Particle and gas phase sampling of PCDD/Fs and dl-PCBs by activated carbon fiber and GC/MS analysis.

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), and polychlorobiphenyls (PCBs) are semi-volatile compounds and can be partitioned in the atmosphere between the gas and particulate phase, due to their physicochemical properties. For this reason, the reference standard methods for air sampling include a quartz fiber filter (QFF) for the particulate and a polyurethane foam (PUF) cartridge for the vapor phase, and it is the classical and most popular sampling method in the air. Despite the presence of the two adsorbing media, this method cannot be used for the study of the gas-particulate distribution, but only for a total quantification. This study presents the results and the performance aim to validate an activated carbon fiber (ACF) filter for the sampling of PCDD/Fs and dioxin-like PCBs (dl-PCBs) using laboratory and field tests. The specificity, precision, and accuracy of the ACF in relation to the QFF + PUF were evaluated through the isotopic dilution technique, the recovery rates, and the standard deviations. Then the ACF performance was assessed on real samples, in a naturally contaminated area, through parallel sampling with the reference method (QFF + PUF). The QA/QC was defined according to the standard methods ISO 16000-13 and -14 and EPA TO4A and 9A. Data confirmed that ACF meets the requirements for the quantification of native POPs compounds in atmospheric and indoor samples. In addition, ACF provided accuracy and precision comparable to those offered by standard reference methods using QFF + PUF, but with significant savings in terms of time and costs.

Molecular signatures of organic particulates as tracers of emission sources.

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and ≥ 24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

Indexes of tobacco smoke contribution to environmental particulates based on molecular fingerprints of alkanes.

Tobacco smoke (TS) is the source of a number of toxicants affecting the atmosphere and poses a threat to smokers and the whole community. Chemical, physical, and toxicological features of smoking products (vapors as well as mainstream, side stream, and third-hand smoke) have been investigated extensively. Special attention is paid to organic compounds (individually or in combination giving rise to peculiar molecular fingerprints), potentially able to act as "chemical signature" of TS. In this regard, the percent distribution of long-chainnormal, iso, and anteiso alkanes was ascertained as typical of TS. Nevertheless, until now no indexes have been identified as suitable for assessing the global TS contribution to environmental pollution, e.g., the TS percentage in carbonaceous aerosol and in deposited dusts, the only exception consisting in the use of nicotelline as tracer. This paper describes the results of an extensive study aimed at chemically characterizing the nonpolar lipid fraction associated to suspended particulates (PMs) and deposition dusts (DDs) collected at indoor and outdoor locations. Based on the iso, anteiso, and normal C29-C34 alkane profile in the samples as well in tobacco smoke- and no-TS-related emissions (literature data), various parameters describing the distribution of compounds were investigated. Finally, a cumulative variable was identified as the tobacco smoke impact index (TS%) suitable for estimating the TS percentage occurring in the particulate matter. The TS% rates were plotted vs. the exceedance of normal C31 alkane with respect to the average of C29 and C33 homologs, which results higher in TS than in most other emissions, revealing a link in the case of suspended particulates but not of deposited dusts. According to back analysis carried out on all particulate matter sets, it was found that traces of TS affect even remote areas, while inside the smokers' homes the contributions of TS to PM could account for up to ~61% and ~10%, respectively, in PM and DD. This confirms the need of valuing the health risk posed by TS to humans, by means of tools easy to apply in extensive investigations.

High altitude underground mining. Acclimatization and possible toxicological risks.

