Per- and polyfluoroalkyl substances (PFAS) encompass a large, heterogeneous group of chemicals of... more Per- and polyfluoroalkyl substances (PFAS) encompass a large, heterogeneous group of chemicals of potential concern to human and environmental health. Based on information for some legacy PFAS, such as perfluorooctane sulfonate and perfluorooctanoate, there is an increasing awareness that they can represent a serious environmental risk. Although the environmental occurrence and fate of some legacy PFAS and their toxicity under controlled laboratory conditions have been investigated, to date, there is a dearth of information on the exposure and potential adverse effects of these compounds towards free-living organisms. The present review summarizes the findings of field studies investigating the accumulation and adverse effects induced by the exposure to environmental mixtures of both legacy and emerging PFAS in the wildlife living nearby fluorochemical production plants (FCP). Biomonitoring campaigns performed close to FCP, which can be considered as hotspots of PFAS contamination, ...
Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied appro... more Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using ...
Reference EPFL-ARTICLE-223263doi:10.1002/etc.3545View record in Web of Science Record created on ... more Reference EPFL-ARTICLE-223263doi:10.1002/etc.3545View record in Web of Science Record created on 2016-11-21, modified on 2016-11-25
Background: The European Commission Implementing Decision EU 2015/495 included three steroidal es... more Background: The European Commission Implementing Decision EU 2015/495 included three steroidal estrogens, namely 17a-ethinyl estradiol, 17b-estradiol, and estrone, in the so-called "watch list" of the EU Water Framework Directive (WFD). The monitoring of these compounds is difficult because the detection limits of the majority of the available analytical methods cannot achieve the very low target concentrations required to meet proposed environmental quality criteria. In 2014, a combined Science-Policy Interface/Chemical Monitoring of Emerging Pollutants project was launched to meet this monitoring challenge. The project involved 24 research organizations and environmental agencies from 12 different countries. Methods: Sixteen surface water (SW) and 17 wastewater (WW) samples were collected across Europe and analysed using five in vitro effect-based and three chemical analytical methods. A general description of the project and data evaluation is provided by K€ onemann and colleagues in the companion publication 2018. In our study, we compared bioanalytical and chemical analytical results with regard to their application for aquatic status assessment. Therefore we considered the potential to predict populationrelevant risks for aquatic organisms and the specificity and sensitivity of the various methods used in
Several studies have demonstrated that the most effective way to control eutrophication is to red... more Several studies have demonstrated that the most effective way to control eutrophication is to reduce phosphorus input at the scale. Water quality monitoring programs need to separately evaluate the different polluting sources to provide a suitable estimate of their relative contributions and thus accurately prioritize possible restoration actions. Urban area cases, where a portion of untreated wastewater is often discharged directly into receiving surface waters by combined sewer overflows (CSOs) during rain events, remain unsolved. In this context, an urban watershed located in Northern Italy with 60 CSOs has been chosen as a case study, and four rainy events have been hourly monitored. The proposed monitoring program consists of the combined use of caffeine and turbidity to estimate the volume and phosphorus load spilled into the river from the CSOs, respectively. Caffeine proved to be a suitable molecule to quantify the volume of wastewater discharged into water bodies, based on a per capita caffeine load of 10.8 mg inhab −1 d −1 , estimated in the present work. This research showed that, on average, more than half of the total phosphorus loads transported by the river is due to the CSO discharges (56.5%). The knowledge of the prevailing responsibility of the CSO discharges for the Lambro River quality allows prioritizing effective restoration actions.
Per- and polyfluoroalkyl substances (PFASs) have multiple emission sources, from industrial to do... more Per- and polyfluoroalkyl substances (PFASs) have multiple emission sources, from industrial to domestic, and their high persistence and mobility help them to spread in all the networks of watercourses. Diffuse pollution of these compounds can be potentially mitigated by the application of green infrastructures, which are a pillar of the EU Green Deal. In this context, a phytoremediation pilot plant was realised and supplied by a contaminated well-located in Lonigo (Veneto Region, Italy) where surface and groundwaters were significantly impacted by perfluoroalkyl acids (PFAAs) discharges from a fluorochemical factory. The investigation involved the detection of perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) inside the inlet and outlet waters of the phytoremediation pilot plant as well as in reed grasses grown into its main tank. The obtained results demonstrate that the pilot plant is able to r...
