal concentrations in sediment ranged from 2.85 to 341.06 mg/kg for Hg, 0.05 to 44.46 mg/kg for Cd and 2.20 to 1256.16 mg/kg for Pb. The results indicate that the concentrations of these metals in the sediments rapidly decrease with distance downstream from sites of contamination. In the selected fish species, the metals were detected but at levels that are considered safe for human consumption, with concentrations of 2.14 to 6.82 μg/kg for Hg, 0.035 to 0.068 μg/kg for Cd, and 0.019 to 0.529 μg/kg for Pb.

Geographic Variation of Notified Ross River Virus Infections in Queensland, Australia, 1985-1996

The spatial and temporal variations of Ross River virus infections reported in Queensland, Australia, between 1985 and 1996 were studied by using the Geographic Information System. The notified cases of Ross River virus infection came from 489 localities between 1985 and 1988, 805 between 1989 and 1992, and 1,157 between 1993 and 1996 (chi2(df = 2) = 680.9; P < 0.001). There was a marked increase in the number of localities where the cases were reported by 65 percent for the period of 1989-1992 and 137 percent for 1993-1996, compared with that for 1985-1988. The geographic distribution of the notified Ross River virus cases has expanded in Queensland over recent years. As Ross River virus disease has impacted considerably on tourism and industry, as well as on residents of affected areas, more research is required to explore the causes of the geographic expansion of the notified Ross River virus infections.