Fluorine and chlorine behavior in chlorine-rich volcanic rocks from White Island, New Zealand

Extraordinarily high chlorine-bearing volcanic bombs were erupted from White Island volcano on January 25, 1987. The concentrations of fluorine and chlorine were measured in these paralava bombs and their likely parent rocks. The paralavas contain glass with over 1.0 wt.% and up to 1.7% of chlorine. The F/Cl ratios and their relationship with other constituents show that the fluorine and chlorine in the bombs were derived from hydrothermal fluid, most likely concentrated brine in an active Crater Pool.     

Radiochemical separation methods for the determination of some toxic elements in biological reference materials

The present paper describes radiochemical separation procedures developed for the determination of the elements As, Cr, Hg, Sb and Se in biological reference materials. The methods chosen utilize ion exchange, retention on inorganic exchangers and solvent extraction techniques for the isolation of the elements of interest. These procedures are more rapid than previously used methods, such as distillation and precipitation. As to the sample dissolution, the following procedures were tested using radioactive tracers and reference materials: treatment of the materials in teflon bombs with a mixture of HNO₃+H₂SO₄ or HNO₃ only in a normal oven, and with HNO₃ in a microwave oven using specially designed digestion bombs.     

Teflon bomb decomposition of silicate materials in a microwave oven

A method is described for the decomposition of silicate materials in 20-tal Tefion- TFE bombs by using a domestic microwave oven. A domestic pressure cooker was used as a precautionary device to contain acid fumes. Total decomposition of the reference materials, marine sediment MESS-1 and granite G-2, was achieved in 60 s with a mixture of hydrofluoric acid and aqua regia. By using flame or graphite-furnace atomic absorption spectrometry, recoveries greater than 97% were obtained for aluminium, chromium and zinc and greater than 93% for silicon in the samples and for silicon in a pure quartz rod.     

Bombes calorimetriques en atmosphere fluorante

Several calorimetric bombs models using fluorine gas or other volatils fluorinated compounds are described for gas/gas, liquide/gas and liquide/liquide reactions.Five experiments and results are given.     

Partition and determination of cadmium, copper, lead and zinc in marine suspended particulate matter

A method for the determination of Cd, Cu, Pb, and Zn in the total and acetic acid (25%) soluble fraction of suspended particulate matter collected on Nuclepore membranes is described. The acetic acid leaching was carried out in a modified Millipore vacuum filtration apparatus. The total sample and the acetic insoluble fraction were decomposed in teflon bombs with HF/aqua regia. Flame or graphite furnace AAS was used for metal determinations. Sequential acetic acid extractions (3) show that on the average 76.4-92.0% of the metals are removed with the first extraction. Cadmium is potentially most easily available to biota with 90.4% of the total metal concentration located in the acetic acid soluble fraction.     

Determination of Cd and Zn by isotope dilution-thermal ionisation mass spectrometry using a sequential analysis procedure

Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) was used to examine the certified Cd and Zn content of 4 Certified Reference Materials (CRMs); 2 soils: GBW07401 and GBW07405, 1 plant CRM060 and an animal tissue SRM1566a. The CRMs were chosen to be of contrasting origin and Cd:Zn content. Three digestion procedures were compared: (i) an open tube aqua regia procedure (ii) microwave digestion using Teflon bombs and (iii) hydrofluoric acid (HF) digestion using PTFE bombs. The Cd and Zn levels obtained using ID-TIMS all fell within the published certified range for the CRMs. This was the case regardless of the digestion procedure used, although HF digestion tended to yield marginally higher levels than the other procedures and in one instance, Cd in GBW07401, was significantly different (P<0.05) from the certified range. A filament loading procedure was developed, to allow sequential analysis of Cd and Zn on the same single filament during thermal ionisation mass spectrometry analysis. The sequential analysis technique was evaluated to ensure that Zn did not fractionate during Cd analysis and there was no inter-element interference. No marked difference in the precision and accuracy of the isotope ratio measurements were obtained from sequential element analyses on the same filament when compared to individual element analyses for a range of standard solutions or for sample digests. The most efficient procedure in terms of costs and productivity for future work of this kind would be a combination of microwave digestion and sequential analysis of Cd and Zn on the same filament.     

