Pharmaceutical residues in plastic tablet containers: Impacts on recycling and the environment.

High-density polyethylene tablet containers are potentially very suitable for recycling, but no data are publicly available on active pharmaceutical ingredients' (API) residues in empty containers and if they affect the recyclability of pharmaceutical packaging. Plastic tablet containers represented 15 % of pharmaceutical primary packages sold in Finland in 2020 and 2021, equalling 350 tons of plastic per year. We studied the residues of six APIs remaining or adsorbed inside plastic tablet containers. The effects of tablet coating and usage in dose-dispensing services versus households on the API residues, and rinsing water's ability to remove the residues were evaluated. Up to 940,000 µg/kg of carbamazepine was detected in a container of uncoated carbamazepine tablets. The residues from coated tablets containing the other five APIs were 2.4-6,100 µg/kg. Ten times higher paracetamol residues were obtained in containers from household use than from a dose-dispensing unit. Rinsing can remove most API residues, but it leads to environmental emissions. For example, rinsing water can double carbamazepine emissions from a Finnish wastewater treatment plant where plastic packaging waste effluents are processed. Considering the API concentrations, decreasing residues by rinsing and dilution with other plastic packaging waste, the residues of the studied APIs are not considered an obstacle to the recycling of plastic tablet containers. However, further research is needed on more toxic APIs and the fate of APIs in the plastics recycling process.

Pharmaceutical emissions on the example of the Baltic Sea catchment: comparing measurements with multi-tier predictive models.

Currently, there is uncertainty about emissions of pharmaceuticals into larger closed ecosystems that are at risk such as the Baltic Sea. There is an increasing need for selecting the right strategies on advanced wastewater treatment. This study analysed 35 pharmaceuticals and iodinated X-ray contrast media in effluents from 82 Wastewater Treatment Plants (WWTPs) across Denmark, Estonia, Finland, Germany, Latvia, Lithuania, Poland and Sweden. Measured concentrations from Finland and Denmark were compared to predicted effluent concentrations using different levels of refinement. The concentrations predicted by the Total Residue Approach, as proposed by the European Medicines Agency, correlated with R2 of 0.18 and 0.031 to measured ones for Denmark and Finland, respectively and the predicted data were significantly higher than the measured ones. These correlations improved substantially to R2 of 0.72 and 0.74 after adjusting for estimated human excretion rates and further to R2 = 0.91 and 0.78 with the inclusion of removal rates in WWTPs. Temporal analysis of compound variations in a closely monitored WWTP showed minimal fluctuation over days and weeks for most compounds but revealed weekly shifts in iodinated X-ray contrast media due to emergency-only operations at X-ray clinics during weekends and an abrupt seasonal change for gabapentin. The findings underscore the limitations of current predictive models and findings (...) demonstrate how these methodologies can be refined by incorporating human pharmaceutical excretion/metabolization as well as removal in wastewater treatment plants to more accurately forecast pharmaceutical levels in aquatic environments.

The occurrence, distribution, and risks of PFAS at AFFF-impacted sites in Finland.

Per- and polyfluoroalkyl substances (PFAS) comprise a wide group of persistent chemicals, whose ubiquitous occurrence in the environment, particularly due to their extensive use for fire suppression in aqueous film forming foams (AFFFs), has raised global attention. We evaluated the impacts of PFAS at three firefighting training sites and one industrial site in Finland, to highlight key elements to be considered in the retrospective risk assessment of these chemicals. The site assessments covered the occurrence and distribution of 23 PFAS in multiple environmental matrices, i.e., soil, sediment, surface water, groundwater, and biota, and the subsequent risks to human health and the environment owing to the migration of and exposure to the selected compounds. Our study showed that the extensive use of nowadays restricted or substituted PFAS, particularly PFOS, are still often the predominant compounds detected at AFFF-impacted sites and will continue to cause long-term risks to the environment. The most significant environmental or health risks at these sites are likely to concern aquatic ecosystems, fish consumption or groundwater usage due to the off-site migration of PFAS. Here, even a single fire extinguishing event can be a considerable contributor. We also illustrate that conventional procedures based on simple mass-balance, and exposure models, with a focus on PFOS and other site-specifically relevant PFAS may provide sufficient means to assess the risks. Moreover, we address that despite the exceedance of the very stringent regulatory threshold values issued recently for PFAS, the actual site-specific risks to human health and the environment may remain reasonably low.

