Human exposure to thallium through tap water: A study from Valdicastello Carducci and Pietrasanta (northern Tuscany, Italy)

A geological study evidenced the presence of thallium (Tl) at concentrations of concern in groundwaters near Valdicastello Carducci (Tuscany, Italy). The source of contamination has been identified in the Tl-bearing pyrite ores occurring in the abandoned mining sites of the area. The strongly acidic internal waters flowing in the min- ing tunnels can reach exceptional Tl concentrations, up to 9000 μg/L. In September 2014 Tl contamination was also found in the tap water distributed in the same area (from 2 to 10 μg/L). On October 3, 2014 the local authorities imposed a Do Not Drink order to the population. Here we report the results of the exposure study carried out from October 2014 to October 2015, and aimed at quantifying Tl levels in 150 urine and 318 hair samples from the population of Valdicastello Carducci and Pietrasanta. Thallium was quantified by inductively coupled plasma — mass spectrometry (ICP-MS). Urine and hair were chosen as model matrices indicative of different time periods of exposure (short-term and long- term, respectively). Thallium values found in biological samples were correlated with Tl concentrations found in tap water in the living area of each citizen, and with his/her habits. Thallium concentration range found in hair and urine was 1–498 ng/g (values in unexposed subjects 0.1–6 ng/g) and 0.046–5.44 μg/L (reference value for the European population 0.006 μg/L), respectively. Results show that Tl levels in biological samples were significantly associat- ed with residency in zones containing elevated water Tl levels. The kinetics of decay of Tl concentration in urine samples was also investigated. At the best of our knowledge, this is the first study on human contamination by Tl through water involving such a high number of samples

Influence of environmental and anthropogenic parameters on thallium oxidation state in natural waters

The abandoned mining area of Valdicastello Carducci (Tuscany, Italy) is characterized by the massive presence of thallium in the acid mine drainages and in the valley stream crossing the region. We previously found that Tl(III), generally considered the less stable oxidation state of thallium, is present both in the stream and in tap water distributed in the area, whereas acid mine drainages only contain Tl(I). These findings posed some concern related to the reactivity and dispersion of this toxic element in the environment. Since the valence state of thallium determines its toxicity, distribution and mobility, the study of thallium redox speciation appears crucial to understand its environmental behaviour. In this work, water samples collected from the mine drainages and the contaminated stream were adopted as model to study the distribution of aqueous Tl(I)/Tl(III) as a function of light exposure and solution properties and composition. The influence of three light sources and organic acids was evaluated. Thallium speciation was also assessed in tap water after treatment with common oxidizing agents, and in the rust crust collected from the public waterworks

The Removal of β2-Microglobulin in Spent Dialysate Cannot Be Monitored by Spectrophotometric Analysis

We synthetically present here unpublished results on β2M removal during HD treatments with dialysis membranes having different flux and adsorption capacities to clarify if the spectrophotometric analysis of spent dialysate may allow the possibility to monitor the removal of β2M during HD. These results were obtained from the analyses of serum and spent dialysate samples of the 22 MHD patients (16 men, 6 women). Serum and spent dialysate concentrations of β2M were measured with an immunonephelometric method (Siemens, BNAII) and compared with absorbance and fluorescence values. We conclude that the removal of β2M cannot be evaluated by spectrophotometric analysis of spent dialysate

Influence of sampling on the determination of warfarin and warfarin alcohols in oral fluid

Background and Objective: The determination of warfarin, RS/SR- and RR/SSwarfarin alcohols in oral fluid may offer additional information to the INR assay. This study aimed to establish an optimized sampling technique providing the best correlation between the oral fluid and the unbound plasma concentrations of these compounds. Materials and Methods: Samples of non-stimulated and stimulated oral fluid, and blood were collected from 14 patients undergoing warfarin therapy. After acidification, analytes were extracted with a dichloromethane/hexane mixture and determined by HPLC with fluorescence detection. Plasma samples were also ultrafiltered for the determination of the unbound fraction. The chromatographic separation was carried out in isocratic conditions with a phosphate buffer/methanol mobile phase on a C-18 reversed-phase column. The absence of interfering compounds was verified by HPLC-ESI-Q-TOF. Results: Stimulation generally increased the oral fluid pH to values close to blood pH in about 6 minutes. The concentration of warfarin and RS/SR-warfarin alcohols in oral fluid followed the same trend, whereas the concentration of RR/SS-warfarin alcohols was not affected. Six minute stimulation with chewing gum followed by collection with a polyester swab was the best sampling procedure, with a good repeatability (RSD 〈10%) and relatively low inter-subject variability (RSD =30%) of the oral fluid to plasma ratio. This procedure provided strong correlations between the measured oral fluid and unbound plasma concentration of warfarin (r = 0.92, p 〈0.001) and RS/SR-warfarin alcohols (r =5 0.84, p 〈0.001), as well as between stimulated oral fluid and total plasma concentration of warfarin (r = 0.78, p 〈0.001) and RS/SR-warfarin alcohols (r = 0.81, p 〈0.001). Conclusion: The very good correlation between oral fluid and unbound plasma concentration of warfarin and RS/SR-warfarin alcohols suggests that oral fluid analysis could provide clinically useful information for the monitoring of anticoagulant therapy, complentary to the INR assay

