Spectrophotometric measurements of pH in-situ: laboratory and field evaluations of instrumental performance

Environ Sci Technol. 2006 Aug 15;40(16):5036-44. doi: 10.1021/es0601843.

Abstract

Automated in-situ instrumentation has been developed for precise and accurate measurements of a variety of analytes in natural waters. In this work we describe the use of 'SEAS' (spectrophotometric elemental analysis system) instrumentation for measurements of solution pH. SEAS-pH incorporates a CCD-based spectrophotometer, an incandescent light source, and dual pumps for mixing natural water samples with a sulfonephthalein indicator. The SEAS-pH optical cell consists of either a liquid core waveguide (LCW, Teflon AF-2400) or a custom-made PEEK cell. Long optical path lengths allow use of indicators at low concentrations, thereby precluding large indicator-induced pH perturbations. Laboratory experiments show that pH measurements obtained using LCW and PEEK optical cells are indistinguishable from measurements obtained using conventional spectrophotometric cells and high-performance spectrophotometers. Deployments in the Equatorial Pacific and the Gulf of Mexico demonstrate that SEAS-pH instruments are capable of obtaining vertical pH profiles with high spatial resolution. SEAS-pH deployments at a fixed river-site (Hillsborough River, FL) demonstrate the capability of SEAS for observations of diel pH cycles with high temporal resolution. The in-situ precision of SEAS-pH is assessed as 0.0014 pH units, and the system's measurement frequency is approximately 0.5 Hz. This work indicates that in-situ instrumentation can be used to provide accurate, precise, and highly resolved observations of carbon-system transformations in the natural environment.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Automation
  • Carbon / analysis*
  • Environmental Monitoring / methods*
  • Equipment Design
  • Fresh Water / chemistry*
  • Hydrogen-Ion Concentration
  • Light
  • Models, Chemical
  • Models, Theoretical
  • Oceans and Seas
  • Rivers
  • Spectrophotometry / instrumentation*
  • Spectrophotometry / methods*
  • Temperature

Substances

  • Carbon