Bacterial diversity and predicted enzymatic function in a multipurpose surface water system - from wastewater effluent discharges to drinking water production.

BACKGROUND: Rivers and lakes are used for multiple purposes such as for drinking water (DW) production, recreation, and as recipients of wastewater from various sources. The deterioration of surface water quality with wastewater is well-known, but less is known about the bacterial community dynamics in the affected surface waters. Understanding the bacterial community characteristics -from the source of contamination, through the watershed to the DW production process-may help safeguard human health and the environment. RESULTS: The spatial and seasonal dynamics of bacterial communities, their predicted functions, and potential health-related bacterial (PHRB) reads within the Kokemäenjoki River watershed in southwest Finland were analyzed with the 16S rRNA-gene amplicon sequencing method. Water samples were collected from various sampling points of the watershed, from its major pollution sources (sewage influent and effluent, industrial effluent, mine runoff) and different stages of the DW treatment process (pre-treatment, groundwater observation well, DW production well) by using the river water as raw water with an artificial groundwater recharge (AGR). The beta-diversity analysis revealed that bacterial communities were highly varied among sample groups (R = 0.92, p <  0.001, ANOSIM). The species richness and evenness indices were highest in surface water (Chao1; 920 ± 10) among sample groups and gradually decreased during the DW treatment process (DW production well; Chao1: 320 ± 20). Although the phylum Proteobacteria was omnipresent, its relative abundance was higher in sewage and industrial effluents (66-80%) than in surface water (55%). Phyla Firmicutes and Fusobacteria were only detected in sewage samples. Actinobacteria was more abundant in the surface water (≥13%) than in other groups (≤3%). Acidobacteria was more abundant in the DW treatment process (≥13%) than in others (≤2%). In total, the share of PHRB reads was higher in sewage and surface water than in the DW treatment samples. The seasonal effect in bacterial communities was observed only on surface water samples, with the lowest diversity during summer. CONCLUSIONS: The low bacterial diversity and absence of PHRB read in the DW samples indicate AGR can produce biologically stable and microbiologically safe drinking water. Furthermore, the significantly different bacterial communities at the pollution sources compared to surface water and DW samples highlight the importance of effective wastewater treatment for protecting the environment and human health.

A preliminary study on the ecotoxic potency of wastewater treatment plant sludge combining passive sampling and bioassays.

Sewage sludge is an inevitable byproduct produced in wastewater treatment. Reusing nutrient-rich sludge will diminish the amount of waste ending in soil dumping areas and will promote circular economy. However, during sewage treatment process, several potentially harmful organic chemicals are retained in sludge, but proving the safety of processed sludge will promote its more extensive use in agriculture and landscaping. Environmental risk assessment of sludge requires new methods of characterizing its suitability for various circular economy applications. Bioavailable and bioaccessible fractions are key variables indicating leaching, transport, and bioaccumulation capacity. Also, sludge treatments have a significant effect on chemical status and resulting environmental risks. In this study, the concentrations of polyaromatic hydrocarbons (PAHs), triclosan (TCS), triclocarban (TCC), methyl triclosan (mTCS), and selected active pharmaceutical ingredients (APIs) were determined in different sludge treatments and fractions. Passive samplers were used to characterize the bioavailable and bioaccessible fractions, and the sampler extracts along the sludge and filtrate samples were utilized in the bioassays. The TCS and PAH concentrations did not decrease as the sludge was digested, but the contents diminished after composting. Also, mTCS concentration decreased after composting. The API concentrations were lower in digested sludge than in secondary sludge. Digested sludge was toxic for Aliivibrio fischeri, but after composting, toxicity was not observed. However, for Daphnia magna, passive sampler extracts of all sludge treatments were either acutely (immobility) or chronically (reproduction) toxic. Secondary and digested sludge sampler extracts were cytotoxic, and secondary sludge extract was also genotoxic. The measured chemical concentration levels did not explain the toxicity of the samples based on the reported toxicity thresholds. Bioassays and sampler extracts detecting bioavailable and bioaccessible contaminants in sludge are complementing tools for chemical analyses. Harmonization of these methodswill help establish scientifically sound regulative thresholds for the use of sludge in circular economy applications.

