Estimation of per- and polyfluoroalkyl substances (PFAS) half-lives in human studies: a systematic review and meta-analysis.

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) constitute a heterogeneous group of synthetic compounds widely used in industrial applications. The estimation of PFAS half-life (t1/2) is essential to quantify their persistence, their toxicity and mechanism of action in humans. OBJECTIVES: The purpose of this review is to summarize the evidence on PFAS half-lives in humans from the available literature, and to investigate the limitations and uncertainties characterizing half-life estimation. METHODS: The search was conducted on PubMed, Scopus, and Embase databases up to July 03, 2023 and was aimed at identifying all papers that estimated PFAS half-life in human populations. We excluded studies on temporal trends or providing estimates of half-life based solely on renal clearance. As persistent and ongoing exposures can influence half-life estimation, we decided to include only studies that were conducted after the main source of exposure to PFAS had ceased. A random-effects meta-analysis was conducted on studies that reported perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) or perfluorohexanesulfonic acid (PFHxS) half-life estimation. Risk of bias was evaluated using the OHAT tool. RESULTS: A total of 13 articles were included in the review, with 5 studies conducted in exposed general populations and 8 studies conducted in exposed workers; the estimated mean half-life ranged from 1.48 to 5.1 years for PFOA, from 3.4 to 5.7 years for total PFOS, and from 2.84 to 8.5 years for PFHxS. High heterogeneity among studies was observed; potential reasons include the variability among the investigated populations, discrepancies in considering ongoing exposures, variability in PFAS isomeric compositions, accounting for background exposure, time since exposure stopped and methods used for half-life estimation. DISCUSSION: Despite the efforts made to better understand PFAS toxicokinetics, further studies are needed to identify important characteristics of these persistent chemicals. Biomonitoring studies should focus on persistent and unaccounted sources of exposure to PFAS and on individual characteristics potentially determining half-life, to ensure accurate estimates.

Agricultural application of digestates derived from agricultural and municipal organic wastes: a health risk-assessment for heavy metals.

A Human-health Risk Assessment was performed for an agricultural site in North-East Italy undergone digestate application to (i) check the compliance of digestate land spreading with the Italian and European regulations on contaminated agricultural soils and (ii) evaluate how resulting risk estimations can be influenced by the applied modeling assumptions. The assessment estimated the risk related to adults and children intake of Heavy Metals (HM) contained in crops at concentrations estimated by a soil-plant transfer model based on the substance-specific soil-water partition coefficients. Eight different scenarios were investigated, according to different digestate type (from biowaste and agro-industrial byproducts), digestate application techniques and soil background concentrations. Non-risky situations resulted in all scenarios involving digestate application. The totality of calculated non-carcinogenic Hazard Indexes (HI) and carcinogenic total risk (RTOTC) resulted below 0.02 and 3E10-9, respectively. In contrast with the definition, non-carcinogenic risks were associated with the considered soil background concentrations, with HI s up to 1.7 for child receptors, while carcinogenic risk was calculated below the concern threshold (i.e., RTOTC < 10-5). Accordingly, this study highlighted (i) non-concerning situations related with lawful application of digestates and (ii) the need to improve the modeling of bioavailability to plant of HMs background content of soil.

Quantitative Determination of Fluorine Content in Blends of Polylactide (PLA)-Talc Using Near Infrared Spectroscopy.

Near-infrared spectroscopy (NIRS) has been widely used for quantitative and/or qualitative determination of a wide range of matrices. The objective of this study was to develop a NIRS method for the quantitative determination of fluorine content in polylactide (PLA)-talc blends. A blending profile was obtained by mixing different amounts of PLA granules and talc powder. The calibration model was built correlating wet chemical data (alkali digestion method) and NIR spectra. Using FT (Fourier Transform)-NIR technique, a Partial Least Squares (PLS) regression model was set-up, in a concentration interval of 0 ppm of pure PLA to 800 ppm of pure talc. Fluorine content prediction (R²cal = 0.9498; standard error of calibration, SEC = 34.77; standard error of cross-validation, SECV = 46.94) was then externally validated by means of a further 15 independent samples (R²EX.V = 0.8955; root mean standard error of prediction, RMSEP = 61.08). A positive relationship between an inorganic component as fluorine and NIR signal has been evidenced, and used to obtain quantitative analytical information from the spectra.

