Cadmium isotope fractionation during coal combustion: Insights from two US coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of similar to 70% amorphous Al-Si-rich glasses and similar to 30% mineral phases of quartz (SiO2) and mullite (Ai(6)Si(2)O(13)). The Cd isotope compositions (delta Cd-14, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from -0.51 to + 0.47%o) are distinctively heavier than those of BA samples ( - 0.75 to - 0.52%o) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+ 1.10 to +7.09 parts per thousand), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (- 0.43 to + 1.18 parts per thousand). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.