Purification and Characterization of meta-Cresol Purple for Spectrophotometric Seawater pH Measurements

Spectrophotometric procedures allow rapid and precise measurements of the pH of natural waters. However, impurities in the acid–base indicators used in these analyses can significantly affect measurement accuracy. This work describes HPLC procedures for purifying one such indicator, meta-cresol purple (mCP), and reports mCP physical–chemical characteristics (thermodynamic equilibrium constants and visible-light absorbances) over a range of temperature (T) and salinity (S). Using pure mCP, seawater pH on the total hydrogen ion concentration scale (pHT) can be expressed in terms of measured mCP absorbance ratios (R = λ2A/λ1A) as follows:where −log(K2Te2) = a + (b/T) + c ln T – dT; a = −246.64209 + 0.315971S + 2.8855 × 10–4S2; b = 7229.23864 – 7.098137S – 0.057034S2; c = 44.493382 – 0.052711S; d = 0.0781344; and mCP molar absorbance ratios (ei) are expressed as e1 = −0.007762 + 4.5174 × 10–5T and e3/e2 = −0.020813 + 2.60262 × 10–4T + 1.0436 × 10–4 (S – 35). The mCP absorbances, λ1A and λ2A, used to calculate R are measured at wavelengths (λ) of 434 and 578 nm. This characterization is appropriate for 278.15 ≤ T ≤ 308.15 and 20 ≤ S ≤ 40.

[1]  R. Feely,et al.  The role of pH measurements in modern oceanic CO2-system characterizations: Precision and thermodynamic consistency , 1995 .

[2]  A. Dickson Standard potential of the reaction: , and and the standard acidity constant of the ion HSO4− in synthetic sea water from 273.15 to 318.15 K , 1990 .

[3]  R. Feely,et al.  Discrete water column measurements of CO2 fugacity and pHT in seawater: A comparison of direct measurements and thermodynamic calculations , 1998 .

[4]  R. Byrne,et al.  Spectrophotometric determination of freshwater pH using bromocresol purple and phenol red. , 2001, Environmental science & technology.

[5]  Robert H. Byrne,et al.  High precision multiwavelength pH determinations in seawater using cresol red , 1989 .

[6]  R. Byrne,et al.  Procedures for measurement of carbonate ion concentrations in seawater by direct spectrophotometric observations of Pb(II) complexation , 2008 .

[7]  F. Millero,et al.  A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media , 1987 .

[8]  T. A. DelValls,et al.  The pH of buffers based on 2-amino-2-hydroxymethyl-1,3-propanediol (‘tris’) in synthetic sea water , 1998 .

[9]  R. Byrne,et al.  Impurities in indicators used for spectrophotometric seawater pH measurements: Assessment and remedies , 2007 .

[10]  R. Byrne,et al.  Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behavior of thymol blue , 1996 .

[11]  C. Culberson,et al.  MEASUREMENT OF THE APPARENT DISSOCIATION CONSTANTS OF CARBONIC ACID IN SEAWATER AT ATMOSPHERIC PRESSURE1 , 1973 .

[12]  Robert H. Byrne,et al.  Standardization of standard buffers by visible spectrometry , 1987 .

[13]  Andrew G. Dickson,et al.  Guide to best practices for ocean CO2 measurements , 2007 .

[14]  R. Byrne,et al.  In-situ spectrophotometric pH measurements: the effect of pressure on thymol blue protonation and absorbance characteristics , 2000 .

[15]  Robert H. Byrne,et al.  Spectrophotometric determination of seawater pH using phenol red , 1985 .

[16]  R. Byrne,et al.  Simplified seawater alkalinity analysis: Use of linear array spectrometers , 1998 .

[17]  R. Feely,et al.  The role of pHT measurements in marine CO2-system characterizations , 1999 .

[18]  Robert H. Byrne,et al.  Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results , 1993 .