Uptake and translocation of brominated flame retardants in tomato plants (Solanum lycopersicum L.): Results from a standard soil-based biotest.

The uptake and translocation of four polybrominated diphenyl ethers (PBDEs) and four novel brominated flame retardants (NBFRs) in tomato plants (Solanum lycopersicum L.) were investigated via the RHIZOtest, a standard soil-based biotest, optimized for organic compounds. Tomato plants were exposed to soil samples spiked with 0 (i.e. control), 5.00 or 50.00 ng g-1dw of each compound. Compared of those of the control, exposure to increasing spiking concentrations resulted in average reductions of 13% and 26% (w/w) in tomato plant biomass. Higher concentrations of NBFRs were analyzed both in roots, ranging from 0.23 to 8.01 ng g-1dw for PBDEs and from 1.25 to 18.51 ng g-1dw for NBFRs, and in shoots, ranging from 0.09 to 5.58 ng g-1dw and from 0.47 to 7.78 ng g-1dw for PBDEs and NBFRs, respectively. This corresponded to an average soil uptake of 5% for PBDEs and 9% for NBFRs at the lower soil-spiking level, and 3% for PBDEs and 6% for NBFRs at the higher soil spiking level. Consequently, among both initial spiking levels, the soil-root concentration factor (RCF) values were lower on average for PBDEs (0.13 ± 0.05 g dw soil g-1dw roots) than for NBFRs (0.33 ± 0.16 g dw soil g-1dw roots). Conversely, nondifferent values of the root-shoot transfer factor (TF) were calculated for both PBDEs (0.54 ± 0.13 g dw roots g-1dw shoots) and NBFRs (0.49 ± 0.24 g dw roots g-1dw shoots). The differences and similarities reported in the RCF and TF between and within the two groups of compounds can be explained by their properties. The calculated RCF and TF values of the PBDEs exhibited a decreasing trend as the number of bromine atoms increased. Additionally, a robust negative linear correlation was observed between RCF values and the respective logKow values for the PBDEs, at both soil-spiking levels. The root uptake of NBFRs exhibited a negative correlation with their hydrophobicity; however, this was not observed in the context of root-to-shoot transfer. The presence of a second aromatic ring appears to be the key factor influencing the observed variations in NBFRs, with biphenyl NBFRs (BTBPE and DBDPE) characterized by lower uptake and reduced translocation potential than monophenyl PBEB and HBB. Understanding the transfer of these compounds to crops, especially near plastic recycling waste sites, is crucial for understanding the risks of their potential inclusion in the human food chain.

Fragrance materials affect life history parameters and gene expression in Daphnia magna: An emerging issue for freshwater ecosystems.

A chronic toxicity test (21 d exposure) with the model organism Daphnia magna was performed to study the single-compound and combined effects of four fragrance materials (FMs), including musk xylene (MX), Celestolide™ (ADBI), Galaxolide™ (HHCB), and ethylene brassylate (MT). Furthermore, the transcriptional responses of ten target genes related to detoxification, molting and reproduction (DHR96, P-gp, CYP360A8, GST, CYP314, EcRb, Vtg, CAT, GPX, and GCLC) were determined by performing a quantitative real-time polymerase chain reaction (qRT‒PCR) after juvenile D. magna was exposed for 48 h. The results showed that MX, ADBI and HHCB affected development and reproduction after chronic exposure at a concentration of 10 µg L-1. Conversely, MT did not affect reproduction, growth or molting during the 21 d exposure. In juvenile D. magna, gene expression was significantly altered by ADBI (DHR96, CYP260A8, and GCLC) and MX (DHR96, CYP360A8, EcRb, Vtg, CYP314, and GCLC) but not by HHCB. These results suggest that compared to biochemical measures, conventional biological endpoints provide more informative data regarding the effects of this FM. Compared to single substances in the chronic test, the mixture of the four FMs showed effects at lower concentrations and increased gene expression for EcRb and CYP314 during juvenile exposure, indicating a possible additive or synergistic effect of the four FMs compared to single compound exposure.

