Assessment of the Health Benefits of Calcium and Magnesium Enrichment in Drinking Water: A Case Study in Kokava nad Rimavicou, Slovak Republic.

doi:10.21203/rs.3.rs-2992337/v1

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Assessment of the Health Benefits of Calcium and Magnesium Enrichment in Drinking Water: A Case Study in Kokava nad Rimavicou, Slovak Republic.

https://doi.org/10.21203/rs.3.rs-2992337/v1

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In the village of Kokava nad Rimavicou, we enriched the drinking water with Ca and Mg using a recarbonatization reactor (RR). In the RR, carbonate rock is dissolved using CO₂. In the RR, we produce a concentrate with a Ca and Mg content of approximately 100 mg l^− 1, which is then added directly to the water reservoir at a ratio of approximately 1:10. On average, the Ca and Mg content in the drinking water increased by 10–15 mg l^− 1. Subsequently, we monitored the positive effect of the increased Ca and Mg content in the drinking water by measuring the arterial stiffness of the residents, which characterizes the state of the cardiovascular system of people. We measured the arterial stiffness four times in six-month intervals. The first time was before the start of the enrichment of the drinking water with Ca and Mg, and subsequently three times after the enrichment. The increased content of Ca and Mg in the drinking water resulted in a significant improvement in the arterial stiffness. The arterial age of the people improved by approximately ten years, and the speed of the pulse wave velocity decreased by 0.9 m s^− 1.

Drinking water

arterial stiffness

arterial age

recarbonatization

The impact of deficient levels of Ca and Mg in drinking water on the cardiovascular system (CVS) of humans has been known for over 70 years (Kobayashi, 1957; Shroeder, 1960). Since then, this influence has been confirmed by thousands of studies conducted in various countries around the world, including three meta-analyses (Catling et al., 2008; Jiang et al., 2016; Gianfredi et al., 2017). The deficient levels of Ca and Mg in drinking water have also been associated with increased incidence/mortality of oncological diseases and diabetes mellitus over the past 20–30 years (Yang et al., 1998; Butler et al., 2010; Naumann et al., 2017). Furthermore, it has been confirmed that individuals supplied with "soft" drinking water have a shorter lifespan by 4–5 years compared to those supplied with "hard" drinking water (Rapant et al., 2021). A very illustrative example of the impact of deficient levels of Ca and Mg in drinking water is observed in countries where drinking water produced from seawater using reverse osmosis has been used for drinking purposes. This water is characterized by an extremely low content of Ca and Mg, resulting in increased incidence/mortality of cardiovascular and oncological diseases in these countries (WHO, 2011; Avni et al., 2013; Lesimple et al., 2020).

In this study, we address the issue of deficient levels of Ca (< 30 mg/l) and Mg (< 10 mg/l) in drinking water by enriching (recarbonating) drinking water using RR. We increase the content of Ca and Mg by approximately 10–15 mg/l. Subsequently, we observe how this increased content of Ca and Mg in drinking water affects arterial stiffness. The main objective of this study is to determine whether there is an improvement in the cardiovascular system of individuals (which is monitored by measuring arterial stiffness) originally supplied with "soft" drinking water after enriching this water with Ca and Mg.

Area description

The village of Kokava nad Rimavicou has a population of approximately 3,000 inhabitants and is located in the southern part of the Slovak Republic (Fig. 1). It is supplied with potable water from the Klenovec reservoir. After pre-treatment and disinfection, the potable water is led by pipeline to the local water reservoir in the village Kokava nad Rimavicou. The rock environment around the Klenovec reservoir is mainly composed of granitoid and metamorphic rocks, resulting in water with very low mineralization and very low levels of Ca and Mg (Table 1). The reservoir in the village Kokava nad Rimavicou is supplied by water quantity according to the current consumption, which averages at approximately 100,000 m³ per year. In the summer months, consumption is approximately 20–30% higher than in the winter months, with an average consumption of approximately 3.0 l s^− 1.

