Isotopic Characterization of Lead in the Scottish Upland Environment

Abstract

Experimental plots have been set up at two Research Stations in upland areas of Scotland with the intention of characterising environmental samples using lead isotopic composition which varies according to the original source of the lead. Thermal ionisation mass spectrometry (TIMS) was used to measure lead isotope ratios with high precision. The ²⁰⁶Pb/²⁰⁷Pb ratios in rainwater were in the range from 1.101 to 1.153 over a period of two years at the two sites. Low ratios were associated with the very low ratios found in Britain in petrol additives during that period whereas higher ratios indicated a larger component derived from industrial sources at the Hartwood site. The ²⁰⁶Pb/²⁰⁷Pb ratios in the surface (0–2.5 cm) soil from a roadside plot were low (1.1126 and 1.1159 in 1989 and 1990, respectively) but the ratios in surface soils in plots distant from the road were considerably higher. Whereas the lead in roadside soil had a ²⁰⁶Pb/²⁰⁷Pb ratio indicating its source to be predominantly in recent petrol lead, there were significant components from other sources in the soils away from the road. The washing of grass samples resulted in no significant change in the lead isotope ratios. The lead isotope ratios measured in grass samples reflect the isotopic character of current atmospheric inputs but those in surface soil samples are an integrated record of atmospheric deposition over a long period of time. An undisturbed plot under a tree canopy had high concentrations of lead in the surface soil and low ²⁰⁶Pb/²⁰⁷Pb ratios. The ratios in fallen leaves on this plot were slightly but significantly lower than those in the grass grown on the plot. It would appear that the tree canopy is effective at scavenging lead carried in the atmosphere.     

Determination of sources of lead in tap water by inductively coupled plasma mass spectrometry (ICP-MS)

We measured the concentrations of Pb and its isotope ratios in coconmittantly obtained tap water and plumbing materials by inductively coupled mass spectrometry (ICP-MS). The Pb concentrations were determined by external calibration with²⁰⁹Bi as an internal standard. Isotope ratios were measured and mass discrimination corrected by normalization to NIST SRM-981 (common lead isotopic standard). Student/s t-test was used to compare the isotopic ratios of²⁰⁶Pb/²⁰⁷Pb,²⁰⁶Pb/²⁰⁸Pb, and²⁰⁷Pb/²⁰⁸Pb in the tap water with those in various plumbing materials. The comparisons revealed that the source of Pb in most of the tap water samples was derived from copper pipe or solder.     

Accuracy and long-term reproducibility of lead isotopic measurements by multiple-collector inductively coupled plasma mass spectrometry using an external method for correction of mass discrimination

The precision of isotopic measurements of Pb by thermal ionization mass spectrometry (TIMS) is limited by the fact that this element does not possess an invariant isotope ratio that can be used for the correction of mass fractionation by internal normalization. Multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) can overcome this limitation, because with plasma ionization, elements with overlapping mass ranges are thought to display identical mass discrimination. With respect to Pb, this can be exploited by the addition of Tl to the sample solutions; the mass discrimination factor obtained for Tl can then be used for the correction of the measured Pb isotope ratios. In this article we present the results of a detailed study that investigates the accuracy and precision of such an external correction technique for mass discrimination based upon the results of multiple analyses of a mixed standard solution of NIST SRM-981 Pb and SRM-997 Tl. Our data indicate that normalization of the Pb isotope ratios to the certified isotopic composition of SRM-997 Tl produces Pb isotopic results that are significantly lower than recently published reference values by TIMS. This systematic offset can be eliminated by renormalization of the Pb data to a different Tl isotopic composition to obtain an empirically determined mass discrimination factor for Pb that generates accurate results. It is furthermore shown that a linear law is least suited for the correction of mass discrimination, whereas a power or exponential law function provide significantly more accurate and precise results. In detail, it appears that a power law may provide the most appropriate correction procedure, because the corrected Pb isotope ratios display less residual correlations with mass discrimination compared to the exponentially corrected data. Using an exponential or power law correction our results, obtained over a period of over seven months, display a precision (2σ) of better than 60 parts per million (ppm) for ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁷Pb/²⁰⁶Pb and of better than 350 ppm for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb. This represents a significant improvement compared to conventional TIMS techniques and demonstrates the potential of MC-ICPMS for routine, high-precision measurements of Pb isotopic compositions.     

