From packages/arduino/hardware/samd/1.8.11/variants/nano_33_iot/variant.h:
#define PIN_SPI_MISO (12u)
#define PIN_SPI_SCK (13u)
#define PIN_SPI_MOSI (11u)
#define PIN_SPI_SS (10u)
So it looks like the default SS pin is Pin 10.