Introduction Tobacco kills nearly 6 million people each year

Introduction
Tobacco kills nearly 6 million people each year. More than five million of those deaths are the result of direct tobacco use, while more than 600 000 are the result of non-smokers being exposed to second-hand smoke. Unless urgent action is taken, the annual death toll could rise to more than eight million by 2030.

Smoking tobacco using a narghile waterpipe has become a popular phenomenon world-wide, particularly among youth Users appear to be lured by the highly aromatic and sweetened tobacco paste known as ma’ssel, involving many new and young smokers. Because of its high moisture content, ma’ssel does not burn in a self-sustaining fashion as does cigarette tobacco; it requires a continuous external heat source to produce the smoke. Normally, the heat source used is burning charcoal, which is placed atop the ma’ssel. Thus the smoke inhaled by the waterpipe user includes charcoal combustion products in addition to constituents emanating from the ma’ssel. Mainstream and sidestream waterpipe smoke has been found to contain alarmingly high quantities of carcinogenic PAH, CO, volatile aldehydes, ultrafine particles and other toxicants
Description of waterpipes and waterpipe smoking:
Generally, waterpipes have a head, body, water bowl, and hose (figure 1). Holes in the bottom of the head allow smoke to pass into the body’s central conduit. This conduit is submerged in the water that half-fills the water bowl. The hose is not submerged, exits from the water bowl’s top, and ends with a mouthpiece, from which the smoker inhales. The tobacco that is placed into the head is very moist (and often sweetened and flavoured): it does not burn in a self-sustaining manner. Thus, charcoal is placed atop the tobacco-filled head (often separated from the tobacco by perforated aluminium foil. When the head is loaded and the charcoal lit, a smoker inhales through the hose, creating a vacuum above the water, and drawing air through the body and over the tobacco and charcoal. Having passed over the charcoal, the heated air, which now also contains charcoal combustion products, passes through the tobacco, and the mainstream smoke aerosol is produced. The smoke passes through the waterpipe body, bubbles through the water in the bowl, and is carried through the hose to the smoker. During a smoking session, smokers typically replenish and adjust the charcoal periodically. A pile of lit charcoal may be kept in a nearby firebox for this purpose. As an alternative, smokers may opt for commercially available quick-lighting charcoal briquettes.

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12331703181985Figure SEQ Figure * ARABIC 1: Actual waterpipe (left) and schematic (right) showing main parts. Reproduced from (Maziak, 2008, 2011).

0Figure SEQ Figure * ARABIC 1: Actual waterpipe (left) and schematic (right) showing main parts. Reproduced from (Maziak, 2008, 2011).

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There are regional and/or cultural differences in some waterpipe design features, such as head or water bowl size, number of mouthpieces, etc., but all waterpipes contain water through which smoke passes prior to reaching the smoker. Names for the waterpipe also differ, and include “narghile” in East Mediterranean countries including Turkey and Syria, “shisha” and “goza” in Egypt and some North African countries, and “hookah” in India.

Waterpipes can be purchased from dedicated supply shops, including Internet vendors, which also sell charcoal, tobacco and accessories. Waterpipes are now being marketed as portable, with the introduction of accessories such as carrying cases with shoulder straps. Some accessories are sold with claims to reduce the harmfulness of the smoke, such as mouthpieces that contain activated charcoal or cotton, chemical additives for the water bowl, and plastic mesh fittings to create smaller bubbles. None of these accessories have been demonstrated to reduce smokers’ exposure to toxins or risk of tobacco-caused disease and death.
Body
Charcoal Manufacturing:
Brazil is considered the largest producer of charcoal in the world; in 2003 about 4.4 million tons of charcoal were produced, with 49% from planted forests using mainly Eucalyptus sp. The charcoal is produced usually in rudimentary furnaces built of bricks and clay. The wood pyrolysis in the furnace for the charcoal production takes place in limited conditions of oxygen and at the temperature of 400–450 1C. Wood pyrolysis under atmospheric pressure with long vapor residence time is called carbonization.Wood carbonization produces three main products: charcoal, liquids, and gas with yields of 37–50% char, 4–11% wood tar, 30–36% aqueous phase, and 14–29% by weight of noncondensable gases. When the wood is heated in an environment with poor oxygen content, vaporization of the water (100–110 1C) occurs initially; following this, the temperature rises and at about 270 1C the wood begins to spontaneously decompose (precarbonization). At the same time, the heat increases and carbonization becomes complete at about 450 1C. The recovery of the pyrolysis liquids is a very well-known technique in developed countries, as it reduces emissions to the atmosphere and increases production profits. The biomass carbonization, mainly wood, can result in a significant emission of particulate matter (PM) and polycyclic aromatic hydrocarbons (PAH) into the atmosphere PAH in PM was found in smoke from Eucalyptus fuel and the high rate of wood burning (1.78 kg/h) resulted in the highest total 18 PAH emission rate (208 mg/h) and concentration (957 mg/m3), leading to a high exposure of toxic pollutants.