High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry

A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2 L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a ²⁰⁷Pb–²⁰⁴Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28 ± 21 pg (1sd) and typical Pb recoveries of 40–60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12 ± 4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700–1500 ppm and 1000–2000 ppm were achieved for ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor ²⁰⁴Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the ²⁰⁶Pb/²⁰⁴Pb ratios are well correlated with ²⁰⁷Pb/²⁰⁶Pb, underlining the significant improvement achieved in the measurement of the minor ²⁰⁴Pb isotope.     

Precise isotope-ratio measurements of lead species by capillary gas chromatography hyphenated to hexapole Multicollector ICP–MS

The precision and accuracy of lead isotope-ratio determination on a short transient signal has been assessed by coupling capillary gas chromatography to the Isoprobe (Micromass, UK), a single-focusing inductively coupled plasma mass spectrometer with multicollector detection. A T-piece connecting the GC transfer line to the torch enabled continuous aspiration of thallium solution for mass-bias correction. The volatile lead species PbEt₄ was derivatized from NIST isotopic certified lead standard SRM 981 and different amounts of PbEt₄ dissolved in iso-octane were injected into the GC. Chromatograms were recorded in multicollection mode by use of Faraday cups; seven isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb, ²⁰³Tl, ²⁰⁵Tl, and ²⁰²Hg) were monitored simultaneously at a transient resolution of 160 ms. PbEt₄ peaks were obtained with a half-width of 1.2 s and a base width of 3.5 s. Lead isotope ratios were calculated from the peak areas integrated for each lead isotope, giving precision in the range of 0.02 to 0.07% for ratios of high-abundant isotopes and injections of 5 and 50 pg absolute amount as lead (five replicates). Mass bias was found to be about 0.5% per mass unit and was corrected by using the continuously measured thallium signals at ²⁰³Tl and ²⁰⁵Tl. After mass-bias correction, deviation of the certified lead ratio values was found to be in the range of 0.02 to 0.15% accuracy.     

Precise determination of cadmium and lead isotopic compositions in river sediments

A method for the accurate determination of Cd and Pb isotope compositions in sediment samples is presented. Separation of Cd and Pb was designed by using an anionic exchange chromatographic procedure. Measurements of Cd isotopic compositions were carried out by multi-collector inductively coupled plasma mass spectrometer (MC-ICPMS), by using standard-sample bracketing technology for mass bias correction and Pb isotopic ratios were determined by thermal ionization mass spectrometry (TIMS). The factors that affect the accurate and precise Cd isotope compositions analysis, such as instrumental mass fractionation and isobaric interferences, were carefully evaluated and corrected. The Cd isotopic results were reported relative to an internal Cd solution and expressed as the δ^114/110Cd. Five Cd reference solutions and one Pb standard were repeatedly measured in order to assess the accuracy of the measurements. Uncertainties obtained were estimated to be lesser than 0.11‰ (2s) for the δ^114/110Cd value. Analytical uncertainties in 2s for Pb isotopic ratios were better than 0.5‰. The method has been successfully applied to the investigation of Cd and Pb isotope compositions in sediment samples collected from North River in south China.     

Isotopic fingerprint method: Assessment of the origin of rare earth compounds from the isotope ratios of lead impurities

The isotope ratios ²⁰⁷Pb:²⁰⁶Pb and ²⁰⁸Pb: ²⁰⁶Pb are measured by means of inductively coupled plasma mass spectrometry (ICP-MS) for monazite minerals and commercial rare earth compounds and are evaluated with respect to the initial composition of the minerals and the origin of the samples. The application of the isotopic fingerprint method is demonstrated.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Isotopic precision for a lead species (PbEt4) using capillary gas chromatography coupled to inductively coupled plasma-multicollector mass spectrometry

