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.

An enhanced procedure for the rapid digestion of high silicate archeological specimens followed by ICP-MS determination of traces of rare earth elements (REE's)

A straightforward procedure for the acid digestion of geological samples with SiO2 concentrations ranging between about 40 to 80%, is described. A powdered sample (200 mesh) of 500 mg was used and fused with 1000 mg spectroflux at about 1000 degreesC in a platinum crucible. The molten was subsequently digested in an aqueous solution of HNO3 at 100 degreesC. Several systematic digestion procedures were followed using various concentrations of HNO3. It was found that a relationship could be established between the dissolution-time and acid concentration. For an acid concentration of 15% an optimum dissolution-time of under 4 min was recorded. To verify that the dissolutions were complete, they were subjected to rigorous quality control tests. The turbidity and viscosity were examined at different intervals and the results were compared with that of deionised water. No significant change in either parameter was observed. The shelf-life of each solution lasted for several months, after which time polymeric silicic acid formed in some solutions, resulting in the presence of a gelatinous solid. The method is cost effective and is clearly well suited for routine applications on a small scale, especially in laboratories in developing countries. ICP-MS was applied to the determination of 13 Rare Earth Elements and Hf in a set of 107 archaeological samples subjected to the above digestion procedure. The distribution of these elements was examined and the possibility of using the REE's for provenance studies is discussed.

A study, by fire-assay and ICP-MS, of the distribution of rhodium, platinum, and gold in iron-age pottery

Forty-six archaeological specimens were treated by fire-assay and subsequently analysed by ICP-MS for selected precious metals: Ph, Pt and Au. The investigation was prompted by the possibility that archaeological samples could serve as "indicators" of the precious metal composition of the clays from the excavated sites. Therefore, the experimentally obtained concentrations were carefully studied to determine if there were anomalous levels of these precious metals in the deposits from which the specimens originated. Furthermore, the analytical data were used to establish if it was feasible to distinguish ancient potsherds based on precious metal concentrations, for employment as a basis in provenance studies.

Combining HPLC-DAD and ICP-MS data for improved analysis of complex samples: Classification of the root samples from Cortex moutan

A combined data matrix consisting of high performance liquid chromatography–diode array detector (HPLC–DAD) and inductively coupled plasma-mass spectrometry (ICP-MS) measurements of samples from the plant roots of the Cortex moutan (CM), produced much better classification and prediction results in comparison with those obtained from either of the individual data sets. The HPLC peaks (organic components) of the CM samples, and the ICP-MS measurements (trace metal elements) were investigated with the use of principal component analysis (PCA) and the linear discriminant analysis (LDA) methods of data analysis; essentially, qualitative results suggested that discrimination of the CM samples from three different provinces was possible with the combined matrix producing best results. Another three methods, K-nearest neighbor (KNN), back-propagation artificial neural network (BP-ANN) and least squares support vector machines (LS-SVM) were applied for the classification and prediction of the samples. Again, the combined data matrix analyzed by the KNN method produced best results (100% correct; prediction set data). Additionally, multiple linear regression (MLR) was utilized to explore any relationship between the organic constituents and the metal elements of the CM samples; the extracted linear regression equations showed that the essential metals as well as some metallic pollutants were related to the organic compounds on the basis of their concentrations

Fingerprinting of complex mixtures with the use of high performance liquid chromatography, inductively coupled plasma atomic emission spectroscopy and chemometrics

The molecular and metal profile fingerprints were obtained from a complex substance, Atractylis chinensis DC—a traditional Chinese medicine (TCM), with the use of the high performance liquid chromatography (HPLC) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) techniques. This substance was used in this work as an example of a complex biological material, which has found application as a TCM. Such TCM samples are traditionally processed by the Bran, Cut, Fried and Swill methods, and were collected from five provinces in China. The data matrices obtained from the two types of analysis produced two principal component biplots, which showed that the HPLC fingerprint data were discriminated on the basis of the methods for processing the raw TCM, while the metal analysis grouped according to the geographical origin. When the two data matrices were combined into a one two-way matrix, the resulting biplot showed a clear separation on the basis of the HPLC fingerprints. Importantly, within each different grouping the objects separated according to their geographical origin, and they ranked approximately in the same order in each group. This result suggested that by using such an approach, it is possible to derive improved characterisation of the complex TCM materials on the basis of the two kinds of analytical data. In addition, two supervised pattern recognition methods, K-nearest neighbors (KNNs) method, and linear discriminant analysis (LDA), were successfully applied to the individual data matrices—thus, supporting the PCA approach.

