The analytical method outlined in this feasibility study has been used to show that trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) can be detected and measured in exhaled breath condensate (EBC) samples. EBC samples and urine samples were collected from a cohort of 58 workers occupationally exposed to hexavalent chromium compounds and 22 unexposed volunteers (control group). Levels of Cr(III) and Cr(VI) were determined in EBC samples and total chromium levels were determined in urine samples. Pre and post working week samples for both EBC and urine were collected in tandem. Total chromium in urine samples was analysed by inductively coupled plasma mass spectrometry (ICP-MS). Analysis of Cr(III) and Cr(VI) in EBC samples used a hyphenated micro liquid chromatography (μLC) system coupled to an ICP-MS. Separation was achieved using an anion exchange micro-sized column. The results showed that the occupationally exposed workers had significantly higher levels of Cr(III) and Cr(VI) in their EBC samples than the control group, as well as higher levels of total chromium in their urine samples. However, for the exposed workers no significant difference was found between pre and post working week EBC samples for either Cr(III) or Cr(VI). This study has established that Cr(III) and Cr(VI) can simultaneously be detected and measured in 'real' EBC samples and will help in understanding inhalation exposure.

This study provides background levels for five arsenic species in urine, based on urinary data obtained from 95 nonoccupationally exposed volunteers based in the UK. Using a novel, sensitive, robust and reliable speciation methodology, five species of arsenic (arsenobetaine [AB], arsenite [As³⁺], arsenate [As⁵⁺], monomethylarsonic acid [MMA⁵⁺] and dimethylarsinic acid [DMA⁵⁺]) were determined in urine samples collected from 95 adults. The analytical instrumentation used to analyze the urine samples was a hyphenated micro liquid chromatography (μLC) system coupled to an inductively coupled plasma mass spectrometry (ICP-MS). Separation was achieved using an anion exchange micro-sized column. The results presented give the 95th percentile of concentrations, both uncorrected for creatinine (µg/L) and creatinine corrected (µmol/mol) in urine for the 95 volunteers. Statistical analysis was performed on the dataset using a Bayesian model to determine and quantify effects of gender, smoking and diet. The statistical results show that the consumption of fish, shellfish and red wine has a significant elevating effect on AB, DMA and MMA urinary concentrations; however, no significant effect was observed for smoking. The regression model results indicate that creatinine correction was effective for arsenic species As³⁺, MMA, DMA and AB. The background levels established here can be used as reference values to help aid interpretation of arsenic speciation results and better assess exposure.

The method described in this study is a robust and sensitive method for the simultaneous determination of trivalent and hexavalent chromium (Cr(III) and Cr(VI)) in an exhaled breath condensate (EBC) sample and drinking water proficiency testing material sample. The method uses a hyphenated micro liquid chromatography (μLC) system coupled to inductively coupled plasma mass spectrometry (ICP-MS). The optimised method incorporates a pH adjusted EDTA complexation step to stabilise Cr(VI) and Cr(III). Separation was achieved using an anion exchange micro-sized column. The limits of quantification were 0.040 μg L⁻¹ and 0.013 μg L⁻¹ for Cr(III) and Cr(VI) respectively. EBC is the non-invasive collection of condensate from cooled exhaled breath during regular tidal breathing. We propose that EBC may be a suitable alternative biological matrix to give a more comprehensive picture of exposure to Cr(VI) following an inhalation exposure. This study shows that water samples and EBC samples containing Cr(III) and Cr(VI) can be stored in the fridge (∼4 °C) for up to 6 weeks when they have been diluted 10 fold with an EDTA solution, and that EBC samples must not be frozen after collection if the integrity of Cr(VI) is to be maintained. This study has demonstrated a practical approach to collecting EBC samples from workers potentially occupationally exposed to hexavalent chromium and that the integrity of the chromium species will be maintained prior to analysis.

This study investigates the identity of two unexpected arsenic species found separately in a number of urine samples sent to the Health and Safety Executive’s Health and Safety Laboratory for arsenic speciation (arsenobetaine, AB; arsenite, As³⁺; arsenate, As⁵⁺; monomethylarsonic acid, MMA⁵⁺; and dimethylarsinic acid, DMA⁵⁺). Micro liquid chromatography coupled to inductively coupled plasma mass spectrometry (µLC-ICP-MS) and electrospray time of flight tandem mass spectrometry (ESI-QqTOF-MS/MS) were used to identify the two arsenic peaks by comparison to several characterized arsenicals: arsenocholine, AC; trimethyl arsine oxide, TMAO; dimethylarsenoacetate, DMAA; dimethylarsenoethanol, DMAE; thio-dimethylarsinate, thio-DMA; thio-dimethylarsenoacetate, thio-DMAA and thio-dimethylarsenoethanol, thio-DMAE. The results from both the ICP-MS and ESI-QqTOF-MS/MS investigations indicate that the unexpected arsenic species termed peak 1 was thio-DMA. While the unexpected arsenic species termed peak 2 has yet to be identified, this investigation shows that it was not AC, TMAO, DMAA, DMAE, thio-DMA, thio-DMAA or thio-DMAE. This study demonstrates the incidence of unexpected arsenic species in both routine and non-routine urine samples from both workers and hospital patients.

Background: To evaluate whether salivary lead can be used as a surrogate for blood lead, and if so, over what concentration range. Methodology: Three saliva devices were evaluated and one chosen to undertake this project. Paired saliva and blood samples were collected from 89 UK lead workers. Lead concentrations were determined using ICP-MS. In addition, haemoglobin and ZPP levels were determined in the blood samples and albumin was determined in the saliva samples to investigate standardisation using protein adjustments. Results: The chosen saliva device gave low but consistent recoveries for lead in saliva and the blank levels were low. The mean +/- SD blood lead level was 19.9 +/- 14 μg/dl; the mean +/- SD saliva lead level was 19.1 +/- 32.5 μg/l for 89 workers. Log10-transformed data showed correlation of r=0.69. The protein adjustments did not improve the blood-saliva correlation. Conclusions: This study has demonstrated that salivary lead measurement is feasible and correlated with blood lead levels, at least at occupational exposure levels, and may have value as a screening technique. Correlation may improve at environmental levels where exposures are generally more consistent and chronic, although this needs to be demonstrated in a genuine environmental population.