Determination of major and trace elements in moassel for water pipes in Jordan
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https://www.eduzhai.net Public Health Research 2014, 4(1): 39-44 DOI: 10.5923/j.phr.20140401.07 Determination of Macro and Trace Elements in Moassel Used in Waterpipe in Jordan Akeel Al-Kazwini1,*, Stephanie Sdepanian2, Adi J. Said3 1Department of Biomedical Engineering, School of Applied Medical Sciences, German Jordanian University, Amman-Jordan 2Scientific Research Centre, Knowledge Sector, Royal Scientific Society, Amman-Jordan 3Department of Pharmaceutical Engineering, School of Applied Medical Sciences, German Jordanian University, Amman-Jordan Abstract The growing trend of waterpipe smoking worldwide is supporting the need to investigate the health effects of this form of tobacco use. While a number of studies have begun bridging the knowledge gap, few have attempted to quantify the concentration of toxic and essential metals smokers are exposed to. This study aims to determine the amount of Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V smokers are exposed to in one smoking session using the waterpipe. Commercially available waterpipe tobacco samples (Moassel) were selected and the total metal content quantified through acid digestion, and the amount of metal available through smoke was then calculated. Comparing the findings of this study to recommended dietary intakes of the metals in question, it was concluded that heavy smokers and chronic users were most at risk from the adverse effects of prolonged metal exposure. Keywords Waterpipe, Moassel, Smokers, Tobacco, Toxic metals, Macro nutrients, Trace elements 1. Introduction The practice of waterpipe smoking has imbedded itself into numerous societies worldwide[1,2]. There have been a number of studies investigating the prevalence of waterpipe tobacco smoking. In a study by Maziak (2011) it was found that between 6% and 34% of Middle Eastern adolescents and between 5% and 17% of American adolescents were waterpipe users. With the increasing popularity of waterpipe smoking worldwide, the dangers of water pipe tobacco are no longer restricted to the African and Asian countries where the tradition originates. One of the associated dangers of waterpipe use lies in its social nature. A single pipe may be shared among a number of users increasing the possibility of spreading diseases. More recently, with the pretence of a more hygienic alternative to the traditional leather pipe, the disposable plastic pipe has become more available. However this trend may present new risks to the user as the air tight plastic hose (shown in Figure 1) appeared to greatly increase the extent of carbon monoxide exposure in a study conducted by Saleh and Shihadeh (2008). While the influence of hose material has not been investigated for metals it may follow a similar trend in terms of exposure. Several studies have investigated the concentration and exposure of waterpipe users to polyaromatic hydrocarbons, * Corresponding author: firstname.lastname@example.org (Akeel Al-Kazwini) Published online at https://www.eduzhai.net Copyright © 2014 Scientific & Academic Publishing. All Rights Reserved volatile organic compounds, carbon monoxide, nitrogen monoxide, furanic compounds and radionuclides[7-10]; there are only a few studies focusing on the study of metals in waterpipe tobacco. Figure 1. An example of the waterpipe (‘Shisha’) set-up including the ‘head’ for containing the tobacco, the plastic hose for drawing smoke and the water vessel through which the smoke is bubbled Waterpipe tobacco (otherwise known as ‘Moassel’) is a mixture of tobacco leaves, molasses and glycerine. The mixture is often enhanced through the use of essential oils, flavouring material and humectants such as glycerol and 40 Akeel Al-Kazwini et al.: Determination of Macro and Trace Elements in Moassel Used in Waterpipe in Jordan propylene glycol. The flavouring associated with this form of tobacco has been identified as one of the reasons the practise has increased in popularity worldwide, especially among the youth. The social nature of waterpipe tobacco smoking is thought to add to the misconception that it is safer and less addictive than smoking cigarettes[7,13]. In the fourth instalment of Narghile (waterpipe) and Health by Chaouachi (2006) fifteen reasons are listed for the world escalation in waterpipe smoking, three of which are: the perception that it is easy to quit, general acceptance even for non-smokers and the television/media. For the purposes of evaluating the concentration of Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V that users of waterpipe tobacco can potentially be exposed to, thirteen samples of waterpipe ('Moassel') tobacco were analysed for the metal content in the fresh