Characterisation of soluble components and PAH in PM10 atmospheric particulate matter in Brisbane

Fours sets of PM10 samples were collected in three sites in SEQ from December 2002 to August 2004. Three of these sets of samples were collected by QLD EPA as a part of their regular air monitoring program at Woolloongabba, Rocklea and Eagle Farm. Half of the samples were used in this study for the analysis of water-soluble ions, which are Na+, K+, Mg2+, Ca2+, NH4 +, Cl-, NO3 -, SO4 2-, F-, Br-, NO2 -, PO4 -3 and the other half was retained by QLD EPA. The fourth set of samples was collected at Rocklea, specifically for this study. A quarter of the samples obtained from this set of samples were used to analyse water-soluble ions; a quarter of the sample was used to analyse Pb, Cu, Al, Fe, Mn and Zn; and the rests were used to analyse US EPA 16 priority PAHs. The water-soluble ions were extracted ultrasonically with water and the major watersoluble anions as well as NH4 + were analysed using IC. Na+, K+, Mg2+, Ca2+ Pb, Cu, Al, Fe, Mn and Zn were analysed using ICP-AES while PAHs were extracted by acetonitrile and analysed using HPLC. Of the analysed water-soluble ions, Cl-, NO3 -, SO4 2-, Na+, K+, Mg2+ and Ca2+ were high in concentration and determined in all the samples. F-, Br-, NO2 -, PO4 -3 and NH4 + ions were lower in concentration and determined only in some samples. Na+ and Cl- were high in all samples indicating the importance of a marine source. Principal Component Analysis (PCA) was used to examine the temporal variations of the water-soluble ions at the three sites. The results indicated that there was no major difference between the three sites. However, comparing the average concentrations of ions and Cl-/Na+ it was concluded that Woolloongabba had more marine influence than the other sites. Al, Fe and Zn were detected in all samples. Al and Fe were high in all samples indicating the significance of a source of crustal matter. Cu, Mn and Pb were in low concentrations and were determined only in some samples. The lower Pb concentrations observed in the study than in previous studies indicate that the phasing-out of leaded petrol had an appreciable impact on Pb levels in SEQ. This study reports for the first time, simultaneous data on the water-soluble, metal ion and PAH levels of PM10 aerosols in Brisbane, and provides information on the most likely sources of these chemical species. Such information can be used alongside those that already exist to formulate PM10 pollution reduction strategies for SEQ in order to protect the community from the adverse effects of PM pollution.

Characterisation of soils with the use of instrumental techniques : a multivariate forensic study

The value of soil evidence in the forensic discipline is well known. However, it would be advantageous if an in-situ method was available that could record responses from tyre or shoe impressions in ground soil at the crime scene. The development of optical fibres and emerging portable NIR instruments has unveiled a potential methodology which could permit such a proposal. The NIR spectral region contains rich chemical information in the form of overtone and combination bands of the fundamental infrared absorptions and low-energy electronic transitions. This region has in the past, been perceived as being too complex for interpretation and consequently was scarcely utilized. The application of NIR in the forensic discipline is virtually non-existent creating a vacancy for research in this area. NIR spectroscopy has great potential in the forensic discipline as it is simple, nondestructive and capable of rapidly providing information relating to chemical composition. The objective of this study is to investigate the ability of NIR spectroscopy combined with Chemometrics to discriminate between individual soils. A further objective is to apply the NIR process to a simulated forensic scenario where soil transfer occurs. NIR spectra were recorded from twenty-seven soils sampled from the Logan region in South-East Queensland, Australia. A series of three high quartz soils were mixed with three different kaolinites in varying ratios and NIR spectra collected. Spectra were also collected from six soils as the temperature of the soils was ramped from room temperature up to 6000C. Finally, a forensic scenario was simulated where the transferral of ground soil to shoe soles was investigated. Chemometrics methods such as the commonly known Principal Component Analysis (PCA), the less well known fuzzy clustering (FC) and ranking by means of multicriteria decision making (MCDM) methodology were employed to interpret the spectral results. All soils were characterised using Inductively Coupled Plasma Optical Emission Spectroscopy and X-Ray Diffractometry. Results were promising revealing NIR combined with Chemometrics is capable of discriminating between the various soils. Peak assignments were established by comparing the spectra of known minerals with the spectra collected from the soil samples. The temperature dependent NIR analysis confirmed the assignments of the absorptions due to adsorbed and molecular bound water. The relative intensities of the identified NIR absorptions reflected the quantitative XRD and ICP characterisation results. PCA and FC analysis of the raw soils in the initial NIR investigation revealed that the soils were primarily distinguished on the basis of their relative quartz and kaolinte contents, and to a lesser extent on the horizon from which they originated. Furthermore, PCA could distinguish between the three kaolinites used in the study, suggesting that the NIR spectral region was sensitive enough to contain information describing variation within kaolinite itself. The forensic scenario simulation PCA successfully discriminated between the ‘Backyard Soil’ and ‘Melcann® Sand’, as well as the two sampling methods employed. Further PCA exploration revealed that it was possible to distinguish between the various shoes used in the simulation. In addition, it was possible to establish association between specific sampling sites on the shoe with the corresponding site remaining in the impression. The forensic application revealed some limitations of the process relating to moisture content and homogeneity of the soil. These limitations can both be overcome by simple sampling practices and maintaining the original integrity of the soil. The results from the forensic scenario simulation proved that the concept shows great promise in the forensic discipline.

