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Using total suspended solids (TSS) and turbidity

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 Applied Geochemistry 68 (2016) 1e9

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Using total suspended solids (TSS) and turbidity as proxies for

evaluation of metal transport in river water
T. Nasrabadi a, *, H. Ruegner b, c, Z.Z. Sirdari d, M. Schwientek b, c, P. Grathwohl c
a
University of Tehran, Graduate Faculty of Environment, Tehran, Iran
b
Water & Earth System Science (WESS) Competence Cluster, c/o Eberhard Karls University of Tübingen, Ho €lderlinstr. 12, 72074 Tübingen, Germany
c €lderlinstr. 12, 72074 Tübingen, Germany
Eberhard Karls University of Tübingen, Center of Applied Geoscience, Ho
d
Islamic Azad University, Islamshahr Branch, Department of Civil Engineering, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The present study was carried out in Haraz basin (Iran) that is located in south of the Caspian Sea. The
Received 23 January 2016 goal of this study was to establish correlations amongst total suspended solids concentration (TSS) and
Received in revised form turbidity with total pollutant concentrations to evaluate the dissolved and particle-bound concentrations
8 March 2016
of major toxic metals. It also aimed to validate TSS and/or turbidity measurements as proxies to monitor
Accepted 10 March 2016
Available online 11 March 2016
pollutant fluxes. Eight metals, namely nickel, lead, cadmium, copper, zinc, cobalt, arsenic and strontium
were analyzed for dissolved and total concentrations in water at ten locations within the catchment. TSS
and turbidity were also measured. Sampling campaigns were designed to cover both the rainy
Keywords:
Heavy metal
(December) and the dry (May) season within the basin. The robust relationship between TSS (202
Dissolved concentration e1212 mg/l) and turbidity (63e501 NTUs) in both seasons warranted their interchangeable potential as
Particle-bound proxies within the observed ranges. Total element concentrations were plotted in separate attempts
Regression versus TSS and turbidity for all locations and both events. Very good linear correlations were attained
Proxy where the slopes represent the metals concentration on suspended solids and the intercept the dissolved
concentration in water. The results achieved by these linear regressions were in very good agreement
with independently measured values for dissolved concentration and concentrations on river bed sed-
iments taken at the same locations. This demonstrates that turbidity and/or TSS measurements may be
used for monitoring of metal loads if once calibrated against total concentration of metals. The results
also revealed that in the lower Haraz catchment metal concentrations on suspended and river bed
sediment were homogeneously distributed along the investigated river stretch. This is assumed to be due
to intensive gravel and sand mining activities in the upper and middle part of the catchment.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Heavy metals/metalloids are among the most notorious threats
for water and soil ecosystems. Transfer of such pollutants from solid
to aqueous phase at the interface of sediments/particles facilitates
their entry into the food chain and further bioaccumulation in
neighboring fauna and flora (Fabure et al., 2015; Nasrabadi et al.,
2015; Kargar et al., 2012; Biati et al., 2010; Ogundiran et al., 2012;
Conceicao et al., 2013; Bu-Olayan and Thomas, 2013). A vast vari-
ety of geogenic (rocks weathering and soil erosion) and anthro-
pogenic sources (mining activities, urban and agricultural run-offs,
* Corresponding author. Graduate faculty of environment, University of Tehran,
#25, Azin Avenue, Ghods Street, Enghelab Square, 1417853111 Tehran, Iran
E-mail addresses: tnasrabadi@ut.ac.ir, tnasrabadi@gmail.com (T. Nasrabadi).
industrial and municipal sewer overflows, etc.) may cause toxic
metals discharge into water bodies. The metals can be dissolved in
the water column, absorbed/adsorbed to the sediments/particu-
lates or accumulated in biota. Accordingly, during recent years a
great attention has been paid to studies where the behavior of
metals in different media is discussed (La Colla et al., 2015; Hejabi
et al., 2011; Adekola and Eletta, 2007; Li et al., 2006; Jain et al.,
2005; Chow et al., 2005; Olivares-Rieumont et al., 2005; Hope,
2006). In comparison with other media, river bed and suspended
sediments play a more significant role in overall pollution and
environmental risks (Foerstner and Muller, 1973; Foster and Hunt,
1975; Throne and Nickless, 1981; Sakai et al., 1986; Karbassi et al.,
2007; Nasrabadi and Shirani Bidabadi, 2013). A remarkable num-
ber of relevant studies focus on concentrations associated with
suspended or bed sediments, but only few try to assess the

