Pollutant emissions from coal fires have caused serious concerns in major coal-producing countries. Great efforts have been devoted to suppressing them in China, notably at the notorious Wuda Coalfield in Inner Mongolia. Recent surveys revealed that while fires in this coalfield have been nearly extinguished near the surface, they persist underground. However, the impacts of Hg volatilized from underground coal fires remain unclear. Here, we measured concentrations and isotope compositions of atmospheric Hg in both gaseous and particulate phases at an urban site near the Wuda Coalfield. The atmospheric Hg displayed strong seasonality in terms of both Hg concentrations (5-7-fold higher in fall than in winter) and isotope compositions. Combining characteristic isotope compositions of potential Hg sources and air mass trajectories, we conclude that underground coal fires were still emitting large amounts of Hg into the atmosphere that have been transported to the adjacent urban area in the prevailing downwind direction. The other local anthropogenic Hg emissions were only evident in the urban atmosphere when the arriving air masses did not pass directly through the coalfield. Our study demonstrates that atmospheric Hg isotope measurement is a useful tool for detecting concealed underground coal fires.

The Wuda coalfield, Inner Mongolia, China, has been suffering from serious coal fire disaster for more than half a century. In the past decade, the central and local governments have carried out many fire-fighting projects to put out the coal fires, but coal fires still sporadically occur in the coalfield. Previous studies showed that coal fires could release large amounts of mercury (Hg) into the environment. Meanwhile, the rapid industrial development in recent years in Wuda area has also discharged a certain amount of Hg. Identification and quantification of the Hg emitted from coal fires and industrial sources is critical to formulate appropriate environmental policies. This study determined Hg isotope compositions in different types of coals from Wuda coal fire area and surface soils with different distances to the coal fire area, with an aim of anchoring the potential Hg sources in soils. The results showed that the coals had moderately negative δ202Hg (−2.02∼-1.21‰) and slightly negative Δ199Hg (−0.14–0.00‰), while the soils generally had more positive δ202Hg (−1.97∼-0.26‰) and Δ199Hg (−0.07–0.04‰) with distinct isotope ranges among different sampling sites. According to characteristic Hg isotope compositions of different sources, we concluded that the Hg in Wuda soils mainly sourced from cement plants and coal fires, and coal fires were still an important Hg contamination source in Wuda area.

Concentrations of mercury and other heavy metals were measured in soils surrounding the Wuda Coalfield, Inner Mongolia where underground coal fires are regarded as an important contamination source. Soil samples at the downwind direction were nearly all enriched mercury in surface layers, with their concentrations ~ 10 times higher than those from upwind soils. Mercury concentrations generally increased along soil profiles upward, indicative of increasing atmospheric mercury deposition in recent decades. We suggest that underground coal fire emissions were the potential mercury contamination source and the key factor controlling mercury enrichment in soils. Other heavy metals showed no clear spatial and vertical trends, suggesting that underground coal fire emissions may not the main factor for their enrichment in soils. Antimony showed the highest enrichment followed by tin, while chromium, mercury and cadmium only exhibited slight enrichment. Risk evaluation indicated that heavy metals in the studied soils pose no ecological threats.

The Wuda Coalfield, Inner Mongolia suffers from serious coal fires for more than half a century. Fire-extinguishing projects have been carried out to suppress the coal fires since the last decade, but sporadic surface fires still occur and underground fires are more prevailing. Here, we used a real-time RA-915M Mercury Analyzer with modified inlet to monitor gaseous Hg concentrations in fumes emitted from boreholes that were designed to detect and control the underground coal fires. Meanwhile, offline methods were used to collect the fumes and analyze the contents of the gases including CO, CO2, CH4, C2H6, C2H4 and C2H2. The results showed that gaseous Hg concentrations in fumes from boreholes ranged from 6.42 ± 0.73 to 123.53 ± 34.66 ng m-3, with an average value of 49 ± 44 ng m-3. We suggest that the amounts of coal left for burning or smoldering mainly accounted for the large variation in fume Hg concentrations of underground coal fires. The gaseous Hg concentrations in near-surface air surrounding boreholes varied from 2.38 ± 0.28 to 13.10 ± 0.97 ng m-3, with a mean value of 6.68 ± 3.09 ng m-3. They were higher than the ambient air Hg concentrations measured at a background site near the Yellow River (<2 ng m-3), suggesting underground coal fires were one significant Hg pollution source. Importantly, we found that gaseous Hg concentrations in the boreholes had significantly positive correlations with temperatures and CO (a traditional coal-fire index gas) contents, implying that Hg has the potential to serve as an index gas to monitor the occurrences of underground coal fires in mining goafs.