Cadmium determination in wrapping paper

Summary The determination of cadmium in wrapping paper was carried out by the Inorganic Constituents working group in an interlaboratory comparison. Pressure digestion in PTFE bombs and high pressure ashing in quartz vessels with nitric acid were used. Eleven participants used ET AAS and only two DPASV for cadmium determination. The mean of all (13) participants was 0.059±0.027 mg/kg. Individual data are presented.     

Determination of rare earth elements in USGS rock standards by isotope dilution mass spectrometry and comparison with neutron activation and inductively coupled plasma atomic emission spectrometry

Rare earth element (REE) concentrations in United States Geological Survey (USGS) rock standards AGV-1, GSP-1, G-2 and PCC-1 were determined by isotope dilution mass spectrometry (IDMS), neutron activation and inductively coupled argon plasma atomic emission spectrometric techniques. The procedure involved acid digestion of samples in PTFE pressure bombs and group separation of REEs by an ion-exchange method. For IDMS an additional separation step using α-hydroxyisobutyric acid as an eluent was used in a cation-exchange column to split the REEs into subgroups. Comparison of the results with literature values showed that the IDMS values are the most precise and accurate. However, the precisions and the accuracies of the other techniques are acceptable.     

Major components of aerosols emitted by the Lonquimay volcano,Chile

PIXE (Particle Induced X-ray Emission) analysis has been performed on aerosols emitted by a vent opened near the crater of the volcano Lonquimay in the Southern part of Chile. Contents of eight major elements have been obtained from samples collected in the early stage of the eruption in sites within 20 kilometers from the vent. Results indicate Al, Si, Ca, and Fe as the most abundant elements in proportions comparable with chemical and X-ray diffraction studies on ash and bombs.     

Rolle und Bedeutung der Chemie im Terrorismus

Terrorism is directed by terrorist organizations and terrorist individuals with different ways of carrying out acts of violence against the democratically established order with the aim of political or religious changes. The focus is still the increasing number of attacks with explosives, which is discussed in this article more detailed. Also incendiary bombs are a simple possibility of attack. A major potential risk is seen through the spreading of toxic chemicals (chemical warfare agents, products from industrial production). This is also the case of attacks with radioactive materials by help of explosives. The misuse of chemistry is dicussed also under consideration of potential terrorist attacks by biological and nuclear weapons. Then due to the responsibility of our scientific community we can better engage ourselves in the discussion about terrorism, threats through attacks and possible avoidance strategies.     

Determination of trace elements in granites by inductively coupled plasma mass spectrometry

Proposed is a simple and reliable method for the dissolution of granite and the determination of 38 elements by inductively coupled plasma mass spectrometry. One hundred milligrams of sample are digested with 1 ml of HF and 0.5 ml of HNO(3) in screw top PTFE-lined stainless steel bombs at 190 degrees C for 12 h. Insoluble residues are dissolved using 8 ml of 40% HNO(3) (v/v) heated to 110 degrees C for 3 h. Six granite standard reference materials (GSR-1, JG-2, G-2, NIM-G, SG-3, SG-1a) were studied. Analytical calibration was accomplished using aqueous standard solutions. Rhodium was used as an internal standard to correct for matrix effects and instrument drift. We report data for: Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Cs, Ba, Hf, Ta, W, Pb, Th, U and 14 of the rare earth elements. The recoveries for most of these elements in granite ranged from 90 to 110%.     

Fabrication of novel molecular recognition membranes by physical adsorption and self-assembly for surface plasmon resonance detection of TNT

Recent concern on international terrorism and weapons of mass destruction demands the development of novel analytical methods for identification and quantification of explosive molecules. In this article, we describe the development of high-performance immunosensors for detection of 2,4,6-trinitrotoluene (TNT), a prime component of the landmines and bombs used by terrorist and military forces. The immunosensors were constructed by physical adsorption and self-assembly methods, and their binding interactions with a monoclonal anti-TNT antibody were evaluated for TNT detection using the surface plasmon resonance technique. A home-made 2,4,6-trinitrophenyl-keyhole limpet hemocyanine conjugate was used for physical adsorption. A poly(ethylene glycol) hydrazine hydrochloride thiolate was used in the construction of self-assembled monolayer surface and was immobilized with trinitrophenyl-β-alanine by the amide coupling method. The immunosensors were highly selective, regenerable, rapid, and exhibited remarkable sensitivity down to the parts-per-trillion level for TNT by the indirect competitive inhibition principle.     