Shisha Charcoal Types Used in Lebanon:
Charcoal used in waterpipe smoking is generally sold as formed briquettes or as lump charcoal. The briquettes are formed by compressing pulverized charcoal in a press with a binder (e.g. starch), or by pyrolyzing extruded logs formed from biomass particles (e.g. ground coconut shells). Some briquette products are “easy-light” and contain an ignition agent. Lump charcoal, in contrast, comes in a variety of irregular shapes traceable in form to the original biomass used to make it (e.g. tree branches). The latter are commonly made by small producers using traditional kilns. traditional lump charcoal, as well as two charcoal briquette products (Three Kings™, Holland; CocoNara™, Lebanon) commonly sold in Lebanon. The Three Kings™ brand contains an ignition agent, while the CocoNara™ and lump charcoal products do not. According to its packaging, CocoNara™ is manufactured from coconut shell, and is “environmentally friendly” and “100% natural”.

Moassel Tobacco Ingredients and Types:
Tobacco used for narghile smoking has three main forms: moassel (”mu’assel” as a proper transliteration, meaning ”honeyed” in Arabic), jurak and tumbak. Their compositions are variable and not well standardized. Moassel contains about 30% tobacco and up to 70% honey or molasses/sugar cane, in addition to glycerol and flavoring essences. The nicotine content varies significantly with a median value of 3.4 mg/g. Jurak contains about 30% tobacco, 50% juice of sugarcane, 20–25% various spices and dried fruits.
The bulk of moassel and jurak is usually made of dark, firecured or sun-cured tobacco. It is also mixed with other imported varieties such as Burley. The dark tobacco is also the one used as tumbak (ajamy); however, it is prepared in a different way and not analyzed in this study. It would belong to the Petunioides sub-genus/Nicotiana Alata Persica variety. However, it was also suggested that given its resemblance to Russian Makhorka, it would relevantly be classified under the Nicotiana Rustica sub-genus.

The definite date of the first production of sweetened flavoured waterpipe tobacco, commonly called maassel, is unknown, but it was already in use in the Middle East in the early 1990s. Circumstantial evidence suggests a temporal link between the production of maassel at the beginning of the 1990s and the surge in the number of waterpipe smokers in the Middle East. Maassel is typically manufactured by fermentation of tobacco with molasses, glycerine and fruit essence, producing a moist, pliable mixture. Before the introduction of maassel, most waterpipe smokers used some form of raw tobacco that they manipulated (e.g. crushed, mixed with water, squeezed and moulded) before use. This method usually produces strong, harsh smoke, unlike the smooth aromatic smoke produced from maassel.

Shisha Toxicity Sources
Shisha smoke has been found to contain alarmingly high quantities of carcinogenic PAH, CO, volatile aldehydes, ultrafine particles and other toxicants. But is moassel tobacco only responsible for these generated chemicals, or charcoal, or both??!
Toxic Chemicals Generated From Coal:
Note: All the Methodologies used in the analysis are provided in the Experimental Part.

Study A:

Because shisha smoking normally involves the use of burning charcoal, smoke inhaled by the user contains constituents originating from the charcoal in addition to those from the tobacco. Because charcoal production involves wood pyrolysis under conditions which are favorable for PAH formation there is good reason to suspect that the charcoal sold to waterpipe users is contaminated by PAH. So PAH residues had been measured on three kinds of raw waterpipe charcoal (Three Kings™, CocoNara™ and Lump charcoal) commonly sold in Lebanon sampled from Beirut stores and cafés.
Results of PAH quantified in the three charcoal products are given in Figure 2. It can be seen that all the charcoal products tested contained significant quantities of PAH residues, including benzo(a)pyrene, an International Agency for Research for Cancer (IARC) Group 1 carcinogen, and that the quantities varied widely across charcoal types. The total PAH mass per gram of CocoNara™ briquette was more than 6 times that of the lump charcoal. The large intra-product variability in naphthalene however resulted in overlap in 95% confidence intervals of total PAH mass between the Three Kings™ and both of the other charcoal types. Removing naphthalene from the total, the differences in PAH mass between all three charcoal products attained statistical significance at the 95% confidence level (bottom of Figure 2). Differences in the sums of 5- and 6-membered ring PAH compounds (i.e. those appearing below chrysene in Figure 2), are less drastic, with the CocoNara™ containing about two times the quantities of the lump charcoal. As shown, differences between Three Kings™ and the lump charcoal were not statistically significant for the sum of 5-and 6-ring PAH compounds.

Figure SEQ Figure * ARABIC 2 :PAH residues in three types of waterpipe charcoal sampled in municipal Beirut. N = 3 samples for each charcoal product. Results expressed as mean (SEM).
By comparing current results with measurements of mainstream and sidestream smoke using the Three Kings™ charcoal product, we find that the PAH residues in the unburned charcoal amount to 66% of the total PAH mass delivered in the combined sidestream and mainstream smoke, and 15% of the 5- and 6-ring PAH mass (Figure 3). This demonstrates a potential for desorbed PAH residues to account for a significant part of the PAH delivered in the smoke, but not the entire balance. The data shown in Table 2 also indicate that the high naphthalene mass provided by the raw charcoal may facilitate the pyrosynthesis of higher molecular weight PAHs through a successive ring build-up mechanism during smoking.

Figure SEQ Figure * ARABIC 3: PAH emitted in combined mainstream and sidestream smoke and unburned charcoal from a narghile waterpipe smoked using 8.4 g of Three Kings™ charcoal.