http://dx.doi.org/10.1016/j.apgeochem.2016.03.003
0883-2927/© 2016 Elsevier Ltd. All rights reserved.
2 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9

speciation of different metals in these matrices. In the last few
decades, researchers have followed a variety of sequential extrac-
tion techniques to estimate the fractionation of metals in sediments
(Chester and Hughes, 1967; Tessier et al., 1979; Forstner and
Wittmann, 1981; Horowitz et al., 1999; Stamatis et al., 2006;
Tessier et al., 1980; Elsokkary and Muller, 1990; Korfali and
Davies, 2000; Rauret, 1998; Pardo et al., 1990). Dozens of
methods for determining several forms of metals in sediments are
described in literature (Kersten and Foerstner 1991; Lopez-Sanchez
et al., 1993; Das et al., 1995; Li-Jyur et al., 2003). The most wide-
spread methods are based on sequential extraction schemes where
different reagents are utilized consecutively to extract defined solid
phases (Nasrabadi et al., 2010a). Such methods are all time-
consuming, labor-intensive and expensive. Thus generating
continuous or at least semi continuous temporal/spatial data sets is
hardly possible. Focusing on dissolved and adsorbed phases and
consideration of proxies might be a feasible substitution for the
above mentioned complex speciation schemes. Proxies that are
easy and cheap to measure would be very valuable to monitor
pollutant concentrations and loads. A vast range of organic pol-
lutants as well as nitrogen and phosphorus has been proved to be
transported by suspended solids in river systems (Meyer and
Wania, 2008; Meyer et al., 2011; Schwarz et al., ; 2011; Rügner
et al., 2014; Quesada et al., 2014; Spackman Jones et al., 2011;
Hornsburgh et al., 2010; Slaets et al., 2014). Ruegner et al. (2013,
2014) and Schwientek et al. (2013) showed that concentrations of
polycyclic aromatic hydrocarbons (PAHs) in rivers correlate very
well with turbidity and TSS in a number of small catchments in
southern Germany (Neckar at Tuebingen: 2.300 km2; tributaries:
39e139 km2). Not many studies considered toxic metals. Kirchner
et al., 2011 for example, studied the dependence of total Hg con-
centrations on total suspended solids in a river downstream of
Gambonini mine, San Francisco in order to quantify the remedia-
tion effectiveness by comparing contaminant rating curves.
Chebboa and Gromaire (2004) determined the fractions of Pb, Zn
and Cu associated to suspended solids in surface runoff in Paris and
attributed high concentrations to local roofing materials.
2. Theory
By causing light to be scattered, suspended particles concen-
tration may have a meaningful correlation to turbidity. Using lab-
oratory nephelometers and optical backscatter sensors offers the
capability to easily detect the turbidity in the lab and in-situ,
respectively. Although a variety of parameters like density, size
and shape of particles as well as water color may affect the rela-
tionship between the values of TSS and turbidity (Downing, 2006),
turbidity may be considered as a reliable and feasible proxy for
suspended sediment and thus pollutant concentrations within a
given basin if once a precise and meaningful correlation between
TSS and turbidity was established. Such correlations have been
discussed in detail over a wide range of case studies. A common and
routine linear relationship may be defined as:

Fig. 1. Major land use within the study area (adapted from Nasrabadi et al., 2011): B bared land, DF dry farming, OC outcrop, F1 high density forest, F2 Medium density forest, FO
mixed forest/orchard, FP fish pond, I1 agricultural area with low limitation, I2 agricultural area with limitation, IO mixed agriculture/orchard, L2 reservoir, O orchard, OI mixed
orchard/agriculture, R1 grazing land high density, R2 grazing land medium density, RD grazing land/dry farming, U Urban area, U1 installations.
 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9 3

Fig. 2. The study area in lower Haraz basin in Mazandaran Province in Northern Iran as well as the sampling stations.

