Simple Method for Calcium Determination in Crude Oil Emulsion Using Digital Image Colorimetry

Abstract

A portable device for digital image colorimetry (DIC) is reported for the determination of Ca in crude oil emulsions. ASTM D4807 was used for sample preparation for the isolation of saline species containing Ca. DIC was evaluated based on the complexation reactions with Ca using calcein, murexide, and calcon. Partial least squares (PLS) provided the best determination coefficients (higher than 0.990) for all complexing reagents. Significant interference of Mg was observed for the determination of Ca using calcein. PLS models with the lowest root mean square error of cross validation (RMSECV) values were obtained for murexide and calcon for a concentration of 0.250 mmol L⁻¹ at pH of 13. The best conditions for camera focal length were 11 and 2 mm for murexide and calcon. For light intensity, the optimized conditions for murexide and calcon was 180 lux. Stabilities of color complexes over the time were 30 and 15 min for murexide and calcon, respectively. DIC/murexide provided the lowest root mean square error of prediction (RMSEP) and a linear response was observed from 0.5 to 10 mg L⁻¹ Ca and the relative standard deviation (RSD) was lower than 10%. Significant differences were not observed between the results obtained by DIC/murexide and those obtained by microwave-assisted wet digestion (MAWD) with determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). A limit of quantification of 0.50 mg kg⁻¹ Ca were obtained using DIC/murexide. This approach is an alternative and useful method for the determination of Ca in crude oil samples, with advantages of miniaturization, low cost, and ease of operation.

Keywords:

• Calcium determination
• crude oil
• digital image colorimetry (DIC)
• partial least squares (PLS)

Acknowledgments

The authors are grateful to Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Finance Code 001), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, grant numbers 310186/2021-8 and 302816/2023-2) and Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS) for supporting this study. The authors are grateful to CENPES/PETROBRAS for providing the crude oil samples.

Disclosure statement

The authors declare no conflicts of interest.

Additional information

Funding

The authors are grateful to Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Finance Code 001), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, grant numbers 310186/2021-8 and 302816/2023-2) and Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS) for supporting this study. The authors are grateful to CENPES/PETROBRAS for providing the crude oil samples.