1. Natural Mineral Water: Laboratory Analysis & Permitted treatments Dr. Andrew F. Flanagan Executive Analytical Chemist Western Regional Public Analyst’s Laboratory University Hospital – Galway.

2. Categorisation of bottled water –Natural Mineral Water (2009/54/EC [recast of 80/777/EC & amendments] + 2003/40/EC) –Spring Water (2009/54/EC [recast of 80/777/EC & amendments] + 2003/40/EC) –‘other’ Bottled Water (98/83/EC – “drinking water directive”) bottled ground water ‘table’ water

3. (i) Natural Mineral Waters DEFINITION: or (A)microbiologically wholesome water*, originating in an underground water table or deposit and emerging from a spring tapped at one or more natural or bore exits. (Must be bottled at source unless exploited before 15/07/80.) A NMW can be clearly distinguished from ordinary drinking water— by its nature, which is characterised by its mineral content, trace elements or other constituents and, where appropriate, by certain effects; by its original state, both characteristics having been preserved intact because of the underground origin of such water, which has been protected from all risk of pollution. ----------------------------------------------------------------------------- The composition, temperature and other essential characteristics of natural mineral water must remain stable within the limits of natural fluctuation; in particular, they must not be affected by possible variations in the rate of flow.

4. (i) Natural Mineral Waters Chemical Analysis of NMW –Certification –Food law enforcement Maximum concentration limits –Compounds must be present in the waters naturally & not result from contamination at source (if concentrations differ from known characteristics but still below Annex I levels => contamination of the source?). –if fluoride concentration > 1.5 mg/L the label must state: “contains more than 1.5 mg/l of fluoride: not suitable for regular consumption by infants and children under 7 years of age” fluoride can be removed from NWM & SpW with act’ alumina. »Regulation (EC) 115 of 2010 –O 3 treatment allowed for removal of “unstable elements” in SpW & NMW

6. (i) Natural Mineral Waters Boron: The tolerable upper intake level for Boron in humans has been determined by the EFSA as 10mg/person/day (EFSA - Q-2003 018; 8 July 2004). The parametric value for Boron in drinking water/spring water & bottled water is 1mg/L (98/83/EC)  Determine the concentration of boron in the water being analysed and then calculate the quantity of water that contains 10mg.

7. (i) Natural Mineral Waters Micro criteria: (source must be protected vs. contamination) –Total colony count => conform to ‘characterised’ count. Any increase must only be due to the increase in the bacteria present at source Regulated after point of bottling (Art 5(1)) => positive batch release!!! –At source & during bottling NWM must not contain: Parasites & Pathogenic Microbes E. coli, coliforms & faecal streptococci in 250 mls sample Sporulated sulphite-reducing anaerobes in 50 mls sample Pseudomonas aeruginosa in 250 mls sample

8. (ii) Spring Waters “Spring waters” are those waters which are - –intended for human consumption in their natural state, –bottled at source, –satisfy the conditions of exploitation laid down … (physical prevention of water contamination – if contamination is found the obligation is on the FBO to suspend production), –satisfy the microbiological requirements imposed in respect of NMWs …, –satisfy the chemical requirements imposed in respect of OWs …, –satisfy the labelling requirements imposed in respect of NMWs …, –have not undergone any treatment other than those permitted (unstable elements – Fe, Mn, S & addition/removal of CO 2 no disinfection treatment), –are intended to be placed on the market in a Member State in bottles or containers. –O 3 treatment allowed for removal of “unstable elements” in SpW & NMW –fluoride can now be removed from NWM & SpW with act’ alumina. »Regulation (EC) 115 of 2010

9. (iii) Other Waters (in bottles or containers) “Other waters” are those waters which are – –intended for human consumption, –not natural mineral waters … (BUT – Irl allow market waters from NWM sources as ‘other waters’ – can’t market it as a NMW) –not spring waters … (BUT – Irl allow market waters from SpW sources as ‘other waters’ – can’t market it as a SpW) –intended to be placed on the market in a Member State in bottles or containers. “Other waters” must: (no restrictions on treatments as per NWMs & SpWs) –be wholesome and clean, –comply with the parametric values set down at the point at which the waters are put into the bottles or containers Official Agencies must: –conduct “regular” monitoring of the quality of Spring and other waters in order to check that the waters available to consumers meet the parametric values set down This sampling must be “representative” of water quality through the year. –setup “appropriate monitoring programmes” to ensure obligations are met

10. Parametric Values => spring and other waters Annex I of 98/83/EC: –Microbiological Parameters (part A) – OW only –Chemical Parameters (part B) –Indicator Parameters (part C) Minimum Sampling Frequency:

11. Parametric Values Microbiological Parameters (part A) (Apply at bottling – to other waters only) exceedances of the p.vals must be investigated & the causes determined remedial action necessary & enforcement action based on level of exceedance & adjudged threat to public heath

12. Parametric Values Chemical Parameters (part B) exceedances of the p.vals must be investigated & the causes determined remedial action necessary & enforcement action based on level of exceedance & adjudged threat to public heath

13. Parametric Values Indicator Parameters (part C) Carbonated bottled water permitted as low as pH 4.5 Not necessary if other monitoring has shown calc’d dose below p.val If p.vals exceed consider risk to p.health & take remedial action if needed

14. Permitted Treatments: Certain allowed, provided “this treatment does not alter the composition of the water as regards the essential constituents which give it its properties” –O 3 to oxidise unstable compounds (Fe, S, Mn, As) => flocculation followed by filter/decant to remove insoluble compounds –CARE!!! Ensure the water meets appropriate microbiological criteria before O 3 use as it can sterilise water – a banned process (would be considered a “bacteriostatic element ” in the water (Article 4(3) of 2009/54/EC).  check microbial levels before & after O 3 use, record results to prove O 3 use is appropriate & within word & spirit of 2003/40/EC –CARE!!! Check dissolved O 3 levels, bromates & bromoforms in the water at bottling: O 3 + bromine (Br - ) = bromate (BrO 3 )

15. Permitted Treatments: Activated Alumina: Al 2 O 3 to remove fluoride (F - ). –Porous material – high surface area per unit weight –Adsorption, not ion exchange –Efficacy related to: Contact time Water temperature pH Alkalinity Concentration of Carbonates Concentration of Ca 2+ –Can be re-generated for further use (basic wash=> acid wash=> rinse) –Can be used in either batch or continuous mode –Check Al 3+ concentration is < 200 mg/L in the post-treatment water Main issue is cost!!! Is the value of the treated water worth the cost of treatment?

16. Natural Mineral & Spring Waters If Al 2 O 3 or O 3 used Competent Authorities must be informed –Ok to remove “unstable” & undesirable elements from the water but must not alter the characteristic constituents of it. –Must not be used to lower microbial levels, i.e. the micro levels must have been ok before O 3 used. –O 3 treatment must not leave residues above limits or that could pose a risk to public health.

17. Thank You!