Table 1

Ca, Mg and water hardness contents of drinking water in Kokava nad Rimavicou compared to the standard values of the Slovak drinking water standard and proposed concentrations of Ca, Mg and water hardness after recarbonatization (RC).
	Ca	Mg	Water hardness
	[mg l^− 1]		[mmol l^− 1]
Kokava nad Rimavicou	19.1	3.52	0.62
Slovak drinking water standard^*	> 30	10–30	1.1-5.0
Proposed values after RC^**	25–30	8–12	1.1–1.3

^{* Decree of the Ministry of Health No. 247/2017 Coll., **The proposed values are based on a risk analysis}.

The Slovak drinking water standard only provides recommended values for Ca and Mg contents and water hardness (measured as Ca + Mg in mmol l^− 1). As shown in Table 1, the values for these parameters are at the lower end of the recommended range. The health status of the inhabitants of the village of Kokava nad Rimavicou (KnR) is significantly worse compared to the average of the Slovak Republic (SR), especially regarding cardiovascular diseases (CVD). The relative mortality rate from CVD in the KnR village is 882.4 (period 1995–2006), almost 65% higher compared to the SR average of 531.2 (Rapant et al., 2019; Cvečková and Rapant, 2022). The aforementioned increased mortality from CVD is mainly associated with low content of Ca (19 mg l^− 1) and Mg (3.5 mg l^− 1) in drinking water. Based on the risk analysis, an increased health risk from Ca and Mg deficiency and low hardness of water for the local population has been confirmed (Rapant et al., 2020; Cvečková and Rapant, 2022). The mean hazard quotient level for deficient elements (HQ_d) was found to be 1.59 for Ca, 1.59 for Mg, and 1.56 for hardness water, which is a medium level of health risk. The hazard index for deficient elements (HI_d) for these three parameters was 4.7, which is at a high risk level of developing chronic diseases. To reduce the level of health risk to a low risk level, it is necessary to increase the content of Ca and Mg in drinking water in the KnR village by approximately 10 mg l^− 1.

Carbonate Rock Leaching

To increase the mineral content of drinking water, Half-burnt dolomite (HBD) is utilized as a rock material due to its high solubility of carbonatic rocks (Tuček et al, 2017). HBD is produced by annealing dolomite [CaMg (CO₃)₂] at a temperature range of 600–800°C, which results in the conversion of magnesium to oxide and calcium to carbonate. When HBD is dissolved in the liquid phase, magnesium ions are preferentially released due to the higher solubility of magnesium oxide compared to magnesium carbonate. Magno-Dol, a type of HBD with a size fraction of 2.0-4.5 mm and approved for drinking water treatment in the EU, contains approximately 98.2% Ca and Mg oxides and carbonates, 0.9% Si, Al, and Fe oxides, 0.8% water, and less than 0.1% of other elements. Only trace amounts of toxic heavy metals are present. For dissolving HBD, Food CO₂ from Messer Tatragas, which is approved for food purposes by the EU and contains over 99% CO₂, is used as an oxidizing agent.