Zürich Statement on Future Actions on Per- and Polyfluoroalkyl Substances (PFASs).

Per- and polyfluoroalkyl substances (PFASs) are man-made chemicals that contain at least one perfluoroalkyl moiety, [Formula: see text]. To date, over 4,000 unique PFASs have been used in technical applications and consumer products, and some of them have been detected globally in human and wildlife biomonitoring studies. Because of their extraordinary persistence, human and environmental exposure to PFASs will be a long-term source of concern. Some PFASs such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) have been investigated extensively and thus regulated, but for many other PFASs, knowledge about their current uses and hazards is still very limited or missing entirely. To address this problem and prepare an action plan for the assessment and management of PFASs in the coming years, a group of more than 50 international scientists and regulators held a two-day workshop in November, 2017. The group identified both the respective needs of and common goals shared by the scientific and the policy communities, made recommendations for cooperative actions, and outlined how the science-policy interface regarding PFASs can be strengthened using new approaches for assessing and managing highly persistent chemicals such as PFASs. https://doi.org/10.1289/EHP4158.

Presence of active pharmaceutical ingredients in the continuum of surface and ground water used in drinking water production.

Anthropogenic chemicals in surface water and groundwater cause concern especially when the water is used in drinking water production. Due to their continuous release or spill-over at waste water treatment plants, active pharmaceutical ingredients (APIs) are constantly present in aquatic environment and despite their low concentrations, APIs can still cause effects on the organisms. In the present study, Chemcatcher passive sampling was applied in surface water, surface water intake site, and groundwater observation wells to estimate whether the selected APIs are able to end up in drinking water supply through an artificial groundwater recharge system. The API concentrations measured in conventional wastewater, surface water, and groundwater grab samples were assessed with the results obtained with passive samplers. Out of the 25 APIs studied with passive sampling, four were observed in groundwater and 21 in surface water. This suggests that many anthropogenic APIs released to waste water proceed downstream and can be detectable in groundwater recharge. Chemcatcher passive samplers have previously been used in monitoring several harmful chemicals in surface and wastewaters, but the path of chemicals to groundwater has not been studied. This study provides novel information on the suitability of the Chemcatcher passive samplers for detecting APIs in groundwater wells.

Degradation of artificial sweeteners via direct and indirect photochemical reactions.

We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment.

Estrogenic activity in Finnish municipal wastewater effluents.

Effluents from wastewater treatment plants (WWTPs) are a major source of estrogenic compounds to the aquatic environment. In the present work, estrogenic activities of effluents from eight municipal WWTPs in Finland were studied. The main objectives of the study were to quantify the concentrations of selected estrogenic compounds, to evaluate their contribution to estrogenic potency and to test the feasibility of the commercial bioassays for wastewater analysis. The effluent samples were analyzed by two in vitro tests, i.e. ERα-CALUX(®) and ELISA-E2, and by liquid chromatography mass spectrometry for six estrogenic compounds: estrone (E1), 17ß-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), 17α-estradiol and bisphenol A (BPA). Estrogenic effects were found in all of the effluent samples with both of the bioassays. The concentrations measured with ELISA-E2 (8.6-61.6 ng/L) were clearly higher but exhibited a similar pattern than those with chemical analysis (E2

Contamination risk of raw drinking water caused by PFOA sources along a river reach in south-western Finland.