Waterpipe charcoal products are abundant with PAH when purchased off the shelf. While we have previously learned that the burning charcoal releases large quantities of carcinogenic PAH into the mainstream and sidestream smoke of the narghile waterpipe, the current study demonstrates that charcoal products contain significant quantities of carcinogenic PAH even before they are lit, and that these residues may constitute a significant fraction of the PAH emitted by the charcoal. This study also demonstrates that these PAH residues vary widely and systematically by product. Taken together, these findings suggest that public health agencies following TobReg’s recommendations should therefore move to regulate smoked charcoal products alongside tobacco. Finally, the study also shows that charcoal products marketed as “environmentally friendly” and “natural” can contain more man-made carcinogens than products not marketed as such.

Study B:
Another study, which focuses on the role of charcoal as a unique toxicant source in narghile smoking.In particular, the relative contributions of the charcoal and tobacco to CO and PAH yields in mainstream narghile smoke are assessed by comparing yields when the narghile is smoked with charcoal to those when it is smoked using an equivalent electrical heating source. The differences in yields between these two conditions can be considered the contribution of the charcoal. CO and PAH were selected because they respectively represent components of the smoke that are considered major causative agents in cardiovascular disease and lung cancer.

The results are that the tobacco consumed and Total Particles Matter(TPM) yield ratio are given for the electric heating and charcoal heating cases in Figure 4. It can be seen that the electrically heated condition had greater tobacco consumption and TPM yield, consistent with its elevated tobacco temperature (Figure 5), though the TPM yield ratio was the same as for the base condition, indicating similar heat and mass transport processes.

Figure SEQ Figure * ARABIC 4: Tobacco consumed, TPM yield, and yield ratio (mean ± SEM) for base case and electrical heating condition.

Figure SEQ Figure * ARABIC 5: Normalized PAH yields for the two smoking conditions and for raw charcoal extracts.

Figure SEQ Figure * ARABIC 6: Summary of findings
CO yields for the base and electrically heated conditions were 57.2 ± 4.79 and 5.70 ± 2.07 mg, respectively.CO yield thus dropped by circa 90% when the charcoal was removed. The PAH yields in the mainstream smoke for the two experimental conditions are given in Figure 5 and summarized in Table 3.The base condition provided significantly greater PAH yields than the electric heater condition. Without charcoal, yields for all of the carcinogenic 4- and 5-ring compounds dropped to below detectable limits. Also reported in Figure 5 are PAHs found in samples of unburned charcoal extracts. Thus in addition to in situ pyronsynthesis, PAHs may be introduced to the mainstream aerosol by desorption of preexisting PAHs (i.e. residuals from the charcoal manufacturing process) as the narghile is smoked. It should be noted that the quantities of PAHs reported for the charcoal in Figure 5 assume extraction efficiencies of 100%; in all likelihood, the extraction efficiency is considerably less, meaning that the values reported for charcoal represent lower bounds. It should also be noted that similar levels of PAHs were measured for two samples of traditional hardwood charcoal (sindyan) commonly used to smoke narghile in Lebanon.

The results are summarized in Figure 6, where it can be seen that charcoal is responsible for the majority of the PAH and CO content of the smoke. This finding is consistent with the slow pyrolysis kinetics expected at the relatively low temperatures prevalent in the tobacco. The
distribution of PAH concentrations in the mainstream smoke and unburned charcoal extracts are shown graphically in Figure 7, where it can be seen that the PAH composition for the base condition closely resembles that of the unburned charcoal extract. An R2 of 0.94 is obtained when the compound-by-compound charcoal PAH concentrations are correlated to those for the base smoking condition. These PAH distributions also bear remarkable similarity to PAH emissions measured from a charcoal-burning food grill, also shown in Figure 7. Correlation of the PAH data reported by Dyremark and Westerholm (1995) to that of the base case in the current study yields an R2 of 0.96. In contrast, the PAH distribution for the electrically heated condition is uncorrelated (R2 ; 0.02) to that of the base condition. Simply put, narghile smoke PAH profiles closely resemble those emitted from burning charcoal, not tobacco. The high correlation between the PAH distributions of narghile smoke condensates, unburned charcoal extracts, and charcoal grill emissions provide strong corroborating evidence of the charcoal origin of the PAHs measured in narghile smoke. These compounds may be synthesized as the charcoal burns on the narghile head, or transferred to the smoke by desorption of PAH residues left on the char surface from the charcoal manufacturing process.

Figure SEQ Figure * ARABIC 7: Relative PAH concentrations measured in the mainstream smoke of the base and electrically heated conditions, and in extracts of the unburned charcoal. PAH concentrations from smoke collected from a charcoal grill by Dyremark and Westerholm (1995) shown for comparison. Correlation coefficients are shown relative to the base condition. Unburned charcoal extract, charcoal grilling smoke, and base case narghile smoke exhibit similar PAH patterns. Electrically heated condition produces a different PAH pattern.

Finally This study has demonstrated that the high yields of CO and PAHs in mainstream narghile smoke mainly derive from the charcoal. Thus, not only is the production of tobacco-derived particulate matter sensitive to variations in charcoal application (as shown by Shihadeh and Saleh, 2005), but the charcoal is itself an important toxicant source for narghile users and those in their company. Though this study focuses on toxicants generated by the charcoal, we do not suggest that the charcoal poses the only important risks to smokers; toxicants transferred from the tobacco, such as nicotine, ”tar”, and carcinogenic nitrosamines may present equally or more important health hazards.

Toxic Chemicals generated by Moassel Tobacco:
Metal Content:
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. The mixtures of tobacco used are of the ‘Moassel’.