Table 1
TSS vs. turbidity relationships from this and similar studies (No.: number of samples; m ± standard error and R2 from linear regressions; mMean ± standard deviation represents
the average of all TSS/turbidity ratios).

Case study Turbidity range No. a

m (mg l1 NTU1) R2 mMean (mg l1 NTU1) Reference

Lower Haraz basin 63e501 20 2.28 ± 0.06 0.96 2.36 ± 0.45 This study
Steinlach 14e888 26 1.67 ± 0.04 0.97 1.60 ± 0.40 Ruegner et al., 2014
Ammer 13e560 31 2.79 ± 0.10 0.94 2.35 ± 0.85
a
Intercept is set to zero in all cases.

TSS ¼ m Turbidity ½NTU (1)

Ruegner et al. (2013) found linear relationships between TSS and
1400 turbidity with m values of 1e2.8 mg l1 NTU1 (average
1.9 mg l1 NTU1) for naturally suspended sediments in rivers in S-
1200
Germany. Other studies report slightly lower or higher m values
Total suspended solids (mg/L)

1000 (e.g. 1.1 mg l1 NTU1 for particles from karstic springs or up to
3 mg l1 NTU1 for suspended sediments in the Lake Tahoe basin,
800 respectively; Schwarz et al., 2011; Stubblefield et al., 2007).
Total concentration in river water includes the dissolved and
600 particulate-bound fraction of a contaminant:
400
Cw;tot ¼ Cw þ Csus TSS (2)
y = 2,28x
200 R² = 0,96 Cw,tot, Cw and Csus are the total and dissolved concentrations of a
pollutant in river water and its concentration on suspended parti-
0
0 100 200 300 400 500 600 cles, respectively. The slope of a linear regression in a TSS (in mg l1)
Turbidity (NTU) versus Cw,tot (in mg l1) plot thus corresponds to Csus (in mg mg1)
and its intercept to the dissolved concentration in river water Cw (in
Fig. 3. TSS-turbidity correlation for water samples collected in lower Haraz basin. mg l1). In a turbidity (in NTU) versus Cw,tot (in mg l1) plot, the slope
4 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9

Co Cd
0.03 0.012

Total concentraƟon (mg/L)

Total concentraƟon (mg/L)

0.025 0.01
0.02 0.008
0.015 0.006
0.01 0.004
0.005 R² = 0.93 0.002 R² = 0.95
0 0
0 500 1000 1500 0 500 1000 1500
Total suspended solids (mg/L) Total suspended solids (mg/L)

Cu As
0.06 0.14

Total concentraƟon (mg/L)

Total concentraƟon (mg/L)

0.05 0.12
0.04 0.1
0.08
0.03
0.06
0.02 0.04
0.01 R² = 0.87 0.02 R² = 0,91
0 0
0 500 1000 1500 0 500 1000 1500
Total suspended solids (mg/L) Total suspended solids (mg/L)

Zn Sr
0.14 1
Total concentraƟon (mg/L)

Total concentraƟon (mg/L)

0.12
0.8
0.1
0.08 0.6
0.06 0.4
0.04
0.2
0.02 R² = 0.89 R² = 0.90
0 0
0 500 1000 1500 0 500 1000 1500
Total suspended solids (mg/L) Total suspended solids (mg/L)

Pb Ni
0.035 0.08
Total concentraƟon (mg/L)
Total concentraƟon (mg/L)

0.03
0.025 0.06
0.02
0.04
0.015
0.01 0.02
0.005 R² = 0.88 R² = 0.94
0 0
0 500 1000 1500 0 500 1000 1500
Total suspended solids (mg/L) Total suspended solids (mg/L)

Fig. 4. Linear regressions of total concentration of elements in water and total suspended solids (TSS) during two December (dry, open rectangles) and May (wet, open triangles)
sampling campaigns.

