A system for pressurized liquid extraction and purification of solid samples includes a pressurized liquid extraction (PLE) module including a PLE cell, a heating element, a high-pressure source of an extraction solvent, a pressure regulator, and a cooling coil. The PLE module continuously performs high-pressure, high-temperature extraction on the solid sample to yield liquid sample. The liquid sample is concurrently provided to a purification module including one or more columns. The purification module yields a purified liquid sub-sample containing substantially all of a specific trace substance present in the solid sample. The sub-samples are transferred to a concentrator assembly through a collector inlet. The concentrated sub-sample can be used in subsequent analysis to determine the concentration of the trace substance in the original solid sample.

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