Thirteen commercially available samples of waterpipe tobacco were used in this study. The samples were purchased from the local market. Figures reported in (Figure 10) show the total concentrations of Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V for each tobacco sample measured. It could be speculated that the chemical composition of the flavouring varied between the samples 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. In another study on metal exposure using ‘Jurak’ in Saudi Arabia it was found that of the total metal concentration present reported as 14685?g of metal for every 1 g of ‘Jurak’ only 3.075?g.

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.

Figure SEQ Figure * ARABIC 8: Labelling of tobacco samples. List of four analysed tobacco samples each with flavour and colour specified.

Figure SEQ Figure * ARABIC 9: 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.

Figure SEQ Figure * ARABIC 10: Total amount of metal (?g) 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.

Volatile aldehydes:
The identification and quantification of volatile aldehydes in the gas and particle phases of mainstream narghile smoke generated using a popular type of flavored ma’ssel tobacco mixture is performed. The Aldehyde yields for six repeated smoking sessions are summarized in Figure 11. To account for the inherent variability of the smoking method (see Shihadeh, 2003), the results shown in Table 1 are normalized by the amount of tobacco mixture consumed in a given session. The results show that among the aldehyde target compounds, only formaldehyde is found in significant proportions in the particle phase of the smoke. This may be attributed to the higher solubility of formaldehyde in water as compared to the other aldehyde compounds, in light of the fact that the narghile aerosol particles are rich in water (circa 40% water by mass; see Shihadeh, 2003). Henry’s constant is reported to be 3000 mol/Latm for formaldehyde, whereas that of acetaldehyde is 11.4 mol/Lat.

Figure SEQ Figure * ARABIC 11: Aldehyde yields in the whole narghile smoke (lg/g of tobacco mixture consumed) and fraction accounted for in the gas phase.

Several conclusions may be drawn from the obtained results. First, the identified aldehyde compounds are found exclusively in the gas phase of narghile smoke, except for formaldehyde. Approximately 40% of the amount of formaldehyde found in mainstream narghile smoke is in the particulate phase. This could be explained by the high solubility of formaldehyde in the water-rich aerosol of mainstream narghile smoke, in contrast to the other identified species.

Nicotine, pH and PAAs :
A study was carried to determine nicotine and pH levels of waterpipe tobacco. The results are in Figure 12 and Figure 13.

Figure SEQ Figure * ARABIC 12: pH and Nicotine Concentrations among Various Waterpipe Tobacco Brands.

The nicotine content of waterpipe tobacco ranged from nicotine-free for ‘herbal’ products to 3.30 mg/g for products claiming to contain nicotine (mean = 1.13 mg/g, N = 140). In products that claimed to, and contained, tobacco (N = 120), the label did not predict actual nicotine content. All waterpipe tobacco labeled as tobacco-free (N = 20) was found to be nicotine-free. Measured pH levels ranged from 3.81 to 5.84 (mean = 5.04, N = 218).

In a study on the identification and quantification of primary aromatic amines (PAAs), there was dection of 31.3 ± 2.2 ng aniline and 28.0 ± 1.6 ng 4,4-oxydianiline in the smoke of one waterpipe session.

Water Filtering Effect:
For three replicate smoking sessions with water we determined an average TPM of 2.28± 0.15 g, whereas for smoking sessions without water 2.07 ± 0.19 g were detected. Charcoal and tobacco consumption were 7.49 ± 0.06 g and 3.60 ± 0.24 g with water and 7.57 ± 0.06 g and 3.96 ± 0.29 g without water. It is likely that the pH shift in the water was caused by dissolving carbon dioxide present in the air or smoke. At the same time, decreasing pH values (acidification of the water) might be the reason for the filter capacity of the water with respect to the PAAs present in the smoke (see below). In the waterpipe smoke we detected only 9 PAAs, including aniline (ANL) and the two naphthylamines (ANPs). ANL and 4,4-ODA revealed with highest concentrations of 31.3 ± 2.2 and 28.0 ± 1.6ng/session, respectively. Experiments carried out without water showed consistently higher values for the PAAs, thus indicating a filtering effect of the bowl water. As a result, o-ASD and 3,5-DCA could be detected quantitatively. For ANL, 4,4-ODA, m-PDA and 1-ANP roughly 40 percent and for 2-ANP and 2-ABP roughly 10 percent were retained by the water. The water in the bowl exerted a small but considerable filter effect on PAAs. So The water in the bowl exerted a small but considerable filter effect on PAAs.

Figure SEQ Figure * ARABIC 13: Results for the determination of PAAs in waterpipe mainstream smoke
The water will tolerate so much smoke because the it filters out some of the nicotine. Otherwise, the smoker would have to stop smoking very quickly due to nauseousness from the high dose. The water also has the effect of cooling the smoke, which serves to mask the harshness of the tobacco so as to allow the smoker to inhale deeper and for longer. The water in the bowl exerted a small but considerable filter effect on PAA, but however, even after bubbling through water levels of carbon monoxide and heavy metals remains high.

Shisha and Microbiological Risk:
Microbiological risk is that the hookah is used by several people at the same time, the moist of the tobacco creates conditions for the development and growth of various microorganisms, some individuals do not change the water in the hookah for each smoking session and its structure make difficult washing of all its parts, for these reasons the HS may be exposed to different microorganisms that may be harmful to health.
Mycobacterium tuberculosis is one of the pathogens transmissible through hookah, because they have been documented cases of patients with pulmonary tuberculosis where hookah and the mouthpiece were responsible for transmission vehicles.

