Ciaran Geraghty

Measurements of lead in human tibiae. A comparison between K-shell x-ray fluorescence and electrothermal atomic absorption spectrometry

The aim of this study was to validate 109Cd-based K-shell x-ray fluorescence measurements against atomic absorption spectrometry (AAS) measurements of core and surface tibia lead. The lead content of nine adult human cadaver tibiae was measured using 109Cd-based K-shell x-ray fluorescence (XRF) spectrometry and the results compared to measurements obtained using electrothermal atomization atomic absorption spectrometry following acid digestion. Each tibia was divided into nine cross-sectional segments, which were further separated into tibia core and surface samples for the AAS analytical measurements. Proximal-distal variability in tibia lead concentration as determined by AAS was previously described for both surface and core segments and was found to decrease towards the ends of the tibia, in contrast to XRF in which lead was found to increase towards the tibia ends. The effect of this contrasting behaviour on the agreement between XRF and AAS measurements was examined. Lead concentrations determined by AAS ranged from 3 to 19 microg of lead per gram of dry weight bone (microg g(-1)) for tibia core and from 5 to 32 microg g(-1) for tibia surface. Lead concentrations determined by XRF ranged from 2 to 35 microg g(-1) dry weight. No statistically significant difference was found between mean XRF-measured concentrations and mean surface lead concentrations measured by AAS, but XRF significantly overestimated tibia core lead concentrations by between 5 and 8 microg g(-1).

An assessment of contemporary atomic spectroscopic techniques for the determination of lead in blood and urine matrices

Abstract The preparation and validation of a number of clinical reference materials for the determination of lead in blood and urine is described. Four candidate blood lead reference materials (Lots, 047–050), and four candidate urine lead reference materials (Lots, 034, 035, 037 and 038), containing physiologically-bound lead at clinically relevant concentrations, were circulated to up to 21 selected laboratories specializing in this analysis. Results from two interlaboratory studies were used to establish certified values and uncertainty estimates for these reference materials. These data also provided an assessment of current laboratory techniques for the measurement of lead in blood and urine. For the blood lead measurements, four laboratories used electrothermal atomization AAS, three used anodic stripping voltammetry and one used both ETAAS and ICP-MS. For the urine lead measurements, 11 laboratories used ETAAS (most with Zeeman background correction) and 10 used ICP-MS. Certified blood lead concentrations, ±S.D., ranged from 5.9±0.4 μg/dl (0.28±0.02 μmol/l) to 76.0±2.2 μg/dl (3.67±0.11 μmol/l) and urine lead concentrations ranged from 98±5 μg/l (0.47±0.02 μmol/l) to 641±36 μg/l (3.09±0.17 μmol/l). The highest concentration blood lead material was subjected to multiple analyses using ETAAS over an extended time period. The data indicate that more stringent internal quality control practices are necessary to improve long-term precision. While the certification of blood lead materials was accomplished in a manner consistent with established practices, the urine lead materials proved more troublesome, particularly at concentrations above 600 μg/l (2.90 μmol/l).

L-shell x-ray fluorescence measurements of lead in bone: accuracy and precision

This study aimed to quantify the accuracy and precision of a method for in vivo measurements of lead in bone using L-shell x-ray fluorescence (LXRF), the former via comparison with independent measurements of lead in bone obtained using electrothermal atomic absorption spectrometry (AAS) following acid digestion. Using LXRF. the lead content of adult human cadaver tibiae was measured, both as intact legs and as dissected tibiae with overlying tissue removed, the latter at several proximal-distal locations. After LXRF, each tibia was divided into nine cross-sectional segments, which were further separated into tibia core and surface samples for AAS measurement. The proximal-distal variability of AAS-measured core and surface tibia lead concentrations has been described elsewhere (the lead concentration was found to decrease towards both ends of the tibia). The subjects of this paper are the proximal-distal variability of the LXRF-measured lead concentrations, the measurement uncertainty and the statistical agreement between LXRF and AAS. There was no clear proximal-distal variability in the LXRF-measured concentrations; the degree of variability in actual tibia lead concentrations is far less than the LXRF measurement uncertainty. Measurement uncertainty was dominated by counting statistics and exceeded the estimate of lead concentration in most cases. The agreement between LXRF and AAS was reasonably good for bare bone measurements but poor for intact leg measurements. The variability of the LXRF measurements was large enough, for both bare bone and intact leg measurements, to yield grave concerns about the analytical use of the technique in vivo.

Are songbirds at risk from lead at small arms ranges? An application of the spatially explicit exposure model.