Precision and accuracy of lead isotope ratios of a volatile lead species (PbEt₄) were determined by coupling a capillary GC to a magnetic sector multicollector ICP-MS. PbEt₄ was prepared by ethylation of a certified lead isotope solution (NIST SRM 981). Coupling was achieved by a transfer line, which allowed simultaneous introduction of a thallium standard solution to correct for mass discrimination. Seven isotopes (²⁰²Hg, ²⁰³Tl, ²⁰⁴Pb, ²⁰⁵Tl, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were monitored simultaneously with a transient resolution of 50 ms. Pb isotope ratios for the PbEt₄ peaks were calculated using transient peak integrals of each isotope signal. Absolute detection limits were 20 (²⁰⁴Pb), 0.7 (²⁰⁶Pb), 1 (²⁰⁷Pb) and 0.3 pg (²⁰⁸Pb). Precision was assessed for five replicate injections of PbEt₄ in iso-octane, corresponding to a total amount of 300 pg of Pb. Precision of isotope ratios for ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb were better than 0.07% (RSD), with ratios including ²⁰⁴Pb being one order of magnitude worse. Accuracy using mass bias correction via ²⁰³Tl/²⁰⁵Tl ranged from 0.18% for ²⁰⁸Pb/²⁰⁶Pb to 0.9% for ²⁰⁸Pb/²⁰⁴Pb.     

Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes

The potential of high‐precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA‐MC‐ICP‐MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in‐house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured‐corrected Ca isotope ratio values (⁴³Ca/⁴⁴Ca and ⁴²Ca/⁴⁴Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured‐corrected Pb isotope ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)‐ICP‐MS instrument. The use of LA‐MC‐ICP‐MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of lead concentrations and isotope ratios in recent snow samples from high alpine sites with a double focusing ICP-MS

A double focusing ICP-MS, equipped with a Micro Concentric Nebulizer, has been used to determine concentrations and isotopic ratios of lead in recent snow samples (1993–1996) from high alpine sites in Switzerland. Concentrations varied between 0.02 ± 0.002 and 5.5 ± 0.15 ng/g and are slightly lower than concentrations reported by Atteia [1], by Batifol et al. [2], and by Wagenbach et al. [3] for precipitation samples from similar remote sites in Europe. Since concentrations of lead in the fresh snow samples were mainly in the lower pg/g range, the method to determine the isotopic ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb had to be optimized. They could finally be determined with an average standard error of 0.14% within 12 min and a total sample consumption of 0.8 mL. The average ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb were 0.875 and 2.117, respectively. These values are comparable to isotopic compositions of lead in aerosols collected in Western Europe [4] and are less radiogenic than predicted by Grousset et al. [5]. Our data indicate that, although lead emissions from traffic have decreased largely during the last 10 years, the contribution from this source in modern snow is still detectable and seems to be equal to the lead input from other anthropogenic sources (e.g. waste incineration, industry).     

<Superscript>206</Superscript>Pb/<Superscript>207</Superscript>Pb ratios in dry deposit samples from the Metropolitan Zone of Mexico Valley

²⁰⁶Pb/²⁰⁷Pb isotope ratios of dry deposit samples in the Metropolitan Zone of Mexico Valley (MZMV) were determined and correlated with some contemporary environmental material such as gasoline, urban dust, etc., as possibile pollution sources, the latter presenting different signatures ²⁰⁶Pb/²⁰⁷Pb ratios were determined in samples “as is” by ICP-MS, using an Elan-6100. A standard material NIST-981 was used to monitor accuracy and to correct mass fractionation. The calculated enrichment factors of lead (taking rubidium as a conservative endogenous element) show its anthropogenic origin with percentages higher than 97.65%. ²⁰⁶Pb/²⁰⁷Pb ratio in dry deposit samples ranges from 0.816 to a maximum of 1.154, following a normal distribution. Arithmetic mean was 0.9967±0.0864 lower than those of possible pollution sources: 1.1395±0.0165 for gasoline, 1.071±0.008 for industrially derived lead and, for the more radiogenic natural soil and urban dust values ranging from 1.2082±0.022 to 1.211±0.108. The possible origin of lead in gasoline used prior to 1960 is discussed.     

Evaluation of extraction/digestion techniques used to determine lead isotopic composition in forest soils

Lead isotopic studies in soils provide an efficient tool for tracing the sources of lead pollution. Five different extraction/digestion techniques (0.05 M EDTA, 0.5 M HNO₃, 2 M HNO₃, aqua regia, total digestion) were used for lead isotopic composition (²⁰⁶Pb/²⁰⁷Pb) determination in three forest soil profiles with different kinds of prevailing Pb contamination (unpolluted area, smelting area and vicinity of a motorway). The results obtained showed that all extraction/digestion methods used for the determination of ²⁰⁶Pb/²⁰⁷Pb ratios in surface horizons containing high organic matter contents gave statistically identical values (according to the Tukey test). In mineral soil horizons, differences between the individual extraction/digestion methods could be observed (the lowest ²⁰⁶Pb/²⁰⁷Pb ratios were obtained from EDTA extracts, corresponding to weakly bound anthropogenic lead, and the highest ²⁰⁶Pb/²⁰⁷Pb ratios were obtained from total digestion). The combination of total digestion and EDTA extraction (labile lead fraction) seems to be the optimal combination for ²⁰⁶Pb/²⁰⁷Pb ratio determination and optimal result interpretation.     