The Presence of significant amounts of microbes in Shisha water jars suggests the strong possibility of inhalation of aerosols containing microbes by shisha smokers. The polymicrobial nature of the isolates especially suggests the formation of bacterial biofilms in the Shisha water jar. LPS from the cell walls may be an etiological agent of acute and chronic airway obstruction and disease seen in smokers. It is strongly recommended that a larger study be carried out to evaluate biofilm formation, bacterial load and species of organisms within the Shisha water bowl. This may help in decreasing the incidence of chronic obstructive airway disease seen in chronic smokers.

Another Study Indicates That the hoses of waterpipe devices might be a good environment for the growth of bacterial pathogens that can be transmitted to users, and that show resistance to commonly used antibiotics, thus they could be the source for potential infections outbreaks.

Second Hand Smoke (Side stream):
Figure 14 summarizes the results for different organic substances. A distinct increase was especially found for benzene (0.11 vs. 15.0 lg/m3), 2,5-dimethylfuran (<0.05 vs. 8.8 lg/m3), nicotine (<0.05 vs. 18.0 lg/m3) and total volatile organic compounds (730 vs. 1800 lg/m3) when comparing both 4-h sampling periods. The sum of all measured 16 gaseous and particle-bound PAH were approximately twice as high during the smoking session, compared with the prior control session. This total concentration of PAH was dominated by the more volatile naphthalene, phenanthrene, acenaphthene and fluorene. With regard to the seven PAHs classified as probable carcinogens by the US-EPA, the concentration increased from 1.86 ng/m3 during the nonsmoking session to 4.86 ng/m3 during the smoking session.

In conclusion, the observed indoor air contamination of different harmful substances during a waterpipe session is high, and exposure may pose a health risk for smokers but in particular for secondhand smoke exposed non-smokers.

Figure SEQ Figure * ARABIC 14: Concentrations of organic substances during a waterpipe session and the day before without any smoke exposure (4-h averaging time).

Comparison between Shisha and Cigarette Smoking Gas Composition:
Ultrafine particles and size distribution
Average ultrafine sidestream particle emissions for 4 repeated waterpipe smoking sessions was 3.99 ± 0.60 x1012 particles/ waterpipe, while for 4 repeated cigarette trials it was 0.638 ± 0.188 x1012 particles/cigarette. waterpipe emissions contain a significantly larger proportion of particles below 100 nm.

Carbon monoxide:
Determinations of carbon monoxide for 13 replicate waterpipe smoking sessions yielded an average of 2269 ± 108 mg/waterpipe. Carbon monoxide for 9 replicate cigarette sessions was 65.5 ± 5.5 mg/cigarette.

Particle polyaromatic hydrocarbons:
Results of PAHs Comparison between waterpipe and cigarette are showed in Figure 14.

Volatile aldehydes:
Analysis of SS from six replicate waterpipe sessions yielded 5234 ± 1011 mg formaldehyde, 5084 ± 1211 mg acetaldehyde, 1135 ± 297 mg acrolein, 441 ± 129 mg propionaldehyde, and 110 ± 30 mg methacrolein per waterpipe. Analysis of SS from 5 replicate cigarette sessions yielded 357 ± 143 mg formaldehyde, 2136 ± 384 mg acetaldehyde, 144 ± 21 mg acrolein, 213 ± 65 mg propionaldehyde, and 104 ± 11 mg methacrolein per cigarette.

Figure SEQ Figure * ARABIC 15: Sidestream emissions to mainstream smoke toxicant yield ratios for narghile
Conclusion
In fact, the waterpipe smoker likely emits as much aldehydes and PAH into the immediate environment as do two cigarette smokers, and as much CO as 10 cigarette smokers. The available evidence therefore indicates that waterpipe smoking results in environmental emissions of ultrafine particles, aldehydes, PAHs, and carbon monoxide well in excess of those resulting from cigarette smoking, regardless whether the comparison is made per unit smoked or smoker per unit time.

Experimental Part:
ICP-MS:
ICP-MS is a type of mass spectrometry which is capable of detecting metals and several non-metals at concentrations as low as one part in 1015 (part per quadrillion, ppq) on non-interfered low-background isotopes. This is achieved by ionizing the sample with inductively coupled plasma and then using a mass spectrometer to separate and quantify those ions. Inductively coupled plasma is plasma that is energized (ionized) by inductively heating the gas with an electromagnetic coil, and contains a sufficient concentration of ions and electrons to make the gas electrically conductive. However, the concentration of a sample can be determined through calibration with certified reference material such as single or multi-element reference standards.

Study A (Charcoal Toxicity):
Charcoal sample collection and preparation
sampling was adapted to collect CocoNara™ and Three Kings™ charcoal samples. Four packages of each charcoal product were collected from ten retail outlets in municipal Beirut (i.e. 40 packages of each brand were procured in total). One package of each type was chosen randomly, and five pieces of charcoal were taken from it. The five pieces were ground and well-mixed and 5 g was taken to form a single sample. This procedure was repeated three times to make three different random samples each of CocoNara™ and Three Kings™ charcoal from the same 40 store-bought packages. Lump charcoal used for waterpipe smoking was purchased from ten waterpipe-serving cafés in municipal Beirut. Samples were prepared by randomly selecting equal quantities of charcoal from five of the ten cafés, grinding, mixing, and selecting a 5 g sample for analysis. This procedure was repeated three times to form three different random samples of lump charcoal from the ten café batch. All samples were collected in February 2009.