Maize plant (Zea mays) uptake of organophosphorus and novel brominated flame retardants from hydroponic cultures.

The root uptake and root-shoot translocation of seven organophosphorus flame retardants (OPFRs) and four novel brominated flame retardants (NBFRs) were assessed in this investigation using hydroponic grown maize plants (Zea mays). Three initial liquid concentrations for each considered compound were examined (i.e., 0.3 µg L-1, 3 µg L-1, 30 µg L-1). The results indicated that the 30 µg L-1 treatments were phytotoxic, as they resulted in a significant decrease in shoot dry weight. Plant-driven removal of the tested FRs decreased with the increasing initial spiking level and were reportedly higher for the NBFRs (range 42%-10%) than OPFRs (range 19%-7%). All the considered FRs were measured in the roots (range 0.020-6.123 µg g-1 dry weight -DW-) and shoots (range 0.012-1.364 µg g-1 DW) of the tested plants, confirming that there was uptake. Linear relationships were identified between the chemical concentrations in the plant parts and the tested hydroponic concentrations. Root concentration factors were positively correlated with the specific lipophilicity (i.e., logKow) of the tested FRs and were determined to be higher for the NBFRs than the OPFRs. The NBFRs had a higher root uptake rate than the OPFRs, and this trend was more significant with the increasing treatment concentrations. Shoot/root concentration factors were found to be lower than the unity value for 10 of the 11 tested compounds. These results can be related to the specific molecular configurations and the occurrence of different functional groups in the tested compounds. The results will help to improve risk assessment procedures and fine tune our understanding of human receptor responses to the ingestion of maize crops grown on agricultural sites irrigated with water contaminated by FRs.

Characterization of bacterial communities isolated from municipal waste compost and screening of their plant-interactive phenotypes.

Four batches of commercial compost obtained from the organic fraction of municipal solid waste were analyzed from chemical and microbiological standpoints. The working hypothesis was that, being this type of compost derived partly from plant waste, it could contain plant-growth promoting bacterial endophytes, prone to be active again upon its usual delivery as fertilizer. Culturable bacteria were isolated at different temperatures, quantified by colony morphology, identified taxonomically by 16S sequencing and screened for plant-growth promoting phenotypes including auxin and siderophore production, phosphate solubilization and peptide mineralization to ammonia. In parallel, the total community was assessed by culture independent DNA metabarcoding. The capability of plants to select, uptake and internally multiply bacteria from these compost samples was analyzed using grapevine in-vitro rooting cuttings from which acquired bacteria were reisolated, quantified and their identities determined as above. Major differences in compost bacterial composition were observed as function of the season, with the winter sample being rather distinct from the summer ones. Bacillales and Actinomycetales dominated the culturable communities while Alteromonadales, Oceanospirillales and Flavobacteriales prevailed in the total community. In spite of the challenging composting cycle conditions, the plant nature of the main input substrates appeared determinant in guaranteeing that 82% of the culturable bacteria were found endowed with one or more of the plant growth-promoting phenotypes tested. Beside its fertilization role, compost proved to be also a potential inoculant carrier for the in-soil delivery of plant beneficial microorganisms. Furthermore, upon an in vitro passage through grapevine plants under axenic conditions, the subsequently recoverable endophyte community yielded also members of the Rhizobiales order which had not been detectable when culturing directly from compost. This observation further suggests that compost-borne plant-interacting taxa could be also rescued from non-culturable states and/or enriched above detectability levels by a contact with their potential host plants.

