Pumping-induced ebullition: A unified and simplified method for measuring multiple dissolved gases

The incorporation of multiple dissolved gas measurements in biogeochemical studies remains a difficult and expensive challenge. Incompatibilities in collection, handling, and storage procedures generally force the application of multiple sampling procedures for multiple gases. This paper introduces the concept and application of pumping-induced ebullition (PIE), a unified approach for routine measurement of multiple dissolved gases in naturalwaters and establishes a new platform for development of in situ real-time dissolved gas monitoring tools. Ebullition (spontaneous formation of bubbles) is induced by pumping a water sample through a narrow-diameter tube (a "restrictor") to decrease hydrostatic pressure (P-H) below total dissolved gas pressure (PT). Buoyancy is used to trap bubbles within a collection tower where gas accumulates rapidly (1 mL/min) to support multiple chemical analyses. Providing for field collection of an essentially unlimited and unified volume of gas sample, PIE afforded accurate and precise measurements of major (N-2, O-2, Ar), trace (CO2, N2O, CH4) and ultratrace (CFC11, CFC12, CFC113, SF6) dissolved gases in Wisconsin groundwater, revealing interrelationships between denitrification, apparent recharge age-dates, and historical land use. Compared to conventional approaches, PIE eliminates multiple gas-specific sampling methods, reduces data computations, simplifies laboratory instrumentation, and avoids aqueous production and consumption of biogenic gases during sample storage. A lake depth profile for CO2 demonstrates PIE's flexibility as an in situ real-time platform for dissolved gas measurements. The apparent departures of some gases (SF6, H-2, N2O, CO2) from solubility equilibrium behavior warrant further confirmation and theoretical investigation.