PAH extraction and cleaning
Internal deuterated standards were added to 5g of each charcoal type and extracted with 15 ml of toluene for two hours at 30°C by sonication. The obtained solutions were filtered and preconcentrated using a flow of nitrogen. The volume was reduced to approximately 1 ml. An SPE silica cartridge was used to clean the sample and PAHs were collected using 10 ml of hexane. The sample was then concentrated by reducing the volume down to 150 ?l using a flow of nitrogen. The sample was then injected on GC-MS.

Study B:
the smoke issuing from the narghile mouthpiece was split into two parallel streams, and each passed through a 47 mm glass fiber filter to trap the particle phase. The filters were changed at 40, 60, and 80 puffs to avoid overloading, resulting in four pairs of filter samples for each smoking session. Downstream of the filters circa 1% of the flow was sampled by a diaphragm pump that was automatically actuated during each puff. The pump exhausted into an inert grab sampling bag, whose contents were analyzed using an electrochemical CO meter at the end of each smoking session. Because the CO is a gas-phase component, the particle filters located upstream of the sampling location do not affect the CO concentration.
Total particulate matter (TPM) yield was determined by pre- and post-weighing each filter assembly (filter + holder). Tobacco consumed during each smoking session was also determined gravimetrically by weighing the narghile head (without the heating source) before and after smoking.
For PAH determination, each filter was sonicated in 15 ml of toluene, and the resulting solution was concentrated under a flow of nitrogen. The concentrated solution was eluted with 10 ml of hexane through a conditioned SPE cartridge, and evaporated to 1 ml under a flow of nitrogen. The resulting solutions for each group of 4 filters (constituting all the filters of a single flow branch from a given smoking session) were combined as a single sample and evaporated to dryness under a flow of nitrogen. The solid phase was reconstituted in 0.1 ml of acetonitrile and analyzed by GC–MS. Chromatographic separation was achieved with an Alltech ATTM-5ms column (30 m 0.25 mm, 0.25 lm film thickness), using helium gas as the carrier phase. Quantification was done in the selected ion current mode.

The final design of electrical heater incorporated a steel wire mesh between the heater assembly and the aluminum foil cover of the head. The mesh allowed air to easily flow between the heater and waterpipe head, while also serving to reduce conductive heat transfer from heater to head. With this increased resistance to conductive transfer, the problem of ”cooking” the tobacco between puffs was eliminated, and the temperature of the heater could be increased sufficiently to ensure that the air passing under it became hot enough to deliver a significant pulse of convective thermal energy each puff. This resulted in good thermal penetration into the head, and temperature profiles and TPM yield ratios that similar to those when charcoal was used. The final heater design is heating element mounted on a brass disk, as shown in Figure 17. Electric power from a DC power supply was delivered to the coil through the body of the heater assembly. A constant voltage was applied during each smoking session.

Figure SEQ Figure * ARABIC 16: Schematic of the electrical heater apparatus used in this study.

Metal Content:
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 metals analysed were Bi, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb and V.

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 was used and prior to digestion was further purified through sub-boiling distillation in a Teflon still. 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’, 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 and flour Both quality control standards were selected for the reason 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.

Sample Analysis: All digested samples were analysed using Inductively Coupled Plasma- Mass Spectrometry (ICP-MS).
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.
Volatile Aldehydes:
Materials and reagents: Tobacco mixture with the brand name Nakhla Tobacco (Egypt) ”two apples” flavor was obtained from local retail outlets, as were the Three Kings (Holland) brand quick-light charcoal disks used in this study.

Sampling of aldehyde compounds in the gas and particle phases of narghile smoke:. Intrinsic air infiltration rate through the permeable leather hose used in this study was measured and found to be 2.2 L/min at a waterpipe flow rate of 12.2 L/min; this infiltration rate was monitored throughout the study and found to be invariable. Because hose infiltration was found to be an important determinant of toxicant yields, it is recommended that it be routinely specified in any toxicant yield measurement with the narghile. For the purpose of direct comparison between the amounts of aldehyde compounds found in the gas and particle phases of narghile smoke, both phases were sampled and assessed simultaneously during each full smoking session (171 puffs, 2.6 s puff duration, 17 s inter puff interval and 12.2 L/min total flow rate). A schematic diagram of the sampling system employed in this study is illustrated in Figure 18. The sampled mainstream smoke was split into two parallel streams, each flowing at 0.72 L/min as shown in Figure 18. One stream was used to trap only the gas phase aldehydes, while the other was used to trap both gas and particle phase aldehydes. The proportion of gas phase to total aldehydes was computed as the ratio of the aldehydes trapped in the two streams. Small fractions of the smoke were sampled, as shown in Figure 18, due to the limited capacity of the SPE cartridges employed (643 lg/cartridge). Sampling both phases was accomplished by collecting and derivatizing aldehyde compounds on two DNPH-coated 47 mm filter pads connected in series. The second DNPH-coated filter pad was used to ensure the derivatization of all aldehyde compounds in the sampled smoke, in case the capacity of the first DNPH-coated filter was exceeded. The two DNPH-coated filters were succeeded by a blank filter (non DNPH-coated) and an H-30 DNPH cartridge used for derivatizing any unreacted aldehyde compounds in the gas phase of the sampled smoke (Figure 18). Meanwhile, aldehyde compounds in the gas phase of the smoke were sampled on a single DNPH cartridge preceded by a blank filter pad used for trapping the particulate phase. The flow rates through each stream were measured before and after each run to ensure the consistency of the smoking system.

