Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world’s rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

A considerable knowledge gap exists with respect to the fate and environmental relevance of transformation products (TPs) of polar organic micropollutants in surface water. To narrow this gap we investigated the fate of 20 parent compounds (PCs) and 11 characteristic TPs in four wastewater-impacted rivers. Samples were obtained from time-integrated active sampling as well as passive sampling using polar organic chemical integrative samplers (POCIS). Seventeen out of the 20 PCs were detected in at least one of the rivers. All the PCs except acesulfame, carbamazepine, and fluconazole were attenuated along the studied river stretches, with the largest decrease found in the smallest river which had an intense surface water-pore water exchange. Seven TPs were detected, all of which were already present directly downstream of the WWTP outfall, suggesting that the WWTPs were a major source of TPs to the recipients. For anionic compounds, attenuation was the highest in the two rivers with the lowest discharge, while the pattern was not as clear for neutral or cationic compounds. For most compounds the results obtained from active sampling were not significantly different from those using POCIS, demonstrating that the cost and labor efficient POCIS is suitable to determine the attenuation of organic micropollutants in rivers.

Surface seawater concentrations of PCBs, relative congener abundance, and possible effects of cold condensation were studied along a transect from the southern Norwegian Sea to the central Arctic Ocean (62°N-89°N). Large volume samples were collected from an ice breaker using a stainless steel surface seawater intake connected online to an ultra-clean laboratory. Concentrations of all studied PCB congeners, except for trichlorinated PCB 18, decreased with latitude. For instance, PCB 52 decreased from 470 fg L -1 at 62°N to 110 fg L -1 at 89°N and PCB 180 from 110 to 12 fg L -1 . Concentrations in the central Arctic Ocean were on the order of 10-100 fg L -1 for the most abundant congeners. The relative contribution of trichlorinated PCBs to the total PCB concentration increased with latitude, the tetrachlorinated contribution to the total PCBs did not show any correlation to latitude, and the relative contribution of heavier congeners decreased with latitude. This study establishes the occurrence at very low abundances of PCBs in seawater in the central Arctic Ocean and demonstrates a northward concentration decrease. The latitudinal shift in congener pattern is reflecting the relative propensity of the PCB congeners to undergo long-range transport in the Arctic and is consistent with their relative vapor pressures.

From previous laboratory and field studies, it remains unclear whether partitioning of hydrophobic organic contaminants (HOCs) to phytoplankton from water is kinetically limited or may be treated as an equilibrium process. Here, we report on the partitioning of polychlorinated biphenyls (PCBs) to particulate organic carbon (POC), dominated by planktonic primary production, in the open Baltic Sea during a 25-month period. The organic carbon-normalized partition coefficient (Koc) was corrected for temperature, salinity, and sorption to filter-passing organic carbon. At all 21 sampling occasions, the log Koc-log Kow regression was significantly linear, despite a large variation in biogeochemical parameters such as POC concentration and composition, primary production, and phytoplankton species composition. These data strongly suggest that partitioning of PCBs to POC in temperate surface waters is equilibrated and therefore not kinetically limited by factors such as rapid phytoplankton growth rate or large cell size. The partitioning of PCBs to the POC was described throughout seasonal cycles by log Koc = 0.88 +/- 0.07 log Kow + 0.90 +/- 0.47 (95% confidence interval). The slope of the log Koc-log Kow regression for the single sampling occasions varied between 0.56 and 1.25, and there was a seasonal variation in the POC sorbent quality (e.g., log Koc for PCB 28 varied between 5.5 and 6.9; median 5.9). These variations reflect the variability in structural composition of the POC pool in such pelagic waters. Being able to predict particle-water partitioning of HOCs significantly reduces the required complexity of both food web uptake models and predictions of POC-mediated export of HOCs to the deep ocean.

The hyporheic zone—the transition region beneath and alongside the stream bed—is a central compartment for attenuation of organic micropollutants in rivers. It provides abundant sorption sites and excellent conditions for biotransformation. We used a bench-scale flume to study the fate of 19 parent pharmaceuticals (PPs) and the formation of 11 characteristic transformation products (TPs) under boundary conditions similar to those in hyporheic zones. The persistence of PPs ranged from readily degradable with a dissipation half-life (DT50) as short as 1.8 days (acetaminophen, ibuprofen) to not degradable (chlorthalidone, fluconazole). The temporal and spatial patterns of PP and TP concentrations in pore water were heterogeneous, reflecting the complex hydraulic and biogeochemical conditions in hyporheic zones. Four TPs (carbamazepine-10,11-epoxide, metoprolol acid, 1-naphthol, and saluamine) were exclusively formed in the sediment compartment and released to surface water, highlighting their potential to be used as indicators for characterizing hyporheic transformation of micropollutants in streams. The accumulation of certain TPs over the experimental period illustrates that we might face a peak of secondary contamination by TPs far from the point of release of the original contaminants into a stream. Such TPs should be considered as priority candidates for a higher-tier environmental risk assessment.

