Exposure to and Biomarker Responses From Legacy and Emerging Contaminants Along Three Drainages in the Milwaukee Estuary, Wisconsin, USA.

Legacy contaminants and contaminants of emerging concern (CECs) were assessed in tree swallow (Tachycineta bicolor) tissue and diet samples from three drainages in the Milwaukee estuary, Wisconsin, USA, to understand exposures and possible biomarker responses. Two remote Wisconsin lakes were assessed for comparative purposes. Bioaccumulative classes of contaminants, such as polybrominated diphenyl ethers and per- and polyfluoroalkyl substances, while at higher concentrations than the reference lakes, did not vary significantly among sites or among the three drainages.

Free Ethynylarsinidene and Ethynylstibinidene: Heavier Analogues of Nitrenes and Phosphinidenes.

Until now, there has been very little experimental evidence for the existence of free arsinidenes and stibinidenes, apart from the hydrides, AsH and SbH. Here, we report on photogeneration of triplet ethynylarsinidene, HCCAs, and triplet ethynylstibinidene, HCCSb, from ethynylarsine and ethynylstibine, respectively, in solid argon matrices. The products were identified using infrared spectroscopy and the associated UV absorption spectra are interpreted with the aid of theoretical predictions.

Multi-omics responses in tree swallow (Tachycineta bicolor) nestlings from the Maumee Area of Concern, Maumee River, Ohio.

A multi-omics approach was utilized to identify altered biological responses and functions, and to prioritize contaminants to assess the risks of chemical mixtures in the Maumee Area of Concern (AOC), Maumee River, OH, USA. The Maumee AOC is designated by the United States Environmental Protection Agency as having significant beneficial use impairments, including degradation of fish and wildlife populations, bird or animal deformities or reproduction problems, and loss of fish and wildlife habitat. Tree swallow (Tachycineta bicolor) nestlings were collected at five sites along the Maumee River, which included wastewater treatment plants (WWTPs) and industrial land-use sites.

Unusual Quartet-Doublet Phosphorescence from the Phosphaethynyl Radical, CP.

We report the first detection of phosphorescence from the phosphaethynyl radical. This rare instance of quartet-doublet emission, studied here in solid argon, is presumably promoted by efficient intersystem crossing from the originally photoexcited doublet (B Σ ) to the adjacent second quartet state, 1 Δ. Vibronic progressions were traced for the a Σ -X Σ and a Σ -A П systems from their origins up to (v'=0)→(v''=5) and (v'=0)→(v''=2) bands, respectively.

Using tree swallows to assess reductions in PCB exposure as a result of dredging at Great Lakes Restoration Initiative (GLRI) sites in the Upper Midwest, USA.

Tree swallows (Tachycineta bicolor) were used to assess the effectiveness of reducing polychlorinated biphenyl (PCB) exposure to wildlife as a result of contaminated sediment removal at locations across the Great Lakes under two dredging scenarios, full or spot dredging. For comparative purposes, other locations where no dredging occurred were also assessed. Calculating accumulation rate, from the mass of a contaminant in tree swallow eggs and nestling carcasses, is a useful tool to assess the effectiveness of sediment removal.

An Efficient Photochemical Route Towards Triplet Ethynylphosphinidene, HCCP.

While the archetypal free phosphinidene, H-P, has been studied for over a century, reports on uncomplexed, univalent phosphorus compounds are very sparse. Here we demonstrate production of HCCP in solid argon through the UV-induced rearrangement and subsequent dehydrogenation of phosphapropyne, CH CP. Migration of H atoms along the CCP backbone of CH CP resulted in production of the previously unobserved species 1-phosphapropadiene, CH =C=PH, followed by ethynylphosphine, HCCPH .

Legacy and Contaminants of Emerging Concern in Tree Swallows Along an Agricultural to Industrial Gradient: Maumee River, Ohio.

Exposure to multiple classes of contaminants, both legacy and contaminants of emerging concern (CECs), were assessed in tree swallow (Tachycineta bicolor) tissue and diet samples from 6 sites along the Maumee River, Ohio, USA, to understand both exposure and possible effects of exposure to those CECs for which there are little avian data. The 6 sites represented a gradient from intensive agriculture upstream to highly urbanized and industrial landscapes downstream; 1 or 2 remote Wisconsin lakes were assessed for comparative purposes. Cytochrome P450 induction, DNA damage, and thyroid function were also assessed relative to contaminant exposure.

Isomerization of cyanopropyne in solid argon.