Effect of pH on the uptake of arsenate and vanadate and the stability of these anions in alkaline solutions – a Raman spectroscopic study

Hydrotalcites have been synthesised using three different pH solutions to assess the effect of pH on the uptake of arsenate and vanadate. The ability of these hydrotalcites to remove vanadate and arsenate from solution has been determined by ICP-OES. Raman spectroscopy is used to monitor changes in the anionic species for hydrotalcites synthesised at different pH values. The results show a reduction in the concentration of arsenate and vanadate anions that are removed in extremely alkaline solutions. Hydrotalcites containing arsenate and vanadate are stable in solutions up to pH 10. Exposure of these hydrotalcites to higher pH values results in the removal of large percentages of arsenate and vanadate from the hydrotalcite interlayer.

Automatic in-bucket volume estimation for dragline operations

This paper presents a method for calculating the in-bucket payload volume on a dragline for the purpose of estimating the material’s bulk density in real-time. Knowledge of the bulk density can provide instant feedback to mine planning and scheduling to improve blasting and in turn provide a more uniform bulk density across the excavation site. Furthermore costs and emissions in dragline operation, maintenance and downstream material processing can be reduced. The main challenge is to determine an accurate position and orientation of the bucket with the constraint of real-time performance. The proposed solution uses a range bearing and tilt sensor to locate and scan the bucket between the lift and dump stages of the dragline cycle. Various scanning strategies are investigated for their benefits in this real-time application. The bucket is segmented from the scene using cluster analysis while the pose of the bucket is calculated using the iterative closest point (ICP) algorithm. Payload points are segmented from the bucket by a fixed distance neighbour clustering method to preserve boundary points and exclude low density clusters introduced by overhead chains and the spreader bar. A height grid is then used to represent the payload from which the volume can be calculated by summing over the grid cells. We show volume calculated on a scaled system with an accuracy of greater than 95 per cent.

Real-time volume estimation of a dragline payload

This paper presents a method for measuring the in-bucket payload volume on a dragline excavator for the purpose of estimating the material's bulk density in real-time. Knowledge of the payload's bulk density can provide feedback to mine planning and scheduling to improve blasting and therefore provide a more uniform bulk density across the excavation site. This allows a single optimal bucket size to be used for maximum overburden removal per dig and in turn reduce costs and emissions in dragline operation and maintenance. The proposed solution uses a range bearing laser to locate and scan full buckets between the lift and dump stages of the dragline cycle. The bucket is segmented from the scene using cluster analysis, and the pose of the bucket is calculated using the Iterative Closest Point (ICP) algorithm. Payload points are identified using a known model and subsequently converted into a height grid for volume estimation. Results from both scaled and full scale implementations show that this method can achieve an accuracy of above 95%.

Effective adsorption of sodium dodecylsulfate (SDS) by hydrocalumite (CaAl-LDH-Cl) induced by self-dissolution and re-precipitation mechanism

Hydrocalumite (CaAl-LDH-Cl) were synthesized through a rehydration method involving a freshly prepared tricalcium aluminate (C3A) with CaCl2 solution. To understand the intercalation behaviour of sodium dodecylsulfate (SDS) with CaAl-LDH-Cl, X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectrometer (ICP) and elemental analysis have been undertaken. The sorption isotherms with SDS reveal that the maximum sorption amount of SDS by CaAl-LDH-Cl could reach 3.67 mmol•g-1. The results revealed that CaAl-LDH-Cl holds a self-dissolution property, about 20-30% of which is dissolved. And the dissolved Ca2+, Al3+ ions are combined with SDS to form CaAl-SDS or Ca-SDS precipitation. It has been highlighted that the composition of resulting products is strongly dependent upon the SDS concentration. With increasing SDS concentrations, the main resulting product changes from CaAl-SDS to Ca-SDS, and the value of interlayer spacing increased to 3.27 nm.