SUMMARY: Background. Aim of our study was to measure the first responses to hypobaric hypoxia: changes in ventilation minute, heart rate, and hemoglobin saturation which are important parameters involved in the health of mine-workers at high-altitude. Material and Methods. We develop a study of parameters mentioned on Chilean miners working in an underground mine at high altitude, between 3.070 and 3.656 masl, in an unusual shift system consisting of 12-hour daily work during 4 days, and consecutive 4 resting days. The results obtained at high altitude are contrasted with the corresponding for clerks working at 800 masl. Results. Either miners who has work less than 6 months at HA as those who are exposed at their workplace to contaminants, as diesel and others, show Hemoglobin Saturation below 90%. Heart Rate increases in response to exposure to acute and/or chronic hypoxia at high altitude. Miners during their resting period at 800 masl or less show an average heart rate lower than clerks no exposed to high altitude. Average Minute Volume of miners at high altitude, on each and every day of the shift, is higher than the mean volume of clerks at 800 masl. Conclusions. The most of studied miners present acclimatization responses at high altitude in all the studied parameters. The increase in Minute Volume implies a risky condition due to the increase of inhaled toxic inherent to the production process. It appears as an urgency to study the combined effects of hypobaric at high altitude and toxics present at the underground mine.

Validation studies on activated carbon fiber passive sampler for PCDD/Fs and PCBs in water.

The toxicity of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) is well known, and for this reason studying and monitoring these chemicals is fundamental. Activated carbon fibers (ACFs) are made of an adsorbent material widely used in the industrial field for the removal of micropollutants. The first step in this work was to perform a physico-chemical characterization of the adsorbent, focused on the analytical use of it. In particular, its specific surface area was defined around 2500 m2/g consisting in a homogeneous microporosity distribution and the characterization of ACF surface functional groups pointed out a balance between basic and acidic group. The validity of using the ACF as solid phase extraction and as passive sampler for PCDD/Fs and PCBs in water, has been evaluated by the percentage recovery (R %) of 13C12-labeled standards of PCDD/Fs and PCBs added in a known volume of water. The results were compared to the R% of Liquid-Liquid Extraction which showed a better reproducibility of the results and the proposed method satisfy completely the requirements of US EPA reference methods.

Respiratory parameters at varied altitudes in intermittent mining work.

OBJECTIVES: Workers in the mining industry in altitude are subjected to several risk factors, e.g., airborne silica and low barometric pressure. The aim of this study has been to assess the risks for this work category, evaluating single risk factors as airborne silica, altitude and work shift, and relating them with cardiovascular and ventilatory parameters. MATERIAL AND METHODS: Healthy miners employed in a mining company, Chile, working at varied altitudes, and subjected to unusual work shifts, were evaluated. Cardiovascular and respiratory parameters were investigated. Exposure to airborne silica was evaluated and compared to currently binding exposure limits. RESULTS: At varied altitudes and work shifts, alterations emerged in haemoglobin, ventilation and respiratory parameters, related to employment duration, due to compensatory mechanisms for hypoxia. Haemoglobin increased with altitude, saturation fell down under 90% in the highest mines. The multiple linear regression analysis showed a direct relationship, in the higher mine, between years of exposure to altitude and increased forced vital capacity percent (FVC%), and forced expiratory volume in 1 s (FEV1). An inverse relationship emerged between forced vital capacity (FVC) and years of exposure to airborne silica. In the workplace Mina Subterrànea (MT-3600), statistically significant inverse relationship emerged between the Tiffeneau index and body weight. CONCLUSIONS: The working conditions in the mining industry in altitude appeared to be potentially pathogenic; further investigations should be realized integrating risk assessment protocols even in consideration of their undeniable unconventionality. Int J Occup Med Environ Health 2018;31(2):129-138.

Is urinary 1-hydroxypyrene a valid biomarker for exposure to air pollution in outdoor workers? A meta-analysis.

