Molecular Alterations and Severe Abnormalities in Spermatozoa of Young Men Living in the "Valley of Sacco River" (Latium, Italy): A Preliminary Study.

The Valley of Sacco River (VSR) (Latium, Italy) is an area with large-scale industrial chemical production that has led over time to significant contamination of soil and groundwater with various industrial pollutants, such as organic pesticides, dioxins, organic solvents, heavy metals, and particularly, volatile organic compounds (VOCs). In the present study, we investigated the potential impact of VOCs on the spermatozoa of healthy young males living in the VSR, given the prevalent presence of several VOCs in the semen of these individuals. To accomplish this, spermiograms were conducted followed by molecular analyses to assess the content of sperm nuclear basic proteins (SNBPs) in addition to the protamine-histone ratio and DNA binding of these proteins. We found drastic alterations in the spermatozoa of these young males living in the VSR. Alterations were seen in sperm morphology, sperm motility, sperm count, and protamine/histone ratios, and included significant reductions in SNBP-DNA binding capacity. Our results provide preliminary indications of a possible correlation between the observed alterations and the presence of specific VOCs.

A novel human biomonitoring study by semiconductor gas sensors in Exposomics: investigation of health risk in contaminated sites.

Two areas in central-southern Italy Land of Fires in Campania and Valley of Sacco river in Lazio are known to be contaminated sites, the first due to illegal fly-tipping and toxic fires, and the second due to an intensive industrial exploitation done by no-scruple companies and crooked public administration offices with dramatic consequences for environment and resident people. The work is intended to contribute to Human BioMonitoring (HBM) studies conducted in these areas on healthy young male population by a semiconductor gas sensor array trained by SPME-GC/MS. Human semen, blood and urine were investigated. The fingerprinting of the Volatile Organic Compounds (VOCs) by a gas sensors system allowed to discriminate the different contamination of the two areas and was able to predict the chemical concentration of several VOCs identified by GC/MS.

Human Biomonitoring of Environmental and Occupational Exposures by GC-MS and Gas Sensor Systems: A Systematic Review.

Environmental chemicals and contaminants coming from multiple external sources enter the human body, determining a potential risk for human health. Human biomonitoring (HBM), measuring the concentrations of biomarkers in human specimens, has become an emerging approach for assessing population-wide exposure to hazardous chemicals and health risk through large-scale studies in many countries. However, systematic mapping of HBM studies, including their characteristics, targeted hazardous pollutants, analytical techniques, and sample population (general population and occupationally exposed workers), has not been done so far. We conducted a systematic review of the literature related to airborne hazardous pollutants in biofluids to answer the following questions: Which main chemicals have been included in the literature, which bodily fluids have been used, and what are the main findings? Following PRISMA protocol, we summarized the publications published up to 4 February 2021 of studies based on two methods: gas-chromatography/mass spectrometry (GC/MS) and electronic noses (e-noses). We screened 2606 records and 117 publications were included in the analysis, the most based on GC/MS analysis. The selected HBM studies include measurements of biomarkers in different bodily fluids, such as blood, urine, breast milk, and human semen as well as exhaled air. The papers cover numerous airborne hazardous pollutants that we grouped in chemical classes; a lot of hazardous and noxious compounds, mainly persistent organic pollutants (POPs) and volatile organic compounds (VOCs), have been detected in biological fluids at alarming levels. The scenario that emerged from this survey demonstrates the importance of HBM in human exposure to hazardous pollutants and the need to use it as valid tool in health surveillance. This systematic review represents a starting point for researchers who focus on the world of pollutant biomonitoring in the human body and gives them important insights into how to improve the methods based on GC/MS. Moreover, it makes a first overview of the use of gas sensor array and e-noses in HBM studies.

Blood, urine and semen Volatile Organic Compound (VOC) pattern analysis for assessing health environmental impact in highly polluted areas in Italy.

Volatile Organic Compound (VOC) analysis is usually applied in pollution assessment by checking for toxic or harmful volatile compounds in air, water and soil samples. In this study, exogenous VOCs and their derivatives, metabolized by cells, were valued into specific body fluids. In particular, the VOC profiles of blood, urine and human semen samples collected from young men living in two high pollution areas in Italy, i.e. Land of Fires and Valley of Sacco River, were fingerprinted. The analysis is based on Headspace Solid Phase MicroExtraction (HS-SPME) followed by Gas Chromatography-Mass Spectrometric detection (GC-MS). The volatile composition of the three body fluids showed that some VOCs are in common between blood, urine and human semen samples, whereas others are present only in a body fluid. Some compounds, as well as also some chemical classes show a higher affinity for a specific body fluid. Statistical analysis allowed to discriminate the two contaminated areas and identify those compounds which significantly contribute to the two areas classification. Some of these compounds are toxic and found prevalently in Valley of Sacco River samples, correspondingly to sperm analysis results for young men living in this zona worse than those living in Land of Fires.

Chromatographic analysis of VOC patterns in exhaled breath from smokers and nonsmokers.

Cigarette smoking harms nearly every organ of the body and causes many diseases. The analysis of exhaled breath for exogenous and endogenous volatile organic compounds (VOCs) can provide fundamental information on active smoking and insight into the health damage that smoke is creating. Various exhaled VOCs have been reported as typical of smoking habit and recent tobacco consumption, but to date, no eligible biomarkers have been identified. Aiming to identify such potential biomarkers, in this pilot study we analyzed the chemical patterns of exhaled breath from 26 volunteers divided into groups of nonsmokers and subgroups of smokers sampled at different periods of withdrawal from smoking. Solid-phase microextraction technique and gas chromatography/mass spectrometry methods were applied. Many breath VOCs were identified and quantified in very low concentrations (ppbv range), but only a few (toluene, pyridine, pyrrole, benzene, 2-butanone, 2-pentanone and 1-methyldecyclamine) were found to be statistically significant variables by Mann-Whitney test. In our analysis, we did not consider the predictive power of individual VOCs, as well as the criterion of uniqueness for biomarkers suggests, but we used the patterns of the only statistically significant compounds. Probit prediction model based on statistical relevant VOCs-patterns showed that assessment of smoking status is heavily time dependent. In a two-class classifier model, it is possible to predict with high specificity and sensitivity if a subject is a smoker who respected 1 hour of abstinence from smoking (short-term exposure to tobacco) or a smoker (labelled "blank smoker") after a night out of smoking (long-term exposure to tobacco). On the other side, in our study "blank smokers" are more like non-smokers so that the two classes cannot be well distinguished and the corresponding prediction results showed a good sensitivity but low selectivity.