Transport and fate of aqueous film forming foam in an urban estuary.

The deployment of aqueous film forming foams (AFFF) used for firefighting during emergencies and training often releases per- and polyfluoroalkyl substances (PFAS) into the environment. In October 2018, first responders in Providence, RI, USA applied an AFFF during a fuel spill. Due to the proximity of the incident to the upper reaches of Narragansett Bay (NB), an unknown quantity of gasoline and AFFF entered the estuary via surface runoff and stormwater drains. Water samples near the spill were collected approximately 15 h after the incident and analyzed for 24 PFAS. Minor increases in measured PFAS concentrations were observed relative to pre- and post-spill samples at monitoring sites near the incident, except 6:2-fluorotelomer sulfonate (6:2-FTS) that peaked post-spill (max 311 ng/L). After performing the total oxidizable precursor (TOP) assay on water samples and the AFFF concentrate, significant increases in perfluorocarboxylic acids (PFCAs) were observed. One compound, 6:2 fluorotelomer mercaptoalkylamido sulfonate (6:2-FTSAS), was identified as a major component of the AFFF used. Peak areas of 6:2-FTSAS and the degradation product 6:2-FTSAS-sulfoxide corresponded to observed increases in the TOP assay results and were useful as tracers of AFFF in surrounding waters. Elevated levels of PFAS at the time of sampling were limited to a confined area of the Providence River due to river flow and tidal action. Observed concentrations were also compared to hydrodynamic model results, and results confirmed rapid dissipation of AFFF components with distance from the spill. However, modeled results did not capture possible secondary releases of AFFF from local municipal stormwater and sewer infrastructure, as observational data suggest. The multiple lines of evidence of PFAS present in surface waters permitted a better assessment of the potential environmental impacts from products such as AFFF for which the chemical composition is largely unknown.

Legacy and Novel Per- and Polyfluoroalkyl Substances in Juvenile Seabirds from the U.S. Atlantic Coast.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic, globally distributed chemicals. Legacy PFAS, including perfluorooctane sulfonate (PFOS), have been regularly detected in marine fauna but little is known about their current levels or the presence of novel PFAS in seabirds. We measured 36 emerging and legacy PFAS in livers from 31 juvenile seabirds from Massachusetts Bay, Narragansett Bay, and the Cape Fear River Estuary (CFRE), United States. PFOS was the major legacy perfluoroalkyl acid present, making up 58% of concentrations observed across all habitats (range: 11-280 ng/g). Novel PFAS were confirmed in chicks hatched downstream of a fluoropolymer production site in the CFRE: a perfluorinated ether sulfonic acid (Nafion byproduct 2; range: 1-110 ng/g) and two perfluorinated ether carboxylic acids (PFO4DA and PFO5DoDA; PFO5DoDA range: 5-30 ng/g). PFOS was inversely associated with phospholipid content in livers from CFRE and Massachusetts Bay individuals, while δ 13C, an indicator of marine versus terrestrial foraging, was positively correlated with some long-chain PFAS in CFRE chick livers. There is also an indication that seabird phospholipid dynamics are negatively impacted by PFAS, which should be further explored given the importance of lipids for seabirds.

Evaluation of the artificial sweetener sucralose as a sanitary wastewater tracer in Narragansett Bay, Rhode Island, USA.

Narragansett Bay is an urban estuary that historically has been impacted by long-term discharge of sanitary wastewater (WW) effluents. High-density water sampling was conducted in Narragansett Bay, RI, USA, in an effort to understand the distribution and behavior of sucralose, an artificial sweetener that has shown utility as a sanitary wastewater tracer. Water samples were collected at sixty-seven sites and analyzed for sucralose, whose performance was compared to other tracers present in wastewater effluents. Concentrations of sucralose were much higher than the other tracers measured, carbamazepine and caffeine, ranging from 18 to 3180 ng/L and corresponded well with salinity (r2 = 0.88), demonstrating conservative behavior throughout the Bay. Mapped interpolation data using an empirical bayesian kriging model clearly show the spatial trends of WW and how estuarine processes influence dilution and dispersion throughout the Bay. These findings provide further evidence of the efficacy of sucralose as a wastewater tracer in large urban estuaries where continuous high-volume discharge of WW occur.