The aim of this study was to evaluate the usefulness and specificity of urinary 1-hydroxypyrene (1-OHPu) as a biomarker of the exposure from urban pollution to polycyclic aromatic hydrocarbons (PAHs) among outdoor workers in a meta-analysis. Our meta-analysis was performed according to standard methods, and the results show that the concentrations of 1-OHPu tend to be higher in exposed workers than in unexposed workers (if we exclude two highly heterogeneous articles), in exposed non-smokers than in unexposed non-smokers and in exposed than in unexposed workers who were carriers of the CYP1A1 genotype and in those with the glutathione-S-transferase M1 (-)genotype. These genotypes enhance the effect of exposure, particularly in non-smokers. Smoking reduces the differences between exposed and unexposed subjects. In conclusion, our results suggest that the use of the 1-OHPu biomarker appears to be reliable for studying occupational exposure to PAHs from urban pollution, as long as environmental and behavioural factors are considered.

Liquid chromatography-negative ion atmospheric pressure photoionization tandem mass spectrometry for the determination of brominated flame retardants in environmental water and industrial effluents.

We describe the development of a liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometric (LC/NI-APPI/MS/MS) method for the simultaneous determination of tetrabromobisphenol A (TBBP-A) and five polybrominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) in water. A mobile phase methanol/acetone/water was used, where acetone acts also as dopant. NI-APPI produced precursor ions corresponding to [M-H](-) for TBBP-A, [M-Br+O](-), and [M-2Br+O](-) for the BDE congeners studied. Each compound was quantified operating in multiple reaction monitoring mode. Linearity was observed in the range 0.025-10 ng injected for all compounds. Coefficients of determination R(2) ranged from 0.9934 to 0.9982. BDEs were poorly retained by solid-phase extraction (SPE) from river water and sewage treatment plant effluent, thus liquid-liquid extraction (LLE) by n-hexane should be used for these samples. The recoveries of TBBP-A and PBDEs from tap water (SPE), river water and industrial wastewater (LLE) were in the range of 81-88%, 78-92%, and 43-99%, respectively, with relative standard deviations below 17%. The limits of detection, based on signal-to-noise ratio of 3, ranged from 0.004 to 0.1 ng injected, and method quantification limits were 0.2-3.3 ng L(-1) but BDE47 (20.3 ng L(-1)). Only TBBP-A was found in a treated industrial sewage at 4 ng L(-1), while BDE-99 and BDE-100 were detected on suspended solids.

Occurrence of organophosphorus flame retardant and plasticizers in three volcanic lakes of central Italy.

The concentration levels, distribution, and seasonal fluctuations of 12 organophosphorus flame retardants and plasticizers (OPs), of which some are reported to be toxic to aquatic organisms, were investigated in lakes from June 2006 to June 2007. Three volcanic lakes located in the Lazio area (Central Italy) and characterized by a different anthropical impact were selected. Analysis of lake water samples showed that in closed ecosystems (hydrogeological systems), such as small volcanic lakes, OP contamination may occur even in the absence of industries and treated or untreated waste discharges. The selected substances were found at ng/L concentrations in all lakes. In the two more anthropized lakes tributyl phosphate and tripropyl phosphate were the most abundant OPs, with peaks of respectively 784 and 951 ng/L. Maximum pollution levels were reached in October-November, and concentrations decreased to a minimum value in March-April. Chlorinated OPs showed the same trend, but their concentrations were 1 order of magnitude lower and the level decreasing was shifted with respectto alkyl OPs. On the contrary, tris(2-butoxyethyl) phosphate concentrations were quite similar among all water samples analyzed, indicating that their sources were different in nature. One of the three lakes is an important source of drinkable water, so nine wells situated in its neighborhood were also examined. No correlation between lake water and groundwater contamination could be found.

Determination of aflatoxins in hazelnuts by various sample preparation methods and liquid chromatography-tandem mass spectrometry.

