The aim of the study was to develop a fast and effective approach that would enable subsequent integrated risk assessment in micro- and low-order catchments. The procedure involved an alternative sampling strategy, a rapid one-step cyclohexane extraction, extract purification through florisil, concentration, and analysis using an Agilent Cary 630 FTIR spectrometer equipped with a TumblIR 100 sampling module, with possible adaptation to 1,000 µm or other commercially available systems to achieve lower detection limits. Validation results showed that for soil matrices (wet soil, bottom sediments) the method provides good internal consistency with a relative standard deviation of approximately 11% (n = 10) and a systematic bias of approximately −11.5%, with recovery of 88.5%. The expanded measurement uncertainty is ±24% for soil and ±31.9% for water, which corresponds to typical levels for these environmental matrices. For water matrices (surface and drainage waters, soil washings, percolates) recovery exceeds 94%, systematic bias is small, and precision is at an acceptable level. Model experiments evaluating the effects of the sampling strategy revealed significant systematic shifts: −47% for soil percolate, −43.5% for soil (w = 45%), and −40.3% for water-saturated soil, indicating heterogeneous TPH distribution in samples prior to extraction. Assessment using green analytical chemistry indices via AGREE and AGREEprep tools demonstrated the advantages of the developed procedure over conventional standard methods: the overall AGREE index for the developed method is 0.61 (compared to 0.20-0.33 for the gravimetric method, infrared (IR) method according to the MVI, and ASTM D7678-17. It was established that, within Ivano-Frankivsk, concentrations in road dust and roadside soils ranged from 1.6-2.8 × 10³ mg/kg and locally reached 4.7-6.5 × 10⁵ mg/kg, posing high risks associated with stormwater runoff and pollutant discharge into storm drains, eventually entering the Bystrytsia Solotvynska River