Determination of sevoflurane and isopropyl alcohol in exhaled breath by thermal desorption gas chromatography-mass spectrometry for exposure assessment of hospital staff

Volatile anaesthetics and disinfection chemicals pose ubiquitous inhalation and dermal exposure risks in hospital and clinic environments. This work demonstrates specific non-invasive breath biomonitoring methodology for assessing staff exposures to sevoflurane (SEV) anaesthetic, documenting its metabolite hexafluoroisopropanol (HFIP) and measuring exposures to isopropanol (IPA) dermal disinfection fluid. Methods are based on breath sample collection in Nalophan bags, followed by an aliquot transfer to adsorption tube, and subsequent analysis by thermal desorption gas chromatography-mass spectrometry (TD-GC-MS). Ambient levels of IPA were also monitored. These methods could be generalized to other common volatile chemicals found in medical environments. Calibration curves were linear (r2=0.999) in the investigated ranges: 0.01-1000ppbv for SEV, 0.02-1700ppbv for IPA, and 0.001-0.1ppbv for HFIP. The instrumental detection limit was 10pptv for IPA and 5pptv for SEV, both estimated by extracted ion-TIC chromatograms, whereas the HFIP minimum detectable concentration was 0.5pptv as estimated in SIM acquisition mode. The methods were applied to hospital staff working in operating rooms and clinics for blood draws. SEV and HFIP were present in all subjects at concentrations in the range of 0.7-18, and 0.002-0.024ppbv for SEV and HFIP respectively. Correlation between IPA ambient air and breath concentration confirmed the inhalation pathway of exposure (r=0.95, p<0.001) and breath-borne IPA was measured as high as 1500ppbv. The methodology is easy to implement and valuable for screening exposures to common hospital chemicals. Although the overall exposures documented were generally below levels of health concern in this limited study, outliers were observed that indicate potential for acute exposures

Comparison of sampling bags for the analysis of volatile organic compounds in breath

Nalophan, Tedlar and Cali-5-Bond polymeric bags were compared to determine the most suitable type for breath sampling and storage when volatile organic compounds are to be determined. Analyses were performed by thermal desorption gas chromatography mass spectrometry. For each bag, the release of contaminants and the chemical stability of a gaseous standard mixture containing eighteen organic compounds, as well as the CO2 partial pressure were assessed. The selected compounds were representative of breath constituents and belonged to different chemical classes (i.e. hydrocarbons, ketones, aldehydes, aromatics, sulfurs and esters). In the case of Nalophan, the influence of the surface-to-volume ratio, related to the bag's filling degree, on the chemical stability was also evaluated. Nalophan bags were found to be the most suitable in terms of contaminants released during storage (only 2-methyl-1,3-dioxalane), good sample stability (up to 24 h for both dry and humid samples), and very limited costs (about 1 for a 20 liter bag). The (film) surface-to-(sample) volume ratio was found to be an important factor affecting the stability of selected compounds, and therefore we recommended to fill the bag completely

Determination of volatile organic compounds in exhaled breath of heart failure patients by needle trap micro-extraction coupled with gas chromatography-tandem mass spectrometry

The analytical performances of needle trap micro-extraction (NTME) coupled with gas chromatography tandem mass spectrometry were evaluated by analyzing a mixture of twenty-two representative breath VOCs belonging to different chemical classes (i.e. hydrocarbons, ketones, aldehydes, aromatics and sulfurs). NTME is an emerging technique that guarantees detection limits in pptv range by pre-concentrating low volumes of sample, and it is particularly suitable for breath analysis. For most VOCs, detection limits between 20 and 500 pptv were obtained by pre-concentrating 25 mL of a humidified standard gas mixture at a flow rate of 15 mL/min. For all compounds, inter- and intra-day precisions were always below 15%, confirming the reliability of the method. The procedure was successfully applied to the analysis of exhaled breath samples collected from forty heart failure patients during their stay in the University Hospital of Pisa. The majority of patients (about 80%) showed a significant decrease of breath acetone levels (a factor of 3 or higher) at discharge compared to admission (acute phase) in correspondence to the improved clinical conditions during hospitalization, thus making this compound eligible as a biomarker of heart failure exacerbation

Measurement of Warfarin in the Oral Fluid of Patients Undergoing Anticoagulant Oral Therapy