Temporal trends of chlorinated paraffins (CPs) were analyzed in three sediment cores collected near different potential CP sources along the Swedish Baltic Sea coast. C-C CPs were found in sediment dating back to the 1930s. The maximum CP concentrations found in proximity to a metropolitan sewage treatment plant, a wood-related industrial area, and a steel factory were 48, 160, and 1400 ng/g d.w., respectively, in sediment sections dated from the early 1990s or the 2000s. The temporal trends agree with statistics on CP importation in Sweden or local industrial activities. MCCPs (C-C CPs) and LCCPs (C CPs) predominated in most sediments with average percentage compositions of 47 ± 20% and 37 ± 20%, respectively. Concentrations of SCCPs in the three cores showed a decreasing trend in recent years. The temporal trends of MCCPs indicated that these are currently the predominant CPs in use. This study showed for the first time that LCCPs from C to C, as well as C-C CPs, are persistent in sediments over the last 50-80 years, indicating that CPs are persistent chemicals regardless of alkane-chain lengths.

There is a wealth of studies of polychlorinated biphenyls (PCB) in surface water and biota of the Arctic Ocean. Still, there are no observation-based assessments of PCB distribution and inventories in and between the major Arctic Ocean compartments. Here, the first water column distribution of PCBs in the central Arctic Ocean basins (Nansen, Amundsen, and Makarov) is presented, demonstrating nutrient-like vertical profiles with 5-10 times higher concentrations in the intermediate and deep water masses than in surface waters. The consistent vertical profiles in all three Arctic Ocean basins likely reflect buildup of PCBs transported from the shelf seas and from dissolution and/or mineralization of settling particles. Combined with measurement data on PCBs in other Arctic Ocean compartments collected over the past decade, the total Arctic Ocean inventory of ∑7PCB was estimated to 182 ± 40 t (±1 standard error of the mean), with sediments (144 ± 40 t), intermediate (5 ± 1 t) and deep water masses (30 ± 2 t) storing 98% of the PCBs in the Arctic Ocean. Further, we used hydrographic and carbon cycle parametrizations to assess the main pathways of PCBs into and out of the Arctic Ocean during the 20th century. River discharge appeared to be the major pathway for PCBs into the Arctic Ocean with 115 ± 11 t, followed by ocean currents (52 ± 17 t) and net atmospheric deposition (30 ± 28 t). Ocean currents provided the only important pathway out of the Arctic Ocean, with an estimated cumulative flux of 22 ± 10 t. The observation-based inventory of ∑7PCB of 182 ± 40 t is consistent with the contemporary inventory based on cumulative fluxes for ∑7PCB of 173 ± 36 t. Information on the concentration and distribution of PCBs in the deeper compartments of the Arctic Ocean improves our understanding of the large-scale fate of POPs in the Arctic and may also provide a means to test and improve models used to assess the fate of organic pollutants in the Arctic.

Hyporheic zones are the water-saturated flow-through subsurfaces of rivers which are characterized by the simultaneous occurrence of multiple physical, biological, and chemical processes. Two factors playing a role in the hyporheic attenuation of organic contaminants are sediment bedforms (a major driver of hyporheic exchange) and the composition of the sediment microbial community. How these factors act on the diverse range of organic contaminants encountered downstream from wastewater treatment plants is not well understood. To address this knowledge gap, we investigated dissipation half-lives (DT50s) of 31 substances (mainly pharmaceuticals) under different combinations of bacterial diversity and bedform-induced hyporheic flow using 20 recirculating flumes in a central composite face factorial design. By combining small-volume pore water sampling, targeted analysis, and suspect screening, along with quantitative real-time PCR and time-resolved amplicon Illumina MiSeq sequencing, we determined a comprehensive set of DT50s, associated bacterial communities, and microbial transformation products. The resulting DT50s of parent compounds ranged from 0.5 (fluoxetine) to 306 days (carbamazepine), with 20 substances responding significantly to bacterial diversity and four to both diversity and hyporheic flow. Bacterial taxa that were associated with biodegradation included Acidobacteria (groups 6, 17, and 22), Actinobacteria (Nocardioides and Illumatobacter), Bacteroidetes (Terrimonas and Flavobacterium) and diverse Proteobacteria (Pseudomonadaceae, Sphingomonadaceae, and Xanthomonadaceae). Notable were the formation of valsartan acid from irbesartan and valsartan, the persistence of N-desmethylvenlafaxine across all treatments, and the identification of biuret as a novel transformation product of metformin. Twelve additional target transformation products were identified, which were persistent in either pore or surface water of at least one treatment, indicating their environmental relevance.