corresponds to Csus m (in mg l1 NTU1). covered by dense forests, rice paddies and urban space. A major
The aim of this study is to establish correlations of TSS with anthropogenic activity is given by sand mining installations (see
turbidity and with total pollutant concentrations to (1) estimate Fig. 1). These intensive sand and gravel mining activities usually
dissolved and particle-bound concentrations and (2) to make use of take place close to or directly within the river channels. Once a
TSS and/or turbidity measurements as proxies to estimate major location is exploited activities move to the next suitable location
toxic metals transport in lower Haraz basin south of the Caspian such that numerous locations within the river stretch are affected
Sea. over time. Jurassic passive-margin deposits are represented by the
clastic (sandstone-shale) Shemshak Formation, and the Lar and
3. Materials and methods Delichi carbonates. Comprising largely submarine tuffs, the eocene
Karadj formation is suggestive of the onset of active continental-
The lower part of the Haraz River basin located south of the margin magmatism (Davidson et al., 2004). A detailed description
Caspian Sea, Iran was considered as the study area. The drainage of the geology may be found in Nasrabadi et al. (2010a).
area and the length of main stem are around 4060 km2 and 185 km, Considering the information on pollution by metals within the
respectively. The mean discharge of the river in the lower Haraz basin gained during recent years (Karbassi et al., 2008; Biati and
basin was approximately 30 m3 s-1 during the last fifty years while Karbassi, 2010; Nasrabadi, 2015; Nasrabadi et al., 2010a), eight el-
the annual means varied between 15 and 55 m3 s-1 (Mohseni- ements namely nickel, lead, cadmium, copper, zinc, cobalt, arsenic
Bandpei and Yousefi, 2013). Generally, the study area is mainly and strontium were selected for further analysis. Sampling of water
 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9 5

Table 2
Total/dissolved concentrations of elements in 10 sampling locations (mean concentrations are inserted in mg/L).

Sampling location Ni Pb Cd Cu Zn Co As Sr

Rainy season (December 2012)

1 37/19 11/4 4/4 24/16 77/44 14/9 85/57 531/332
2 39/21 12/7 5/3 26/18 80/40 15/10 90/65 546/364
3 44/31 13/3 6/3 33/17 85/51 17/12 94/70 563/420
4 67/39 29/6 11/3 56/21 125/79 24/13 121/98 780/632
5 47/40 19/5 7/4 32/15 97/89 17/11 99/76 601/513
6 57/48 25/8 9/4 38/22 104/81 20/15 105/91 631/472
7 46/38 20/8 7/3 33/19 97/75 18/17 97/88 609/521
8 43/37 16/7 6/3 31/15 91/68 16/12 95/81 561/493
9 42/32 16/7 5/3 31/13 89/62 15/11 93/73 555/501
10 39/31 13/7 5/3 25/18 89/69 15/10 89/64 541/362
Max 67/48 29/8 11/4 56/22 125/89 24/17 121/68 780/632
Min 37/19 11/3 4/3 24/13 77/40 14/9 85/57 531/332
Mean 46/34 17/6 6.5/3.3 33/17 94/66 17/12 97/76 592/461
SD 9.3/8.8 5.9/1.7 2.1/0.48 9.2/2.8 13/16 3.0/2.5 10/13 73/92
Dry season (May 2012)
1 31/18 6/4 4/4 18/13 75/42 13/9 81/55 498/298
2 34/18 8/5 5/2 21/11 78/40 13/9 82/59 521/385
3 38/27 10/3 5/3 26/12 75/45 14/11 85/67 531/421
4 62/26 28/4 10/3 49/17 113/87 21/16 110/87 659/541
5 41/32 13/5 5/3 36/14 83/72 16/11 95/68 581/502
6 53/39 21/6 8/4 39/20 99/75 19/11 101/91 619/483
7 40/31 14/5 6/3 34/16 88/71 17/14 93/82 587/507
8 37/29 10/6 5/3 26/15 80/64 14/12 88/75 538/452
9 33/22 11/7 5/3 22/11 81/60 14/12 85/63 538/474
10 30/27 9/7 4/3 17/13 75/63 13/10 81/59 520/403
Max 62/39 28/7 10/4 49/20 113/87 21/16 110/91 659/541
Min 30/18 6/3 4/2 17/11 75/40 13/9 81/55 498/298
Mean 40/27 13/5.2 5.7/3.1 29/14 85/62 15/12 90/71 559/446
SD 10/6.5 6.7/1.3 1.9/0.57 10/2.9 12/15 2.8/2.2 9.6/12 51/72

