Determination of Chemical Parameters of Rainfall Water ...Samples in Misurata City and Qasar Ahmad...

54

Determination of Chemical Parameters of Rainfall Water

Samples in Misurata City and Qasar Ahmad Area, Libya

Fathi Hassan Bawa* and Hajer Ali Hawel

Department of Physics, Faculty of Science, Misurata University, Misurata, Libya *E-mail: [email protected]

Abstract— Atomic absorption spectrophotometer (AAS) was used to determine the

concentrations of some trace elements such as Na, Mg, Ca and K in rainfall samples during

April, 2008 at two sites; one site in the industrial area (Qasar Ahmad) and one site in the

residential area (Misurata city) of Libya. In addition to the above elements, some

parameters the total dissolved solids TDS and The total Hardness TH and Cl− were also

detected. Comparison between results of the two sites showed all the above trace elements,

the total dissolved solids and total hardness were found to be highly implicated with

concentration in rainwater sampling site at Qasar Ahmed compared with the Misurata city,

indicating some level of pollution. The difference is caused mainly due to various industrial

activities, and /or pollution Iron and Steel Factory production are responsible for the high

values. While, values of 28.4 versus 14.2 mg/L were obtained for Chlorine ion for Misurata

city and Qasar Ahmad respectively, which is the only exception of the rainwater samples

characterized by high content of the chloride ion. All parameters of rain water samples

agree well with Libyan and World Health Organization WHO drinking water standards.

Keywords: Atomic absorption spectrophotometer, Pollution, Chemical Parameters, Libyan

Rainwater samples.

INTRODUCTION

Concerns about global warming and increasing CO2 emissions have motivated increased

use of green energy, e.g., wind power, solar power and the use of renewable instead of

fossil fuels. However, in the transportation sector (i.e. fuels for vehicles), fossil fuels still

dominate. In addition, environmental issues are becoming increasingly important and a

sustainable urban future, our society must prompt more efforts to be put into making the

drinking water cleaner. Ways in which this can be achieved include the collecting and

storing rainwater from roof surfaces such as tanks and underground check dams for

domestic uses [1, 2], as well as water wells [3]. In general, the air in Qasar Ahmad area is

considerably polluted during whole year (Fig. 1). The coal fired emissions of Iron and Steel

Company (ISCO), sited very near from Qasar Ahmad area. Furthermore, many industrial

processes produce large quantities of nitrates and oxides of sulfur and nitrogen is being

emitted to the atmosphere [4, 5], which clearly exists in this area that cause harm or

discomfort to human or damage the environment. In addition to the above, the atmospheric

air contains water vapour (1-3 percent by volume) and traces of gases like sulphur dioxide,

carbon monoxide, ammonia and including solid particles. This is depending on where the

industries were located with concern to site sampling. Concerning this issue, there have

been many studies which discuss the comparison of the content of trace elements in rain

water, they are mostly for essential components such as sodium (Na), magnesium (Mg),

calcium (Ca), and potassium (K) [6,7,8]. However, all essential trace elements become

The Third Symposium on Theories and Applications

of Basic and Biosciences 3 September 2016

www.misuratau.edu.ly

55 The Third Symposium on Theories and Applications of Basic and Biosciences

toxic when their concentrations becomes excessive [9]. And also toxic heavy metals such as

lead (Pb), thallium (Tl), mercury (Hg), and zinc (Zn) have also been determined [10-12]. In

addition, during the rainy season, dust and gasses in the air and also soil, rocks, dumps

runoffs pick up a lot of dissolved and particulate materials referred as the total dissolved

solids (TDS). It is important to know how much dissolved material is in water because if

there are a lot of dissolved minerals in drinking, can make the water undesirable taste or

odor or may not be fit for use agriculturally. Union and World Health Organization (WHO)

has set guidelines of drinking water quality [13]. It is possible also that rainwater may

polluted by solid particles or any insolvents and aerosol [14]. Then these substances may

have potentially negative effects on the environment and human health [15]. In Jordan,

They studied the dissolved solids concentration has a weighted average of about 30 mg/L,

consisting mainly of Ca, Mg, Na, HCO3, and Cl [16]. In Pakistan, a comprehensive

research regarding the physicochemical assessment of rainwater has been published [17]. In

United Arab Emirates, the physical parameters of water such as temperature electrical

conductivity and hydrogen ion were determined as well as limits of inorganic chemicals in

drinking water such as total dissolved solids and chloride Cl− concentrations [18].

