Characterizing metals in particulate pollution in communities at the fenceline of heavy industry: combining mobile monitoring and size-resolved filter measurements.

Exposures to metals from industrial emissions can pose important health risks. The Chester-Trainer-Marcus Hook area of southeastern Pennsylvania is home to multiple petrochemical plants, a refinery, and a waste incinerator, most abutting socio-economically disadvantaged residential communities. Existing information on fenceline community exposures is based on monitoring data with low temporal and spatial resolution and EPA models that incorporate industry self-reporting. During a 3 week sampling campaign in September 2021, size-resolved particulate matter (PM) metals concentrations were obtained at a fixed site in Chester and on-line mobile aerosol measurements were conducted around Chester-Trainer-Marcus Hook. Fixed-site arsenic, lead, antimony, cobalt, and manganese concentrations in total PM were higher (p < 0.001) than EPA model estimates, and arsenic, lead, and cadmium were predominantly observed in fine PM (<2.5 µm), the PM fraction which can penetrate deeply into the lungs. Hazard index analysis suggests adverse effects are not expected from exposures at the observed levels; however, additional chemical exposures, PM size fraction, and non-chemical stressors should be considered in future studies for accurate assessment of risk. Fixed-site MOUDI and nearby mobile aerosol measurements were moderately correlated (r ≥ 0.5) for aluminum, potassium and selenium. Source apportionment analyses suggested the presence of four major emissions sources (sea salt, mineral dust, general combustion, and non-exhaust vehicle emissions) in the study area. Elevated levels of combustion-related elements of health concern (e.g., arsenic, cadmium, antimony, and vanadium) were observed near the waste incinerator and other industrial facilities by mobile monitoring, as well as in residential-zoned areas in Chester. These results suggest potential co-exposures to harmful atmospheric metal/metalloids in communities surrounding the Chester-Trainer-Marcus Hook industrial area at levels that may exceed previous estimates from EPA modeling.

Electrospun, flexible and reusable nanofiber mat of graphitic carbon nitride: Photocatalytic reduction of hexavalent chromium.

Nanofiber mat of graphitic carbon nitride (g-C3N4) was fabricated from g-C3N4/polyvinylidene fluoride (PVDF) composite using an electrospinning technique. The mat was characterized with SEM, AFM, XRD, FTIR and photoluminescence (PL) spectroscopy. This nanofiber mat is flexible and can be folded or rolled without losing any structural integrity. The nanofiber mat also demonstrates self-cleaning properties in aqueous medium as demonstrated with two dyes, methylene blue and rhodamine B. Hexavalent chromium was successfully reduced by the nanofiber mat of g-C3N4 under visible light. Although the rate of reduction of Cr(VI) was very slow in presence of nanofiber mat of g-C3N4 alone, it was enhanced significantly in presence of trace amounts (0.3%) formic acid. Formic acid played the dual role of hole scavenging agent of g-C3N4 to make the photogenerated electrons more available to the reaction and generating H2 and CO in the system that can also directly reduce Cr(VI) onto Cr(III). The nanofiber mat demonstrated excellent cyclability for photocatalytic reduction of Cr(VI) and self-cleaning properties in presence of visible light.

Photocatalytic and photo-fenton activity of iron oxide-doped carbon nitride in 3D printed and LED driven photon concentrator.

We have synthesized iron oxide doped carbon nitride with 0.5 to 2 wt.% iron oxide and characterized by XPS, TGA, FTIR, SEM, photoluminescence spectroscopy and photoelectrochemical measurements. A herbicide, dicamba was employed as model organic pollutant for degradation in presence with the catalyst and hydrogen peroxide. A 3D printed photon concentrator with two chips on board (COB) LEDs with visible light spectra and two complex parabolic mirror surfaces was used as photo-reactor. The findings revealed that both photocurrent and degradation of dicamba were functions of light intensity and concentrator geometry. The rapid degradation of dicamba can be attributed to the holistic and individual actions of structural components of the photocatalyst. Four distinct phenomena, including photocatalytic activity of carbon nitride, quenching of electron/hole pairs and generation of additional reactive hydroxyl radicals by hydrogen peroxide, Fenton and photo-Fenton activity of iron oxide component of carbon nitride in presence of hydrogen peroxide and photocatalytic activity of iron oxide alone in conjuncture with carbon nitride can contribute to the overall photocatalytic activity of the system. Liquid Chromatography-Mass spectrometry (LCMS) analysis of the degradation products showed loss of chlorine from the aromatic ring and evidence of free radical addition reactions in the course of photocatalysis.

Synthesis of Nitrogen and Sulfur Codoped Nanoporous Carbons from Algae: Role in CO2 Separation.

Nitrogen and sulfur codoped and completely renewable carbons were synthesized from two types of algae, Spirulina Platensis and Chlorella Vulgaris, without any additional nitrogen fixation reaction. The type of activation agents, char-forming temperature, activation agent-to-char ratio, and activation temperature were all varied to optimize the reaction conditions for this synthesis. The maximum Brunauer-Emmett-Teller surface area and total pore volumes of the carbons were 2685 m2/g and 1.4 cm3/g, respectively. The nitrogen and sulfur contents of the carbons were in the range of 0.9-5.69 at. % and 0.05-0.2 at. %, respectively. The key nitrogen functionalities were pyridinic, amino, and pyridonic/pyrrolic groups, whereas the key sulfur functionalities were S-C, O-S-C, and SO x groups. CO2 adsorption isotherms were measured at 273, 298, and 313 K, and the ideal adsorbed solution theory was employed to calculate the selectivity of adsorption of CO2 over N2 and simulate binary adsorption isotherms. The adsorption results demonstrated that the CO2 adsorption amount and the heat of CO2 adsorption were higher for carbons with higher nitrogen content, confirming the influence of nitrogen functionality in CO2 adsorption. The overall results suggested that these algae-derived renewable carbons can serve as potential adsorbents for CO2 separation from N2.

Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SOx. SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m2/g with total pore volume of 0.71-2.3 cm3/g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl2), lead (as Pb(NO3)2), cadmium (as CdCl2), and nickel (as NiCl2) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO4, 14% and 2% of Pb was converted to PbSO4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO4. Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

The relationship between 207Pb NMR chemical shift and solid-state structure in Pb(II) compounds.

The analysis of heavy-metal solids with NMR spectroscopy provides a means of investigating the electronic environment through the dependence of the chemical shift on structure. We have investigated the relation of the 207Pb NMR isotropic chemical shift, span, and skew of a series of solid Pb(II) compounds to lattice parameters. Complementary relativistic spin-orbit density functional calculations on clusters such as PbI64- that model the local environment in the dihalides show a dependence of NMR properties on the local structure in good agreement with experimental results.

Electronic Chemistry Conferences: 7 years of CONFCHEM.

Between the summer of 1993 and August 2001, members of the ACS Division of Chemical Education's Committee on Computers in Chemical Education (CCCE) managed the online facilities for 17 online conferences. One more conference will occur during fall 2001, and several additional conferences are planned for the future. This article describes the history and the nature of these online conferences, including the advantages and disadvantages of the online format.