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The concentration of hexavalent chromium (Cr(VI)), a toxic environmental pollutant and carcinogen, was determined in samples collected from Nacogdoches Wastewater Treatment Plant (NWWTP) using ion chromatography and UV-visible spectrophotometry (IC, UV-Vis). On reaction with 1,5-diphenylcarbazide (DPC) Cr+6forms a 1,5-diphenylcarbazide-Cr(VI) complex, which is then analyzed at 530 nm and 540 nm, respectively. Via ion chromatography Cr(VI) concentrations were in the range of0.00190±0.0020and0.0010±0.0006 ppm at the influent and effluent, respectively. With the use of standard addition wastewater samples were spiked with a 0.5 ppm Cr(VI) standard of various amounts and subsequently analyzed with UV-Vis spectrophotometry. The spiked concentrations gave Cr(VI) concentrations in the range of0.0090±0.0060 ppm and0.0040±0.0061 ppm at the influent and influent wastewater, respectively. The determined Cr(VI) concentrations through the ion chromatography and UV-Vis spectrophotometry are below the maximum USEPA contaminant concentration of 0.1 ppm. From the analysis, the NWWTP efficiently removes Cr(VI) before discharge into the environment through La Nana Creek. The removal efficiency for Cr(VI) was determined to be ≥92.8% along the wastewater treatment stages from the influent (aeration stage) to the effluent stages prior to discharge into the La Nana Creek.

The molecules benzo[a]pyrene (BaP) and 1-, 3-, and 6-nitrobenzo[a]pyrene (1-NBaP, 3-NBaP, 6-NBaP) are currently of significant interest due to their presence in respirable combustion exhaust particulates and their mutagenic and carcinogenic properties. Structure-function correlations as well as spectroscopic signatures for trace analysis are necessary for these benzo[a]pyrene derivatives. In this paper, detailed infrared and Raman spectroscopic data of BaP and its three mononitrated isomers are provided for the first time. By utilizing density functional theory (DFT, B3LYP method with 6-311+G basis set), the molecular geometries and the vibrational spectra are calculated. Good agreement is noted between the calculated and experimental geometry for BaP, and predictions of the vibrational data for all compounds are within approximately 5 cm-1 of the experimental data. Normal mode assignments are proposed with particular emphasis on the nitro group vibrations. The geometrical distortions of the BaP structure upon nitro group substitution and correlations between structural parameters and vibrational data as well as structure-function relationships related to the mutagenicity of this important class of polycyclic aromatic hydrocarbons are discussed.

Spectroscopic properties, including absorption, emission spectra, and excited-state lifetimes of the mononitrated benzo[a]pyrenes (NBaPs), specifically 1-, 3-, and 6-nitrobenzo[a]pyrenes (1-, 3-, and 6-NBaP), are reported, and correlations with structure are developed. With 1- and 3-NBaP, bathochromic shifts are observed in the absorption spectra. The quantum yields of emission display the following trend: BaP >> 6-NBaP > 1-NBaP approximately 3-NBaP. Fluorescence lifetimes for nitrated BaPs were approximately 6 to 7 times shorter than that of BaP. With the help of time-dependent density functional theory (TD-DFT), assignments of the electronic transitions are proposed and are in good agreement with the electronic spectra for the NBaPs in methanol. On the basis of optimization of the triplet states, different photochemical consequences are discussed, and the observed fluorescence quenching is explained. Changes in the electron density distributions in the ground and excited states calculated at the second-order coupled-cluster level using the resolution-of-the-identity approximation (RI-CC2) provide information about the possible mechanism of photochemical reactions of NBaPs. Correlations between the orientation of the nitro group relative to the aromatic plane and the observed properties of the NBaP are discussed.