Cyanopropyne, CH3-C[triple bond, length as m-dash]C-CN, is a simple molecule whose photochemistry is still unexplored. Here we investigate the UV photolysis of this astrophysically significant nitrile trapped in solid argon. The FTIR study was assisted with 15N-isotopic substitution data and with DFT-level computations including the analyses of ground- and excited-state potential energy surfaces.

Photochemistry of XCHCN (X = -Cl, -SH) in Argon Matrices.

We report infrared spectra and photochemical behavior of the potentially astrochemically significant species, mercaptoacetonitrile (HS-CHC≡N) and, for comparison purposes, chloroacetonitrile (Cl-CHC≡N), both suspended in an argon matrix at 6 K. Photolytic formation of the isocyano products HS-CH-NC and Cl-CH-NC were observed as well as CHNSC and CHSCN (in HS-CHCN photolysis). While no dissociation products were observed for Cl-CH-CN, photolysis of HS-CH-CN produced compounds necessitating the loss of the CN group to form CH═S, the SH group to form HC-CN and HC-CN, or both CN and SH to form CH and CH.

Perfluoroalkyl Contaminant Exposure and Effects in Tree Swallows Nesting at Clarks Marsh, Oscoda, Michigan, USA.

A site in northeastern Michigan, Oscoda Township, has some of the highest recorded exposure in birds to perfluorinated substances (PFASs) in the United States. Some egg and plasma concentrations at that location exceeded the lowest reproductive effect threshold established for two avian laboratory species. The objectives of this study were to determine whether there were reproductive effects or physiological responses in a model bird species, the tree swallow (Tachycineta bicolor), associated with this extremely high exposure to PFASs.

Element Concentrations in Tree Swallows (Tachycineta bicolor) from the U.S. and Binational Great Lakes Areas of Concern.

Selected elements were targeted in state Remedial Action Plans as one group of chemicals affecting the Beneficial Use Impairments of Great Lakes Areas of Concern (AOCs). Livers of nestling tree swallows, Tachycineta bicolor, were harvested from 76 sites in the Great Lakes, which included multiple sites at 27 AOCs and 12 reference sites from 2010 to 2015, and were analyzed for 21 elements. Mercury concentrations were at background levels at all sites.

Annual variation in polychlorinated biphenyl (PCB) exposure in tree swallow (Tachycineta bicolor) eggs and nestlings at Great Lakes Restoration Initiative (GLRI) study sites.

Tree swallow (Tachycineta bicolor) eggs and nestlings were collected from 16 sites across the Great Lakes to quantify normal annual variation in total polychlorinated biphenyl (PCB) exposure and to validate the sample size choice in earlier work. A sample size of five eggs or five nestlings per site was adequate to quantify exposure to PCBs in tree swallows given the current exposure levels and variation. There was no difference in PCB exposure in two randomly selected sets of five eggs collected in the same year, but analyzed in different years.

Reproductive success and contaminant associations in tree swallows (Tachycineta bicolor) used to assess a Beneficial Use Impairment in U.S. and Binational Great Lakes' Areas of Concern.

During 2010-2014, tree swallow (Tachycineta bicolor) reproductive success was monitored at 68 sites across all 5 Great Lakes, including 58 sites located within Great Lakes Areas of Concern (AOCs) and 10 non-AOCs. Sample eggs were collected from tree swallow clutches and analyzed for contaminants including polychlorinated biphenyls (PCBs), dioxins and furans, polybrominated diphenyl ethers, and 34 other organic compounds. Contaminant data were available for 360 of the clutches monitored.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern.

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis.

Cryogenic Photochemical Synthesis and Electronic Spectroscopy of Cyanotetracetylene.

HCN is a molecule of astrochemical interest. In this study, it was produced in cryogenic Ar and Kr matrices from UV-photolyzed diacetylene/cyanodiacetylene mixtures. Its strong phosphorescence was discovered and served for the identification of the compound.

Structure and Spectroscopy of CHNO Isomers.

Formyl cyanide has been detected toward Sgr B2 making this chemical and its potential isomers of astrophysical interest. We calculated the precise energies of the five most stable structural isomers of formyl cyanide and found that formyl isocyanide and 2H-azirin-2-one are less stable than formyl cyanide by 55 and 125 kJ/mol, respectively. We present our ab initio coupled cluster predictions of the spectroscopic parameters relevant to their gas-phase rotational and vibrational spectroscopy.

In vitro labeling strategies for in cellulo fluorescence microscopy of single ribonucleoprotein machines.

RNA plays a fundamental, ubiquitous role as either substrate or functional component of many large cellular complexes-"molecular machines"-used to maintain and control the readout of genetic information, a functional landscape that we are only beginning to understand. The cellular mechanisms for the spatiotemporal organization of the plethora of RNAs involved in gene expression are particularly poorly understood. Intracellular single-molecule fluorescence microscopy provides a powerful emerging tool for probing the pertinent mechanistic parameters that govern cellular RNA functions, including those of protein coding messenger RNAs (mRNAs).

