Elemental imaging of MRI contrast agents: benchmarking of LA-ICP-MS to MRI.

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been used to map the spatial distribution of magnetic resonance imaging (MRI) contrast agents (Gd-based) in histological sections in order to explore synergies with in vivo MRI. Images from respective techniques are presented for two separate studies namely (1) convection enhanced delivery of a Gd nanocomplex (developmental therapeutic) into rat brain and (2) convection enhanced delivery, with co-infusion of Magnevist (commercial Gd contrast agent) and Carboplatin (chemotherapy drug), into pig brain. The LA technique was shown to be a powerful compliment to MRI not only in offering improved sensitivity, spatial resolution and signal quantitation but also in giving added value regarding the fate of administered agents (Gd and Pt agents). Furthermore simultaneous measurement of Fe enabled assignment of an anomalous contrast enhancement region in rat brain to haemorrhage at the infusion site.

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS).

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.

Nickel skin levels in different occupations and an estimate of the threshold for reacting to a single open application of nickel in nickel-allergic subjects.

BACKGROUND: Nickel is a frequent allergen throughout the world. However, the extent to which nickel is relevant as an occupational contact allergen as opposed to being simply a reflection of jewellery exposure has been unclear. Some thresholds for cutaneous nickel exposure to induce a dermatitis reaction in nickel-allergic individuals have been defined. Over recent years it has become possible to measure accurately the quantity of nickel on the skin of individuals in a number of occupations. OBJECTIVES: To measure the quantities of nickel on the skin of the fingers in workers employed in occupations for which nickel has been suspected as a contact allergen. To define the threshold for a dermatitis reaction after the single application of a quantity of nickel to the skin of nickel-allergic individuals when read at 2days. METHODS: We employed the 'finger immersion' technique for sample collection and induction coupled plasma mass spectrometry for the nickel measurement. Nickel platers, cashiers, sales assistants, caterers, healthcare assistants, office workers, dental nurses and hairdressers were studied (five in each group except for seven cashiers). A correction was made for the fact that the finger immersion method underestimates the amount of nickel on the fingertip. The threshold for reactivity to a single application of nickel was studied by the application of various concentrations of nickel (µgcm(-2) ) [0·05 (two subjects), 0·5 (two subjects), 2·5 (three subjects), 5·0 (21 subjects), 15 (19 subjects), 30 (19 subjects) and 45 (18 subjects)] in 21 subjects overall using Finn chambers on forearm skin. The reading was made at 2days and reactions were graded using the International Contact Dermatitis Research Group classification. RESULTS: Nickel levels on the fingers of platers, cashiers, sales assistants, caterers, and even office staff, were at or above the 0·035µgcm(-2) level at which 22% of nickel-allergic subjects will react (after applying a correction). The single open application of nickel study demonstrated a dose-response relationship, with no subjects reacting to ≤ 2·5µgcm(-2) , but increasing numbers reacting at the higher concentrations as follows: six of 21 (28%) at 5·0µgcm(-2) , six of 19 (31%) at 15µgcm(-2) , seven of 19 (37%) at 30µgcm(-2) and 11 of 18 (61%) at 45µgcm(-2) . CONCLUSIONS: This study confirms that nickel levels on the skin in coin handling occupations and some others are sufficient to induce an allergic contact dermatitis in some nickel-allergic subjects. A single application of 5µgcm(-2) when read at 2days induced a dermatitis reaction in six of 21 nickel-allergic subjects.

Mapping aerial metal deposition in metropolitan areas from tree bark: a case study in Sheffield, England.

We investigated the use of metals accumulated on tree bark for mapping their deposition across metropolitan Sheffield by sampling 642 trees of three common species. Mean concentrations of metals were generally an order of magnitude greater than in samples from a remote uncontaminated site. We found trivially small differences among tree species with respect to metal concentrations on bark, and in subsequent statistical analyses did not discriminate between them. We mapped the concentrations of As, Cd and Ni by lognormal universal kriging using parameters estimated by residual maximum likelihood (REML). The concentrations of Ni and Cd were greatest close to a large steel works, their probable source, and declined markedly within 500 m of it and from there more gradually over several kilometres. Arsenic was much more evenly distributed, probably as a result of locally mined coal burned in domestic fires for many years. Tree bark seems to integrate airborne pollution over time, and our findings show that sampling and analysing it are cost-effective means of mapping and identifying sources.