Methods

Design of a Fluidized Bed Recarbonatization Reactor

The process of recarbonatization (RC) is used to increase the content of Ca and Mg in drinking water. Various processes and carbonate rocks are used for RC, typically under CO₂ saturation. Flow-through systems are often used, where carbonate rock is added to a device with various filters, through which the treated water flows (Haney & Hamann 1969; Al-Rqobah & Al-Munayyis 1989; Olejko 1999; Withers 2005; Luptáková & Derco 2015). To enrich the drinking water in the village of KnR with Ca and Mg, a prototype of a fluidized bed recarbonatization reactor (RRF) was developed (Fig. 2,3). The RRF contains a layer of solid particles of half-burnt dolomite (HBD), which is kept in motion by the bottom-up flow of water to intensify the dissolution process of the carbonate rock. The recarbonatization reactor was placed directly into the water reservoir without any technical interventions. The device consists of two main parts, the reactor and a circulation tank. The reactor is approximately 3.5 meters tall, cylindrical with a diameter of 40 centimeters, and has a dosing tank on top for adding HBD. The volume of the reactor is approximately 2 m³, and it is connected to the circulation tank with a volume of approximately 10 m³. The system is powered by two pumps: one serves as a circulation pump to circulate water between the reactor and the circulation tank, while the other pumps the produced concentrate into the water reservoir. Carbon dioxide is supplied from pressurized bottles with serial concentration. Three circulation pumps with a capacity of 6.8 m³ sec^− 1 were used. The recharge pump has a capacity of up to 2 m³ h^− 1, while the output of the circulation pump is approximately 10 times higher. This allows for multiple rinsing of the carbonate rock, which results in the formation of a concentrate with a Ca and Mg content ranging from 500 to 1,000 milligrams per liter. The concentrate is added directly to the water reservoir in a ratio of approximately 1:10 to the water consumption. The circulation and discharge pumps are equipped with frequency converters, which can be easily adjusted as needed. A photovoltaic system was built to provide electricity for powering the pumps. Detailed technical documentation of the recarbonatization reactor is available on the website http//fns.uniba.sk/lifewaterhealth/ or Cvečkocá and Rapant (2022).

Measurement of arterial stiffness

The concept of "arterial stiffness" has only entered our awareness in the last 20–30 years. This phrase is a general term that refers to the loss of arterial compliance or changes in vessel wall properties, or both (Shirwany et al., 2010). The measurement of arterial stiffness is a simple technique that has become a useful non-invasive approach to health prevention in the past 20 to 25 years (DeLoach et al., 2008). Markers of arterial stiffness, such as increased aortic pulse wave velocity and increased central aortic pressure, are independent predictors of cardiovascular risk (Illyes, 2005). These markers represent tissue biomarkers of the arteries and have been shown to be better prognosticators than traditional blood pressure measurements, as well as biomarkers in the bloodstream. Furthermore, their significant predictive value specifies the risk assessment provided by traditional risk factors. The measurement of arterial stiffness provides insights into the actual pathological processes through the evaluation of the loss of elasticity of the aorta. Over time, endothelial damage progresses and causes damage to the arterial elasticity, resulting in the loss of elasticity of the vessel wall. In this study, measurements were performed with an arteriograph (Fig. 4) developed in Hungary and patented in over 30 countries (Arteriograph, TensioMed Ltd., Budapest, Hungary). The arteriograph can easily measure, without any health risk, physiological parameters characterizing the state of arteries that are independent of other known risk factors (age, sex, blood pressure, cholesterol, smoking) and can reliably assess the state of the cardiovascular system and predict the risk of complications in asymptomatic, apparently "healthy" patients. These parameters are also confirmed by international guidelines for the diagnosis of target organ damage (Williams et al., 2018). The influence of Ca and Mg content in drinking water on the improvement of arterial stiffness has been demonstrated in the work of Rapant et al. (2019). The Ca and Mg content in drinking water had a greater impact on arterial elasticity than other factors such as obesity, BMI index, smoking, and so on.

We measured arterial stiffness on approximately 60 volunteers in the village of KnR. The basic condition was that the volunteers had a permanent residence in the village for at least five years. People who had been treated for cardiovascular diseases and other diagnoses (especially diabetes mellitus and kidney diseases) were excluded from the measurements. All participants in the measurement gave written consent for the study, and before the measurement, they completed a short questionnaire about their health status, age, height, weight (BMI index), smoking, and alcohol consumption. For the purpose of the study, an ethical commission was established at the Regional Public Health Office based in Zvolen (minutes 1/2021 dated 05. 09. 2021). The basic characteristics of the volunteers from the KnR village are presented in the Table 2.

