Icp-Ms Determination of Trace Metals in Drinking Water sources in Jazan Area, saudi Arabia

Requisite reference facts about essential elements in treated and plastic bottled drinking water is usually mentioned on the products. However, more information is sometime crucial regarding trace elements in treated, bottled and other sources of drinking water such as tap water to evaluate their quality. This study is aimed to evaluate drinking water quality in the main governorates (Jazan, Sabya and Abu Arish) of Jazan province located in the South-Western region of Kingdom of Saudi Arabia. This is the first such study carried out in Jazan city so that the research team can come out with valuable recommendations in the issue. The research team has collected a sum of 68 water samples from different sources comprising hospitals (treated tap water), stations for drinking water treatment (large blue bottles of drinking water) and bottled drinking water (purchased from local markets). Using inductively coupled plasma-mass spectrometry (ICP-MS), the concentrations of 20 elements were determined. The physiochemical parameters of water samples were measured. All parameters were within the recommended limits of the World Health Organization (WHO, 2011) and Gulf Cooperation Council Standardization Organization (GSO, 2008). Trace and major elements were found to be below the standard guideline values, except for uranium in some tap water samples. This preliminary study will significantly improve the awareness and knowledge among the society about the drinking water quality in Jazan area.

Pure drinking water is one of the basic needs for every human being in the world.For a large portion of the African and Asian populations, safe drinking water is not effectively accessible 1 .Out of the 7 billion individuals on earth, more than one billion and half need to get pure and safe drinking water and around 2.7 billion do not have admittance to satisfactory sanitation administrations 2,3 .Not with standing these deficiencies, different sorts of waterborne illnesses execute more than 6 million kids every year i.e. around 20,000 kids a day 4,5 .Water covers 70 percent of the globe's surface, mostly saltwater.Freshwater covers only 3 percent of the world's surface and quite a bit of it falsehoods solidified in the Antarctic and Greenland polar ice 5 .New water that is accessible for human utilization originates from waterways, lakes and subsurface aquifers.These sources represent just a single percent of total water on the earth.Six billion individuals rely on the supply water and a noteworthy segment of the total populace is confronting water deficiencies (Fig. 1) 5 .
Groundwater represents the main source of drinking water in Saudi Arabia 6,7 .The quality of water is of scientific as well as public concerns, till now no serious issue in drinking water quality has been reported in the country 8 .Many resources of chemical and microbial contaminations of groundwater including wastewater, pesticides, fertilizers, and industrial wastes have been reported 9,10 .
In the recent years, there was a considerable increase in the consumption of bottled drinking water.This means that systematic and regular independent tests on the quality of bottled drinking water must be applied, and different organizations worldwide set standards for bottled drinking water 11,12 .
Jazan is located in the South-Western part of the Saudi Arabian Peninsula [16°53'21"N 42°33'40"E], and it is considered the second smallest province which comes after Al bahah region of the kingdom in terms of area considerations.Jazan spreads over 300 km along the southern coast of the Red Sea directly north of yemen.A total of 11,671 km² is the representative area of Jazan province with total population of 1,365,110 according to the 2010 census.Jazan city itself is the capital of the province with its 14 governorates, table 1 13 .
In this area, the drinking water is mainly provided either as bottled water of various capacities ready to use, or filled after treatment in plastic containers (20l or larger).However, the information about the concentrations of heavy metals in the drinking water supplied to Jazan area is inadequate.The aim of this study was to measure the levels of essential and toxic elements, and evaluate the physicochemical properties of drinking water from different available sources.To the best of our knowledge, this is the first scientific effort for determination of heavy metal contents in drinking water from all types of resources in Jazan area.

Water sample collection
Three types of drinking water samples were collected: bottled, filled treated and tap water.The samples of all the three types of water sources were collected during August-September 2016.A total of 68 samples were collected including; (I) tap water samples (n = 12) from 4 different hospitals in the Jazan province, (II) treated (filtered and ozonized) drinking groundwater (n = 17), and (III) bottled drinking water (n = 39) of different brand available in the market.After collection the samples were directly transported to the laboratory and stored in their original package at 4 o C till analysis.