Moreover, regarding to air particulate, El Hossadi et al. have been studied the comparison

of the air dust in Benghazi with that of Prague, Munich and Sendai [19].

In this study, we determined the composition of the trace metals sodium, magnesium,

calcium, and potassium, and how much limit of µg/L in the roof rainwater samples of two

different building in Libya in order to determine any environmental factors contributed to

any differences. The major chloride ion, total hardness, and total dissolved solids

concentrations were also calculated, that the harmful levels of these inorganic compounds

could be determined.

The aim of the present study was to establish levels of Cl ion, TDS, TH using the standard

techniques and trace elements Na, Mg, Ca, and K were examined by applying the AAS

technique in the rainfall water which collected from two Libyan regions, Misurata city and

Qasar Ahmad area.

MARERIALS AND METHODS

2.1. Sampling site

Two certain locations were selected in the north of Libya (Fig. 1). Two roof buildings were

chosen to investigate trace elements and some inorganic metals in the rainwater samples.

The first is Misurata city and is located 200 km east of Tripoli at the Mediterranean coast,

the third largest urban city in Libya, lies in a residential and commercial area with heavy

vehicular traffic whole day, no big industries in the around area, with 500,000 population,

and a much small towns in the area within 3-12 km from the sampling site. It is quite a

strategically important region. The second is Qasar Ahmad area is also nearest to the

Mediterranean coast in presence of high salty soil, an industrial area with lower traffic

density and much less population compared to Misurata city, and it is situated at the

northern part of Misurata city.

56 Determination of Chemical Parameters of Rainfall

Figure (1): Map of Misurata city is showing the places of north-west Libya from where

rainfall waters were collected for analyses.

The major causes of water pollution of the area are the coal combustion industries (big Iron

and Steel Factory), so it was expected to have heavy combustion emissions. At each sample

site, free roof rainwater was sequentially collected using polythene bottles which had

previously been cleaned and rinsed with double distilled water. The vials were stored in a

refrigerator in order to prevent evaporation. All samples were analyzed directly for trace

elements to confirm that these samples are free of contamination.

2.2. Chemical analysis of samples The following trace elements Na, Mg, Ca, and K of the roof rainwater samples collected in

this study were investigated at the Libyan Iron and Steel Company (LISCO) using Atomic

Absorption Spectrophotometer (AAS, 180-30, Hitachi). The concentration of the anion Cl

content has been systematically measured by titration using the formula:

Cl−

(ppm) = a × F × 0.355 × 1000 ∕ Test water (1)

where a equal titration value, and F = average titer value.

Hard drinking water typically contains high concentrations of Ca, Mg and other cations,

and generally not harmful to one's health, but can pose serious problems in the near future.

These ions diminish the effectiveness of quality of the drinking water. Therefore, its desired

to know the relative amounts of Ca and Mg ions as calcium carbonate and magnesium

carbonate or any other polyvalent metal salts and conventionally expressed in terms of ppm

or mg/L. The total hardness (TH) is calculated by putting 25 mL of test water into an

Erlenmeyer flask and add approximately 1 mL of a buffer solution and 0.1 g of an

Erichrome Black T (EBT) indicator. Titrate the solution with standard ethylene diamine

tetra acetic acid (EDTA) solution, and regard as the end point, the point where the red

colour is completely lost due to its change to a blue color. The total Hardness content was

calculated using the relationship

Hardness (ppm) = a × F × 1000 ∕ 25 (2)


by titrating a known sample of water, a = titration value, and knowing titer value F of the

standard EDTA and its molarity. In general TDS is the sum of the cations and anions in

water. Ions and ionic compounds making up TDS usually include carbonate, bicarbonate,

chloride, fluoride, sulfate, phosphate, nitrate, calcium, magnesium, sodium, and potassium,

but any ion that is present will contribute to the total. There are a variety of ways to

measure TDS. The simplest is to filter 500 mL of the water sample, and evaporate it at 105-

110º C in a pre-weighted dish until the weight of the dish no longer changes. The increase in

weight of the dish represents the TDS, and it is reported in mg/L, by using the following

equation:

TDS = (A−B) × (1000) ∕ mL sample (3)

Where A is the weight of dried residue dish in mg and B is the weight of dish in mg.