Table 2

Basic characteristics of volunteers from the KnR village
Age	BMI	Gender	Smoking habbits	Alcohol consumption
53*	28.5*	Male 15	Yes 14	Regularly 0
56**	27.45**	Female 41	No 41	Occasionally 31
16–69***	19.5–53***			Abstinent 25
^{* average, median, * dispersion}

Selected volunteers underwent four measurements of arterial stiffness. The first measurement was conducted before the enrichment of drinking water with Ca and Mg, and the following three measurements were conducted approximately every six months after the enrichment of drinking water with Ca and Mg. The results of arterial stiffness measurement are expressed using pulse wave velocity (PWVao) and arterial age. The lower the pulse wave velocity, the better the condition of the arteries. Similarly, the lower the arterial age (age of the arteries), the better the condition. In a normal case, arterial age corresponds to the actual age. If the condition of the arteries is unfavorable, the arterial age is higher than the actual age and vice versa. Therefore, the results of arterial age are expressed as the difference between arterial age and actual age. The lower this difference, the more favorable the condition of the arteries. In the best case, this difference takes negative values, which means that the age of the arteries is lower than the actual age. Further details on the methodology of arterial stiffness measurement depending on the content of Ca and Mg in drinking water are available in the work of Rapant et al. (2019) and directly in KnR in the work of Cvečková and Rapant (2022).

Recarbonisation of drinking water

The recarbonisation reactor in the KnR village was put into operation on July 12, 2021, according to the schedule of the LIFE - WATER and HEALTH project (http://fns.uniba.sk/lifewaterhealth/).

The basic conditions for recarbonisation were as follows:

Average daily water consumption in KnR: 275–300 m³.
Average daily dose of produced and added concentrate: 25–30 m³ day^-1.
Mixing ratio of concentrate and water from the reservoir: 1:9 (1:10).
Performance of the circulation pump: approximately 10 m³ h^-1.
Average dose of added HBD: 50 kg per week.
Average amount of added CO₂: 230–240 kg per week.
Total volume of the reservoir: 1,300 m³.
Target values for recarbonisation: Ca 25–30 mg l^-1, Mg 8–12 mg l^-1, (Ca + Mg) 1.1–1.3 mmol l^-1.

After the RR was put into operation, a malfunction occurred in the reactor hydraulics. The reactor operated at only about 20% capacity. Due to the COVID-19 pandemic, it took approximately 90 days to resolve the issue and ensure the reactor was operating at full capacity. After that, the RR worked reliably until the end of the LIFE-WATER and HEALTH project (December 31, 2022). The results of the recarbonatization of drinking water in KnR for the years 2021–2022 are shown in Table 3.

Table 3

Results of drinking water recarbonisation in KnR for the years 2021–2022
Month	Ca	Mg	Water hardness	conductivity
Month	[mg l^− 1]		[mmol l^− 1]	[µS cm^− 1]
2021
Original state	19.1	3.5	0.62	110
August	19.9	4.1	0.66	116
September	25.6	4.9	0.83	145
October	30.7	6.9	1.04	165
November	30	8.8	1.11	202
December	32.5	9.2	1.18	222
2022
January	32.9	14.0	1.39	202
February	33.2	13.2	1.33	210
March	35.6	12.8	1.41	225
April	46.4	12.6	1.68	259
May	31.3	9.9	1.19	205
june	42.7	12.5	1.58	235
July	44.8	13.2	1.64	242
August	38.6	11.7	1,44	250
September	42.4	12.8	1.58	239
October	39.6	11.1	1.44	225
November	44.8	15.2	1.74	261
December	40.2	12.8	1.53	229

The Table 3 shows values of Ca, Mg, water hardness, and conductivity at the output in the village (in the branch of the local waterworks center), approximately 2 km from the water source. From April 2022, the local water company began to enrich drinking water with Ca using calcium hydroxide [(Ca(OH)₂]. This was reflected by an increase in the content of Ca in drinking water in KnR.

Measurement of arterial stiffness.