Source identification of Pb in aerosols at Jeju-do, Korea by using 207Pb/206Pb and 208Pb/206Pb

Aerosols and source related materials (fly ash from refuse incinerators, vehicle exhaust and soil) were collected in April, 2002 in the northern areas of Jeju-do, Korea, and the Pb isotopic ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) of the samples were measured in order to estimate the Pb sources of the aerosols. The Pb isotopic ratios of the aerosols were classified into two groups, depending on the sampling date. One group showed similar Pb isotopic ratios with those of the source related materials, suggesting that the contribution of the regional sources to the aerosols was very large. The other showed different Pb isotopic ratios from those of the regional sources and relatively high Pb isotopic ratios compared to the ratios of the first group. The results suggest that in the continental Asia there seems to be a long range transport of Pb with high ratios in desert sands, which are carried by northwest seasonal winds. This revised version was published online in July 2006 with corrections to the Cover Date.     

Laser ablation single-collector inductively coupled plasma mass spectrometry for lead isotopic analysis to investigate evolution of the Bilbilis mint

This work explores the performance of laser ablation—inductively coupled plasma mass spectrometry using different types of single-collector devices (sector field and time-of-flight instrumentation) for lead isotopic analysis of bronze coins, minted in the ancient city of Bilbilis. The aim of the study was achieving sufficient discrimination power to reveal similarities and differences for coins originating from different historical periods, and to obtain information on the possible source of the lead ores used in their production, while restricting the damage inflicted to the samples such that it is not visible to the naked eye.It was found that satisfactory results (RSD in the 0.15-0.30% range for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios) could be finally obtained, despite the noisy nature of signals generated upon ablation of the highly inhomogeneous coins, by means of a methodology based on: (a) selection of the line profiling ablation mode; (b) use of a dual pass spray chamber that permits the simultaneous introduction of a solution (containing thallium of known isotopic composition), thus resulting in a wet plasma that showed an increased robustness towards matrix effects and (c) detection using a TOF-ICPMS unit, which proved to be much better suited to deal with the transient signals obtained, while being also sufficiently sensitive to obtain good counting statistics, owing to the high lead level (average around 5%) present in the samples. Moreover, under these conditions, the simultaneous aspiration of the thallium spike permitted accurate correction for mass discrimination, such that it was not necessary to use external matrix-matched standards for calibration.     

A rapid and reliable method for Pb isotopic analysis of peat and lichens by laser ablation-quadrupole-inductively coupled plasma-mass spectrometry for biomonitoring and sample screening

An analytical protocol for rapid and reliable laser ablation-quadrupole (LA-Q)- and multi-collector (MC-) inductively coupled plasma-mass spectrometry (ICP-MS) analysis of Pb isotope ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) in peats and lichens is developed. This technique is applicable to source tracing atmospheric Pb deposition in biomonitoring studies and sample screening. Reference materials and environmental samples were dry ashed and pressed into pellets for introduction by laser ablation. No binder was used to reduce contamination. LA-MC-ICP-MS internal and external precisions were <1.1% and <0.3%, respectively, on both ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios. LA-Q-ICP-MS internal precisions on ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios were lower with values for the different sample sets <14.3% while external precisions were <2.9%. The level of external precision acquired in this study is high enough to distinguish between most modern Pb sources. LA-MC-ICP-MS measurements differed from thermal ionisation mass spectrometry (TIMS) values by 1% or less while the accuracy obtained using LA-Q-ICP-MS compared to solution MC-ICP-MS was 3.1% or better using a run bracketing (RB) mass bias correction method. Sample heterogeneity and detector switching when measuring ²⁰⁸Pb by Q-ICP-MS are identified as sources of reduced analytical performance.     

