Heavy Metals in Samarra | River | Reservoir

War. Res. Vol. 27, No.

6, pp, 1099-1103,1993 Printed in Great Britain

0043-1354/93$6.00+ 0.00 Pergamon Press Ltd

HEAVY METALS IN THE WATER, SUSPENDED SOLIDS AND SEDIMENT OF THE RIVER TIGRIS IMPOUNDMENT AT SAMARRA
AtO~AR W. S~sm, ~ A. RAsm~D and T ~ I. Department of Ecology, Nuclear Research Center, Baghdad, P.O. Box 765, Iraq
(First received May 1989; accepted in revised form October 1992)

Almraet--The concentrations ofCd, Cu, Co, Fe, Zn, Mn, Pb and Hi were determined in water, suspended solids and surficial sediments of the River Tigris at the Samarra impoundment diLring high (April) and low (July) fiver discharge months in 1988. The recorded concentrations in water were either simnificantly lower or within the Iraqi river water standards and the average dean river water of the world. Variations in the concentrations of heavy mctnls in suspended solids were interpreted to be due to local differee~es in current velocity and distance from the shore line (from sewage source of the residential sector). The concentrations of most of the examined elements in the surficial sediments (except for Mn and Fe during April) were lower than those in the suspended solids. Results stress the importance of the suspended solids in transportation of heavy metals in the River Tigris. Higher concentrations of Co, Mn and Fe are discussed in relation to sedimentation process and the nature of the fiver basin.
Key words----heavy metals, fiver, impoundment

INTRODUCTION There are always heavy metals in water, suspended materials, sediments and organisms from lotic ecosystems but background levels are poorly documented in the fiterature (Frenet, 1981; Salanki et al., 1982; Borg, 1987). Normal metal content in such environments varies from one place to another according to the geological nature of the catchment area. Such data are essential to estimate the impact of pollution sources and for the study of the transfer to man by various means (Hynss, 1970). Only one study of metal concentration in the River Tigris has been reported, that of Mutiak et aL (1980) who studied the levels of Cu, CA, Pb, Ni and Zn in water in the Baghdad area. The aim of the present work, is to provide information on the level of metals in water, suspended 'sofids and sediments of the River Tigris at the Samarra impoundment (on-stream impoundment). These data may be used as a baseline for future work in the area as well as by those interested in the/r transfer to man via the food chain. STUDY
The River Tigris is one of the main rivers in Iraq and is essential to more than half of the country's population. The river water is used for agriculture, human consumption, various industrial activities and other purposes including commercial fishing. The Samarra impoundment (max. width 6 × 22 km long) is located about 180 km (by river) north of Baghdad (Fig. 1). It regulates the water level in the downstream sector o f the River Tigris by directing excess water to the Tharthar reservoir, especially

during high discharge seasons (winter and spring). The water level in the impolmdm~tlt is kept at about 68 m above sea level for electricity generation. The impoundment is shallow (max. depth 6.5 m) and includes many small islands covered with dense river. ine-type vegetation. Three sampling stations were selected (Fig. I). Station I was located in the main channel of the River Tigris within the impoundment. Station 2 was located about 500 m away from the shore. Station 3 was located in a pool connected to the main water body, via a channel, and receives untreated sewage from a small residential sector of Samarra city. More details of sampling stations have been described earlier (Sabri and Rasheed, 1993).
MAI"I~,IALS AND METHODS

Samples were taken during the high (April) and low (July)
fiver discharge months of 1988. From each station, three samples were collectedand mixed prior to analysis.To avoid

contamination during sampling and sample prelmmfion, all bottles, glass ~ters, test tubes, filtration aPlm~tm and laboratory tools, were p~m~dmi thorotqghly in distilled water, soaked with 0.1N HCI t h ~ washed i~in with deionlz~-dlatilkd water. Five-lit~ water mmpim were colk~-ted u~%. ~ prewashed polyethylene bottles. Water was fillm~d using washed 0.45 #m glass fiber filter paper. Then the water was ac/d/fiedwith 1.5 ml I-' 16 N HNO3 and evaporated in an os~n (70--80°C) until the volume reached 50 ml. The weight of "suspended solids" on the glass flb~ filter

was obtained after drying the filter in an oven at 7040°C. T h ~ the fil~ pap~ and ~ solids were ~ with 10m116N HNO3 at 80-8S°C on i hot plate for about lh. The di~mzt rumple w u filtmzl (Wlmtmun No. I f l i t er pap~) and diluted to 50ml with ~ filter water. Suspended solids were analyzed during April only.

