Abstract-Pharmaceuticals and personal care products are being increasingly reported in a variety of biological matrices, including fish tissue; however, screening studies have presently not encompassed broad geographical areas. A national pilot study was initiated in the United States to assess the accumulation of pharmaceuticals and personal care products in fish sampled from five effluent-dominated rivers that receive direct discharge from wastewater treatment facilities in Chicago, Illinois; Dallas, Texas; Orlando, Florida; Phoenix, Arizona; and West Chester, Pennsylvania, USA. Fish were also collected from the Gila River, New Mexico, USA, as a reference condition expected to be minimally impacted by anthropogenic influence. High performance liquid chromatography-tandem mass spectrometry analysis of pharmaceuticals revealed the presence of norfluoxetine, sertraline, diphenhydramine, diltiazem, and carbamazepine at nanogram-per-gram concentrations in fillet composites from effluent-dominated sampling locations; the additional presence of fluoxetine and gemfibrozil was confirmed in liver tissue. Sertraline was detected at concentrations as high as 19 and 545 ng/ g in fillet and liver tissue, respectively. Gas chromatography-tandem mass spectrometry analysis of personal care products in fillet composites revealed the presence of galaxolide and tonalide at maximum concentrations of 2,100 and 290 ng/g, respectively, and trace levels of triclosan. In general, more pharmaceuticals were detected at higher concentrations and with greater frequency in liver than in fillet tissues. Higher lipid content in liver tissue could not account for this discrepancy as no significant positive correlations were found between accumulated pharmaceutical concentrations and lipid content for either tissue type from any sampling site. In contrast, accumulation of the personal care products galaxolide and tonalide was significantly related to lipid content. Results suggest that the detection of pharmaceuticals and personal care products was dependent on the degree of wastewater treatment employed.

Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0-12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.cetaceans | cerumen | persistent organic pollutants

As engineered nanoparticles (NPs) are increasingly used, their entry into the environment has become an important topic for water sustainability. Recent investigations point to the critical role of natural organic matter (NOM) in altering the persistence of NPs by complexing with their surfaces. The NP-NOM complex, in turn, is the new entity that may potentially influence subsequent fate of NPs. To understand the relative impact of humic (HA) and fulvic fraction of NOM on the stability and mobility of silver nanoparticles (AgNPs), a combination of dynamic light scattering and quartz crystal microgravimetry with dissipation monitoring was used. In the absence of unbound NOM, (1) surface modification on either AgNP or silica substrate by different NOM fractions could lead to substantial changes in the extent and kinetics of AgNP aggregation and deposition, and (2) HA has a greater capability to enhance the transport of AgNPs by reducing their aggregation and deposition. With unbound NOM, HA seems to compete more successfully for binding sites on the substrate under electrostatically favorable conditions and formed a steric layer to prevent subsequent deposition of AgNPs. These findings highlighted the importance of NOM fraction in the overall environmental partitioning of AgNPs.

The core parks included three west coast (OLYM, MORA, and SEKI), three Alaska parks (NOAT, GAAR, DENA), and two parks in the Rocky Mountains (ROMO and GLAC). We selected two sampling sites (i.e. lakes) in each park, with the exception of NOAT and GAAR, where we sampled one site in each, for a total of 14 sites. Lakes were selected to have no glaciers in their watersheds, relatively simple bathymetry, minimal inlets and outlets and an established salmonid spp.population that we were permitted to sample. B.) Sample matrices and the rationale for their selection:The WACAP study was designed as a screening study to assess contaminant concentrations across large-scale spatial gradients and temporal scales relevant to western national parks. The seven ecosystem components selected for analysis were: air, snow, water, lake sediments, lichens, conifer needles, and fish. These components were chosen for the reasons described below.End-of-season snowpack samples contain an integrated record of wet and dry contaminant deposition occurring during the snow-accumulation season. A significant proportion of the contaminant load in snowpack may be delivered to the ecosystem during snowmelt (with specific fates varying by contaminant). We used snowpack samples, collected from the vertical face of snow pits dug from the snow surface to the ground, to calculate contaminant flux delivered via snow (3).We used passive air sampling devices (PASD) to: (a) obtain a measure of SOCs in ambient air by means of a simple, standardized technology to compare loadings among parks and across geographic and elevational gradients, (b) compare PASD and vegetation

An analytical method was developed for the trace analysis of a wide range of semivolatile organic compounds (SOCs) in 50-L high-elevation snow and lake water samples. The method was validated for 75 SOCs from seven different chemical classes (polycyclic aromatic hydrocarbons, organochlorine pesticides, amides, triazines, polychlorinated biphenyls, thiocarbamates, and phosphorothioates) that covered a wide range of physical-chemical properties including 7 orders of magnitude of octanol-water partition coefficient (log K(ow) = 1.4-8.3). The SOCs were extracted using a hydrophobically and hydrophilically modified divinylbenzene solid-phase extraction device (modified Speedisk). The average analyte recovery from 50 L of reverse osmosis water, using the modified Speedisk, was 99% with an average relative standard deviation of 4.8%. Snow samples were collected from the field, melted, and extracted using the modified Speedisk and a poly(tetrafluoroethylene) remote sample adapter in the laboratory. Lake water was sampled, filtered, and extracted in situ using an Infiltrex 100 fitted with a 1-microm glass fiber filter to trap particulate matter and the modified Speedisk to trap dissolved SOCs. The extracts were analyzed by gas chromatographic mass spectrometry with electron impact ionization and electron capture negative ionization using isotope dilution and selective ion monitoring. Estimated method detection limits for snow and lake water ranged from 0.2 to 125 pg/L and 0.5-400 pg/L, respectively. U.S. historic and current-use pesticides were identified and quantified in snow and lake water samples collected from Rocky Mountain National Park, CO. The application of the analytical method to the analysis of SOCs in large-volume groundwater samples is also shown.