Transport of perfluorooctanoic acid (PFOA) was simulated in the beginning of River Kokemäenjoki in Finland using one-dimensional SOBEK river model. River Kokemäenjoki is used as a raw water source for an artificial groundwater recharge plant, and the raw water intake plant is located near the downstream end of the model application area. Measured surface water and wastewater concentrations were used to determine the PFOA input to the river and to evaluate the simulation results. The maximum computed PFOA concentrations in the river at the location of the raw water intake plant during the simulation period Dec. 1, 2011-Feb. 16, 2014 were 0.92 ng/l and 3.12 ng/l for two alternative modeling scenarios. These concentration values are 2.3% and 7.8%, respectively, of the 40 ng/l guideline threshold value for drinking water. The current annual median and maximum PFOA loads to the river were calculated to be 3.9 kg/year and 10 kg/year respectively. According to the simulation results, the PFOA load would need to rise to a level of 57 kg/year for the 40 ng/l guideline value to be exceeded in river water at the raw water intake plant during a dry season. It is thus unlikely that PFOA concentration in raw water would reach the guideline value without the appearance of new PFOA sources. The communal wastewater treatment plants in the study area caused on average 11% of the total PFOA load. This raises a concern about the origin of the remaining 89% of the PFOA load and the related risk factors.

Quantification of four artificial sweeteners in Finnish surface waters with isotope-dilution mass spectrometry.

The artificial sweeteners sucralose (SCL), acesulfame (ACS), saccharin (SAC), and cyclamate (CYC) have been detected in environmental waters in Europe and North America. Higher environmental levels are expected in view of the increasing consumption of these food additives. In this study, an isotope-dilution mass spectrometry (IDMS) LC-MS/MS method was developed and validated for quantifying the four artificial sweeteners in boreal lakes (n = 3) and rivers (n = 12). The highest concentrations of ACS, SAC, CYC and SCL were 9,600, 490, 210 and 1000 ng/L, respectively. ACS and SAC were detected in all studied samples, and CYC and SCL in 98% and 56% of the samples. Seasonal trends of ACS and SAC were observed in some rivers. ACS and SCL concentrations in rivers correlated linearly with population equivalents of the wastewater treatment plants in the catchment areas, whereas SAC and CYC concentrations depend more on the source.

Survey of perfluorinated alkyl acids in Finnish effluents, storm water, landfill leachate and sludge.

The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of "a Baltic Sea with life undisturbed by hazardous substances". One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8-14, 8.0-640 and 320-1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9-15 ng/l) followed by PFOS (3.8-20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77%). In the target industry, PFOS concentrations varied between 1,400 and 18,000 µg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 µg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.

Photochemical reactivity of perfluorooctanoic acid (PFOA) in conditions representing surface water.

Potential of perfluorooctanoic acid (PFOA) to degrade via indirect photolysis in aquatic solution under conditions representing surface water was studied. Globally distributed and bioaccumulative PFOA does not absorb solar radiation by itself, but may be potentially photochemically transformed by the natural sensitizers such as dissolved organic matter (DOM), nitrate or ferric iron. Reaction solutions containing purified water, fulvic acid (representing DOM), nitrate, ferric iron or sea water from the Baltic Sea were spiked with PFOA and irradiated with an artificial sun (290-800 nm). In comparison similar samples were also irradiated under UV radiation at 254 nm in order to study the direct photolysis. UV radiation at 254 nm decomposed PFOA to perfluoroheptanoic-, perfluorohexanoic- and perfluoropentanoic acids. The samples irradiated with an artificial sun contained no decomposition products and no decrease in PFOA concentration was observed. According to the detection limit of the products and typical solar radiation at the surface of ocean, the photochemical half-life for PFOA was estimated to be at least 256 years at the depth of 0 m, >5000 years in the mixing layer of open ocean and >25,000 years in coastal ocean. This is significantly more than the previously reported photochemical half-life of PFOA (>0.96 years).