Evaluation of wastewater tracers to predict pharmaceutical distributions and behavior in the Long Island Sound estuary.

Urban estuaries receive large volumes of effluents from municipal wastewater treatment facilities containing numerous contaminants, such as pharmaceuticals residues. Water was sampled for 16 highly prescribed pharmaceuticals at 17 sites along the Long Island Sound (LIS) estuary located in the Northeastern U.S. Pharmaceutical concentrations were highest in western LIS, ranging from non-detect to 71 ng L-1 and declining steadily eastward, while river samples from four major tributaries ranged from non-detect to 83 ng L-1. Two tracers, sucralose and caffeine, accurately predicted pharmaceutical behavior in LIS while only sucralose was effective at the river sites. Sucralose also tracked well with the salinity gradient in LIS, exhibiting conservative behavior along the transect. Attenuation factors were determined for measurable pharmaceuticals and compared against sucralose to estimate the magnitude of decline in concentrations that may be attributable to in situ degradation and partitioning. The results demonstrate sucralose's effectiveness as a tracer of wastewater-borne contaminants under estuarine conditions.

Cellular responses to in vitro exposures to ß-blocking pharmaceuticals in hard clams and Eastern oysters.

Increased consumption and improper disposal of prescription medication, such as beta (ß)-blockers, contribute to their introduction into waterways and may pose threats to non-target aquatic organisms. There has been rising concern about the impacts of these prescription drugs on coastal ecosystems, especially because wastewater treatment plants are not designed to eliminate them from the discharge. Few studies have characterized the sublethal effects of ß-blocker exposures in marine invertebrates. The overall aim of our research is to identify cellular responses of two commercially important filter-feeding marine bivalves, hard clams (Mercenaria mercenaria) and Eastern oysters (Crassostrea virginica), upon exposures to two ß-blocker drugs, propranolol and metoprolol. In vitro exposures with bivalve digestive gland and gill tissues were conducted where tissues were separately exposed to each drug for 24 h. Tissue samples were analyzed for cellular damage (lysosomal membrane destabilization and lipid peroxidation), total antioxidant capacity, and glutathione-s-transferase activity. Elevated damage and changes in enzyme activities were noted in the exposed tissues at environmentally relevant concentrations. Differences in species and tissue sensitivities and responses to exposures were also observed. These studies enhance our understanding of the potential impacts of prescription medication on coastal organisms. Additionally, this work demonstrates that filter-feeders may serve as good model organisms to examine the effects of unintended environmental exposures to ß-blockers. These studies are part of our ongoing work aimed at evaluation of sublethal biomarkers of pharmaceutical exposures and identification of key events that can contribute to the development of adverse outcome pathways (AOPs).

Magnitude of acute toxicity of marine sediments amended with conventional copper and nanocopper.

It is well known that copper (Cu) is toxic to marine organisms. We measured and compared the acute toxicity of several forms of Cu (including nanoCu) amended into a marine sediment with mysids and amphipods. For all the forms of Cu tested, toxicity, measured as the median lethal concentration, ranged from 708 to > 2400 mg Cu/kg (dry sediment) for mysids and 258 to 1070 mg Cu/kg (dry sediment) for amphipods. Environ Toxicol Chem 2018;37:2677-2681. © 2018 SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Spatial patterns of pharmaceuticals and wastewater tracers in the Hudson River Estuary.

The widespread use of pharmaceuticals by human populations results in their sustained discharge to surface waters via wastewater treatment plants (WWTPs). In this study, 16 highly prescribed pharmaceuticals were quantified along a 250 km transect of the Hudson River Estuary and New York Harbor to describe their sources and spatial patterns. Sampling was conducted over two dry weather periods in May and July 2016, at 72 sites which included mid-channel and nearshore sites, as well as locations influenced by tributaries and WWTP outfalls. The detection frequency of the study pharmaceuticals was almost identical between the May and July sampling periods at 55% and 52%, respectively. Six pharmaceuticals were measurable at 92% or more of the sites during both sampling periods, illustrating their ubiquitous presence throughout the study area. Individual pharmaceutical concentrations were highly variable spatially, ranging from non-detect to 3810 ng/L during the study. Major factors controlling concentrations were proximity and magnitude of WWTP discharges, inputs from tributaries and tidal mixing. Two compounds, sucralose and caffeine, were evaluated as tracers to identify wastewater sources and assess pharmaceutical behavior. Sucralose was useful in identifying wastewater inputs to the river and concentrations showed excellent correlations with numerous pharmaceuticals in the study. Caffeine-sucralose ratios showed potential in identifying discharges of untreated wastewater occurring during a combined sewage overflow event. Many of the study pharmaceuticals were present throughout the Hudson River Estuary as a consequence of sustained wastewater discharge. Whereas some concentrations were above published effects levels, a more complete risk assessment is needed to understand the potential for ecological impacts due to pharmaceuticals in the Hudson River Estuary.