samples and in the residue remaining after the smoking process. The difference in values between the fresh sample and that of the ash residue was considered a good representation of the metals available[9, 15]. The mixtures of tobacco used are of the ‘Moassel’ variety and for the purposes of clarity will be referred to as ‘Waterpipe tobacco’ throughout this paper. Despite regional variation in the method of use and structure of waterpipes available the one used during this study is commonly referred to as ‘Shisha’ and is described in the methodology section, the term ‘waterpipe’ used will specifically refer to the procedure described therein. The aim of this study was to determine how much of each metal (Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V) smokers are exposed to during every smoking session by taking an average of all tobacco samples for a more representative figure. In addition, the study aims to establish if tobacco samples are different depending on flavour or colour and will that in turn reveal differences in the concentrations of metal distributed between the ash residue and smoke for the different metals. On average, what percentage of the total metal present signifies a potential risk factor? 2. Methodology Thirteen commercially available samples of waterpipe tobacco were used in this study. The samples were purchased from the local market during July, 2012 covering the most smoked brands and flavours. The tobacco sample labels comprise a number and codes identifying the flavour of the tobacco and finally the colour (Table 1). The samples were analysed in a two-step process; the first step was to calculate total metal concentration using an acid digestion of fresh samples. The second step was performed in order to ascertain the amount of metal remaining as part of the ash residue at the end of the smoking session and for this step 22.0 g of tobacco was previously heated and then acid digested. The 01APPRD tobacco sample was used as an independent quality control sample due to the unavailability of suitable reference material with a comparable matrix. The metals analysed were Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V. All chemical analysis was performed in the Royal Scientific Society laboratories in Amman, Jordan. Table 1. Labelling of tobacco samples. List of four analysed tobacco samples each with flavour and colour specified Sample code 01APPRD 02LWMGR 03WWMRD 04CTLRD 05MELBR 06GRPBR 07APPBR 08CTLBR 09MNTBR 10MELBR 11APPBR 12LWMBR 13LWMBR Flavour Apple Lemon with mint Watermelon with mint Cocktail Melon Grape Apple Cocktail Mint Melon Apple Lemon and mint Lemon and mint Colour Red Green Red Red Brown Brown Brown Brown Brown Brown Brown Brown Brown 2.1. Acid Digestion Fresh waterpipe tobacco samples and ash residue from preheated samples at 250℃ were digested using a nitric acid/hydrogen peroxide solution. Ultra-pure grade 65% nitric acid and 30% pure grade hydrogen peroxide (Scharlau Chemie S.A, Spain) was used and prior to digestion was further purified through sub-boiling distillation in a Teflon still (MLS GmbH, Germany). Acid washed quartz digestion vessels were used for the digestion. For the analysis, 10.0 g of homogenised waterpipe tobacco was used during the digestion and for the ash residue analysis 20.0 g of fresh tobacco was heated at 250℃ to constant weight in order to simulate the burn up of the tobacco during a smoking session. Where, weights of reference materials were taken around 5 g, sample weights were chosen in order to avoid any sampling inhomogeneity. The digestion was carried out in 100 ml tall form glass beakers covered with a watch glass and by using various volumes (25-30 ml) of concentrated HNO3 and 3-5 ml of concentrated H2O2 (added in five steps). The time of digestion was the time required to obtain a clear solution during continuous heating at 80℃. Due to the set-up of the ‘water-pipe’ procedure referred to as ‘Shisha’ where the tobacco is filled into what is referred to as a ‘head’ (Figure 1), the tobacco is not burned but instead heated to a high temperature. The tobacco is usually heated by placing previously ignited charcoal pieces on top of the tobacco mixture. The tobacco mixture is separated by perforated aluminium foil from the charcoal. In order to mimic the residue remaining after the smoking process the tobacco mixture used in this study was heated at 250℃ instead of being ashed or placed in a furnace. Quality control was maintained for the digestion procedure through digestion of standard reference material in the form of tea leaves (Certified reference no. 23, National Institute for Environmental Studies, Jordan) and flour (Certified reference no. 1567a, National Bureau of Standards, Jordan). Both quality control standards were selected for the reason Public Health Research 2014, 4(1): 39-44 41 that they have a high content of organic matrix which resembles the matrix of tobacco mixture. It was concluded that the digestion was accurate with less than 5% variation from the certified values. 