The analytical chemist is faced with several challenges when determining mercury in biological and geological materials. These challenges include widespread mercury contamination, both in the laboratory and the environment, possible losses of mercury during sample preparation and digestion, the wide range of mercury values commonly observed, ranging from the low nanogram per gram or per liter for background areas to hundreds of milligrams per kilogram in contaminated or ore-bearing areas, great matrix diversity, and sample heterogeneity1. These factors can be naturally occurring or anthropogenic, but must be addressed to provide a precise and accurate analysis. Although there are many instrumental methods available for the successful determination of mercury, no one technique will address all problems or all samples all of the time. The approach for the determination of mercury used at the U.S. Geological Survey, Crustal Imaging and Characterization Team, Denver Laboratories, utilizes a suite of complementary instrumental methods when approaching a study requiring mercury analyses. Typically, a study could require the analysis of waters, leachates or selective digestions of solids, vegetation, and biological materials such as tissue, bone, or shell, soils, rocks, sediments, coals, sludges, and(or) ashes. No one digestion or sample preparation method will be suitable for all of these matrices. The digestions typically employed at our laboratories include: (i) a closed-vessel microwave method using nitric acid and hydrogen peroxide, followed by digestion/dilution with a nitric acid/sodium dichromate solution, (ii) a robotic open test-tube digestion with nitric acid and sodium dichromate, (iii) a sealed Teflon? vessel with nitric acid and sodium dichromate, (iv) a sealed glass bottle with nitric acid and sodium dichromate, or (v) open test tube digestion with nitric and sulfuric acids and vanadium pentoxide. The common factor in all these digestions is that they are very oxidative to ensure the conversion of all mercury forms into Hg (II). Each method of digestion has its advantages and limitations. The method of detection used in our laboratories involves a combination of an in-house, custom, classic continuous-flow cold-vapor atomic absorption spectrometry (CVAAS), a commercially available, automated, flow-injection and a continuous flow cold-vapor atomic fluorescence spectrometry (CV-AFS) systems, and a relatively new, automated and integrated approach where solid or liquid samples are thermally decomposed under an oxygen atmosphere (a nitrogen atmosphere is used for coals) and the released mercury vapor trapped onto a gold gauze and then thermally released into an AAS system. Other less frequently used instrumental methods available for the determination of mercury include inductively coupled plasma ? optical emission spectrometry (ICP-OES), inductively couple plasma ? mass spectrometry (ICP-MS) (both solution nebulization and laser ablation), and instrumental neutron activation analysis (INAA). Results from two case studies involving the determination of mercury in the challenging matrices of biological materials will be presented. These will include fillet, liver and stomach-content samples from grayling for a baseline/background study in Alaska, and samples of meat tissue and shell material from Tanner crabs from Glacier Bay, Alaska. These studies show that the method of digestion is more important than a very sensitive detection limit for mercury.