Role of particulate metals in heterogenous secondary sulfate formation

Abstract

A series of field sampling and controlled laboratory experiments were undertaken to quantify the role of trace metals found in ambient fine particulate matter and metal-rich primary sources in the heterogenous catalytic conversion of SO2 gas into sulfate particulate matter (PM) in the atmosphere. Analysis produced source profiles of three primary source materials, fluidized-bed catalytic cracking catalyst, coal-fired combustion fly ash, and paved road dust, featuring 33 elements including rare earth metals, which are not commonly reported in the literature.Subsequently three sets of experiments were conducted exposing 1) source materials, 2) ambient PM, and 3) ambient PM augmented with approximately an equal amount of source material to SO2 gas and measuring sulfate formation. Source material experiments revealed that the greatest extent of reaction was on the surface of coal fly ash with sulfate formation of 19 ± 5 mg sulfate g−1 material. Ambient fine particulate matter (PM) experiments showed sulfate formation ranging from negligible amounts to 180 ± 10 mg sulfate g−1 PM. It was much more difficult to quantify the sulfate formation on ambient filters augmented with the source materials. In these experiments, sulfate formation ranged from negligible amounts to 40 ± 8 mg sulfate g−1 of particles (ambient + augmented material). These three sets of experiments shows that heterogenous sulfate formation is often negligible but, under some conditions can contribute 10% or more to the total sulfate concentrations when exposed to high SO2 concentrations such as those found in plumes.Factor analysis of the source material experiments grouped metals into two categories, crustal components and anthropogenically emitted metals representative of catalyst material, with the former showing the strongest correlation with sulfate formation. Subsequent analysis of data collected from the ambient PM experiments showed a much weaker correlation of sulfate formation with the crustal components, including iron and titanium, remaining clustered with sulfate formation. Independent research has been previously reported in the literature establishing mechanisms for the iron and titanium catalyzed conversion of S(IV) to S(VI) suggesting there may be other metals within these crustal type metal components that behave similarly. Additional experiments spanning a wider range of variables including more sources, SO2 concentrations and exposure times, ambient PM locations, as well as more individual samples may be necessary to obtain more conclusive evidence into the role of various metals in catalyzing the conversion of S(IV) to S(VI).