Geochemical and mineralogical composition of black weathering crusts on limestones from seven different European countries

Twenty-seven samples of black weathering crust and host carbonates were studied from seven European countries (Germany, Hungary, Belgium, Czech Republic, France, Italy and Poland) representing 11 different sites. The samples were collected for sites for which long-term air pollution records are available. The mineralogical analyses (XRD, polarizing microscopy, SEM) have shown that despite decreasing SO2 emissions crust samples are still very rich in gypsum. Further, in all host rock samples gypsum was also detected. Good correlations (R-2 > 0.9) were also found between water-soluble calcium and gypsum content and between sulphate and gypsum content both for black crusts and host rocks. The black gypsum crusts are four or five times richer in sulphate than the host rock. The conductivity of dissolved crust and host rock samples also shows a positive correlation with gypsum content of the samples. LA-ICP-MS analyses allowed the detection of high Pb-levels in black crusts and a negative shift in lead concentration at the crust/host rock transition. The lead content of the host rock is 2-5 mg/kg, while that of the crust is 3-25 mg/kg in the sample collected from Germany, while in the Belgian sample these values are 2-14 mg/kg and 80-870 mg/kg for the host rock and crust, respectively. The GC-MS technique allowed to detect the PAH content of black crusts and host rocks. The former one contains 0.6-15.6 (102.5) mg/kg, while in the host rock values between 0.2 and 2.4 mg/kg were found. The present study suggests that still large amounts of air pollution-related minerals and organic pollutants are found in the black weathering crusts of European carbonate buildings despite decreasing trends in air pollution.