Figure SEQ Figure * ARABIC 17: Schematic diagram of the narghile sampling system and the connections made to sample small percentages of gas and gas + particle smoke.

Filter preparation and extraction: Aldehyde compounds in the particle phase of mainstream smoke were collected and derivatized on DNPH-coated filter pads based on the method proposed by Dong and Moldoveanu (2004) for cigarette smoke. Glass fiber filter pads (47 mm) were manually soaked in a freshly prepared DNPH solution. This 0.015 g/ml solution was prepared by dissolving 1.5 g of recrystallized DNPH in 100 ml of acetonitrile containing 200 ll of 70% percholric acid. The acid plays a role in promoting the derivatization reaction. Filter pads soaked in this solution were then dried and stored at 4 ?C for a maximum of three days prior to sampling. Following sample collection, filters were extracted by sonication in 10 ml of the extraction solution (2% pyridine, 98% ACN). The extracted solution was then filtered and delivered into ambered HPLC vials. The extraction efficiency of the filters was calculated using various sonication and drying times. The results showed that the optimal drying time is 30 min under vacuum, and that the most efficient extraction is achieved upon 10 min sonication. Aldehydes in the gas phase of the smoke were sampled on H-30 SPE cartridges (Lp-DNPH, Supelco). After collection, these cartridges were eluted with 10 ml of ACN, filtered, and delivered into ambered vials for HPLC analysis. It should be noted that both filters and cartridges were wrapped tightly with aluminum foil and stored at low temperatures (4 ?C) after sampling, in order to inhibit thermal and photochemical decomposition of the sampled compounds. A maximum of three days was allowed between sample collection and analysis.

Chromatography: All prepared samples of standards and narghile smoke were analyzed using HPLC equipped with a photodiode array detector at k = 360 nm, and at a flow rate of 1 ml/min. The analytes were identified upon comparing their HPLC retention times with those of the standards (Figure 19). Aldehyde compounds were identified based on their individual retention times as compared to the calibration standards. The filter pads were soaked with ACN, spiked with particular volumes of the standard solution, dried for 30 min under vacuum, and then extracted via sonication in 10 ml ACN. Four standard solutions ranging in concentration between 0.5 and 10 ppm were prepared using a 20 ppm commercial standard solution consisting of 13 standard aldehyde-DNPH compounds in the form of hydrazones. In addition, three injections from each prepared standard concentration were performed in order to check the reproducibility of the HPLC system.

Figure SEQ Figure * ARABIC 18: Overlayed chromatograms of 2 ppm of aldehyde standard solution and 2.75% of the mainstream narghile smoke.

Nicotine Analyses:
determination of nicotine in tobacco and tobacco products by gas chromatography (GC). Methyl tert-butyl ether (MTBE) was the extraction solvent and quinoline was the internal standard (MTBE method). A calibration curve and quality control standards were prepared with each GC run. The limit of detection was determined by assessing whether at least 80% recovery was attained for the lowest value on the calibration curve, resulting in a limit of detection of 0.1mg/g. To standardize sampling methods, and when possible, the waterpipe tobacco product was divided into a grid (4 quadrants for a 50g package; 8 quadrants for a 250g package) and one sample was obtained from each quadrant, resulting in multiple samples for each product package. In instances where using a grid was not possible, such as when the product was sold in a flat envelope, an effort was made to sample from multiple areas of the package. Reference products were prepared and included in each GC run.

pH Analyses:
one gram of waterpipe tobacco was mixed with 10 ml HPLC-grade water, vortexed, sonicated, and allowed to cool. The pH was measured using the Mettler Toledo Seven Compact pH meter.

PAAs Detection:
Reagents and materials: Waterpipe tobacco was purchased from Nakhla Tobacco (Two Apples flavour, Nakhla Tobacco, Egypt). Quick lighting charcoal (Ø 40 mm) was obtained from Three Kings and 92 mm glass fiber filter pads were purchased from Perforated aluminum foil (Ø 15.5 cm, 25 holes).

Figure SEQ Figure * ARABIC 19: Experimental set-up: wind cover (1a); charcoal (1b); tobacco (1c); head (1d); ash tray (1e); steam (2); bowl (3); filter holder with filter (4); pump (5, Borgwaldt Shisha Smoker), and flow diagram of the entire analytical protocol.

Automated smoking conditions: Waterpipe smoking was performed by connecting a Borgwaldt Shisha Smoker machine to a standard laboratory waterpipe with a plastic hose (see Figure 19). Each smoking session consisted of 171 puffs of 530 ml each and 2.6 s duration every 20 s. The bowl was filled with 750 g distilled water and the stem was placed 30 mm underneath the water surface. Ten grams of waterpipe tobacco was loaded into the head of the pipe and covered with perforated aluminum foil in a way that the tobacco did not touch the aluminum foil. A single quick lighting charcoal disk was lit and placed after 60 s atop the perforated foil to start the smoking session. The total particulate matter (TPM) was collected by aspirating the smoke of an entire session through a 92 mm glass fiber filter pad. TPM was determined gravimetrically by weighing the filter holder (including filter pad) before and after smoking. To avoid overloading the filter pads were always changed after puff #105. Method blanks were performed by smoking the waterpipe without charcoal and tobacco.