The effect of hydrogen peroxide concentration on metal ion release from dental amalgam.

OBJECTIVES: The aim of this study was to investigate the effect of hydrogen peroxide (HP) concentration on metal ion release from dental amalgam. METHODS: Dental amalgam discs (n=25) were prepared by packing amalgam into cylindrical plastic moulds (10 mm diameter and 2 mm height). The discs were divided into five equal groups and each group was immersed in 20 ml of either 0%, 1%, 3%, 10% or 30% HP solution for 24 h at 37 degrees C. Samples were taken for metal ion release determination (Hg, Ag, Sn and Cu) using inductively coupled plasma mass spectrometry (ICP-MS). The surface roughness of each disc was measured before and after bleaching. RESULTS: The differences in concentration of metal ions released after treatment with 0% (control) and each of 1%, 3%, 10% and 30% HP were statistically significant (p<0.05). Metal ion release for the elements (Hg, Ag, Sn and Cu) increased with exposure to increasing concentrations of HP. Surface roughness measurements of the samples before and after treatments with HP solutions were not significantly different (p>0.05). CONCLUSIONS: Exposure to HP bleaching agent was associated with increased metal ion released from dental amalgams compared to treatment with a control solution. Ion release was in proportion to the peroxide concentration tested, with the highest concentration associated with the greatest metal ion release for all elements investigated.

Dermal nickel exposure associated with coin handling and in various occupational settings: assessment using a newly developed finger immersion method.

BACKGROUND: The role of nickel in causing hand dermatitis in some occupations has been difficult to assess due to problems with reliable measurement of the exposure to nickel in the workplace and lack of a definitive threshold for nickel allergic contact dermatitis. It is not uncommon to find nickel allergy on patch testing but it is difficult to determine whether this is of relevance to occupational nickel exposure or simply a reflection of past exposure to nickel-plated jewellery or other nonoccupational nickel exposure. OBJECTIVES: To devise a simple and reproducible method to quantify the amount of nickel on the skin and to apply the technique to measure dermal nickel exposure in various occupational settings. METHODS: A rapid and simple sampling procedure was developed for determination of nickel on the skin of workers potentially exposed to nickel by exposing individuals to nickel-releasing coins and measuring exposure by immersing the exposed thumbs and index fingers directly into graduated sample tubes containing ultrapure water and aqueous nickel extracts. The solutions were analysed by inductively coupled plasma-optical emission spectrometry after stabilization with nitric acid. The method shows advantages over alternatives such as wipe testing and tape stripping in terms of extraction efficiency, speed and ease of operation in the field. A pilot survey of dermal nickel exposure for workers in several occupational settings was conducted. RESULTS: The study suggested that a 'normal' level of nickel on the skin is <10 ng cm(-2). Coin handling induced an appreciable increase in the amount of nickel on the skin within 2 min. Experiments indicated a linear relationship between coin handling (exposure time) and measured dermal nickel levels following standardized coin handling. A pilot survey, conducted among cashiers, shop assistants, bar staff, hairdressers and workers in the nickel industry revealed dermal nickel concentrations ranging from <0.9 to 7160 ng cm(-2). The levels of nickel on the skin of cashiers, shop assistants, bar staff and hairdressers were below the threshold level for water-soluble ionic nickel for occluded exposure at which 10% of nickel-allergic subjects react (0.01% or 100 parts per million, equivalent to 530 ng cm(-2)) and the five-times higher threshold for unoccluded exposure (500 parts per million). The levels in some nickel platers and nickel refinery workers approached or exceeded these levels. However, few cases of nickel dermatitis are observed in plating and refinery facilities, perhaps due to immune tolerance, self-selection or, for refinery workers, exposure to water-insoluble rather than water-soluble nickel compounds. The elicitation threshold for water-soluble nickel compounds cannot be compared directly with dermal exposure to water-insoluble nickel compounds as the latter release a significantly lesser amount of nickel ions. CONCLUSIONS: We describe a reproducible, simple and rapid procedure for the assessment of nickel levels in occupationally exposed individuals.

Mapping airborne lead contamination near a metals smelter in Derbyshire, UK: spatial variation of Pb concentration and 'enrichment factor' for tree bark.