This work aimed to investigate the contamination pattern in Kongsfjorden marine environment (Sval... more This work aimed to investigate the contamination pattern in Kongsfjorden marine environment (Svalbard, 79°N 12°E) and to disentangle primary and secondary emissions. Surface seawater, sampled in two seasons, was analysed by GC-MS and LC-MS/MS to detect polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenols (NPs), bisphenol A (BPA) and perfluoroalkyl and polyfluoroalkyl substances (PFASs). In summer, average ΣPAHs, BPA, ΣNPs, ΣPFASs and ΣPCBs concentrations were 17.3 ± 11.1 ng/L, 0.9 ± 0.3 ng/L, 10.0 ± 6.9 ng/L, 0.4 ± 0.7 ng/L and 1.8 ± 1.3 pg/L, respectively; while in winter, they were 13.6 ± 10.1 ng/L, 0.5 ± 0.2 ng/L, 6.8 ± 3.3 ng/L, <LOD and 0.6 ± 0.4 pg/L, respectively. The application of generalized linear models (GLMs) highlighted that: PFAS pattern agrees their predominant long-range hydrospheric transport; the additive effect of the distance to glacier and harbour affected PAH, NP and BPA distributions; the additive effect of season and distance from the glacier, but not their interaction, influenced PCBs distribution, indicating melting glaciers as potential secondary POP sources.
Perfluoroalkyl acids (PFAAs), particularly short-chained ones, have high potential for crop uptak... more Perfluoroalkyl acids (PFAAs), particularly short-chained ones, have high potential for crop uptake, posing a threat to human health in contaminated areas. There is a scarcity of studies using contaminated water as the medium for PFAAs delivery to crops, and a lack of data on the partitioning of PFAA mixtures in growing media. In this context, a controlled experimental study was carried out in a greenhouse to investigate the uptake of a PFAA mixture into red chicory, a typical crop from a major PFAA contamination hot-spot in northern Italy, under treatments with environmentally relevant concentrations in spiked irrigation water and soil, separately and simultaneously. To our knowledge, this is the first study involving multiple exposure media and laboratory adsorption/desorption batch tests as a way of assessing the decrease in the bioavailability of PFAAs from soil. Exposure concentrations for each of the 9 utilized PFAAs were 0, 1, 10 and 80 µg/L in irrigation water and 0, 100 and 200 ng/gdw in soil, combined into 12 treatments. The highest bioaccumulation was measured for PFBA in roots (maximum of 43 µg/gdw), followed by leaves and heads of the chicory plants in all treatments, with the concentrations exponentially decreasing with an increasing PFAA chain length in all plant compartments. The use of irrigation water as the delivery medium increased the transport of PFAAs to the aerial chicory parts, long-chain substances in particular. Additionally, the distribution of PFAAs in the soil was assessed by depth and compared with laboratory measured soil-water equilibrium partition coefficients, revealing only partial dependency of PFAAs bioavailability on the adsorption in soil.
This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) aims to fac... more This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) aims to facilitate the implementation of environmental quality standards (EQS) in biota under the Water Framework Directive by addressing in particular the sampling strategies appropriate for monitoring programmes designed to assess compliance with biota EQS. It is Guidance Document No. 32 in the series of guidance documents prepared to support the Common Implementation Strategy (CIS) for the Water Framework Directive. It elaborates extensively on the content of Guidance Document No. 25 on Chemical Monitoring in Sediment and Biota under the Water Framework Directive, and is complemented by Guidance Document No. 33, the Technical Guidance Document on Analytical Methods for Biota Monitoring. Guidance Documents 32 and 33 together address the requirement for guidance on biota monitoring mentioned in Article 3(8a) of Directive 2008/105/EC as amended by Directive 2013/39/EU. The original Directive 2008/1...