Sample preparation: Smoking of the waterpipe and sample preparation were performed at the same day. For extraction of TPM the 92 mm filter pads were transferred to a 500 ml Erlenmeyer flask covered with aluminum foil, spiked with 100µL of the internal standard solution and 50 ml methanol was added subsequently. The filter pads were then agitated for 1 h on an HS 250 basic shaker. The samples were filtered directly into autosampler vials through a 0.45 µm PTFE syringe filter and analyzed by LC–MS/MS (see Figure 19). For analysis of the bowl water (water of the waterpipe) a 10 ml flask containing 20 µl of the internal standard solution was filled up to the mark, the solution was mixed and then directly injected into the LC–MS/MS sytem. The pH value of bowl water was determined before and after smoking, using a pH-meter.

Instrumental conditions: For sample analysis a HPLC system coupled with an API 4000 Q TRAP mass spectrometer was used. Fifteen microliters of the sample extract were injected into the LC–MS/MS system. Chromatography was performed on a Synergi 4u Polar-RP 80A column (150 mm × 4.6 mm, 4µm particle size) at 40 ?C with a flow rate of 0.8 ml/min. Mobile phases A and B consisted of water and 0.1% formic acid in 25% methanol/75% acetonitrile, respectively. Mass detection conditions were as follows: ionization mode, positive ESI; ion spray voltage, 4500 V; ion source temperature, 550 ?C; curtain gas, nitrogen, setting: 25; ion source gas 1 (GS1), nitrogen, setting: 55.0; ion source gas 2 (GS2), nitrogen, setting: 45.0. Compound-dependent parameters were optimized by flow injection analysis

Figure 20: Analyte-specific parameters and multiple reaction monitoring (MRM) analysis of 33 primary aromatic amines (PAAs) and their corresponding internal standards 27. PAAs listed in the order of their retention times.

Figure 20: Continued

Figure SEQ Figure * ARABIC 21: LC–MS/MS chromatogram of a PAA standard solution containing each analyte in a concentration of 1 ng/ml in methanol and of a waterpipe sample (inlets: PAAs depicted are those for which an individual signal has been received);
SideStream (second hand) Smoke Analysis:
SS from awaterpipe or cigarettewas generated and routed to an experimental chamber which allows dilution and ageing processes characteristic of an indoor environment. The overall experimental setup is shown in Figure 22. The waterpipe hose or cigarette is connected to an external smoking machine, while the rest of the waterpipe or cigarette is placed in a vertically-oriented cylindrical dilution tunnel (24 cm diameter, 67 cm height) fitted with a tapered cone roof. The tunnel captures the smoke coming off the head, dilutes it, and routes it into the 1 x 1 x 1 m ageing chamber. The ageing chamber is fitted with a series of ports which are connected to external sampling pumps whose flow rates are monitored and regulated by a series of computer-controlled valves and mass flow meters. The chamber air change rate is set to 1.5 h-1. The temperature, humidity, CO, and CO2 are continuously recorded using a Kanomax IAQ monitor. All internal surfaces, including the fan and IAQ wand, are coated with Teflon to minimize surface reactions.

Figure SEQ Figure * ARABIC 22: Schematic of the experimental setup used in this study. Air change (1.5 ACH) is driven by computer-controlled sampling trains located on the right hand side of the chamber. SS enters the chamber from the roof of the dilution tunnel, and HEPA-filtered lab air enters at the bottom of the tunnel. All surfaces are Teflon coated.

Sampling and chemical analysis: For PAH, duplicate samples were generated for each experiment using 47 mm glass fiber filters installed on two separate sampling ports of the chamber, each operating at a flowrate of 8 L/min. At the end of each run, the filters were removed and each was sonicated in 10 ml of toluene for 2 h, and the resulting solution was concentrated to 1 ml under a flow of nitrogen. The concentrated solution was eluted with 10ml of hexane through a conditioned SPE silica cartridge, and evaporated to a final volume of 100–200 ml before injection in the GC–MS. Chromatographic separation was achieved with an Alltech AT-5ms column (30m x 0.25mm, 0.25 mm film thickness), using helium gas as the carrier phase. Volatile aldehyde compounds were sampled from a single port of the chamber operating at 0.5 L/min. The aldehydes were collected and derivatized to stable hydrazone species using 2,4-dinitrophenylhydrazine (DNPH) treated SPE cartridges. To prevent particulate matter from blocking the SPE cartridge and its ozone trap, smoke drawn from the chamber was passed through a single 47 mm glass fiber filter located immediately upstream of the SPE cartridge. After sampling, both filters and cartridges were covered with aluminum foil and stored at 4 ?C, normally for less than 24 h. H10 Lp-DNPH cartridges were eluted with 5 ml of HPLC grade acetonitrile, filtered, and analyzed using HPLC–MS system equipped with a photodiode array detector set at l ¼ 360 nm. Gradient elution on a reverse phase C-18 column (25 cm x 4.6 mm, 5 mm) was performed. The solvents used were (A) water/acetonitrile/ THF (6:3:1 v/v/v), (B) water/acetonitrile (2:3 v/v), and (C) acetonitrile. The MS analysis was conducted using atmospheric pressure photo-ionization (APPI). Carbonyl compounds were identified based on their chromatographic retention times as well as the mass spectrometric fragmentation patterns as compared to the calibration standards. Their concentrations were determined using recovered standard calibration curves which accounted for any losses during elution or extraction.

Conclusion:

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