Geochemical analysis of bulk marine sediment by Inductively Coupled Plasma–Atomic Emission Spectroscopy on board the JOIDES Resolution

Geochemical analyses on board the JOIDES Resolution have been enhanced with the addition of a Jobin-Yvon Ultrace inductively coupled plasma-atomic emission spectrometer (ICP-AES) as an upgrade from the previous X-ray fluorescence facility. During Leg 199, we sought to both challenge and utilize the capabilities of the ICP-AES in order to provide an extensive bulk-sediment geochemical database during the cruise. These near real-time analyses were then used to help characterize the recovered sedimentary sequences, calculate mass accumulation rates of the different sedimentary components, and assist with cruise and postcruise sampling requests. The general procedures, sample preparation techniques, and basic protocol for ICP-AES analyses on board ship are outlined by Murray et al. (2000) in Ocean Drilling Program Tech Note, 29. We expand on those concepts and offer suggestions for ICP-AES methodology, calibration by standard reference materials, data reduction procedures, and challenges that are specific to the analysis of bulk-sediment samples. During Leg 199, we employed an extensive bulk-sediment analytical program of ~600 samples of varying lithologies, thereby providing several opportunities for refinement of techniques. We also discuss some difficulties and challenges that were faced and suggest how to alleviate such occurrences for sedimentary chemical analyses during future legs

Silicon recovery from silicon-iron alloys by electrorefining in molten fluorides

Electrorefining of a silicon-iron material (Si-4.7at%Fe) in molten NaF-KF at 850°C has been investigated in view of recovering pure Si, using electrochemical techniques, SEM-EDS and ICP-AES analyses. The selective electrochemical dissolution of Si was evidenced. Electrorefining runs led to a maximum Si recovery of 80% of the initial Si contained in the material, in the form of a dense deposit at the cathode, with very high current efficiencies. The Si purity has been examined and no Fe was detected by ICP-AES analysis: the recovered Si purity is thus assumed to be higher than 99.99%

On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual minicolumns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III). The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 mu g l-1, respectively. The total analysis time was about 9.4 min. The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results. </p

Automated online preconcentration system for the determination of trace amounts of lead using Pb-selective resin and inductively coupled plasma-atomic emission spectrometry

An automated sequential-injection online preconcentration system was developed for the determination of lead by inductively coupled plasma - atomic emission spectrometry (ICP-AES). The preconcentration of lead was performed with a minicolumn containing a lead-selective resin, Analig Pb-01, which was installed between a selection and a switching valve. In an acidic condition ( pH 1), lead could be adsorbed on the resin. The concentrated lead was afterward eluted with 25 mu L of 0.06 M nitrilotriacetic acid (NTA) solution ( pH 9) and was subsequently transported into the nebulizer of ICP-AES for quantification. The selectivity of the resin toward lead was examined using a solution containing a mixture of 61 elements. When a sample volume of 5 mL was used, the quantitative collection of lead ( &#62;= 97%) was achieved, along with an enrichment factor of 19, a sampling frequency of 12 samples hr(-1), a detection limit of 70 pg mL(-1), and a lowest quantification limit of 100 pg mL(-1). The linear dynamic range was 0.1 to 5 ng mL(-1), and the relative standard deviation (n = 9) was 0.5% at a 5 ng mL(-1) Pb level. The detection limit of 30 pg mL(-1) and lowest quantification limit of 50 pg mL(-1) could be achieved when 10 mL of sample volume was used. The accuracy of the proposed method was validated by determining lead in the standard reference material of river water (SLRS-4), and its applicability to the determination of lead in environmental river water samples was demonstrated.</p

A robotic platform for high-throughput electrochemical analysis of chalcopyrite leaching

A novel robotic platform for combinatorial screening of ionic liquid-based Cu extraction from chalcopyrite with real-time, in situ monitoring of dissolved copper.</p

A method for determining elements for elemental signature analysis of groundwater and treated Lake Mead water

Elemental signature analysis (ESA) is a term that describes the use of the presence/absence or relative abundance of elements in samples. Several studies have been performed on the identification of these elemental signatures or fingerprints of water using inductively coupled plasma mass spectrometry (ICP-MS); Lake Mead is the primary water supply for the Las Vegas Valley. During the summer months, several large underground aquifers are used to supplement the Lake Mead water supply. Treated Lake Mead water is recharged during the low demand months to several of these aquifers. The Las Vegas Valley is surrounded by many private groundwater wells that tap smaller aquifers. Water quality varies between these aquifers. Many of the wells are exposed to controlled or uncontrolled contamination from a variety of sources, including cross-contamination between aquifers; Aquifers were identified by using the available literature and data obtained from ICP atomic emission spectrometer (ICP-AES) trace-metal analysis of water from 62 private wells in the Las Vegas Valley; Private groundwater wells in the northwest, southwest, and southeast areas of the Las Vegas Valley and water from three recharge wells were sampled and analyzed by ICP-AES for 14 elements and by ICP-MS for 58 elements; Element concentrations obtained using ICP-MS and statistical analysis were used to identify elements for use as an elemental signature of the treated Lake Mead water used for recharge of the Las Vegas Valley aquifers. Ratios of the elements identified as suitable markers for elemental signature analysis, were determined to identify potential trends in the data between areas and treated Lake Mead water; Results of the study indicate that element concentrations vary significantly between areas in the Las Vegas Valley, thus allowing them to be used as criteria to distinguish between two water sources. (Abstract shortened by UMI.)