Top-down fabrication of nano-scaled Bi2Se(0.3)Te(2.7) associated by electrochemical Li intercalation

A convenient top-down method for preparation of Bi(2)Se(0.3)Te(2.7) crystalline nano-particles has been demonstrated. It contains two steps: (1) lithium was intercalated between the van der Waals bonded quintuple-layers by electrochemical process inside lithium ion batteries with precisely controlled speed and amount; (2) subsequent alcohol exposure of Li(x)Bi(2)Se(0.3)Te(2.7) to make the intercalated Li atoms explode like atom-scaled bombs and exfoliate the original micro/macro scaled materials into nano-scaled single crystalline particles with sizes around 10 nm. The intercalation process does not cost external energy, and can be scaled up by amplification of the intercalation devices.     

Determination of platinum in biotic and environmental samples by graphite furnace atomic absorption spectrometry after its electrodeposition into a graphite tube packed with reticulated vitreous carbon

Summary Tobacco, beans, slag and dust samples were digested with nitric and hydrochloric acids in high-pressure PTFE bombs. Pt in the sample solutions was electrochemically deposited at –0.9 to –1.2 V in a flow system incorporating a 3-electrode flow-through cell with a graphite counter and Ag/AgCl reference electrodes. A pyrolytically coated graphite tube packed with reticulated vitreous carbon (RVC) served as the working electrode with the RVC filling axially bored to let the light beam pass through the tube during the AAS measurements. This opening was plugged with a glass rod during the preconcentration step. After the electrodeposition the tube was placed into the graphite furnace and an atomization temperature of 2700°C was applied. The geometry of the cell, flow rate for electrodeposition, deposition potential and electrolyte composition were optimized. The absolute detection limit was found to be about 0.3 ng Pt.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday On leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Slovakia     

A straightforward protocol for Hf purification by single step anion-exchange chromatography and isotopic analysis by MC-ICP-MS applied to geological reference materials and zircon standards

A straightforward one-step Hf purification protocol for geological samples using common anion-exchange chromatography and isotopic measurements by multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) is described in this paper. The sample is dissolved in concentrated HF–HNO₃ mixtures with round-bottom Savillex? Teflon screw-top capsules or high-pressure stainless steel jacketed Teflon bombs. After complete dissolution, the chemical separation between Hf and isobarically interfering elements such as Lu, Yb, and matrix elements like Ti, is performed and achieved simultaneously using a common one-step anion exchange resin (AG1-X8). The Hf yields are >90% and total procedural blanks are lower than 20 pg. This protocol not only avoids using multiple-stage ion exchange resins, but also eliminates perchloric acid to break down fluorides after HF treatment of the sample. In addition to whole rock, this protocol is also practical for zircon and baddeleyite Hf purification prior to isotopic measurement. New Hf isotopic data for zircon 91500, Temora, CN92-1 and FM0411, together with Phalaborwa baddeleyite are presented for this method. Multiple analyses of the international geological reference materials and standard zircon and baddeleyite used in U–Pb geochronology demonstrate that this method is simple, economic, efficient and reproducible.     

Determination of total chromium in terrestrial and marine samples by electrothermal atomic absorption spectrometry after pressure digestion

A comparison between two commonly used sample digestion procedures was performed for the determination of total chromium in biological matrices. Ten reference materials (terrestrial and marine matrices) have been digested in HNO₃, HNO₃ + HClO₄ and HNO₃ + HF, respectively, under pressure in quartz vessels of a high pressure asher (HPA) or in PTFE bombs with external heating. Much lower chromium values than expected were obtained in most of the reference materials by using quartz vessels with nitric acid because of adsorption of chromium at quartz surfaces. Determinations after sample digestion in PTFE vessels with external heating showed expected results, except in some reference materials which precipitated more silica. An improvement of the results was observed by using a mixture of nitric acid and perchloric acid, but only the combination of nitric acid and a small amount of HF provided the desired results in all the reference materials studied. Received: 29 January 1997 / Revised: 20 May 1997 / Accepted: 22 May 1997     