Assessing the release of copper from nanocopper-treated and conventional copper-treated lumber into marine waters II: Forms and bioavailability.

One application of nanocopper is as a wood-preserving pesticide in pressure-treated lumber. Recent research has shown that pressure-treated lumber amended with micronized copper azole (MCA), which contains nanosized copper, releases copper under estuarine and marine conditions. The form of copper released (i.e., ionic, nanocopper [1-100 nm in size]) is not fully understood but will affect the bioavailability and toxicity of the metal. In the present study, multiple lines of evidence, including size fractionation, ion-selective electrode electrochemistry, comparative toxicity, and copper speciation were used to determine the form of copper released from lumber blocks and sawdust. The results of all lines of evidence supported the hypothesis that ionic copper was released from MCA lumber and sawdust, with little evidence that nanocopper was released. For example, copper concentrations in size fractionations of lumber block aqueous leachates including unfiltered, 0.1 µm, and 3 kDa were not significantly different, suggesting that the form of copper released was in the size range operationally defined as dissolved. These results correlated with the ion-selective electrode data which detects only ionic copper. In addition, comparative toxicity testing resulted in a narrow range of median lethal concentrations (221-257 µg/L) for MCA lumber blocks and CuSO4 . We conclude that ionic copper was released from the nanocopper pressure-treated lumber under estuarine and marine conditions. Environ Toxicol Chem 2018;37:1969-1979. Published 2018 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Assessing the release of copper from nanocopper-treated and conventional copper-treated lumber into marine waters I: Concentrations and rates.

Little is known about the release of metal engineered nanomaterials (ENMs) from consumer goods, including lumber treated with micronized copper. Micronized copper is a recent form of antifouling wood preservative containing nanosized copper particles for use in pressure-treated lumber. The present study investigated the concentrations released and the release rate of total copper over the course of 133 d under freshwater, estuarine, and marine salinity conditions (0, 1, 10, and 30‰) for several commercially available pressure-treated lumbers: micronized copper azole (MCA) at 0.96 and 2.4 kg/m3 , alkaline copper quaternary (ACQ) at 0.30 and 9.6 kg/m3 , and chromated copper arsenate (CCA) at 40 kg/m3 . Lumber was tested as blocks and as sawdust. Overall, copper was released from all treated lumber samples. Under leaching conditions, total release ranged from 2 to 55% of the measured copper originally in the lumber, with release rate constants from the blocks of 0.03 to 2.71 (units per day). Generally, measured release and modeled equilibrium concentrations were significantly higher in the estuarine conditions compared with freshwater or marine salinities, whereas rate constants showed very limited differences between salinities. Furthermore, organic carbon was released during the leaching and demonstrated a significant relationship with released copper concentrations as a function of salinity. The results indicate that copper is released into estuarine/marine waters from multiple wood treatments including lumber amended with nanoparticle-sized copper. Environ Toxicol Chem 2018;37:1956-1968. Published 2018 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Particle-bound metal transport after removal of a small dam in the Pawtuxet River, Rhode Island, USA.