3. Results and Discussion

The results of the measurements Na, Mg, Ca, K, TDS, TH, and Cl− obtained after analysis

of the rainwater samples in Misurata city and Qasar Ahmad area are summarized in Table

1.

Table (1): Chemical composition of rainwater samples in two different regions in Libya ________________________________________________________________

Compounds Misurata City Qas WHO Standard[1]

________________________________________________________________

Na (mg/L) 19.09 32.73 200

Mg (mg/L) 2.06 7.56 50

Ca (mg/L) 6.36 17.73 200

K (mg/L) 0.52 5.07 20

TDS (mg/L) 81.2 300.6 500

TH (mg/L) 20 136 0-75

Cl−1 (mg/L) 28.4 14.2 250

____________________________________________________________________ [1]

World Health Organization for drinking water 2006.

A comparison of the chemical characterization of the studied rainfall water samples for

drinking water are shown in Fig. 2. Collected data revealed that there were variations in

chemical properties of examined samples from two different areas. All the parameters Na,

Mg, Ca, K, TDS, TH and Cl− at Qasar Ahmad area were found to be higher and were equal

to 32.73, 7.56, 17.73, 5.07, 300.6, 136 and 14.2 mg/L respectively compared with Misurata

city, 19.09, 2.06, 6.36, 0.52, 81.2, 20 and 28.4 mg/L. The only exception was Cl− (see Table

1 and Fig. 2), which is acceptable concentrations for drinking water.


Figure (2): Variation of concentration of Na, Mg, Ca, K, TDS, TH and Cl

−1 in Misurata

city and Qasar Ahmad area.

However, one should not worry about it because this excess is in a very small quantity. The

reason behind the above results might be attributed to the fact that the polluting commercial

complexes (leather, textile) were mostly situated in Qasar Ahmad area which causing a

massive migration of population from Qasr Ahmad to Misurata city. It is expected that in

the Qasar Ahmad area, the highest level of the above elements get into aquatic environment

from anthropogenic sources and distribution in water, as well as high loading of dust

particles in the atmosphere. As we mentioned above, the concentrations of Na, Mg, Ca, and

K in the Qasar Ahmad area (Fig. 3) were higher than the values obtained for Misurata city

(see Fig. 4). The following order values were obtained (Na>Ca>Mg>K) for both regions.

The high values in the Qasar Ahmad water may be attributed to water fall over exposed

pollutants which is latter associated with TDS and TH and cause aesthetic problems.

Figure ( 3): The concentration of chemical and physical parameters of rainwater at Qasar

Ahmad area

Co

nce

ntr

atio

n (

mg/

L)

Elements

Misurata City

Qasar Ahmad


Figure (4): The concentration of chemical and physical parameters of rainwater at Misurata

city.

Sodium element concentration in rainfall water samples collected was found 32.73 and

19.09 mg/L for Qasar Ahmad and Misurata city respectively, which is permissible limit for

sodium see Table 1. Moreover, the main source of dissolved materials such as Cl− in the

rainwater is sea salt. The processing of water evaporates, leaving an aerosol particle, which

is transported by winds leads to dissolve by rain. Mainly, this process is responsible for

high concentration of Cl− in Misurata city. The concentrations of Ca, Mg and K in

rainwater are come from sea salts and dust volatile in the atmosphere. As shown in Table 1,

the concentrations of Mg, Ca and K in Qasar Ahmad and Misurata city are comparatively

lower from the WHO standard values of fresh water i.e. 50 mg/L, 200 mg/L and 20 mg/L.