2.2. Sample Analysis multi-element solution used originated from CertiPUR Merck No. OC528489. The percentage relative standard deviation for all measured metal concentrations was found to be 5.25%; this value represents the error on all metal concentrations reported unless otherwise specified. All digested samples were analysed using Inductively Coupled Plasma- Mass Spectrometry (ICP-MS) Elan DRCe 9000 (Perkin-Elmer-Sciex, USA). Using a built in operation condition according to the United States Environmental Protection Agency (EPA) method entitled “Laboratory Methods for ICP-MS Analysis of Trace Metals in Precipitation”, 1994. This method contains all the necessary validation parameters regarding measurements on ICP-MS; such as, operating condition, instrument multi-element calibration standards, sensitivity check, internal standard check, reagent blank. The lower limits of detection were calculated as three times the blank figures and it was found to be 0.05, 17.11, 11.00, 344.00, 636.00, 15.44, 0.51, 20.12, 44.66 and 5.89 ppb of Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V, respectively. An independent quality control sample standard was used to certify all measurements in addition to the aforementioned standard reference material, the 3. Results and Discussion Figures reported in Table 2 show the total concentrations of Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V for each tobacco sample measured. Of the different brands 03WWMRD has the largest fraction of metal available in the smoke in comparison to the other samples. In contrast 04CTLRD showed the least available metal in the smoke. The two samples differ in the flavour category but have the same colour. It could be speculated that the chemical composition of the flavouring varied between the two samples enough to alter the availability of the metal. The average individual metal concentrations in 13 samples (Table 3) show that typically, the most abundant metal was magnesium while the least abundant was bismuth; the variation among the individual brands was large. Table 2. Sum of metal concentrations (ppm) for Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V in each tobacco sample. The concentrations and fractions are reported for 13 different tobacco samples, average concentration of total metal in each compartment (including the range) is also given. The associated error with the values is a %relative standard deviation of 5.25% 42 Akeel Al-Kazwini et al.: Determination of Macro and Trace Elements in Moassel Used in Waterpipe in Jordan Table 3. Total amount of metal (µg) in waterpipe smoke calculated in an individual ‘head’ (22g) of tobacco mixture. The metals are listed in order of increasing concentration. The concentrations are reported for 13 different tobacco samples, averages of all samples (including the range) are also given. The associated error with the values is a % relative standard deviation of 5.25% As previously mentioned waterpipe tobacco (or ‘Moassel’) is made up of a mixture of tobacco, sweeteners, flavourings as well as glycerol. ‘Jurak’, another tobacco mixture used in Africa and Asia is reported to contain more nicotine, does not contain glycerol, and is commonly thought to be a stronger mix than ‘Moassel’ despite having the same 30% tobacco content. In a study on metal exposure using ‘Jurak’ in Saudi Arabia it was found that of the total metal concentration present reported as 14685µg of metal for every 1 g of ‘Jurak’ only 3.075µg were transferred to the user. This exposure value represents less than 0.1% of the total metal available, which is much lower than the exposure calculated for the metals tested (Table 2). Other studies have suggested, in support of the findings of this study, that even after bubbling through water levels of carbon monoxide and heavy metals remain high[17,18]. Dietary Reference Intakes are values that quantitatively estimate the amount of safe nutrient intake for different age groups. These reference values include Recommended Dietary Allowances (RDA), Adequate Intake (AI) and Tolerable upper Intake Levels (UL); for various elements and vitamins including some essential trace elements, RDA values are determined by estimating the average dietary requirement and represent the requirements of most individuals (over 97%). In the event RDA values cannot be determined, the AI value is used. The highest dose that unlikely to cause adverse effects is defined through the UL value[19-21]. Some metals tested in this study are known to be toxic with no nutritional value to humans, namely Bismuth