A sensitive and reliable liquid chromatography-tandem mass spectrometric with electrospray ionization method for determining aflatoxins in hazelnuts has been developed. Three different extraction techniques, such as homogenization, ultrasonic extraction, and matrix solid phase dispersion have been tested and compared in terms of recovery, matrix effect, accuracy and precision. Ultrasound extraction was the most performing sample preparation method. Absolute recoveries for analytes and I.S. ranged from 93 to 101%. Accuracy and precision were calculated using matrix matched calibration, and ranged 91-102% and 2-11%, respectively. CC alpha and CC beta for aflatoxin B1 (EU limit=2 microg/kg) were 2.15 and 2.33 microg/kg, respectively. A ruggedness test performed on three other matrices demonstrated that sonication time was critical and a matrix matched calibration must be constructed for every sort of matrix.

Liquid chromatography/tandem mass spectrometry determination of organophosphorus flame retardants and plasticizers in drinking and surface waters.

A liquid chromatography/electrospray ionization tandem mass spectrometric method for analyzing organophophorus flame retardants and plasticizers in drinking and environmental waters was developed. Five alkyl phosphates, three chlorinated alkyl phosphates, two aryl phosphate and triphenylphosphine oxide were selected for this study. These compounds were extracted from water samples by a hydrophilic polymeric solid-phase extraction cartridge. Accuracy and precision were evaluated analyzing 0.5 L of water samples spiked at concentrations of 10 and 100 ng/L for drinking water and at 300 and 1000 ng/L for river water. Except for trimethyl phosphate, analyte recoveries were better than 80%, and were not dependent on the type of aqueous matrix in which they were dissolved. At the spike levels considered, within-day precision was between 3 and 12% for tap water and between 4 and 14% for river water, and estimated method quantification limits ranged from 0.2 to 3.9 ng/L. A short survey conducted by analyzing some river water samples (River Tiber) ascertained the presence of ten organophosphorus compounds at concentration levels ranging from a few nanograms per liter to 323 ng/L for tris(2-butoxyethyl) phosphate.

Evaluation of the atmospheric pressure photoionization source for the determination of benzidines and chloroanilines in water and industrial effluents by high performance liquid chromatography-tandem mass spectrometry.

A solid phase extraction-high performance liquid chromatography-tandem mass spectrometry based analytical method suitable for simultaneous analysis of benzidine, 3,3'-dichlorobenzidine, mono-, di-, and tri-chloroanilines has been developed. Normal phase separation by liquid chromatography was performed using a cyano propyl methyl silica column, and atmospheric pressure photoionization was employed as interface with mass spectrometer. The developed method was evaluated in terms of limit of detection, accuracy, and precision. The quantification limit for all the compounds ranged between 7 and 112ngL(-1), while recovery for all the compounds was higher than 94%. The method was tested by analyzing different industrial wastes, showing residual contamination by most of the analytes.

Automated on-line solid-phase extraction-liquid chromatography-electrospray tandem mass spectrometry method for the determination of ochratoxin A in wine and beer.

An automated on-line solid-phase extraction-liquid chromatography-electrospray tandem mass spectrometry (SPE-LC-ESI-MS/MS) method was developed for the determination of ochratoxin A (OTA) in alcoholic beverages. Mean recoveries for wine and beer were, respectively, 75 and 82%. Detection was achieved in negative ionization with a Q TRAP mass spectrometer operating in multiple-reaction monitoring (MRM) mode or enhanced product ion (EPI) mode, using the third quadrupole as linear ion trap. The MRM mode turned out to be more sensitive; the method allowed accurate determination of OTA in the range of 0.01-25 ng mL(-1) using external calibration. Within-day and between-day relative standard deviation percentages were <6.2 and <9.1%, respectively. In EPI mode, fragmentation spectra at the limit of quantification (0.03 ng mL(-1)) and good linearity could be obtained. Application of the method (MRM mode) to the analysis of several wine and beer samples purchased in local stores revealed OTA levels in the ranges of 0.03-1.44 ng mL(-1) for wines and 0.02-0.14 ng mL(-1) for beers.

Improved analysis of Polycyclic Aromatic Hydrocarbons in atmospheric particulate matter by HPLC-fluorescence.