The first initial measurement of arterial stiffness was carried out in the village of KnR in May 2021. Sixty-four volunteers participated in the measurements. Due to their advanced age (over 67 years), four volunteers were excluded from the sample. This stage took place during a period when the residents were supplied with "soft" drinking water (Ca 19 mg l^− 1, Mg 3.5 mg l^− 1). The next three stages of arterial elasticity measurements were carried out at approximately six-month intervals after enriching drinking water with Ca and Mg (Ca 45 mg l^− 1, Mg 10–15 mg l^− 1). Due to the COVID-19 pandemic, we could not follow the planned six-month interval for the measurements. Measurements were conducted at 5–7 month intervals due to quarantine. Additionally, not all respondents who participated in the first arterial stiffness measurement were able to participate in the measurements of the II.-IV. stages due to COVID-19. Therefore, we also used a smaller sample of substitute volunteers. For this reason, we present the results first without substitute volunteers, and also with substitute volunteers. The results of the arterial stiffness measurement of the inhabitants of the KnR village are shown in Tables 4 and 5, and the entire arterial stiffness measurement database is available on the project website (http://fns.uniba.sk/lifewaterhealth/).

Table 4

Results of the arterial stiffness measurement of respondents in the village of Kokava nad Rimavicou, all respondents
Measurement stage	Measurement date	Number of espondents	PWVao	Actual age	Arterial age	Difference Arterial age - actual age
Measurement stage	Measurement date	Number of espondents	[m s^− 1]	[years]
I.	May 2021	60	9.7	54.11	64.18	10.07
II.	December 2021	53	9.54	53.69	62.77	9.08
III.	June 2022	56	9.37	52.3	61.35	9.5
IV.	December 2022	73	8.91	54.43	55.58	1.15

Table 5

Results of the arterial stiffness measurement of respondents in the village of Kokava nad Rimavicou, excluding substitute respondents
Measurement stage	Measurement date	Number of espondents	PWVao	Actual age	Arterial age	Difference Arterial age - actual age
Measurement stage	Measurement date	Number of espondents	[m s^− 1]	[years]
I.	May 2021	60	9.7	54.11	64.18	10.07
II.	December 2021	46	9.42	53.74	61.24	7.5
III.	June 2022	49	9.25	53.4	59.76	6.36
IV.	December 2022	52	8.83	54.53	54,.67	0.14

Calcium and magnesium are very important essential elements. For healthy human development, their content in drinking water should be at least at the level of Mg 10–20 mg l^− 1 and Ca 30–50 mg l^− 1 (Rosborg and Kožíšek, 2020). As can be seen from Table 3, after the initial technical problems (first 90 days of operation), the reservoir operated reliably. We increased the Ca and Mg content in the drinking water in KnR to the desired level without any problems, by approximately 10–20 mg l^− 1. We then tested the reactor, varying the performance of the circulation pumps, the amount of concentrate discharged, the amount of HBD added, and also the amount of CO₂. The process of dissolving HBD is mainly influenced by the performance of the circulation pump and the amount of added rock. The amount of added CO₂ needs to be limited to such an extent that the residual free CO₂ does not exceed the level of 60–80 mg l^− 1. A relatively large amount of rock micro-particles is released during the fluidization process. The produced concentrate is turbid. However, these micro-particles dissolve in the reservoir water due to the residual free CO₂, thereby increasing the Ca and Mg content in the drinking water by 10–15%. Therefore, there is no risk of acidification. The resulting pH of the water in the village increased only slightly, from about 7.2 to 7.3 and the free CO₂ content from about 4 mg l^− 1 to 8 mg l^− 1. The optimal reactor setting, at which we can ensure an increase in the Ca and Mg content in drinking water by 10–15 mg l^− 1 at the lowest possible operating costs, was a circulation pump performance in the range of 7–9 m² h^− 1, the amount of added HBD of 7–8 kg day^− 1, and the amount of CO₂ of 15–17 kg day^− 1. It is clear from the above that the reactor operated at only about half power, and at maximum reactor output, we can increase the Ca and Mg content by up to for Ca 50 mg l^− 1 and for Mg 25 mg l^− 1. An advantage of the RRF prototype we developed is the relatively low operating costs, which are approximately €0.1 per m³ of drinking water. More detailed results of recarbonatization under different conditions are available on the website http://fns.uniba.sk/lifewaterhealth/ and in the work of Cvečková and Rapant (2022). From the results of the measurements of arterial stiffness (Table 4, 5), it is evident that there was a significant improvement in the condition of the arteries of the residents of the KnR village after enriching the drinking water with Ca and Mg. This was reflected in the decrease in the pulse wave velocity and the reduction in the arterial age of the people. The pulse wave velocity decreased in all volunteers (9.7 to 8.91) and also in the case of volunteers without replacements (9.7 to 8.83). Similarly, the arterial age of the people, expressed as the difference between the arterial age and the actual age, was significantly reduced. In the case of all volunteers, it decreased from 10.07 to 1.15 years and in the case of volunteers without replacements, it decreased from 10.07 to 0.14 years. The values of PWVao and arterial age of the KnR residents have already approached the level of the Central European average (Rapant et al., 2019). Improvement in arterial age and PWVao is truly significant. It can be explained only by the fact that we increased the content of Ca and Mg in drinking water, up to 2–3 times compared to their original levels. Other factors such as stress, genetic predisposition, BMI, excessive consumption of alcohol and smoking also have an impact on the cardiovascular system and therefore the elasticity of the arteries, in addition to the content of Ca and Mg in drinking water. However, statistical testing has shown that the content of Ca and Mg in drinking water has a much greater impact on artery elasticity than, for example, BMI and smoking (Rapant et al., 2019).

