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<p>Upcoming spaceborne imaging spectrometers will retrieve clear-sky total column water vapour (TCWV) over land at a horizontal resolution of 30–80 m. Here we show how to obtain, from these retrievals, exponents describing the power-law scaling of sub-kilometre horizontal variability in clear-sky bulk planetary boundary layer (PBL) water vapour (<span class="inline-formula"><i>q</i></span>) accounting for realistic non-vertical sunlight paths. We trace direct solar beam paths through large eddy simulations (LES) of shallow convective PBLs and show that retrieved 2-D water vapour fields are “smeared” in the direction of the solar azimuth. This changes the horizontal spatial scaling of the field primarily in that direction, and we address this by calculating exponents perpendicular to the solar azimuth, that is to say flying “across” the sunlight path rather than “towards” or “away” from the Sun. Across 23 LES snapshots, at solar zenith angle SZA <span class="inline-formula">=</span> 60<span class="inline-formula">^∘</span> the mean bias in calculated exponent is 38 <span class="inline-formula">±</span> 12 % (95 % range) along the solar azimuth, while following our strategy it is 3 <span class="inline-formula">±</span> 9 % and no longer significant. Both bias and root-mean-square error decrease with lower SZA. We include retrieval errors from several sources, including (1) the Earth Surface Mineral Dust Source Investigation (EMIT) instrument noise model, (2) requisite assumptions about the atmospheric thermodynamic profile, and (3) spatially nonuniform aerosol distributions. By only considering the direct beam, we neglect 3-D radiative effects such as light scattered into the field of view by nearby clouds. However, our proposed technique is necessary to counteract the direct-path effect of solar geometries and obtain unique information about sub-kilometre PBL <span class="inline-formula"><i>q</i></span> scaling from upcoming spaceborne spectrometer missions.</p>