An improved method is reported for determination of Polycyclic Aromatic Hydrocarbons (PAHs) in atmospheric particulate matter by HPLC-FLD. The sampling step (air volume collected during each sampling period varies in the range 10/13 m3) is carried out by means of a medium-flow pumping system (15 L min(-1)) on a glass fiber filter (47 mm diameter) placed as collecting substrate in the sampling-cassette. After sampling, the filter is extracted with 3 ml of acetonitrile in an ultrasonic bath for 30 minutes. As for extraction of PAHs from loaded filters a new criterion here is proposed to evaluate the recovery efficiency of PAHs from the sample, instead of the usual spiking method of standard solution. The extract was then reduced to 100 microL and analysed by HPLC-FLD on line spectra system. The method is rapid (about one hour for extraction and analysis), reproducible and enables to measure with good accuracy the atmospheric concentration of benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(ghi)perylene (BghiP), carcinogenic compounds always present in the urban airborne particulate matter. So it is useful for routine pollution studies and suitable to substitute the official method used now. Monthly average air concentrations, for the four PAHs above mentioned, measured in Rome from July 2001 to June 2002, are reported.

Sample preparation for determination of macrocyclic lactone mycotoxins in fish tissue, based on on-line matrix solid-phase dispersion and solid-phase extraction cleanup followed by liquid chromatography/tandem mass spectrometry.

A new method based on matrix solid-phase dispersion (MSPD) on-line with a solid-phase extraction (SPE) cleanup process followed by liquid chromatography with tandem mass spectrometry (LC/MS/MS) is presented for the determination of 3 macrocyclic lactone mycotoxins in fish tissues: zearalenone, alpha-zearalenol, and beta-zearalenol. The sample was prepared in a device that used a reversed-phase material (C18) or a normal-phase material (neutral alumina) as a matrix dispersing agent, and a graphitized carbon black cartridge was used for sequential cleanup by SPE. LC/MS/MS was used for selective determination. Isocratic elution with acetonitrile-methanol-water was used for LC separation; for MS/MS, 2 types of interfaces (a pneumatically assisted electrospray ionization interface or an atmospheric pressure chemical ionization interface) were evaluated and compared in terms of the intensity of the total ion current produced by each analyte. The use of highly selective MSPD on-line with SPE for sample preparation before analysis allowed the removal of interfering matrix compounds present in tissue extracts that would otherwise cause severe ionization suppression of zearalenone and its metabolites during the ionization process. Average recoveries at 100 ng/g were between 83 and 103% with C18 and > or = 67% with neutral alumina; the relative standard deviations were < 11% with C18 and < 18% with alumina. The limits of detection ranged from 0.1 to 1.0 ng/g. Sample preparation is simple to perform, no special technical equipment is required, and solvent volumes are minimal.

An update of a mortality study of talc miners and millers in Italy.

BACKGROUND: While talc containing asbestiform fibers is considered a human carcinogen, only limited animal and human data are available on non-asbestiform talc. To provide further evaluation on the issue, we updated the analysis of an Italian cohort of talc miners and millers in Val Chisone; talc found here is free from asbestiform fibers. METHODS: The cohort was comprised of 1,795 men who had worked for at least 1 year in the mine and/or in the factory between 1946 and 1995. Vital status and death certificates were obtained from registration offices in the municipality of death or of birth. Employment, termination of employment, and detailed job history were obtained from personnel records at the plant. RESULTS: No excess was found for total cancer mortality, nor mortality for lung cancer. No case of mesothelioma was reported. There was a significant excess mortality from non-neoplastic respiratory diseases (SMR 228.2, 95% CI 190.2-271.5). Mortality excess for non-neoplastic respiratory diseases was mainly due to silicosis. CONCLUSIONS: This study provides additional support for an association between talc in mining and milling and non-neoplastic respiratory diseases, while showing no significant excess risk for lung cancer and mesothelioma. The results also provide additional information of interest to evaluate the potential association between silica and lung cancer.