and Lead. The risks of exposure to metals are not limited to the toxicity of the metals themselves, but also extend to possible interference with prescribed medication. There is evidence to suggest that nutritional supplements (which include essential metals) may interfere with medication. The chemical form in which metals exist in smoke and are absorbed into the body may differ from that of nutritional supplements however it may represent one possible additional risk. There are a number of factors that are important when considering the possible effects of exposure to certain trace and macro elements, for example the metal species and the source of exposure. However, in order to make an initial assessment of the exposure of smokers to metals through waterpipe smoking the total metal concentrations are used. These nutritional and toxicological reference values can be used as benchmarks in the risk assessment of chemicals. Comparing the DRI values for the metals tested in this study (where available) (Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V) to the average amount of metal exposed to (µg) in one session ‘head’ of waterpipe tobacco (22g) (Table 3) the results show that for Chromium and Molybdenum the thresholds for adults and adolescents would be exceeded with a single smoking session. For Chromium (14-18 yearsAI is 35µg (m) and 24 µg (f); Adults- AI is 35 µg (males 19 to 50 years), 25 µg (females 19 to 50 years), 30 µg (males 50+ years), 20 µg (females 50+ years)) smoking one ‘head’ of waterpipe tobacco would on average lead to the exposure to between 9 to 13 times the amount of chromium reported as the adequate daily intake. In the case of Molybdenum (14-18 years- RDA is 43 µg and the UL is 1700µg; Adults- RDA is 45µg and the UL is 2000µg) one smoking session would expose the user to 6 times the RDA value, but the recommended UL value is not exceeded. For the remainder of the metals with reported DRI values, the calculated exposure amounts per ‘head’ of waterpipe tobacco are lower than the recommended values; Magnesium (14-18 yearsRDA is 410 mg (male), 360 mg (female) and the UL is 350 mg; Adults- RDA is 400 mg (males 19 to 30 years), 420 mg Public Health Research 2014, 4(1): 39-44 43 (males 30+ years), 310 mg (females 19 to 30 years), 320 mg (females 30+ years) and the UL is 350mg), Manganese (14-18 years- AI is 2.2 mg (males) and 1.6 mg (females) and the UL is 9.0 mg; Adults- AI is 2.3 mg (males) and 1.8 mg (females) and the UL is 11.0 mg.), Iron (14-18years- RDA is 11mg (males) and 15 mg (females) and the UL is 45mg; Adults- RDA is 8.0 mg (males), 18 mg (females 19 to 50 years), 8.0 mg (females 51+ years) and the UL is 45mg), Copper (14-18 years- RDA is 890µg and the UL is 8000µg; Adults- RDA is 900µg and the UL is 10000µg), Nickel (UL for adults is 1.0 mg- as soluble metal salts) and Vanadium (UL for adults is 1.8mg as elemental vanadium). In the instances where the amount of metal available to the smoker per smoking session is lower than that of the daily recommended values, and would appear to represent a seemingly low risk in terms of metal exposure, the long term effects for heavy smokers, adolescents and the risks from other components of the smoke should not be dismissed. The concentrations of metal reported as exposure concentrations and total amounts (Tables 2 and 3) ultimately refer to the inhaled main smoke stream. The processing of the smoke in the smokers body would ostensibly alter the composition of the smoke that is exhaled and the ‘second-hand’ smoke distributed into the surroundings. Further analysis will have to be done in order to determine the exposure of people surrounded by waterpipe smokers to metals, and this would be especially important if, for those individuals, the exposure is chronic. Chronic exposure to heavy metals has been reported as a factor leading to the increase of certain types of cancer, namely head and neck. In a study on carbon monoxide and polyaromatic hydrocarbon exposure the conclusions directed towards the dangers of passive waterpipe smoke adding that the waterpipe should be included on public smoking bans. 4. Conclusions Of the total amount of metal present in waterpipe tobacco mixtures on average a large proportion, around 65%, will be transferred to the smoke to which the user is exposed. This presents a risk especially for excessive waterpipe smokers and for groups of people who are more sensitive to toxicants, for example children, although further investigation is needed. There is clear variation among different samples and brands of waterpipe tobacco of the ‘Moassel’ variety, but general trends can be deduced. Additional analysis needs to be performed in order to quantify the dangers of passive smoke from waterpipes. 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