Integrated Environmental Assessment and Management
For many years, eggs of diverse bird species have been used as monitoring tools in studies invest... more For many years, eggs of diverse bird species have been used as monitoring tools in studies investigating PFAS contamination, especially in marine and remote areas. Avian eggs are a suitable monitoring matrix because they are relatively easy to collect and their yolks store diverse maternally-transferred PFAS. Moreover, the concentrations of PFAS detected in the eggs are a good proxy of maternal exposure, and allow the assessment of the potential risk for birds. These features support the use of avian eggs as a key monitoring tool in exposure assessment of PFAS-contaminated sites. We first review the recent application of avian eggs in PFAS monitoring in environmental risk assessment schemes, highlighting strengths and limitations and suggesting which criteria should be considered when selecting a proper study species and structuring the sampling and analytical protocol. Eventually, we report findings from a field study realized in 2020 near a perfluoropolymer factory site in the upper Po plain (Northern Italy), revealing unprecedented contamination level of PFOA and C6O4 in three species of wild passerines. In a future, long-term monitoring of PFAS contamination using avian eggs should be maintained, to provide crucial information on the temporal trend of fluorochemical production and waste disposal, while facilitating early identification of emerging PFAS as well as the quantification of their biomagnification across the trophic web. This article is protected by copyright. All rights reserved.
The efficiency of Microwave Assisted Solvent Extraction (MASE) for the simultaneous determination... more The efficiency of Microwave Assisted Solvent Extraction (MASE) for the simultaneous determination of nonylphenol (NP) and nonylphenol ethoxylates (NPE) in river sediments has been evaluated. An optimisation study was carried out in order to identify the variables having the greatest influence on the extraction efficiency. The comparison between the solvents (methanol and acetone-hexane 1:1) shows that the more polar solvent (i.e. methanol) allows a more effective extraction of NP and NPE from sediments. Analytical results show that there is not a considerable improvement by doubling extraction time, while the increase of solvent volume is significant. The comparative study with Soxhlet and pressurised liquid extraction (PLE) methods demonstrates that Microwave Assisted Solvent Extraction is a suitable alternative extraction method for the 4-NP and 4-NPE determination in river sediments, showing an accuracy and precision comparable to those obtained with PLE and better than those obt...
Per- and polyfluoroalkyl substances (PFAS) encompass a large, heterogeneous group of chemicals of... more Per- and polyfluoroalkyl substances (PFAS) encompass a large, heterogeneous group of chemicals of potential concern to human and environmental health. Based on information for some legacy PFAS, such as perfluorooctane sulfonate and perfluorooctanoate, there is an increasing awareness that they can represent a serious environmental risk. Although the environmental occurrence and fate of some legacy PFAS and their toxicity under controlled laboratory conditions have been investigated, to date, there is a dearth of information on the exposure and potential adverse effects of these compounds towards free-living organisms. The present review summarizes the findings of field studies investigating the accumulation and adverse effects induced by the exposure to environmental mixtures of both legacy and emerging PFAS in the wildlife living nearby fluorochemical production plants (FCP). Biomonitoring campaigns performed close to FCP, which can be considered as hotspots of PFAS contamination, ...
Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied appro... more Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using ...