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The sediment was collected using an F.~man grab sampler (15 x 15cm). The stxl/meut was oven dried ( 7 ~ C ) , diBested, filtered and diluted as described above for the .olid.. A / ~ dip~ion,, the toUd conc~tratiom of Cu, Co, F©, Zn, Mn, Pb and Ni were determined in all mmpks ua/ng a Pye Unicam PU 900 FlameleU Atomic Absorption Spec~mphotometer 0Flamdess AAS), Checks on conwmination and instnzme=t accuracy uz~ag standard solutions were carried out prior to munple analysis in a similar manner to that d__e~__'bedby Smith et al, (1981) and Abaychi and Douabul
(19ss). Water temperature was measured with a mercury tlwr-

IW..SUL~SAND DISCUSSION
Water characteristics

momem" (ran~ - 10 to 60°C). The pH values wa'e obtained usinZ a disitsl portable pH meter (CG818, Schott Ges'ate). Cond.ct/.~/ was mmsured in the ~ ~ • disiml portsble conduc~v/ty meter (Model 19300 HACH). Total h m h ~ s was determined by ~u~tion s~ordins to APHA (1975).

The ranges of water temperature, pH, conduct/vity and hardness were 12.7-27°C, 8.2-8.4, 40~401.6/ISom -t and 132-214m8 CaCO3 !-j, respectively (Table 1). All these values are within the range given by Talling (1980) for the River Tiffris. Station 3 was characterized by slightly higher water temperature, while the conductivity and hardness wore lower than that of Stations 1 and 2. Variations at Station 3 were due to the absence of current (Sabri and ~ . I~3).
Heavy metals in water The concentratiom and means of the analyzed heavy metals at the three stations in the Samarra

Heavy metals in the Samarra impoundment Table I. Water characteristicsin the ~marra impoundment Parameter Month Station I Station2 Station 3 Water temp. (°C) April 13.5 12.7 14.7 July 24.0 22.0 27.0 pH April 8.4 8.2 8.4 July 8.4 8.2 8.4 April 405 400 397.5 Conductivity(pS cm-') July 320 330 285 HardmmJ(ms CaCO3I-') April 214 211 189.8 July 178 168 132 Suspendedload (mgl-t) April 850 830 58 July 28 18 3

1101

Mean 13.6 24.3 8.4 8.3 401.6 311.6 207.7 159.3 579.3 16.3

impoundment are presented in Table 2. The ranges (in m g l - I ) of the analyzed heavy metals were ND-4).01 for CA, ND-0.067 for Cu, ND-0.007 for CO, ND-0.08 for Fe, ND-4).48 for Zn, ND-0.06 for Pb and 0.006-0.06 for Ni. Mn was below the detection limit during the present survey. The recorded levels of most heavy metals in the Samarra impoundment were either significantly lower or comparable to those presented for the River Tigris in the Baghdad area (Mutlak et al., 1980), the River Shatt al-Arab (Abaychi and Douabul, 1985; Mustafa, 1985), a Welsh river in Britain (Vivian and Massie, 1977; Whitton, 1975) and the River Rhine in The Netherlands (Van der Weijden and Middelburg, 1989). Furthermore, except for CA, during July almost all other values recorded during the present survey were lower than the maximum limits of the Iraqi standard for river water (Ministry of Health, 1977). This reflects the clean condition of the River Tigris at the Samarra impoundment. July records for CA may be due to local urban pollution. However, it was twice the maximum Iraqi limits (0.005 m81 - t ) for river water and should be checked thoroughly in future studies.