Use of small arms during training is an important activity associated with the development and proficiency of soldiers. These weapons traditionally have used copper-jacketed lead projectiles; the copper facilitates the oxidation of the metallic lead resulting in more mobile oxides and carbonates. Consequently, many ranges at installations have high soil concentrations of lead. Many of these ranges are no longer used and have become habitat for wildlife. To address the potential for adverse effects from lead exposure in songbirds, we compared the outputs of traditional deterministic exposure models with a spatial model and compared the results of both with blood-lead levels from songbird species at two small arms range complexes. An integrative data collection procedure was used and incorporated into the spatially explicit exposure model (SEEM) for two small arms range sites. Site-specific data were used to refine model input parameters. These data included lead soil concentrations, analysis of lead concentrations in nestling food items, acid-insoluble ash content of feces (to estimate soil ingestion), location and mapping of singing males, and nest site location and characteristics. Territorial males also were spot-mapped to determine likelihood of breeding activity. Modeled estimates of risk were compared with blood and feather lead levels of adults and nestlings. Overall, edge species had higher blood-lead concentrations; however, most had concentrations below subclinical effect levels. Conventional deterministic methods produced risk estimates exceeding 10-fold the highest SEEM estimates. The spatially explicit exposure model provided good agreement with field observations and therefore produced more accurate risk estimates. The present study provides support for the application of spatial methods over conventional deterministic methods.

Comparison of clinical methods with isotope dilution inductively coupled plasma mass spectrometry for the new standard reference material 955c lead in caprine blood

The National Institute of Standards and Technology (NIST) has developed Standard Reference Material (SRM) 955c, a new caprine-based, four-level blood standard with certified blood lead levels (BLLs) ranging from 0.4 µg/dL (0.02 µmol/L) Pb to 45 µg/dL (2.2 µmol/L) Pb. Certified values are based on ID-ICP-MS. Strict control and accurate measurement of the procedure blank were necessary to minimize uncertainty for the lowest level (Level 1) and obtain a relative expanded uncertainty (k = 2) of 2.6%. Level 1 is intended to represent a baseline BLL and provides a means to define detection levels and validate methods developed to measure lead at background environmental levels in blood. Level 2 is near 10 µg/dL (0.48 µmol/L), the current threshold defined by the U.S. Centers for Disease Control and Prevention (CDC) for public health action and clinical follow up. The standard has been developed in collaboration with the Wadsworth Center, New York State Department of Health, which provided measurements based on GFAAS and ICP-MS. Results from these clinical methods are statistically compared to the Isotope Dilution (ID) values. The Level 1 SRM 955c standard is below the detection limit of the GFAAS method, but comparison of Level 1 results for the ICP-MS method with the ID-ICP-MS values shows no evidence of statistically significant disagreement, suggesting that the ICP-MS method appears capable of measuring BLLs at background concentrations. Comparison of both GFAAS and ICP-MS results with the ID ICP-MS values for the Level 2 through Level 4 SRM 955c standards similarly shows no statistically significant disagreement between methods at these elevated blood Pb levels. In addition to the SRM 955c data, long-term method performance data are presented for SRM 955b Lead in Bovine Blood and for SRM 966 Toxic Elements in Bovine Blood. The clinical methods performed well within CLIA guidelines for these materials; however, a small negative bias for the ICP-MS value relative to the certified value for SRM 966 requires further investigation.

Development of candidate reference materials for the measurement of lead in bone

The production of modest quantities of candidate bone lead (Pb) reference materials is described, and an optimized production procedure is presented. The reference materials were developed to enable an assessment of the interlaboratory agreement of laboratories measuring Pb in bone; method validation; and for calibration of solid sampling techniques such as laser ablation ICP-MS. Long bones obtained from Pb-dosed and undosed animals were selected to produce four different pools of a candidate powdered bone reference material. The Pb concentrations of these pools reflect both environmental and occupational exposure levels in humans. The animal bones were harvested post mortem, cleaned, defatted, and broken into pieces using the brittle fracture technique at liquid nitrogen temperature. The bone pieces were then ground in a knife mill to produce fragments of 2-mm size. These were further ground in an ultra-centrifugal mill, resulting in finely powdered bone material that was homogenized and then sampled-scooped into vials. Testing for contamination and homogeneity was performed via instrumental methods of analysis.

Regional distribution and accumulation of lead in caprine brain tissues following a long-term oral dosing regimen.

It is well known that the brain is a key target organ for lead (Pb)-induced toxicity, with exposure potentially resulting in numerous adverse neurological effects. However, information on the distribution and accumulation of Pb within different brain regions is scarce. In this study, Pb uptake and accumulation were characterized in brain and related tissues obtained from a convenience sample of goats dosed with Pb. Tissues were harvested postmortem from 10 animals (9 dosed and 1 undosed) that are used to produce blood Pb pools for the New York State Department of Health’s Proficiency Testing program. Whole brains were subdivided into 14 distinct anatomical regions to explore interregional differences. Related tissues included the olfactory epithelium and spinal cord. Where sufficient tissue mass permitted, further subdivision into smaller sections was carried out to examine intraregional Pb variability. Determination of Pb content in these tissues was accomplished using inductively coupled plasma mass spectrometry (ICP-MS), with accuracy assessed using reference materials certified for Pb. Lead content (dry weight) varied from <10 ng/g, that is, below the method detection limit, to as much as 4.45 × 104 ng/g Pb. Olfactory epithelium Pb content was several orders of magnitude greater than found in other regions analyzed. Enrichment of Pb was also observed in the olfactory bulb and choroid plexus. Data for each region analyzed were pooled from all goats to identify regions with the greatest propensity for Pb accumulation. Data related to Pb content were also assessed individually within each goat and significant differences in Pb content between regions were determined.