SARS-CoV-2 in Atmospheric Particulate Matter: An Experimental Survey in the Province of Venice in Northern Italy.

Analysis of atmospheric particulate matter (PM) has been proposed for the environmental surveillance of SARS-CoV-2. The aim of this study was to increase the current knowledge about the occurrence of SARS-CoV-2 in atmospheric PM, introduce a dedicated sampling method, and perform a simultaneous assessment of human seasonal coronavirus 229E. Thirty-two PM samples were collected on quartz fiber filters and six on Teflon using a low- and high-volumetric rate sampler, respectively, adopting a novel procedure for optimized virus detection. Sampling was performed at different sites in the Venice area (Italy) between 21 February and 8 March 2020 (n = 16) and between 27 October and 25 November 2020 (n = 22). A total of 14 samples were positive for Coronavirus 229E, 11 of which were collected in October-November 2020 (11/22; positivity rate 50%) and 3 in February-March 2020 (3/16 samples, 19%). A total of 24 samples (63%) were positive for SARS-CoV-2. Most of the positive filters were collected in October-November 2020 (19/22; positivity rate, 86%), whereas the remaining five were collected in February-March 2020 at two distinct sites (5/16, 31%). These findings suggest that outdoor PM analysis could be a promising tool for environmental surveillance. The results report a low concentration of SARS-CoV-2 in outdoor air, supporting a scarce contribution to the spread of infection.

Organic pollutants in protected plain areas: The occurrence of PAHs, musks, UV-filters, flame retardants and hydrocarbons in woodland soils.

Protected woodlands are rare and small portions of the plain territory of northern Italy, where agricultural, industrial and urban activities strongly dominate the landscape. Such natural areas are frequently set on river floodplains and are therefore potentially conditioned by the contamination brought by the surface waters. We investigated the occurrence of multiple categories of organic pollutants, including Polycyclic Aromatic Hydrocarbons (PAHs), Musk fragrances, UV-filters, organophosphorus and novel brominated Flame Retardants (FRs) and Total Petroleum Hydrocarbons (TPH) in woodland soils of eight different protected areas. The samples collected in the floodplains of the Po, Adige and Fratta rivers resulted more contaminated, with levels of PAHs up to 633 ng g-1. Moreover, these samples for the first time revealed the presence of personal care products, primarily 2-ethylhexyl-4-methoxycinnamate (EHMC) and tonalide (AHTN), in soils of protected woodlands, reaching respectively 3.4 ng g-1 and 5.0 ng g-1, together with the occurrence of both organophosphorus and brominated FRs, with total concentrations up to 15 ng g-1. Higher concentrations of hydrocarbons, with TPH in the range 5-65 µg g-1, were instead reflecting the inputs of long chain n-alkanes from epicuticular waxes more than petrogenic contamination.

Statistical analysis for the quality assessment of digestates from separately collected organic fraction of municipal solid waste (OFMSW) and agro-industrial feedstock. Should input feedstock to anaerobic digestion determine the legal status of digestate?