Analytical Methods
The physiochemical parameters such as Electrical Conductivity and pH were measured using a bluelab combo meter (Tauranga, New Zealand) in the laboratory of Pharmaceutical Analytical Chemistry, Faculty of Pharmacy, Jazan University.
Major and trace elements (beryllium be, magnesium Mg, calcium Ca, aluminum Al, titanium Ti, chromium Cr, manganese Mn, cobalt Co, nickel Ni, copper Cu, zinc Zn, arsenic As, rubidium Rb,

resulTs AnD DIscussIon
Table 3 summarizes the recommended values of heavy metals and physico-chemical properties of the drinking water.In the tables (4-13) the levels of all tested parameters are presented for the samples from all types of water resources.

physico-chemical properties
To know the different physico-chemical parameters of drinking water is very essential for the safety of human beings.The average pH values were compared for all the samples within a type of water and also for the samples of the different types.It was found that the tap water samples and collected from stations have recorded comparatively higher pH values than those of bottled drinking water samples (Tables 4, 5, and 10  Overlapping in the pH values was observed between the range of pH of treated samples from stations of drinking water and those of bottled drinking water.Still the range is within the permissible limit of WHO and other national and international organizations regulating the water quality and related health issues [14].This permissibility is not excluding the tap water samples from hospitals.In general, the pH values of water samples in this study were found to be within the acceptable and permissible limit.Thus, it may be concluded that valuable positive outcome is indicated from water treatment processes in terms of pH, a significant physico-chemical parameter.Even though, pH values of some water samples are marginally near the highest permissible values recommended by WHO and other related organizations.A proper control and follow up is required during all the stages of water treatment and distribution to the consumer points so that to maintain the purity of drinking water and minimize the associated health risks.This will also participate in minimizing water corrosion through distribution systems 15 .
Although the values of other physicochemical parameters such as EC, TDS and TH were found to be within the acceptable range set by the national and international organizations' guidelines, a considerable variation was observed among all the water samples.

Major elements
Presence of sodium, calcium, magnesium and potassium in drinking water is considered to be essential to the heath of mankind is ranging between 10 mg/l to 100 mg/l for sodium and calcium respectively and between 1 mg/l to 10 mg/l for magnesium and potassium 16 .In this study, sodium is not included as one of the 20 elements under investigation.However, calcium (Ca) and magnesium (Mg) concentrations in all representative samples were measured.Treated drinking water of stations and bottled drinking water samples have scored the lower concentrations of the two major elements compared to the samples of tap water from hospitals.. (Table 4, 5 and 8).Depletion of these elements during the treatment processes may be the significant cause of their varying results.Only two samples (Alrraidah, Jazan and Aljisr-bish) from treated drinking water samples of stations were found to contain calcium (Ca).On the other hand, calcium is not detected in bottled drinking water samples indicating the deficiency of this major element in all the brands of bottled water samples tested.

Trace elements
Although, the trace elements contribute in the natural occurrence of dissolved constituents in groundwater by only 1 %, there should be a periodical follow up and measurement of trace element in bottled and treated drinking water to avoid contamination by these toxic metals from unexpected sources.Some of the trace elements are essential to human health such as vanadium, selenium, cobalt and nickel upto certain concentration range.On the other hand some of these trace elements are toxic to human beings such as cadmium, aluminum, arsenic and lead with concentrations not exceeding 1 µg/l and uranium with a concentration lower than 10 µg/l 16 .
Water samples of treated tap water and from stations recorded the highest values of Rb and Sr.However, their concentrations did not exceed the recommended values of the organizations including WHO.The average concentrations of a total of 14 trace elements measured in all the samples were within the permissible limits except three samples from treated drinking water of stations [Alkauther  Waters-Jazan (22.18 mg/l), QatratSehab Waters-Jazan (42.34 mg/l) and Alkauther Waters-Sabeya (22.18 mg/l)] in which the uranium level exceeded the permissible limits of all national and international organizations including Who which might due to the geophysical properties of Sabeya area.
Improvement of distribution systems and application of systematic regular maintenance may be effective to avoid the existence of these toxic elements.These elements can be considered safe at the lower concentrations levels as shown in (Table 3).Cobalt concentration values were very low in all the tested samples and also remained undetected in some of the water samples.The strontium is a naturally occurring element and its permissible limit is 4200 µg/l which is very high as fig. 2: location of the sampling areas (the three governorates) in Jazan province, south-Western region of the saudi Arabian peninsula

Table 4 : parameters measured in treated tap water samples from hospitals of Jazan region
Key: a = Prince Mohammed bin Nasir Hospital (Al-shawajrah); b= Abu Arish Public Hospital (Abu Arish); c = King Fahd Hospital (Abu Arish); d = Jazan Public Hospital (Jazan); n = No. of samples from each hospital; NM = Not mentioned; Nil = Not available in the sample

Table 8 : parameters measured in treated water samples collected from different governorates of Jazan region (group VI elements)
Key: Nil = Not available in the sample