BACKGROUND: Patients on warfarin therapy undergo invasive and expensive checks for the coagulability of their blood. No information on coagulation levels is currently available between two controls. METHODOLOGY: A method was developed to determine warfarin in oral fluid by HPLC and fluorimetric detection. The chromatographic separation was performed at room temperature on a C-18 reversed-phase column, 65% PBS and 35% methanol mobile phase, flow rate 0.7 mL/min, injection volume 25 µL, excitation wavelength 310 nm, emission wavelength 400 nm. FINDINGS: The method was free from interference and matrix effect, linear in the range 0.2-100 ng/mL, with a detection limit of 0.2 ng/mL. Its coefficient of variation was <3% for intra-day measurements and <5% for inter-day measurements. The average concentration of warfarin in the oral fluid of 50 patients was 2.5±1.6 ng/mL (range 0.8-7.6 ng/mL). Dosage was not correlated to INR (r = -0.03, p = 0.85) but positively correlated to warfarin concentration in the oral fluid (r = 0.39, p = 0.006). The correlation between warfarin concentration and pH in the oral fluid (r = 0.37, p = 0.009) confirmed the importance of pH in regulating the drug transfer from blood. A correlation between warfarin concentration in the oral fluid and INR was only found in samples with pH values ≥7.2 (r = 0.84, p = 0.004). CONCLUSIONS: Warfarin diffuses from blood to oral fluid. The method allows to measure its concentration in this matrix and to analyze correlations with INR and other parameters

Impact of Protein Concentration on the Determination of Thiolic Groups of Ovalbumin: A Size Exclusion Chromatography-Chemical Vapor Generation-Atomic Fluorescence Spectrometry Study via Mercury Labeling

We optimized a hyphenated system based on size exclusion chromatography coupled to a microwave/UV mercury oxidation system and an atomic fluorescence detector (SEC–CVG–AFS) for the online oxidation of free and protein-complexed p-hydroxymercuribenzoic acid (pHMB) without the employment of chemical oxidizing agents. This system has been applied to the study of labeling of thiolic groups of native ovalbumin (OVA) as a function of protein concentration. We found that the protein concentration strongly affects the species distribution of OVA, the number of thiolic groups titrated in each species, and thus, the accuracy in the determination of the total number of thiolic groups. The amount of titrated sulfhydryl groups in the protein concentration range investigated (5–100 μmol L–1) varied from 2.40 ± 0.01 to 1.85 ± 0.05 for the monomeric form of OVA and from 4.63 ± 0.01 to 5.63 ± 0.05 for the total OVA, which represents more than four theoretical number of reduced Cys. This information is important from the analytical point of view because it suggests that, unless to operate with diluted concentration of protein, the number of titrated thiolic groups results from both the aspecific interaction of the probe with aggregates species and to the specific bond of the probe with the accessible −SH groups

Effect of altitude and distance from the sea on fractionation processes of Persistent Organic Pollutants (POPs) associated to atmospheric aerosol from Ross Sea to Dome C, Antarctica

This paper deals with both the transport processes of several classes of organic pollutants in a large area of Victoria Land and Ross Sea (Antarctica) and the role played by marine aerosol which involves the exchange process between the sea surface and the atmosphere. The mechanisms of transfer process from the seawater to the atmosphere and aerosol of three major classes of pollutants (Polycyclic Aromatic Hydrocarbons, PAHs, Polychlorobiphenyls, PCBs, and Organochloride Pesticides, OCPs) were investigated in samples of snow and firn collected during several Italian Expeditions from 1996 to 2014 in a large area of Antarctica. The samples were gathered at different distances from the sea (Rennick Glacier and traverse GV7-Talos Dome-Dome C), at different altitudes (Mt. Melbourne) and at different depths (Evans Nevé). The strategic sampling spots allowed the study of the mechanisms involved in the transfer process that occurs from the seawater to the aerosol and the atmosphere and the consequent diffusion of these pollutants in the environment. Organic compounds linked to sea aerosol showed a fractionation depending on the altitude and on the distance from the sea in agreement with their volatility and affinity to aerosol particles. The results highlighted a decreasing trend of the concentration with the increase of the altitude. This behavior is significant for samples coming from the winter storm, when the very heavy sea produces a high quantity of marine aerosol, where the amount of PCBs, OCPs and PAHs reaches respectively a decrease of 50, 70 and 40% compared to the value found at the lowest altitude. A significant decrease of the concentration of the heavier PAHs and of DDT with the altitude was common in all the samples collected in Mount Melbourne, showing a differentiation in the transportation, and hence in the diffusion, of the analytes on the base of their molecular weight. The dependence of the pollutants on the distance from the sea showed an increase of the contaminant in proximity to the Ross Sea. The samples collected on Evans Nevé and GV7 showed a content of PAHs and DDT 1.5 and 3 times higher on superficial snow than the values found at greater depth. This seems to be connected to a significant flow increase of these pollutants in Antarctica in the last decades