Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Synthesis of nanoporous materials for preconcentration and determination of trace elements by ICP-AES ; Investigation and elimination of the memory effects of mercury, gold, silver and boron in ICP-AES

Nanoporous materials with large surface area and well-ordered pore structure have been synthesized. Thiol groups were grafted on the materials' surface to make heavy metal ion pre-concentration media. The adsorption properties ofthe materials were explored. Mercury, gold and silver can be strongly adsorbed by these materials, even in the presence of alkaline earth metal ion. Though the materials can adsorb other heavy metal ions such as lead and copper, they show differential adsorption ability when several ions are present in solution. The adsorption sequence is: mercury> == silver> copper » lead and cadmium. In the second part of this work, the memory effects of mercury, gold, silver and boron were investigated. The addition of 2% L-cysteine and 1% thiourea eliminates the problems of the three metal ions completely. The wash-out time for mercury dropped from more than 20 minutes to 18 seconds, and the wash-out time for gold decreased from more than 30 minutes to 49 seconds. The memory effect of boron can be reduced by the use of mannitol.

HG 186.9-187.0 D.E-1

Coarse grained sediment with a few fine grained matrices. Brown sediment with small to medium sized clasts. Clasts range from sub-angular to sub-rounded. Organic material present.

HG 186.9-187.0 D.E-2

Coarse grained sediment with small patches of a fine grained domain. The domain may contain organic material. Lineations and minor grain stack present throughout the section.

HG 186.9-187.0 D.E-3

Fractured and weathered grains throughout the section. Lineations and grain stacks throughout the section.

HG 186.9-187.0 D.E-4

Fine grained domain within a coarse grained domain. Lineations throughout the section. A few small patches of a clay domain seen towards the top left.

HG 186.15-186.25-1

Coarse grained section with two different fine grained domains. Towards the left hand side the domain is dark and has no inclusions of coarse grains. The right hand side has some coarser materials.

HG 186.15-186.25-2

Major grains crushing towards the top left with two fine grained domains in coarse grained sediment.

HG 186.15-186.25-3

Major grain crushing towards the centre of the section. A few lineations and grain stacks also present.

HG 186.55-186.75-1

Domain boundaries observed between the fine grained and coarse grained sediment. The coarse grained sediment contains lineations.

HG 186.55-186.75-2

Fine grained sediment, quite structure-less.

HG 186.15-186.25 Thin Section

Coarse grained sample with multiple fine grained domains. Clasts range from small to medium and sub-angular to sub-rounded. Mainly contains grain crushing (with grains crushed into one another) and short distance lineations. A few rotation structures are seen and fine grained sand domains can also be seen.

HG 186.80-186.85 Thin section

A coarse grained sample with clay rich domains. Grains range from small to medium and are sub-angular. Rotation structures can be seen around sub-rounded clasts. Lineations can be seen throughout the image, mainly short distance lineations. Small comet structures can also be seen throughout the images.

HG 186.9-187.0 D.E.

Coarse grained sediment with a few fine grained matrices. Brown sediment with small to medium sized clasts. Clasts range from sub-angular to sub-rounded. Organic material present. It contains rotation structures throughout as well as edge-to-edge grain crushing. Fine grained clay domains are present and lineations can also be seen. Minor amounts of grain stacking can also be seen.

HG 186.9-187.0 D.E. Thin Section

Coarse grained sample with grains varying from small to medium in size. They range from sub-angular to sub-rounded in shape. The sample is abundant in lineations and comet structures. Minor amounts of grain stacking are present. Inclusions of a clay rich, fine grained domain.