Reference EPFL-ARTICLE-223263doi:10.1002/etc.3545View record in Web of Science Record created on ... more Reference EPFL-ARTICLE-223263doi:10.1002/etc.3545View record in Web of Science Record created on 2016-11-21, modified on 2016-11-25
Background: The European Commission Implementing Decision EU 2015/495 included three steroidal es... more Background: The European Commission Implementing Decision EU 2015/495 included three steroidal estrogens, namely 17a-ethinyl estradiol, 17b-estradiol, and estrone, in the so-called "watch list" of the EU Water Framework Directive (WFD). The monitoring of these compounds is difficult because the detection limits of the majority of the available analytical methods cannot achieve the very low target concentrations required to meet proposed environmental quality criteria. In 2014, a combined Science-Policy Interface/Chemical Monitoring of Emerging Pollutants project was launched to meet this monitoring challenge. The project involved 24 research organizations and environmental agencies from 12 different countries. Methods: Sixteen surface water (SW) and 17 wastewater (WW) samples were collected across Europe and analysed using five in vitro effect-based and three chemical analytical methods. A general description of the project and data evaluation is provided by K€ onemann and colleagues in the companion publication 2018. In our study, we compared bioanalytical and chemical analytical results with regard to their application for aquatic status assessment. Therefore we considered the potential to predict populationrelevant risks for aquatic organisms and the specificity and sensitivity of the various methods used in
Several studies have demonstrated that the most effective way to control eutrophication is to red... more Several studies have demonstrated that the most effective way to control eutrophication is to reduce phosphorus input at the scale. Water quality monitoring programs need to separately evaluate the different polluting sources to provide a suitable estimate of their relative contributions and thus accurately prioritize possible restoration actions. Urban area cases, where a portion of untreated wastewater is often discharged directly into receiving surface waters by combined sewer overflows (CSOs) during rain events, remain unsolved. In this context, an urban watershed located in Northern Italy with 60 CSOs has been chosen as a case study, and four rainy events have been hourly monitored. The proposed monitoring program consists of the combined use of caffeine and turbidity to estimate the volume and phosphorus load spilled into the river from the CSOs, respectively. Caffeine proved to be a suitable molecule to quantify the volume of wastewater discharged into water bodies, based on a per capita caffeine load of 10.8 mg inhab −1 d −1 , estimated in the present work. This research showed that, on average, more than half of the total phosphorus loads transported by the river is due to the CSO discharges (56.5%). The knowledge of the prevailing responsibility of the CSO discharges for the Lambro River quality allows prioritizing effective restoration actions.
Per- and polyfluoroalkyl substances (PFASs) have multiple emission sources, from industrial to do... more Per- and polyfluoroalkyl substances (PFASs) have multiple emission sources, from industrial to domestic, and their high persistence and mobility help them to spread in all the networks of watercourses. Diffuse pollution of these compounds can be potentially mitigated by the application of green infrastructures, which are a pillar of the EU Green Deal. In this context, a phytoremediation pilot plant was realised and supplied by a contaminated well-located in Lonigo (Veneto Region, Italy) where surface and groundwaters were significantly impacted by perfluoroalkyl acids (PFAAs) discharges from a fluorochemical factory. The investigation involved the detection of perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) inside the inlet and outlet waters of the phytoremediation pilot plant as well as in reed grasses grown into its main tank. The obtained results demonstrate that the pilot plant is able to r...
This work aimed to investigate the contamination pattern in Kongsfjorden marine environment (Sval... more This work aimed to investigate the contamination pattern in Kongsfjorden marine environment (Svalbard, 79°N 12°E) and to disentangle primary and secondary emissions. Surface seawater, sampled in two seasons, was analysed by GC-MS and LC-MS/MS to detect polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenols (NPs), bisphenol A (BPA) and perfluoroalkyl and polyfluoroalkyl substances (PFASs). In summer, average ΣPAHs, BPA, ΣNPs, ΣPFASs and ΣPCBs concentrations were 17.3 ± 11.1 ng/L, 0.9 ± 0.3 ng/L, 10.0 ± 6.9 ng/L, 0.4 ± 0.7 ng/L and 1.8 ± 1.3 pg/L, respectively; while in winter, they were 13.6 ± 10.1 ng/L, 0.5 ± 0.2 ng/L, 6.8 ± 3.3 ng/L, <LOD and 0.6 ± 0.4 pg/L, respectively. The application of generalized linear models (GLMs) highlighted that: PFAS pattern agrees their predominant long-range hydrospheric transport; the additive effect of the distance to glacier and harbour affected PAH, NP and BPA distributions; the additive effect of season and distance from the glacier, but not their interaction, influenced PCBs distribution, indicating melting glaciers as potential secondary POP sources.