Electronic Spectroscopy of Methylcyanodiacetylene (CH C N).

The results of a study devoted to the electronic spectroscopy of gaseous, solid, and cryogenic matrix-isolated methylcyanodiacetylene (CH C N) are reported. UV absorption and optical phosphorescence spectra of the compound are described here for the first time, and the corresponding vibronic assignments are proposed. UV absorption, studied directly or through the excitation of phosphorescence, revealed the B˜   E--X˜   A system, very weak A˜   A -X˜   A bands, and a strong, broad absorption feature, tentatively identified as D˜   E-X˜   A .

A novel method to accurately locate and count large numbers of steps by photobleaching.

Photobleaching event counting is a single-molecule fluorescence technique that is increasingly being used to determine the stoichiometry of protein and RNA complexes composed of many subunits in vivo as well as in vitro. By tagging protein or RNA subunits with fluorophores, activating them, and subsequently observing as the fluorophores photobleach, one obtains information on the number of subunits in a complex. The noise properties in a photobleaching time trace depend on the number of active fluorescent subunits.

Organic contamination in tree swallow (Tachycineta bicolor) nestlings at United States and binational Great Lakes Areas of Concern.

Contaminant exposure of tree swallows, Tachycineta bicolor, nesting in 27 Areas of Concern (AOCs) in the Great Lakes basin was assessed from 2010 to 2014 to assist managers and regulators in their assessments of Great Lakes AOCs. Contaminant concentrations in nestlings from AOCs were compared with those in nestlings from nearby non-AOC sites. Polychlorinated biphenyl (PCB) and polybrominated diphenyl ether concentrations in tree swallow nestling carcasses at 30% and 33% of AOCs, respectively, were below the mean concentration for non-AOCs.

Infrared and Raman Spectroscopy of Methylcyanodiacetylene (CH C N).

A spectroscopic study combining IR absorption and Raman scattering is presented for methylcyanodiacetylene (CH C N). Gas-phase, cryogenic matrix-isolated, and pure solid-phase substance was analyzed. Out of 16 normal vibrational modes, 14 were directly observed.

Density Functional Exploration of C4H3N Isomers.

Molecules having C4H3N stoichiometry are of astrophysical interest. Two of these, methylcyanoacetylene (CH3C3N) and its structural isomer allenyl cyanide (H2CCCHN), have been observed in interstellar space, while several more have been examined in laboratories. Here we describe, for a broad range of C4H3N isomers, density functional calculations (B3LYP/aug-cc-pVTZ) of molecular parameters including the energetics, geometries, rotational constants, electric dipole moments, polarizabilities, vibrational IR frequencies, IR absorption intensities, and Raman activities.

Concentrations and spatial patterns of organic contaminants in tree swallow (Tachycineta bicolor) eggs at United States and binational Great Lakes Areas of Concern, 2010-2015.

Tree swallows, Tachycineta bicolor, were sampled across the Great Lakes basin in 2010 through 2015 to provide a system-wide assessment of current exposure to organic contaminants. The results provide information identified as critical by regulators to assess the "bird or animal deformity or reproductive problems" beneficial use impairment. Eggs were collected from 69 sites across all 5 Great Lakes, including 27 Areas of Concern (AOCs), some with multiple sites, and 10 sites not listed as an AOC.

Mercury Concentrations in Eggs of Red-Winged Blackbirds and Tree Swallows Breeding in Voyageurs National Park, Minnesota.

Most investigations of the environmental effects of mercury (Hg) have focused on aquatic food webs that include piscivorous fish or wildlife. However, recent investigations have shown that other species, including passerine songbirds, may also be at risk from exposure to methylmercury (MeHg). We quantified Hg concentrations in eggs of two species of songbirds, red-winged blackbirds (Agelaius phoeniceus) and tree swallows (Tachycineta bicolor), nesting in Voyageurs National Park, Minnesota, USA.

Chromosomal damage and EROD induction in tree swallows (Tachycineta bicolor) along the Upper Mississippi River, Minnesota, USA.

The health of tree swallows, Tachycineta bicolor, on the Upper Mississippi River (UMR) was assessed in 2010 and 2011 using biomarkers at six sites downriver of Minneapolis/St. Paul, MN metropolitan area, a tributary into the UMR, and a nearby lake. Chromosomal damage was evaluated in nestling blood by measuring the coefficient of variation of DNA content (DNA CV) using flow cytometry.