Jitka Bečanová

Perfluoroalkyl substances (PFAS) in river and ground/drinking water of the Ganges River basin: Emissions and implications for human exposure

Many perfluoroalkyl substances (PFAS) are ubiquitous environmental contaminants. They have been widely used in production processes and daily-use products or may result from degradation of precursor compounds in products or the environment. India, with its developing industrialization and population moving from traditional to contemporary lifestyles, represents an interesting case study to investigate PFAS emission and exposure along steep environmental and socioeconomic gradients. This study assesses PFAS concentrations in river and groundwater (used in this region as drinking water) from several locations along the Ganges River and estimates direct emissions, specifically for PFOS and PFOA. 15 PFAS were frequently detected in the river with the highest concentrations observed for PFHxA (0.4-4.7 ng L(-1)) and PFBS (<MQL - 10.2 ng L(-1)) among PFCAs and PFSAs, respectively. Prevalence of short-chain PFAS indicates that the effects of PFOA and PFOS substitution are visible in environmental samples from India. The spatial pattern of C5-C7 PFCAs co-varied with that of PFOS suggesting similar emission drivers. PFDA and PFNA had much lower concentrations and covaried with PFOA especially in two hotspots downstream of Kanpur and Patna. PFOS and PFOA emissions to the river varied dramatically along the transect (0.20-190 and 0.03-150 g d(-1), respectively). PFOS emission pattern could be explained by the number of urban residents in the subcatchment (rather than total population). Per-capita emissions were lower than in many developed countries. In groundwater, PFBA (<MQL - 9.2 ng L(-1)) and PFBS (<MQL - 4.9 ng L(-1)) had the highest concentrations among PFCAs and PFSAs, respectively. Concentrations and trends in groundwater were generally similar to those observed in surface water suggesting the aquifer was contaminated by wastewater receiving river water. Daily PFAS exposure intakes through drinking water were below safety thresholds for oral non-cancer risk in all age groups.

Organophosphate esters flame retardants in the indoor environment

Concentrations of 13 organophosphate ester flame retardants (OPEs) were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013 to look for abundances, differences among regions, and partitioning behavior. In general, we observed the highest concentrations for halogenated OPEs, particularly TCEP, TCIPP and TDCIPP, and also non-halogenated TPHP. Differences between regions strongly depended on the matrix. The concentrations of OPEs in dust were significantly higher in the US than in Canada (CAN) and Czech Republic (CZ). CZ had the highest concentrations in window film and CAN in air. ΣOPE concentrations were 2-3 and 1-2 orders of magnitude greater than ΣBFRs in air, and dust and window films, respectively. We found a significant relationship between the concentrations in dust and air, and between the concentrations in window film and air for OPEs with log KOA values <12, suggesting that equilibrium was reached for these compounds but not for those with log KOA>12. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for OPEs with log KOA values >12.

Perfluorinated alkyl substances (PFASs) in household dust in Central Europe and North America

Concentrations of 20 perfluorinated alkyl substances (PFASs) were measured in dust samples from 41 homes in Canada, the Czech Republic, and United States in the spring-summer of 2013. The most frequently detected compounds were perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS). PFOS and perfluorooctanoic acid (PFOA) had the highest concentrations of PFASs in all countries. PFOS median concentrations for the three countries were between 9.1 and 14.1ng/g, and PFOA medians ranged between 8.2 and 9.3ng/g. In general, concentrations in North America were higher than in the Czech Republic, which is consistent with usage patterns. No differences were found for perfluorooctane sulfonamides/sulfonamidoethanols (FOSA/Es) levels due to the low number of detections. Homologue profiles suggest that the shift from longer to shorter chain PFASs is more advanced in North America than in Europe. Significant relationships were found among individual homologues and between PFAS concentrations in dust and type of floor, number of people living in the house, and building age.

Extraction and determination of trinitrotoluenes and products of their biotransformation in soil samples

The separation of a mixture of trinitrotoluenes (TNTs) and their metabolites by reverse phase liquid chromatography using different columns with octadecyl stationary phase is presented. The retention behaviour of a mixture of TNTs and their metabolites was studied under different chromatographic conditions. The mixture of methanol/water was used as a mobile phase in isocratic and gradient modes. The effect of content of organic modifier and temperature of mobile phase has been investigated. Very good RP-HPLC separation of 14 nitroaromatic compounds was obtained using stepped gradient elution. Different properties of extraction procedures for isolation of trinitrotoluenes and their metabolites from soil were tested. Experimental conditions of Soxhlet warm extraction (extractant type, extraction time) suitable for efficient extraction of individual analytes were studied. Recoveries over 80% for all studied compounds and over 90% for almost all (11 compounds) were obtained in short extraction time (1 hour). The formation of precipitate during the Soxhlet extraction was observed and the further treatment of extract was necessary. The amount of precipitate formed from an artificial soil was higher than that from a natural one. THF was found as the best solvent suitable for total dissolution of precipitate.

Retention performance of three widely used SPE sorbents for the extraction of perfluoroalkyl substances from seawater

Some per- and polyfluoroalkyl substances (PFASs) have been detected ubiquitously in the environment. Owing to the polar character conferred by the presence of the carboxylic or sulfonic acid groups and their resistance to degradation, aquatic environments became their major reservoirs, including marine waters. The procedure of PFAS analysis in aqueous matrices consists usually of solid-phase extraction (SPE) followed by high-performance liquid chromatography coupled to tandem mass spectrometry. Moreover, passive sampling approach using various SPE sorbents may be applied. This study deals with the assessment of retention characteristics of a selected group of PFASs in marine water on three sorbent media widely used in SPE or passive sampling techniques. The influence of type of sorbent, matrix pH, salinity and eluent on the PFAS recovery from aquatic samples was investigated. The best overall extraction conditions were found to be at pH 8 and 50%/100% matrix seawater content using Oasis® HLB/Strata™-X as SPE sorbents and methanol as eluent. The matrix properties found to be the most appropriate for extraction of investigated PFASs from aqueous samples (i.e., pH and salinity levels) match well the natural properties of marine and brackish waters. Acid-base behavior was found to be the main driver influencing the recovery of PFASs. These research findings can be used to optimize PFAS extraction conditions from aquatic samples and also to develop efficient extraction procedures for multiresidual analyses.

PCBs and organochlorine pesticides in indoor environments - A comparison of indoor contamination in Canada and Czech Republic

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are restricted compounds that are ubiquitously detected in the environment, including indoor matrices such as air and residential dust. We report concentrations of PCBs and selected OCPs in indoor air and dust from homes in Canada (23 homes) and Czech Republic (20 homes). Indoor air concentrations of PCBs and OCPs were ∼10 times higher than that outdoors. PCB concentrations of ∼450 ng/m3 were similar in both countries, higher in homes built before the restrictions on PCBs, and had congener profiles consistent with PCB mixtures manufactured or used in each country. All OCP air concentrations were higher in the Czech Republic than in the Canadian samples, suggesting greater indoor use of, for example, DDT and HCH. These data emphasize the persistence of these organochlorine compounds indoors and their presence in homes even decades after new usage was prohibited. Indoor levels of these legacy POPs remain at similar concentrations to compounds of current concern, such as brominated flame retardants and perfluorinated alkyl substances, emphasizing that they deserve ongoing attention in view of knowledge of PCB and OCP toxicity.