Perfluoroalkyl acids (PFAAs), particularly short-chained ones, have high potential for crop uptak... more Perfluoroalkyl acids (PFAAs), particularly short-chained ones, have high potential for crop uptake, posing a threat to human health in contaminated areas. There is a scarcity of studies using contaminated water as the medium for PFAAs delivery to crops, and a lack of data on the partitioning of PFAA mixtures in growing media. In this context, a controlled experimental study was carried out in a greenhouse to investigate the uptake of a PFAA mixture into red chicory, a typical crop from a major PFAA contamination hot-spot in northern Italy, under treatments with environmentally relevant concentrations in spiked irrigation water and soil, separately and simultaneously. To our knowledge, this is the first study involving multiple exposure media and laboratory adsorption/desorption batch tests as a way of assessing the decrease in the bioavailability of PFAAs from soil. Exposure concentrations for each of the 9 utilized PFAAs were 0, 1, 10 and 80 µg/L in irrigation water and 0, 100 and 200 ng/gdw in soil, combined into 12 treatments. The highest bioaccumulation was measured for PFBA in roots (maximum of 43 µg/gdw), followed by leaves and heads of the chicory plants in all treatments, with the concentrations exponentially decreasing with an increasing PFAA chain length in all plant compartments. The use of irrigation water as the delivery medium increased the transport of PFAAs to the aerial chicory parts, long-chain substances in particular. Additionally, the distribution of PFAAs in the soil was assessed by depth and compared with laboratory measured soil-water equilibrium partition coefficients, revealing only partial dependency of PFAAs bioavailability on the adsorption in soil.
This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) aims to fac... more This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) aims to facilitate the implementation of environmental quality standards (EQS) in biota under the Water Framework Directive by addressing in particular the sampling strategies appropriate for monitoring programmes designed to assess compliance with biota EQS. It is Guidance Document No. 32 in the series of guidance documents prepared to support the Common Implementation Strategy (CIS) for the Water Framework Directive. It elaborates extensively on the content of Guidance Document No. 25 on Chemical Monitoring in Sediment and Biota under the Water Framework Directive, and is complemented by Guidance Document No. 33, the Technical Guidance Document on Analytical Methods for Biota Monitoring. Guidance Documents 32 and 33 together address the requirement for guidance on biota monitoring mentioned in Article 3(8a) of Directive 2008/105/EC as amended by Directive 2013/39/EU. The original Directive 2008/1...
Integrated Environmental Assessment and Management
For many years, eggs of diverse bird species have been used as monitoring tools in studies invest... more For many years, eggs of diverse bird species have been used as monitoring tools in studies investigating PFAS contamination, especially in marine and remote areas. Avian eggs are a suitable monitoring matrix because they are relatively easy to collect and their yolks store diverse maternally-transferred PFAS. Moreover, the concentrations of PFAS detected in the eggs are a good proxy of maternal exposure, and allow the assessment of the potential risk for birds. These features support the use of avian eggs as a key monitoring tool in exposure assessment of PFAS-contaminated sites. We first review the recent application of avian eggs in PFAS monitoring in environmental risk assessment schemes, highlighting strengths and limitations and suggesting which criteria should be considered when selecting a proper study species and structuring the sampling and analytical protocol. Eventually, we report findings from a field study realized in 2020 near a perfluoropolymer factory site in the upper Po plain (Northern Italy), revealing unprecedented contamination level of PFOA and C6O4 in three species of wild passerines. In a future, long-term monitoring of PFAS contamination using avian eggs should be maintained, to provide crucial information on the temporal trend of fluorochemical production and waste disposal, while facilitating early identification of emerging PFAS as well as the quantification of their biomagnification across the trophic web. This article is protected by copyright. All rights reserved.
The efficiency of Microwave Assisted Solvent Extraction (MASE) for the simultaneous determination... more The efficiency of Microwave Assisted Solvent Extraction (MASE) for the simultaneous determination of nonylphenol (NP) and nonylphenol ethoxylates (NPE) in river sediments has been evaluated. An optimisation study was carried out in order to identify the variables having the greatest influence on the extraction efficiency. The comparison between the solvents (methanol and acetone-hexane 1:1) shows that the more polar solvent (i.e. methanol) allows a more effective extraction of NP and NPE from sediments. Analytical results show that there is not a considerable improvement by doubling extraction time, while the increase of solvent volume is significant. The comparative study with Soxhlet and pressurised liquid extraction (PLE) methods demonstrates that Microwave Assisted Solvent Extraction is a suitable alternative extraction method for the 4-NP and 4-NPE determination in river sediments, showing an accuracy and precision comparable to those obtained with PLE and better than those obt...
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