The results presented in the article clearly confirmed the improvement of arterial stiffness, thus the cardiovascular system of KnR residents, after consuming drinking water enriched with Ca and Mg. This improvement was reflected in a significant reduction in pulse wave velocity and arterial age of people. The deficient content of Ca and Mg in drinking water not only worsens the condition of the human cardiovascular system but also increases the mortality rate from other diseases, especially cancer and diabetes mellitus. It also results in a shorter lifespan by up to five years compared to people who are supplied with "hard" drinking water. Therefore, we believe that, based on many studies published in the world literature, Ca and Mg should be included among the regulated parameters of drinking water. We also believe that the content of Ca and Mg in bottled drinking water should be regulated, especially in cases where bottled drinking water is produced by desalination of seawater.

Funding

This work was supported by the project „Improvement of health status of population of the Slovak Republic through drinking water recarbonization LIFE – Water and Health LIFE17 ENV/SK/000036“.

Competing Interests

Financial interests : Author S. Rapant received an honorarium as the project leader of LIFE - Water and Health LIFE17 ENV/SK/000036.

Author V. Cvečková received an honorarium as the assistant to the project leader of LIFE - Water and Health LIFE17 ENV/SK/000036.

Author P. Čermák had no financial interests and is currently a PhD. student at Comenius University.

Author I. Hajduk received an honorarium as the project leader of LIFE - Water and Health LIFE17 ENV/SK/000036.

Author Ľ. Jurkovič received an honorarium as the project leader of LIFE - Water and Health LIFE17 ENV/SK/000036.

Author Contributions

S.R. conceptualized the study; P.Č., L. J. and V.C. prepared and wrote the original draft; reviewed and edited the article; S.R. visualized the study, designed the reactor, prepared the methodology of the experiment. I.H. conducted the measurement of arterial stiffness. All authors have read and agreed the article to be published.

Ethics approval

For the measurement of arterial stiffness an ethical commission was established at the Regional Public Health Office based in Zvolen (minutes 1/2021 dated 05. 09. 2021).

Consent to participate

Written informed consent was obtained from the parents.

Consent to publish

The authors confirm that human research participants provided informed consent for the publication of the collected data.

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Assessment of the Health Benefits of Calcium and Magnesium Enrichment in Drinking Water: A Case Study in Kokava nad Rimavicou, Slovak Republic.

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Measurement of arterial stiffness

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