ALBERT

Description: In contrast to predominantly hydrocarbon-rich natural gases in the western part of the Central European Basin (CEB), accumulations of natural gases from the eastern part of the North German Basin (NGB) are nitrogen-rich with up to 90% N2. This study is focused on the behaviour of fixed ammonium in clay minerals of organic-rich Palaeozoic sediments in the eastern part of the NGB as a major source of nitrogen-rich natural gases. Carboniferous shales have been investigated for a better understanding of nitrogen fixing during diagenesis, storage during burial and release during devolatilization processes or fluid–rock interactions. The total nitrogen contents in the studied Carboniferous shales of the NGB reach up to 2700 ppm with an inorganic fixed portion (in the form of NH4 +–N) of more than 60%. The results of this study indicate an increasing proportion of the mineralogically fixed ammonium with increasing thermal maturity and storage up to catagenetic conditions. The isotopic composition of fixed-NH4 is relatively homogeneous in the majority of the shales and ranges from +1 to +3.5‰. In contrast, samples from the basin centre show a significant decrease in ammonium contents down to 460 ppm coupled with a shift in δ15N up to +5.6‰ suggesting a release of nitrogen on a large scale. Calculation of nitrogen loss and isotopic fractionation indicate that more than 30% of nitrogen was released as ammonium probably as a consequence of fluid-rock interaction with highly saline brines.