Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter February 13, 2006

Experimental and computer modelling speciation studies of the effect of pH and phosphate on the precipitation of calcium and magnesium salts in urine

  • Simon M. Darn , Ravinder Sodi , Lakshminarayan R. Ranganath , Norman B. Roberts and John R. Duffield

Abstract

Background: pH and phosphate concentration are the major determinants of precipitation in urine of the salts of calcium and magnesium. This study aims to model the process of salt precipitation and establish whether the acidification of urine samples is necessary for the accurate measurement of calcium and magnesium in a clinical laboratory setting.

Methods: Urine samples were collected from 21 patients, aliquots were taken from each patient sample and the pH was adjusted to cover the range 2.0–10.0. The analytical and biological variation for each analyte was established and used to calculate percentage changes and critical differences. The critical difference was used to assess whether there was a significant difference between acidified and un-acidified samples. The JESS (Joint Expert Speciation System) thermodynamic computer-modelling program was used to predict the distribution of salt species formed with varying pH values and phosphate levels in simulated urine.

Results: The results showed that at a pH greater than 6.5, measured calcium, magnesium and phosphate significantly decreased as a result of precipitation (p<0.0001), although the critical difference was generally not exceeded. Computer modelling showed that both pH and phosphate concentration affected the distribution of salt species formed, as well as the precipitation patterns of calcium and magnesium phosphates. Overall, calcium phosphate precipitation tends to predominate at lower phosphate concentrations and at pH values below about 6.5, while both calcium and magnesium phosphate precipitation occur at higher phosphate concentrations and pH values greater than 6.5.

Conclusions: For accurate analysis of these analytes in urine, the pH should be routinely measured and acidification should be undertaken prior to analysis if the pH is greater than 6.5. Based on the findings of this study, acidification or the lack of it does not result in a clinically significant change in calcium, magnesium and phosphate measured in urine. This study also predicted the likely salt species formed at varying urinary pH values and phosphate concentrations.


Corresponding author: Ravinder Sodi, Department of Clinical Biochemistry & Metabolic Medicine, Royal Liverpool & Broadgreen University Hospital, Prescot Street, Liverpool, L7 8XP, UK Phone: +44-151-706-4245,

References

1. Pak CY, Eanes ED, Ruskin B. Spontaneous precipitation of brushite in urine: evidence that brushite is the nidus of renal stones originating as calcium phosphate. Proc Natl Acad Sci USA 1971; 68:1456–60.10.1073/pnas.68.7.1456Search in Google Scholar

2. Suller MT, Anthony VJ, Mathur S, Feneley RC, Greenman J, Stickler DJ. Factors modulating the pH at which calcium and magnesium phosphates precipitate from human urine. Urol Res 2005; 33:254–60.10.1007/s00240-004-0458-ySearch in Google Scholar

3. Burtis CA, Ashwood ER, editors. Tietz textbook of clinical chemistry, 2nd ed. Philadelphia: WB Saunders Company, 1994:71.Search in Google Scholar

4. Gowans EM, Fraser CG. Biological variation in analyte concentrations in urine of apparently healthy men and women. Clin Chem 1987; 33:847–50.10.1093/clinchem/33.6.847Search in Google Scholar

5. Nicoll GW, Struthers AD, Fraser CG. Biological variation of urinary magnesium. Clin Chem 1991; 37:1794–5.10.1093/clinchem/37.10.1794Search in Google Scholar

6. Ricos C, Jimenez CV, Hernandez A, Simon M, Perich C, Alvarez V, et al. Biological variation in urine samples used for analyte measurements. Clin Chem 1994; 40:472–7.10.1093/clinchem/40.3.472Search in Google Scholar

7. Konigsberger E, Konigsberger L-C, May PM, Hefter GT. Complexation of iron(III) and iron(II) by citrate. Implications for iron speciation in blood plasma. J Inorg Biochem 2000; 78:175–84.10.1016/S0162-0134(99)00222-6Search in Google Scholar

8. Udert KM, Larsen TA, Gujer W. Estimating the precipitation potential in urine collecting systems. Water Res 2003; 37:2667–77.10.1016/S0043-1354(03)00071-XSearch in Google Scholar

9. Ostwald W. The formation and changes of solids. Z Phys Chem 1897; 22:289–330.10.1515/zpch-1897-2233Search in Google Scholar

10. Shephard MD, Penberthy LA, Fraser CG. Short- and long-term biological variation in analytes in urine of apparently healthy individuals. Clin Chem 1981; 27:569–73.10.1093/clinchem/27.4.569Search in Google Scholar

11. Westenberg A, Harper M, Zafirakis H, Shah PJ. Bladder and renal stones: management and treatment. Hosp Med 2002; 63:34–41.10.12968/hosp.2002.63.1.1723Search in Google Scholar PubMed

12. Wickham JE. Treatment of urinary tract stones. Br Med J 1993; 307:1414–7.10.1136/bmj.307.6916.1414Search in Google Scholar

13. Mattle D, Hess B. Preventive treatment of nephrolithiasis with alkali citrate – a critical review. Urol Res 2005; 33:73–9.10.1007/s00240-005-0464-8Search in Google Scholar

14. Laube N, Zimmermann DJ. The influence of freezer storage of urine samples on the BONN Risk Index for calcium oxalate crystallization. Clin Chem Lab Med 2004; 42:665–9.10.1515/CCLM.2004.113Search in Google Scholar

15. Coe FL, Evan A, Worcester E. Kidney stone disease. J Clin Invest 2005; 115:2598–608.10.1172/JCI26662Search in Google Scholar

16. Werness PG, Brown CM, Smith LH, Finlayson B. EQUIL 2: a basic computer program for the calculation of urinary supersaturation. J Urol 1985; 134:1242–4.10.1016/S0022-5347(17)47703-2Search in Google Scholar

17. Tiselius HG. Risk formulas in calcium oxalate urolithiasis. World J Urol 1997; 15:176–85.10.1007/BF02201855Search in Google Scholar PubMed

18. Laube N, Hergarten S, Hoppe B, Schmidt M, Hesse A. Determination of the calcium oxalate crystallization risk from urine samples: the BONN Risk Index in comparison to other risk formulas. J Urol 2004; 172:355–59.10.1097/01.ju.0000123822.20291.4dSearch in Google Scholar PubMed

Received: 2005-8-12
Accepted: 2005-11-1
Published Online: 2006-2-13
Published in Print: 2006-2-1

©2006 by Walter de Gruyter Berlin New York

Downloaded on 9.5.2024 from https://www.degruyter.com/document/doi/10.1515/CCLM.2006.034/html
Scroll to top button