Heavy metals in suspended matter
The concentrations (in p g g - l ) of those determined during April were 0.678-5.44 for CA, 56.8-351.3 for Cu, 16.3-68.2 for Co, 23.4-816.3 for Zn, 16.3-98.6 for Fe, 37.4-400.2 for Mn, 142.8-904.7 for Pb,

54.08-598.6 for Ni (Table 2). The data show considerable variations in concentrations between the suspended matter and water for the analyzed metals. Such results stress the importance of suspended matter in long distance metal transportation 0Vlagnutson and Rasmussen, 1982). Moreover, the River Shatt al-Arab is formed by the junction between the Rivers Tigris and Euphrates in southern Iraq. Comparison between the data of the present survey with those given for the River Shatt al-Arab (Abaychi and Douabul, 1985) during the same month (i.e. April) reveals several differences. The mean concentration values (in ~ g g - ~ ) in the Samarra impoundment and Shatt al-Arab were 2.68-55 for CA, 61.9-31,742 for Fe, 183.34-1731 for Mn, 266-3807 for Ni, 222.24-77 for Cu, 35-6.6 for Co, 357.13-77 for Zn and 416.23-93 for Pb, respectively. This indicates that most of the Cu, CO, Zn and Pb in the suspended matter originated from the upstream section. Their lower values in the south could be attributed to the sedimentation process of most of the suspended matter when the Tigris enters the delta of the southern Samarra region (Rzoska, 1980). More CA, Fe, Mn and Ni were present in Shatt al-Arab. This is due t o increased urbanization, industrialization and agricultural activities in the downstream areas as well as the nature o f the petroleum,rich sediment of the southern region (AI-Shahristani and AI Attiya, 1978). The contribution of the River Euphrates to Shatt al-Arab metals should not be ignored. In

Table 2. The concentration leveh of the analyzed metals in water, suspendedmlids and sediments Filtered water (msl-I) Suspended solids 0~Sg-I) Sediments(~SS-') St.l St. 2 St. 3 Mean St.I St. 2 SL3 Mean St. I CA April ND ND ND ND 0.678 1.931 5.442 2.683 0.035 29.7 July ND 0.011 0.01i 0.011 Cu April 0.003 0.067 0.023 0.031 56.88 351.351 258.503 222.24 12.15 July 0.005 0.01 ND 0.007 38.5 Co April 0.002 0.005 ND 0.1)03 16.387 68.211 20.408 35.002 7.55 July 0.007 ND ND 0.007 22.75 Fe April ND 0.001 0.002 0.001 16.387 70.785 98.639 61.937 10500 July ND 0.02 0.08 0.05 18745 Zn April ND ND ND ND 23.411 231.660 816.326 357.132 27.0 July 0.08 0.01 0.48 0.19 59.0 Mn ~ ND ND ND ND 112.373 400.257 37.415 183.348 293.05 July ND ND ND ND 6.5 Pb Ap~ ND 0.04 0.055 0.047 201.100 904.7762 142.837 416.239 24.5 July ND 0.002 0.O6 0.031 30.5 Hi AprU 0.013 0.OO6 0.011 0.01 54.O'/9 145.431 598.639 266.049 57.4 July 0.01 0.06 0.02 0.03 157.0 ND: Belowdetectionlimits and not includedin mean calculation. St.: Station. St. 2 ND 30.7 18.4 39.5 6.55 23.75 8250 15495 19.0 56.5 218.05 6.5 17.45 26.0 49.4 104.5 St. 3 0.08 63.7 16.3 52.0 7.9 30.75 1i 250 22995 33.0 79.5 373.05 6.5 29.25 30.0 79.4 184.5 Mean 0.057 41.36 15.616 43.333 7.333 25.75 1000 19078.3 26.333 65.0 294.716 6.5 23.733 28.833 62.066 148.666

1102

A~IAR W. Sxmtl et al.

Table3. Simplecorrelationcoefficientanalysisbetweenheavymetalconcentrationin the sedimentand with suspended load Cd' Cu Co Fe Zn Mn Pb Suspended load d.f. Cd -0.568 4 -0.717 5 Cu 0.971' Co -0.970 0.987* -0.731 5 Fe -0.839* -0.714 0.693 -0.737 5 Zn -0.987* -0.961" 0.982" 0.746 -0.785" 5 Mn -0.845* -0.915" -0.907* -0.457 -0.820* 0.526 5 Pb 0.473 0.524 0.601 0.396 0.718 -0.313 -0.824* 5 Ni 0.917 0.917" -0.606 -0.735 0.960* -0.774* 0.747 -0.755* 5 *r = 0.811, P < 0.05, n = 5. • = 0.754, P < 0.05, n = 6. contrast with other rivers of the world such as the Amazon, Mississippi, Rhone and Rhine (Oregioni et al., 1978; Van der Weijden and Middelburg, 1989) the most characteristic feature is the high level of Ni and the low concentration of Mn in the suspended matter of the River Tigris. The high level of Ni is due to the petroleum-rich sediment of the river basin, while the low Mn is due to the nature of the soil which is low in Mn and enriched in Na and Ca (Rzoska, 1980).
Heavy metals in sediments

