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Peroxyoxalate chemiluminescence (PO-CL) spectra obtained simultaneously and continuously using a CCD spectrometer provide evidence of the complexity of PO-CL reactions. [ABSTRACT FROM AUTHOR]

Peroxyoxalate chemiluminescence (PO-CL) spectra obtained simultaneously and continuously using a CCD spectrometer provide evidence of the complexity of PO-CL reactions., (© The Royal Society of Chemistry 2011)

Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agency's Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence (OD4MI-CL) were studied. The influences of these two factors on the complex OD4MI-CL reaction are discussed within a conceptual prototype for developing aqueous and non-aqueous capillary electrophoresis (ACE and NACE) devices with OD4MI-CL detection. The reaction channel length and OD4MI yield from the reaction between bis(2,4,6-trichlorophenyl) oxalate (TCPO) and 4-methylimidazole in the channel will be influenced by pH, water volume fraction, and cosolvent properties of the solution. Optimum OD4MI-CL efficiency is observed at pH 6.5 when 1-propanol, which has a low dielectric constant (epsilon = 20.8), is used as the NACE solvent in the separation channel. Water (epsilon = 80.1), the solvent in the ACE separation channel, acts similarly to a high dielectric constant organic solvent in NACE because the disadvantages normally associated with TCPO-CL reactions in water disappear due to the faster OD4MI-CL reaction versus OD4MI decomposition in aqueous solution. Therefore, it is expected that the OD4MI-CL detection system can be used in both NACE and ACE devices without requiring detector modifications. We also conclude that OD4MI-CL detection in NACE and ACE devices will be much more sensitive than the TCPO-CL detection used in current NACE devices.

Quantification of the copper content of and copper leaching from a disc brake wear debris sample was performed using microwave-assisted acid digestion, the Federal Toxicity Characteristic Leaching Procedure (TCLP), and the State of California Waste Extraction Test (WET). The brake wear debris tested was a composite sample obtained from a brake dynamometer test of one brake pad source material. Comparative digestion studies demonstrated that a modified aqua regia matrix (HNO3:HCl:H2O2 = 1:3:0.5) optimized the digestion effectiveness for determining the total copper content in the brake wear debris. No significant sample heterogeneity within the brake wear debris was observed, based on statistically indistinguishable total copper content results for subsamples with a wide range of sample masses. Upon pooling all subsample results, an overall total copper content for the composite brake wear debris sample was determined to be 10.8% (g/g), with a 95% confidence limit of +/- 0.5% (g/g). Copper leaching increased with decreasing solid-to-liquid ratios in TCLP tests, but was unaffected by the solid-to-liquid ratio in the WET. For a 1:10(4) (g/g) solid-to-liquid ratio, 85% and 99% of the total mass of copper present in the composite brake wear debris sample was leached into solution during the TCLP and WET, respectively. Rate studies also demonstrated that the WET resulted in a faster rate and higher extent of copper leaching relative to the TCLP. Compared to reference copper-containing materials, the composite brake wear debris sample exhibited relatively higher TCLP and WET copper leaching characteristics. The higher copper leaching exhibited by the brake wear debris sample may have resulted from its higher specific surface area and/or from changes in the chemical form of copper that occurred during the braking process.