Samples of tree bark, collected over an area of 4 km2 near a small non-ferrous metals smelter in Derbyshire, UK, were analysed for Pb and Al by inductively coupled plasma atomic emission spectroscopy (ICP-AES). Analyte concentrations varied from 100 to over 25,000 mg kg-1 and 5 to 1000 mg kg-1, respectively. While an inverse relationship between the Pb content of bark and distance from the smelter was observed, concentrations fluctuated, indicating a variability in sample collection efficiency and problems in standardization. To overcome these effects, the Pb/Al ratio was calculated and subsequently normalized to the average Pb/Al ratio in continental crust (0.00015). On the assumption that the time-averaged concentration of airborne Al in this area is relatively constant and derived principally from wind-blown soil, the measurement represents an anthropogenic 'enrichment factor' (PbEF). PbEF varied from 10,000 to over 1,000,000, and showed a consistent reduction with distance from the smelter. Isolines of equal PbEF were subsequently defined on a map of the sampled area. Pb contamination was greatest in the vicinity of the smelter, and preferential transport along the NW-SE axis of the valley (in which the smelter is situated) was observed. The use of enrichment factors thus proved valuable in defining the relative level of airborne-derived Pb pollution.

Airborne uranium contamination--as revealed through elemental and isotopic analysis of tree bark.

A new strategy for characterisation of airborne uranium contamination based on ICP mass spectrometric analysis of tree bark is described. The uranium content of tree barks (50 samples) obtained from diverse locations (remote, rural, industrial) varied over almost four orders of magnitude (0.001-8.3 micrograms/g U) with maximum concentrations recorded in the vicinity of a nuclear fuel fabrication plant (0.70-8.3 micrograms/g U). Elevated concentrations were also observed near a coal-fired power station (0.25-0.38 microgram/g U). Isotopic analysis revealed significant deviation from the natural uranium isotope ratio (235U/238U, 0.00725) at four nuclear installations (235U/238U, 0.0055-0.0097). These findings indicate that tree bark serves as an effective biomonitor for uranium and, with isotopic analysis, discrimination between nuclear and non-nuclear emissions is realised.

The potential of elemental and isotopic analysis of tree bark for discriminating sources of airborne lead contamination in the UK.

Samples of tree bark, which accumulate airborne material, were collected from seven locations in the UK to provide an indication of the magnitude and source of lead pollution. Measurement of the Pb content and 206/207Pb stable isotope ratio by inductively coupled plasma mass spectrometry revealed significant differences between the sites. The concentration of Pb varied over almost four orders of magnitude from 7.2 to 9,600 micrograms g-1, the maximum values being found near a 'secondary' Pb smelter. The 206/207Pb isotope ratios varied from 1.108 +/- 0.002 to 1.169 +/- 0.001. The lowest Pb concentrations and highest isotope ratios were detected in bark samples from the Scilly Isles, reflecting the low-level of industry and road traffic. In contrast, samples obtained from a city centre (Sheffield) and near a motorway (M1) contained 25-46 micrograms g-1 Pb and recorded the lowest 206/207Pb ratios. Higher concentrations in the vicinity of a coal-fired power station recorded a 206/207Pb ratio of 1.14, suggesting a significant contribution from fly-ash. The relative contribution of lead from petrol (206/207Pb = 1.08) and other sources such as coal (206/207Pb = 1.18) were thus estimated using mass balance equations. Tree bark near the lead smelter recorded an intermediate 206/207Pb ratio of 1.13 reflecting the processing of material of mixed origin.

Characterisation of airborne uranium and thorium contamination in northern England through measurement of U, Th and 235U/238U in tree bark.

Samples of tree bark were collected from four locations in Northern England (a typical rural site, a coal-fired power station, a uranium (isotopic) enrichment plant and a nuclear fuel fabrication facility), to assess the nature and extent of airborne uranium and thorium contamination. The U and Th concentrations of bark were determined by inductively coupled plasma mass spectrometry after conventional nebulisation of bark digests, whilst measurement of 235U/238U isotopic ratio utilised high efficiency nebulisation. Uranium concentrations varied between and within the sites (range, 0.01-12 micrograms g-1), with maximum values recorded within 1 km of the nuclear fuel fabrication plant (Springfields). In comparison, the concentration of Th in bark was low (mean, 0.018 microgram g-1) at all sites with the exception of the area affected by coal combustion (0.2-0.8 microgram g-1). The U/Th ratio varied from 0.5 to 3900 compared with the average crustal ratio of 0.3. Low values (< 2) were recorded at the 'coal' and 'rural' sites whilst Capenhurst and Springfields showed high values indicating the relative magnitude of uranium elevation. Significant enrichment of the natural 235U/238U ratio (0.00725) was observed near the nuclear installations, in particular, the enrichment plant (Capenhurst).