Determination of total chromium in terrestrial and marine samples by electrothermal atomic absorption spectrometry after pressure digestion

A comparison between two commonly used sample digestion procedures was performed for the determination of total chromium in biological matrices. Ten reference materials (terrestrial and marine matrices) have been digested in HNO₃, HNO₃ + HClO₄ and HNO₃ + HF, respectively, under pressure in quartz vessels of a high pressure asher (HPA) or in PTFE bombs with external heating. Much lower chromium values than expected were obtained in most of the reference materials by using quartz vessels with nitric acid because of adsorption of chromium at quartz surfaces. Determinations after sample digestion in PTFE vessels with external heating showed expected results, except in some reference materials which precipitated more silica. An improvement of the results was observed by using a mixture of nitric acid and perchloric acid, but only the combination of nitric acid and a small amount of HF provided the desired results in all the reference materials studied. Received: 29 January 1997 / Revised: 20 May 1997 / Accepted: 22 May 1997     

An overview of non-traditional nuclear threats

Summary In view of the terrorist threats to the United States, the country needs to consider new vectors and weapons related to nuclear and radiological threats against our homeland. The traditional threat vectors, missiles and bombers, have expanded to include threats arriving through the flow of commerce. The new commerce-related vectors include: sea cargo, truck cargo, rail cargo, air cargo, and passenger transport. The types of weapons have also expanded beyond nuclear warheads to include radiation dispersal devices (RDD) or &ldquo;dirty&apos; bombs. The consequences of these nuclear and radiological threats are both economic and life threatening. The defense against undesirable materials entering our borders involves extensive radiation monitoring at ports of entry. The radiation and other signatures of potential nuclear and radiological threats are examined along with potential sensors to discover undesirable items in the flow of commerce. Techniques to improve radiation detection are considered. A strategy of primary and secondary screening is proposed to rapidly clear most cargo and carefully examine suspect cargo.     

Deconvolution of three-dimensional beta-gamma coincidence spectra from xenon sampling and measurement units

Summary In view of the terrorist threats to the United States, the country needs to consider new vectors and weapons related to nuclear and radiological threats against our homeland. The traditional threat vectors, missiles and bombers, have expanded to include threats arriving through the flow of commerce. The new commerce-related vectors include: sea cargo, truck cargo, rail cargo, air cargo, and passenger transport. The types of weapons have also expanded beyond nuclear warheads to include radiation dispersal devices (RDD) or &ldquo;dirty&apos; bombs. The consequences of these nuclear and radiological threats are both economic and life threatening. The defense against undesirable materials entering our borders involves extensive radiation monitoring at ports of entry. The radiation and other signatures of potential nuclear and radiological threats are examined along with potential sensors to discover undesirable items in the flow of commerce. Techniques to improve radiation detection are considered. A strategy of primary and secondary screening is proposed to rapidly clear most cargo and carefully examine suspect cargo.     

Comparative study of pretreatment methods for the determination of metals in atmospheric aerosol by electrothermal atomic absorption spectrometry

A comparative study of pretreatment methods for the determination of 10 elements (As, Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) in atmospheric aerosols by electrothermal atomic absorption spectrometry (ETAAS) was conducted. For the digestion of the particulates collected in filters, six methods were compared using a mixture of HNO₃ and HF with or without the addition of various oxidative agents (HClO₄ or H₂O₂) or acids (HCl). The comparative study was performed using loaded cellulose filter samples, which were digested in Parr bombs and heated in a conventional oven at 170 °C for 5 h. The extraction efficiency and blanks were compared and it was proved that the digestion method using only HNO₃–HF extracted most of the metals and gave the lowest blanks. The HNO₃–HF mixture was selected for the development of an improved microwave digestion method specific for aerosol-loaded filters. The operating parameters were optimized, so that quantitative recovery of the reference materials NIST 1649a urban dust and NIST 1648 urban particulate matter was achieved. The blank of cellulose and teflon filters were also determined and compared. Teflon filters present the lowest blanks for all the elements. The obtained limits of detection for each type of filters were adequate for environmental monitoring purposes. ETAAS instrumental operation was also optimized for the compensation and the elimination of interferences. The temperature optimization was performed for each metal in every type of filter and optimized parameters are proposed for 10 elements.