Green analytical methods for total petroleum hydrocarbons determination in soils and sediments: a comparative review using AGREEprep and BAGI metrics

The determination of total petroleum hydrocarbons (TPH) in soils and sediments is a critical task in environmental monitoring, site assessment, and forensic investigations. Analytical workflows differ substantially in their environmental footprint and practical applicability, largely due to variations in sample preparation. This review applies two complementary metrics – AGREEprep for preparation-stage greenness and the Blue Applicability Grade Index (BAGI) for analytical applicability – to 32 PRISMA-selected peer-reviewed studies on TPH determination in soils and sediments. Methods were classified into solvent-intensive extraction (n = 24; AGREEprep median 0.11, BAGI median 62.5), direct and non-destructive analytical methods (n = 7; AGREEprep median 0.74, BAGI median 77.5), and microextraction (n = 1; HS-SPME, AGREEprep 0.34, BAGI 67.5). Direct spectroscopic methods reached the highest scores on both axes simultaneously, with fluorescence spectroscopy attaining the dataset maximum BAGI of 92.5. Within the solvent-intensive class, an ultra-fast GC-FID workflow with reduced solvent volume reached BAGI 80.0, demonstrating that high applicability is achievable even when preparation greenness is low. The integrated greenness–applicability assessment provides ranked recommendations for three analytical scenarios: rapid qualitative screening (first choice: fluorescence spectroscopy or NIR), quantitative compound-level determination (first choice: HS-SPME–GC–MS), and forensic source apportionment (first choice: HS-SPME–GC–MS where volatility permits). The review positions green TPH analysis within the White Analytical Chemistry framework and identifies inconsistent reporting in the published literature as a major obstacle to reproducible greenness assessment.