load. Such a result needs further investigation on the particle size-metal concentration relationships which is beyond the scope of the present work.
Local and seasonal variations

Sediments act as a trap for different elements
(Thomas et al., 1977) therefore, their metal concen-

trations may reflect the degree of pollution in an area (Edgren, 1987). The concentrations and means of the analyzed heavy metals in surficial sediments are presented in Table 2. The concentration ranges (in p g g - l ) were ND~3.7 for CA, 12.1-52 for Cu, 6.5-30.7 for CO, 8250-22,995 for Fe, 19-79.5 for Zn, 6.5-373 for Mn, 17.4-30.5 for Pb and 49.4-184.5 for Ni. Metal concentrations are generally lower in surface sediments than in the suspended matter (in April) except for Fe and Mn. This could be attributed to the prevention of sedimentation process by water currents. Such a result again stresses the importance of suspended matter in the transportation of local heavy metals in such environments. In view of the absence of any significant pollutant source in the area and the capacity of large rivers, such as the Tigris, to minimi~ the effects of upstream inputs (Hynes, 1974), higher values in the sediments, especially for Fe, probably reflect the character of the soil in the region. This conclusion needs further confirmation. Similar results were presented by Ahaychi and Douabul (1985) for the River Shatt al-Arab. The inter-relationships between heavy metals in surficlal sediments are presented as correlations in Table 3. The high number of si~nifieant correlations may indicate that concentrations are controlled by heavy metal abundances in the rocks and soft of the catch_n~n_ area. This is in line with the known t character of the River Tigris basin (Rzoska, 1980). Negative significant correlation values of Mn with almost all the analyzed heavy metals could indicate the oompetition between cations in the sediments (Wood, 1987). Concentrations ofZn, Pb and Ni were significantly (negatively) correlated with suspended

Local differences in heavy metals concentration were evident in the results, especially in the suspended matter and sediment (Table 2). In suspended matter, some concentrations at Stations 3 (Fe, Zn, Ni) and 2 (Co, Pb, Mn) were higher than that at Station 1. Variations in the suspended load at the studied stations were evident. This is attributed to changes in the velocity (Sabri and Rasheed, 1993). Although particle size distribution was not carried out during the present survey, it is known to be current velocity dependent (Rzoska, 1980). Thus, finer particle size at Station 3 (due to the absence of water current) would account for higher concentrations of metal ions~ This conclusion is in line with results presented by many investigators (Brown, 1977; Sakai et al., 1986). On the other hand, higher concentrations of heavy metals which were observed in the sediment at Station 3 may be due mainly to the location of Station 3 in a pool near the pollution source (i.e. the residential sector of Samarra city), while Station I was in the main stream of the River Tigris. Another reason would be the nature of the sediment. At Station 3 clay was the dominant component, while sand silt was dominant at Station 1. Station 2 was intermediate between the two stations (Sabri and Rasheed, 1993). Clay is known to adsorb trace metals more e~iciently than silt or sand (Bowen, 1966; Wood, 1987). Seasonal variations were evident during the present investigation. It was found that the concentrations of heavy metal ions in the filtered water and sediment increased substantially during July, except for Co and Cu in filtered water and Mn in sediment. Similarly, during July higher water temperature, lower sediment load and hardness were observed (Table I). The low river discharge season extended from June to October in the River Tisris system (Rzoska, 1980). There have been reported increased concentrations of metal ions in aquatic environments (Stiff, 1971; Gibbs, 1973; Williams et al., 1973; Brown, 1977; Sakai et al., 1986). However, the relationship between particle size and both Co and Mn needs further investigation to explain their levels during April.

Heavy metals in the Samarra impoundment IW.J~.nNCIgS

1103

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