Inter-ligand intramolecular through-space anisotropic shielding in a series of manganese carbonyl phosphorous compounds.

Eight novel manganese carbonyl complexes of the type [Mn(bpy-tBu)(CO)3PR3]+ (bpy-tBu = 4,4'-di-tert-butyl-2,2'-bipyridine; R = Cy, nBu, Me, p-tol, Ph, p-F-Ph, OEt, and OMe), have been synthesized and characterized by 1H NMR, FTIR, UV/Vis, HRMS and CV. X-ray crystallographic structures of [Mn(bpy-tBu)(CO)3(PCy3)]+ and [Mn(bpy-tBu)(CO)3(PPh3)]+ were obtained. The short Mn-P bond length allows for close proximity of the bipyridine ligand and the phosphine R groups, resulting in strong anisotropic shielding of certain bipyridine protons by aryl R groups (reordering the bipyridine 1H NMR pattern in the most extreme case). Electrochemical analysis of the compound series reveals that while each is a competent precatalyst for electrochemical carbon dioxide reduction (to carbon monoxide), the lability of the PR3 ligand results in similar catalytic performance amongst the series.

Canadian house dust study: lead bioaccessibility and speciation.

Vacuum samples were collected from 1025 randomly selected urban Canadian homes to investigate bioaccessible Pb (Pb(S)) concentrations in settled house dust. Results indicate a polymodal frequency distribution, consisting of three lognormally distributed subpopulations defined as "urban background" (geomean 58 µg g(-1)), "elevated" (geomean 447 µg g(-1)), and "anomalous" (geomean 1730 µg g(-1)). Dust Pb(S) concentrations in 924 homes (90%) fall into the "urban background" category. The elevated and anomalous subpopulations predominantly consist of older homes located in central core areas of cities. The influence of house age is evidenced by a moderate correlation between house age and dust Pb(S) content (R(2) = 0.34; n = 1025; p < 0.01), but it is notable that more than 10% of homes in the elevated/anomalous category were built after 1980. Conversely, the benefit of home remediation is evidenced by the large number of homes (33%) in the background category that were built before 1960. The dominant dust Pb species determined using X-ray Absorption Spectroscopy were as follows: Pb carbonate, Pb hydroxyl carbonate, Pb sulfate, Pb chromate, Pb oxide, Pb citrate, Pb metal, Pb adsorbed to Fe- and Al-oxyhydroxides, and Pb adsorbed to humate. Pb bioaccessibility estimated from solid phase speciation predicts Pb bioaccessibility measured using a simulated gastric extraction (R(2) = 0.85; n = 12; p < 0.0001). The trend toward increased Pb bioaccessibility in the elevated and anomalous subpopulations (75% ± 18% and 81% ± 8%, respectively) compared to background (63% ± 18%) is explained by the higher proportion of bioaccessible compounds used as pigments in older paints (Pb carbonate and Pb hydroxyl carbonate). This population-based study provides a nationally representative urban baseline for applications in human health risk assessment and risk management.

Extending wipe sampling methodologies to elements other than lead.

Wipe sampling is the USA regulatory protocol for determination of "dust lead loadings" in residential environments. Few studies have applied the wipe sampling method to metals other than lead (Pb) for the purpose of residential exposure assessments. This study was undertaken to develop and expand the wipe method for quantifying additional metal(loid)s including arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and antimony (Sb); and to provide information on typical background loadings for these metals in urban Canadian homes. A total of 932 wipe samples, 220 field blanks, and 220 duplicate wipes were collected from 222 homes located in three cities in Ontario, Canada using the ASTM 1728 standard. The wipes were digested using a modified version of the ASTM 1644 standard for Pb, which prescribes a hot nitric acid/hydrogen peroxide digestion. The key modification was the addition of hydrofluoric acid to improve recoveries of the target elements, and determination using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Generally, a large proportion of the results fell below the limits of detection (LOD) and quantification (LOQ). To distinguish "elevated" metal loadings from loadings characterized as "urban background", an upper background threshold for each element was derived using a normality (Q-Q) plot. LOQ was determined to be the appropriate minimum threshold based on quality assurance criteria. It is concluded that wipes are a useful sampling option to investigate multi-element loadings in residential environments.