The presence of chlorine ion in concentrations above 0.5 ppm in natural waters should be

considered evidence of pollution [20]. Aerosols of local and land origin will continuously

be lifted up and as a result a high level of aerosol concentration is maintained in the

atmosphere. The Cl− at Misurata city was found to be higher (28.4) versus (14.2) compared

to Qasr Ahmad region. The permissible limit for chloride in drinking water is 250 ppm

[25], the chloride of rainfall water of both areas were within the prescribed desirable limit.

In addition, the presence of Cl− in large amounts in the rainfall water of Misurata may be an

indication of pollution from sources such as seawater especially it is located near to the

coast. Accumulation with increasing distance from the coast, Cl− released from sea salt

particles subsequent to their formation might be expected to give rise to increase in the

value in Misurata city. These features account for the highest concentration of Cl ion.

Further, inhalation of chlorine gas can cause difficulty breathing, chest pains, cough, eye

irritation, increased heartbeat and death. The concentrations of Ca, Mg and K investigated

in rainwater samples were within the permissible limits (Table 1). Total dissolved solids is

a measure of inorganic salts and small amount of organic substances contained in solution

in water [20]. Concentrations of TDS from natural sources have been found to vary from

less than 30 mg/L to as much as 6000 mg/L[21], when TDS level exceed 1000 mg/L, it is


generally considered unfit for human consumption. In addition, most often high levels of

TDS are caused by the presence of potassium, chlorides and sodium, which determines the

conductivity of the water. These ions have little or no short term effects, but toxic ions

(lead, arsenic, cadmium, nitrate and others) may also be dissolved in the water. Water

containing TDS concentration below 1000 mg/L is usually acceptable to consumers, may

vary according to circumstances, and low concentrations of TDS may also be unacceptable.

The total dissolved solids was recorded highest in the Qasar Ahmad area 300.6 mg/L as

shown in Fig. 3, and lowest in the Misurata city 81.2 mg/L, see Fig. 4. In Libya, the

concentration of TDS in Qasr Ahmad area was found 306.3 mg/L, see Fig. 3, this result was

agreed with the results obtained by [22], and also in Eben sena Hospital in Sirte city was

667.333 mg/L [23]. The concentration of TDS of the rainwater samples conform to the

standard for safe drinking water (Table 1). Furthermore, high TDS value was observed for rainwater at location Qasar Ahmad may be because the rain has accumulated various

particles of dust and airborne aerosols that interact before deposition. The highest

concentration value of the total hardness was found in Qsar Ahmad rainwater sample, it

reached (136 mg/L). This result is much higher than that obtained by Misurta city rainwater

sample (20 mg/L), see Table 1. and Fig. 2. The reason is may be due to the region is

suffering of sea water contents high rates of salts, particularly rock salt, magnesium and

calcium, while the low concentration of hardness in Misurata city is due to low

concentration of magnesium and calcium ions dissolved in the rainwater. According to

Sawyer and MaCarty [24], total hardness classification scheme indicates the water samples

were very hard (>300). Our results are less than the results of TH obtained by [25], where

the total hardness was amounted 309 mg/L. In addition, the taste of threshold for the

calcium ion is in the range of 100-300 mg/L and for magnesium is probably lower than that

of calcium [26].

CONCLUSION

Samples were studied for trace elements Na, Mg, Ca and K, Cl- and chemical parameters

TDS and TH. Analysis was done on rainfall water samples collected from two different

sites Misurata city and Qsar Ahmad region. The parametric concentrations are ranged in the

order of TDS > Cl− > TH > Na > Ca > Mg > K, while it is TDS > TH > Na > Ca > Cl

− >

Mg > K for Misurata city and Qsar Ahmed region respectively. However, all the values for

Qsar Ahmad water were found higher except for Cl ion compared with Misurata city.

Though, the rainfall water is safe for drinking water in both regions, however, presence of

dust and other particles is often inevitable in Qsar Ahmad, hence, aesthetically unacceptable

because Iron and steel complex sited very near from Qsar Ahmad area. Results also showed

that the chemical of the rainfall water investigated met the WHO drinking water standards,

which are suitable for human consumption.

ACKNOWLEDGEMENTS

The authors would like to thank the authorities of Libyan Iron and Steel Company for

providing the necessary laboratory facilities and support.

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