Speciation and Mobilization of Toxic Heavy Metal Ions by Methanogenic Bacteria

HWRIC Project HWR 92-09

Structural and Optical properties of Zn(1-x)MgxO nanocrystals obtained by low temperature method

In this paper we report structural and optical properties of Magnesium substituted Zinc Oxide (Zn1-xMgxO) nanocrystals (~10-12nm) synthesized by low temperature route. In the low temperature synthesis route it was possible to reach x = 0.17 without segregation of Mg rich phase. The exact chemical composition has been established by quantitative analysis. Rietveld analysis of the XRD data confirms the Wurzite structure and a continuous compaction of the lattice (in particular the c-axis parameter) as x increases. There is an enhancement of the strain in the lattice as the Mg is substituted. The bandgap also gets enhanced as x is increased and reaches a value of 4eV for x = 0.17. From the TEM and the XRD data it has been concluded that when there is a phase segregation for x > 0.17, there is a shell of Mg(OH)2 on the ZnO. The absorption also shows persistence of the excitoinc absorption on Mg substitution. The nanocrystals show near band edge photo luminescence (PL) at room temperature which shows blue shift on Mg incorporation. In addition to the near band edge emission the ZnO and Zn1-xMg xO alloy nanocrystals show considerable emission in the blue-green region at wavelength of ~550 nm. We find that the relative intensity of the green emission increases with the Mg concentration for very low x (upto x = 0.05) and on further increase of the Mg concentration there is a sharp decrease of relative intensity of the green emission eventually leading to a complete quenching of blue emission. It is concluded that due to phase segregation (for x \geq 0.20), the formation of the shell of Mg(OH)2 on the ZnO leads to quenching of the green emission .However, this shell formation does not have much effect on the near band edge PL

Uptake and cytotoxicity of citrate-coated gold nanospheres : comparative studies on human endothelial and epithelial cells

The use of gold nanoparticles (AuNPs) for diagnostic applications and for drug and gene-delivery is currently under intensive investigation. For such applications, biocompatibility and the absence of cytotoxicity of AuNPs is essential. Although generally considered as highly biocompatible, previous in vitro studies have shown that cytotoxicity of AuNPs in certain human epithelial cells was observed. In particular, the degree of purification of AuNPs (presence of sodium citrate residues on the particles) was shown to affect the proliferation and induce cytotoxicity in these cells. To expand these studies, we have examined if the effects are related to nanoparticle size (10, 11 nm, 25 nm), to the presence of sodium citrate on the particles' surface or they are due to a varying degree of internalization of the AuNPs. Since two cell types are present in the major barriers to the outside in the human body, we have also included endothelial cells from the vasculature and blood brain barrier. Results Transmission electron microscopy demonstrates that the internalized gold nanoparticles are located within vesicles. Increased cytotoxicity was observed after exposure to AuNPs and was found to be concentration-dependent. In addition, cell viability and the proliferation of both endothelial cells decreased after exposure to gold nanoparticles, especially at high concentrations. Moreover, in contrast to the size of the particles (10 nm, 11 nm, 25 nm), the presence of sodium citrate on the nanoparticle surface appeared to enhance these effects. The effects on microvascular endothelial cells from blood vessels were slightly enhanced compared to the effects on brain-derived endothelial cells. A quantification of AuNPs within cells by ICP-AES showed that epithelial cells internalized a higher quantity of AuNPs compared to endothelial cells and that the quantity of uptake is not correlated with the amount of sodium citrate on the nanoparticles’ surface. Conclusions In conclusion the higher amount of citrate on the particle surface resulted in a higher impairment of cell viability, but did not enhance or reduce the uptake behavior in endothelial or epithelial cells. In addition, epithelial and endothelial cells exhibited different uptake behaviors for citrate-stabilized gold nanoparticles, which might be related to different interactions occurring at the nanoparticle-cell-surface interface. The different uptake in epithelial cells might explain the higher reduction of proliferation of these cells after exposure to AuNPs treatment although more detailed investigations are necessary to determine subcellular events. Nevertheless an extrinsic effect of sodium-citrate stabilized particles could not be excluded. Thus, the amount of sodium citrate should be reduced to a level on which the stability of the particles and the safety for biomedical applications are guaranteed