Management options for digestate produced by anaerobic digestion plants influence the environmental and economic sustainability of the biogas sector. Further, digestate can be both used or disposed of according to its legal classification: that is, waste or by-product, or product (by using End of Waste procedure). Currently, legal digestate status is decided by EU member states on a case-by-case basis, according to specific positive lists of input feedstocks and quality requirements in terms of physical properties and chemical concentrations. Biased exclusion of input feedstock can force digestate to a specific waste classification and undergo post-treatment and disposal options that can negatively affect the profitability of biogas installations. This is the case of the Italian regulation, where the positive list of input feedstock excludes a priori separately collected organic fractions of municipal solid waste (OFMSW), while including agro-industrial residues (AGRO). This study determined the differences between the two digestate typologies (OFMSW versus AGRO) through statistical analysis, implemented on a dataset, designed to gather data about digestate's physical-chemical parameters from relevant scientific literature and unpublished private databases. The datasets consisted of 190 entries, derived from more than 2,000 samples. Further, the study provided a compliance assessment between the resulting parameter means and the current regulation limits. Upper confidence limits for the means (level of significance α = 0.05) calculated for both digestate typologies were found to be compliant with the legal requirements. Therefore, no statistical ratio seems to support the difference in the legislative approach as proposed by Italian law-makers. OFMSW resulted significantly different from AGRO for VS (650.1 g/kg TS vs. 843.8 g/kg TS, respectively), N-NH4 (81.9 g/kg TS vs. 46.19 g/kg TS), N-TOT (109.7 g/kg TS vs. 65.32 g/kg TS), P-TOT (7.22 g/kg TS vs. 21.9 g/kg TS), Pb (18.6 mg/kg TS vs. 4.66 mg/kg TS), Ni (11.03 mg/kg TS vs. 8.20 mg/kg TS), Cr-TOT (12.74 mg/kg TS vs. 8.74 mg/kg TS) and Hg (0.08 mg/kg TS vs. 0.05 mg/kg TS). However, the statistical analysis must be implemented on a wider set of parameters not covered by this study (e.g. ecotoxicological features).

Distribution of fragrances and PAHs in the surface seawater of the Sicily Channel, Central Mediterranean.

The Mediterranean Sea is highly influenced by several anthropic pressures, including different kinds of organic pollutants. Fragrance Materials (FMs) and Polycyclic Aromatic Hydrocarbons (PAHs) were investigated in the surface seawater of the Sicily Channel in offshore and coastal areas. Total concentrations of FMs and PAHs resulted respectively up to 112ngL-1 and 43ngL-1, with similar distributions of both classes of analytes. Low values were detected in some coastal samples, due to the upwelling of deep and unpolluted waters, while the presence of gyres probably accumulates contaminants in offshore areas. Confirming previous works, the allergenic and oestrogenic Salicylates generally resulted the most abundant FMs and diagnostic ratios indicated combustion processes as the sources of PAHs. The coupling of the well-known PAHs with a new class of Personal Care Products (PCPs) helped the identification of the major environmental drivers: the results highlighted the role of mesoscale hydrodynamics and suggested long-range atmospheric transport as key factors. The first detection of the selected FMs in open sea areas supports the hypothesis of their environmental persistence.

3,3'-dichlorobiphenyl (non-Aroclor PCB-11) as a marker of non-legacy PCB contamination in marine species: comparison between Antarctic and Mediterranean bivalves.

In this study the accumulation of the 3,3'-dichlorobiphenyl (PCB-11) in monitoring organisms from the Antarctic and Mediterranean coastal environments has been investigated. This lesser-known PCB congener, unrelated to the industrial use of commercial mixtures, continues to be generated and released into the environment mainly as an unintentional by-product of pigment manufacturing. Specimens of the filter-feeders Adamussium colbecki from Terra Nova Bay and of Mytilus galloprovincialis and Ruditapes philippinarum from the north-western Adriatic coasts were collected and analyzed for PCB-11 by Gas Chromatography coupled both to Low-Resolution and High-Resolution Mass Spectrometry (LRMS, HRMS). In order to assess the influence of PCB-11 with respect to the legacy contamination, 126 PCB congeners related to the Aroclor commercial mixtures were simultaneously analyzed. PCB-11 was detected in all the samples, regardless of the species and of the geographical area, representing on average 17.6% and 15.6% of the total PCBs (n = 127) in Antarctic and Mediterranean samples, respectively. In the Adriatic area the highest concentrations were related to the influence of industrial activities or ship traffic, while the highest value found in Antarctic specimens, namely those collected in the austral summer 1997-1998, was ascribed to a local anthropogenic source. The occurrence of PCB-11 in the other samples from Terra Nova Bay may be related to Long-Range Atmospheric Transport (LRAT), facilitated by the higher volatility of the analyte compared to the heavier PCB congeners. Nevertheless, more in-depth studies are needed in order to evaluate the relative contribution of local and distant sources.