The Pawtuxet River in Rhode Island, USA, has a long history of industrial activity and pollutant discharges. Metal contamination of the river sediments is well documented and historically exceeded toxicity thresholds for a variety of organisms. The Pawtuxet River dam, a low-head dam at the mouth of the river, was removed in August 2011. The removal of the dam was part of an effort to restore the riverine ecosystem after centuries of anthropogenic impact. Sediment traps were deployed below the dam to assess changes in metal concentrations and fluxes (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) from the river system into Pawtuxet Cove. Sediment traps were deployed for an average duration of 24 days each, and deployments continued for 15 months after the dam was removed. Metal concentrations in the trapped suspended particulate matter dropped after dam removal (e.g., 460 to 276 mg/kg for Zn) and remained below preremoval levels for most of the study. However, particle-bound metal fluxes increased immediately after dam removal (e.g., 1206 to 4248 g/day for Zn). Changes in flux rates during the study period indicated that river volumetric flow rates acted as the primary mechanism controlling the flux of metals into Pawtuxet Cove and ultimately upper Narragansett Bay. Even though suspended particulate matter metal concentrations initially dropped after removal of the dam, no discernable effect on the concentration or flux of the study metals exiting the river could be associated with removal of the Pawtuxet River dam. Integr Environ Assess Manag 2017;13:675-685. Published 2016. This article is a US Government work and is in the public domain in the USA.

Temporal and spatial behavior of pharmaceuticals in Narragansett Bay, Rhode Island, United States.

The behavior and fate of pharmaceutical ingredients in coastal marine ecosystems are not well understood. To address this, the spatial and temporal distribution of 15 high-volume pharmaceuticals were measured over a 1-yr period in Narragansett Bay (RI, USA) to elucidate factors and processes regulating their concentration and distribution. Dissolved concentrations ranged from below detection to 313 ng/L, with 4 pharmaceuticals present at all sites and sampling periods. Eight pharmaceuticals were present in suspended particulate material, ranging in concentration from below detection to 44 ng/g. Partitioning coefficients were determined for some pharmaceuticals, with their range and variability remaining relatively constant throughout the study. Normalization to organic carbon content provided no benefit, indicating other factors played a greater role in regulating partitioning behavior. Within the upper bay, the continuous influx of wastewater treatment plant effluents resulted in sustained, elevated levels of pharmaceuticals. A pharmaceutical concentration gradient was apparent from this zone to the mouth of the bay. For most of the pharmaceuticals, there was a strong relationship with salinity, indicating conservative behavior within the estuary. Short flushing times in Narragansett Bay coupled with pharmaceuticals' presence overwhelmingly in the dissolved phase indicate that most pharmaceuticals will be diluted and transported out of the estuary, with only trace amounts of several compounds sequestered in sediments. The present study identifies factors controlling the temporal and spatial dynamics of dissolved and particulate pharmaceuticals; their partitioning behavior provides an increased understanding of their fate, including bioavailability in an urban estuary. Environ Toxicol Chem 2017;36:1846-1855. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Israeli medical education: international perspectives, and reflections on challenges and changes.

Medical education is a dynamic and continually evolving process, some of which is style, and some of which is linked to changing perspectives in medical practice. A paper by Reis et al., taken in conjunction with the recent paper from an ad hoc International Review Committee (Schoenbaum et al.), provides a reflective view of where Israeli medical education stood in 2014 and places it in an international perspective. Reis at al also take this further, showing that in Israel change is occurring as a result of this review and comment on a number of important issues where further reflection, discussion, and work is required.

Selected pharmaceuticals entering an estuary: Concentrations, temporal trends, partitioning, and fluxes.

In many coastal watersheds and ecosystems, rivers discharging to estuaries receive waters from domestic wastewater-treatment plants resulting in the release and distribution of pharmaceuticals to the marine environment. In the present study, 15 active pharmaceutical ingredients were measured regularly over 1 yr in the dissolved and particulate phases as they entered Narragansett Bay from the Pawtuxet River in Cranston (Rhode Island, USA). Of the active pharmaceutical ingredients measured, 14 were consistently present in the dissolved phase, with concentrations ranging from below detection to >310 ng/L, whereas 8 were present in the particulate phase (0.2-18 ng/g). Partition coefficients (Kd s and KOC s) were determined, and organic carbon normalization reduced variability associated with Kd s for the active pharmaceutical ingredients evaluated. Flux estimates based on river flow were calculated for both dissolved and particulate-phase active pharmaceutical ingredients, with particulate fluxes being low (1-12 g/yr) and dissolved fluxes of active pharmaceutical ingredients being 155 g/yr to 11 600 g/yr. Results indicate that the pharmaceuticals measured in the present study reside primarily in the dissolved phase and thus are likely bioavailable on entering the estuarine waters of Narragansett Bay. This long-term temporal study provides important information on seasonal and annual dynamics of pharmaceuticals in an urban estuarine watershed. Environ Toxicol Chem 2016;35:2665-2673. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and, as such, is in the public domain in the United States of America.

