Isn't zstd primarily designed to provide decent compression ratios at amazing speeds? The reason it's exciting is mainly that you can add compression to places where it didn't necessarily make sense before because it's almost free in terms of CPU and memory consumption. I don't think it has ever had a stated goal of beating compression ratio focused algorithms like brotli on compression ratio.

I actually thought zstd was supposed to be better than Brotli in most cases, but a bit of searching reveals you're right... Brotli, especially at the highest compression levels (10/11), often exceeds zstd at the highest compression levels (20-22). Both are very slow at those levels, although perfectly suitable for "compress once, decompress many" applications which the PDF spec is obviously one of them.