Airborne emission of enriched uranium at Tokai-mura, Japan.

A new strategy for characterisation of airborne uranium contamination based on elemental/isotopic analysis of tree bark is described. Bark samples collected at Tokai-mura (Japan) were subjected to high sensitivity ICP mass spectrometric analysis; for control purposes, samples from the remote Yakushima island (Southern Japan) and central Tokyo were also analysed. The uranium contents of tree bark for Tokyo and Yakushima were of similar magnitude to that at Tokai-mura (U, 0.01-1.0 microg/g - all samples), however, there were marked differences in isotope ratio values between the sites. Whereas natural uranium isotope ratio values (235U/238U, 0.0072) were observed for Yakushima and Tokyo, non-natural and natural signatures (235U/238U, 0.00697-0.01448) were realised at Tokai-mura. These findings are consistent with the release of enriched uranium at Tokai-mura.

On-line separation and determination of bromate in drinking waters using flow injection ICP mass spectrometry.

A flow injection (FI) system with a microcolumn of anion exchanger has been used to effect rapid on-line separation of bromate and bromide prior to quantitation by ICP mass spectrometry. Basic performance studies are described including the effect of key FI parameters, i.e., sample injection volume, carrier stream flow rate, and eluent concentration on system response. The new approach permitted ultratrace determinations of bromate in drinking waters, the main benefits being low limit of detection (0.13 microg/L based on a 500-microL sample injection), rapid analysis time (10 min/sample), and good precision (2.8% at the 5 microg/L level). Accuracy was checked via an EC-sponsored interlaboratory trial.

Interlaboratory trial to determine the analytical state-of-the-art of bromate determination in drinking water.

The new European Directive for water intended for human consumption has established a regulatory level for bromate at 10 microg L(-1). This Maximum Admissible Concentration requires analytical methods with detection limits of a least 2.5 microg L(-1). A project funded by the Standards, Measurements and Testing Programme of the European Commission has enabled the improvement and/or development of methods for the determination of bromate at such concentration levels. This collaborative work was concluded by the organisation of an interlaboratory trial involving 26 European laboratories, which enabled the testing of both a draft ISO Standard method and alternative methods. This paper presents the results of this interlaboratory trial, along with results of a bromate stability study. The progress made with respect to the analytical state-of-the-art for bromate will greatly benefit the quality of measurements carried out in water quality monitoring.

Determination of trace elements including platinum in tree bark by ICP mass spectrometry.

The increasing emission of Pt-group metals from automobile catalytic converters requires the development of highly sensitive procedures for ultratrace analysis of environmental and biological systems. Tree bark, located close to motorway or industrial areas, was utilised as a substrate for collection of airborne particulate matter and samples after digestion (microwave assisted dissolution with HNO3 and HCl) were analysed by ICP mass spectrometry. The study targeted Pt and other metallic contaminants and involved analysis of some 57 tree bark samples using both quadrupole and double-focusing sector field ICP mass spectrometers. Detection limits for platinum determination in tree bark were 0.03 ng/g (DF-ICP-MS) and 0.2 ng/g (ICP-QMS). The platinum content of the bark samples ranged from 0.07-5.4 ng/g.

Rapid sequential determination of inorganic mercury and methylmercury in natural waters by flow injection-cold vapour-atomic fluorescence spectrometry.

A novel method for the rapid sequential determination of inorganic mercury and methylmercury in natural waters at the ng/l. level has been developed. Trace enrichment and separation of mercury species are achieved using a microcolumn of sulphydryl cotton which has a relatively high affinity for methylmercury. The limit of detection for methylmercury based on processing of a 0.5-ml sample volume was 6 ng/l. Application to river waters is demonstrated.