Caffeine in Boston Harbor past and present, assessing its utility as a tracer of wastewater contamination in an urban estuary.

Sites throughout Boston Harbor were analyzed for caffeine to assess its utility as a tracer in identifying sources of sanitary wastewater. Caffeine ranged from 15ng/L in the outer harbor to a high of 185ng/L in the inner harbor. Inner harbor concentrations were a result of combined sewage overflow (CSO) events as well as illicit discharge of sanitary sewage into municipal storm drains. Comparing current results to data from 1998 to 1999 shows reductions in caffeine levels. Reductions are attributed to termination of effluent discharge to the harbor, declines in the number of CSOs and discharge volume along with efforts to eliminate illicit discharges. Spatial distributions of caffeine identified CSOs as major contemporary sources to the inner harbor. The findings further establish the utility of caffeine as a tracer for sanitary wastewater contamination in urban estuaries and demonstrate the efficacy of pollution reduction strategies undertaken in recent decades in Boston Harbor.

Source determination of benzotriazoles in sediment cores from two urban estuaries on the Atlantic Coast of the United States.

Benzotriazoles (BZTs) are used in a broad range of commercial and industrial products, particularly as metal corrosion inhibitors and as ultraviolet (UV) light stabilizer additives in plastics and polymers. In this study, dated sediment cores from two east coast estuaries were analyzed for commonly used BZTs. In Narragansett Bay, UV stabilizing BZTs (UV-BZTs) were present at high levels from 1961 on, reflecting their patent date, local production and long-term preservation in sediment. In Salem Sound, UV-BZTs were present at concentrations consistent with other coastal marine locations not influenced by BZT production. Anticorrosive BZTs (AC-BZTs) were found in both cores, with the highest levels reported to date present in Narragansett Bay, indicating sorption to, and preservation in, sediments. This study revealed that both classes of BZTs have remained structurally intact over time in coastal sediment cores, demonstrating their resistance to degradation and persistence in environmental compartments.

Policy issues related to educating the future Israeli medical workforce: an international perspective.

A 2014 external review of medical schools in Israel identified several issues of importance to the nation's health. This paper focuses on three inter-related policy-relevant topics: planning the physician and healthcare workforce to meet the needs of Israel's population in the 21(st) century; enhancing the coordination and efficiency of medical education across the continuum of education and training; and the financing of medical education. All three involve both education and health care delivery. The physician workforce is aging and will need to be replenished. Several physician specialties have been in short supply, and some are being addressed through incentive programs. Israel's needs for primary care clinicians are increasing due to growth and aging of the population and to the increasing prevalence of chronic conditions at all ages. Attention to the structure and content of both undergraduate and graduate medical education and to aligning incentives will be required to address current and projected workforce shortage areas. Effective workforce planning depends upon data that can inform the development of appropriate policies and on recognition of the time lag between developing such policies and seeing the results of their implementation. The preclinical and clinical phases of Israeli undergraduate medical education (medical school), the mandatory rotating internship (stáge), and graduate medical education (residency) are conducted as separate "silos" and not well coordinated. The content of basic science education should be relevant to clinical medicine and research. It should stimulate inquiry, scholarship, and lifelong learning. Clinical exposures should begin early and be as hands-on as possible. Medical students and residents should acquire specific competencies. With an increasing shift of medical care from hospitals to ambulatory settings, development of ambulatory teachers and learning environments is increasingly important. Objectives such as these will require development of new policies. Undergraduate medical education (UME) in Israel is financed primarily through universities, and they receive funds through VATAT, an education-related entity. The integration of basic science and clinical education, development of earlier, more hands-on clinical experiences, and increased ambulatory and community-based medical education will demand new funding and operating partnerships between the universities and the health care delivery system. Additional financing policies will be needed to ensure the appropriate infrastructure and support for both educators and learners. If Israel develops collaborations between various government agencies such as the Ministries of Education, Health, and Finance, the universities, hospitals, and the sick funds (HMOs), it should be able to address successfully the challenges of the 21st century for the health professions and meet its population's needs.