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Unsaturated zone pore water has the potential to record history of recharge, palaeoenvironment, pollution movement and water-rock interaction as it percolates through and moves towards the water table. In this study, two 6-m cores from the Badain Jaran desert (NW China) were collected to explore this potential using directly extracted moisture. Pore waters in these unsaturated zone sediments (1–5% moisture by wet weight) were directly extracted using immiscible liquid displacement and then analysed for major anions, cations and trace elements. Results show enrichment in pore water chemistry in the top 1–2 m where strong temperature and moisture fluxes occur. The enrichment in cations relative to chloride is primarily due to silicate mineral dissolution during infiltration. High nitrate and low iron concentrations indicate the overall oxidizing environment, which allows the mobility of oxyanions, such as uranium, arsenic and chromium. The trace elements show enrichment in the upper zone of fluctuation where chemical gradients are strong, but with lesser reaction lower in the profile. The calculated groundwater recharge rates using the chloride mass balance are negligible in this arid region between 1.5 and 3.0 mm/year. The modern rainfall infiltration signature contrasts with that of the underlying groundwater body, which has a distant, regional recharge signature. This reconnaissance study demonstrates the potential for a new geochemical approach to studying geochemical processes in the unsaturated sediments in semi-arid environments due to both natural and human influences. The use of directly extracted water, rather than extraction by dilution (elutriation), facilitates an improved understanding of hydrological and geochemical processes in the unsaturated zone and into the capillary fringe at the water table, because it avoids potential chemical changes induced during elutriation. [ABSTRACT FROM AUTHOR]