11th International Conference on Methods and Applications of Radioanalytical Chemistry (MARC XI) introduction

Nuclear terrorism has led to newer investigative methods for building national nuclear forensic libraries. The objective of this work was to resolve these signatures by applying the ICP-MS for isotope ratio (IR) analysis on uranium containing samples. Lead (Pb) isotope ratios for the studied gold mine has ²⁰⁷Pb/²⁰⁴Pb values between 13–20 and ²⁰⁶Pb/²⁰⁴Pb values ranging from 16–25, which confirm that the Carletonville gold fields are of uraninite detrital pyrite deposits. Trace elemental concentrations indicated a pyrite type of uranium deposit. Uranium in the deposit exhibits geochemical signatures of the radiogenic formations of the ore enhanced in ²⁰⁶Pb.     

不同赋存形态土壤铅同位素比值用于判别地域性差异的研究

由于各地区地质结构不同,造成了铅同位素组成具有地域特征。本研究利用电感耦合等离子体质谱测定了福建不同茶园土壤的铅同位素比值,比较了土壤全消解和残渣态两种赋存形态的铅同位素比值的差异,发现残渣态的铅的地域性特征较强,可用来作为地区土壤的判别依据。     

Isotope-ratio measurements of lead in NIST standard reference materials by multiple-collector inductively coupled plasma mass spectrometry

The capability of a second-generation Nu Instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been evaluated for precise and accurate isotope-ratio determinations of lead. Essentially the mass spectrometer is a double-focusing instrument of Nier-Johnson analyzer geometry equipped with a newly designed variable-dispersion ion optical device, enabling the measured ion beams to be focused into a fixed array of Faraday collectors and an ion-counting assembly. NIST SRM Pb 981, 982, and 983 isotopic standards were used. Addition of thallium to the lead standards and subsequent simultaneous measurement of the thallium and lead isotopes enabled correction for mass discrimination, by use of the exponential correction law and 205Tl/203Tl = 2.3875. Six measurements of SRM Pb-982 furnished the results 206Pb/204Pb = 36.7326(68), 207Pb/204Pb = 17.1543(30), 208Pb/204Pb = 36.7249(69), 207Pb/206Pb = 0.46700(1), and 208Pb/206Pb = 0.99979(2); the NIST-certified values were 36.738(37), 17.159(25), 36.744(50), 0.46707(20), and 1.00016(36), respectively. Direct isotope lead analysis in silicates can be performed without any chemical separation. NIST SRM 610 glass was dissolved and introduced into the MC-ICP-MS by means of a micro concentric nebulizer. The ratios observed were in excellent agreement with previously reported data obtained by TIMS and laser ablation MC-ICP-MS, despite the high Ca/Pb concentration ratio (200/1) and the presence of many other elements at levels comparable with that of lead. Approximately 0.2 microg lead are sufficient for isotope analysis with ratio uncertainties between 240 and 530 ppm.     

Application of routine estimation of Pb isotopic ratios by inductively coupled plasma mass spectrometry for studying the Pb origin in hair of children living in polluted areas. A pilot study

The analysis of ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb isotope ratios for environmental Pb markers (leaded gasoline, air-borne particulate matter, house window dust) and hair of children was undertaken by the routine quadrupole inductively coupled argon plasma mass spectrometry (Q-ICP-MS). Hair samples collected from 10-year-old children living in Krakow in 1995 and 35 randomly selected children, aged 11, both sexes were included in the current study. Air-borne particles were collected by PM-2.5 (an aerodynamic diameter dac <2.5 μm) and PM-10 (fraction with an dac <10 μm) samplers in the proximity of steel factories situated near Krakow. Imprecision of routine estimations was approximately 0.6–0.7% or less, and was the lowest for the ²⁰⁷Pb/²⁰⁸Pb ratio (approx. 0.2%). These conditions were sufficient to distinguish Pb from air-borne dust from that in gasoline or window dust. No differences were found between Pb in PM-2.5 and PM-10 particles. The associations of the Pb in the these environmental sources and that in hair of children were discussed. The relationships of the Pb isotope ratios and other parameters related to environmental pollution were also analyzed. The analysis of distribution of the ²⁰⁷Pb/²⁰⁸Pb ratio in the hair of children, provided some evidence of the fact that hair lead of approximately 20% of the investigated population could arise from gasoline, while the Pb from air-borne dust and remaining sources can be attributed to approximately 80% of the population.