IIRC, after that point there is no further non-return valve, so in normal operation there will be hot boiler water there. Given it's a coolish spot, probably with a small 'dead leg' and eddies tending to drop particles in the 'branch' off the main flow, I suspect what you dug out was 'precipitated' magnetite, which forms hard, crusty deposits.
So chances are your system has no or insufficient corrosion inhibitor in it! This is also probably bad news for your secondary heat exchanger - as it's a combi.
So chances are your system has no or insufficient corrosion inhibitor in it! This is also probably bad news for your secondary heat exchanger - as it's a combi.