and suspended sediments were executed within two distinct
campaigns e one in May and the other in December 2012. May and
December have the lowest and highest amount of average monthly
precipitation by 34.5 and 121.2 mm, respectively (Nasrabadi et al.,
2011). So the campaigns were designed to cover both rainy and
dry seasons within the basin. Ten sampling locations were selected
(Fig. 2) in order to cover variability in land use (agricultural, in-
dustrial and urban activities), geology and hydrology within the
catchment area. Locations largely coincide with locations selected
in former studies to allow for comparison of results.
Samples were collected in 500 ml high density polyethylene
(HDPE) bottles, which had been carefully washed and rinsed in
advance. Water was collected at a certain distance from the
riverbed and sufficiently far from the banks, natural or artificial
obstacles and turbid water zones. The bottles were first rinsed with
river water before being filled. The samples designed for determi-
nation of dissolved metal concentration (Cw) were filtered through
0.45 mm filters, while the ones for determination of total concen-
trations were not filtered. Filtered samples were then acidified to
pH 2 with 1% Merck nitric acid and transported to the laboratory for
analysis.
To determine total concentration of metals in water samples
(Ctot) a digestion process according to US EPA, Method 200.2 (1999)
was considered. Each sample was first well shaken for homogeni-
zation before a 50 mL sub-sample was taken for digestion and
added to a mixture of concentrated (70%) nitric acid and concen-
trated (40%) hydrochloric acid (1.0 ± 0.1 ml conc. HNO3 and
0.50 ± 0.05 ml conc. HCl). The samples were then digested for
2e2.5 h at 95 ± 5  C. Details are well described in US EPA Method
200.2. Method blank, laboratory control sample and lab duplicates
were considered according to the mentioned reference. For each
metal, average accuracy values laid within 90e110%. The analysis of
metals in final solutions was carried out by an inductively coupled
plasma atomic emission spectrometer (ICP-AES) according to EPA e
3005 method. Accuracy was determined by measurement of stan-
dards and of duplicates and deviation from standards was less than
±4% for each metal.
The concentration of total suspended solids (TSS) was deter-
mined according to Standard methods 2540 D by filtering a defined
water volume through a membrane filter (cellulose nitrate
0.45 mm) and weighing the dried residues. Turbidity was analyzed
by a nephelometer (Hach 2100N Turbiditimeter) and reported in
Nephelometric Turbidity Units (NTU). Calibration was based on
formazin, which is an aqueous suspension of hydrazine sulfate and
hexamethylenetetramine.
For linear regressions in TSS vs. turbidity plots catchment spe-
cific slopes (m values) were calculated. For Cw,tot vs. TSS or turbidity
plots element specific intercepts and slopes (Cw and Csus values,
respectively) were calculated. For all regression coefficients (slopes
and intercepts) standard errors were calculated according to algo-
rithms used in Excel 2013 software. Details of calculations can be
found e.g. in Sachs and Hederich (2006).
4. Results and discussion
TSS-turbidity relationships: Besides the slope value of linear
regression (m) and standard errors of the regressions, mean values
and standard deviation of TSS/turbidity ratios (m Mean) were also
calculated. The overall results (Table 1) are in good agreement with
literature data on turbidity-TSS correlations for suspended sedi-
ments (e.g. Ruegner et al., 2014), in particular with sampling
campaigns which cover a comparable turbidity range and which
were performed in catchments with comparable land-use (Ammer
and Steinlach in S-Germany as well as the Haraz catchment in Iran
were all characterized by a mix of agricultural/urban land-use and
forest; Grathwohl et al., 2013; Nasrabadi et al., 2011, respectively).
Table 1 e TSS vs. turbidity relationships from this and similar
studies (No.: number of samples; m ± standard error and R2 from
6 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9

Co Cd

Total concentraƟon (mg/L)

0.012

Total concentraƟon (mg/L)

0.03
0.025 0.01
0.02 0.008
0.015 0.006
0.01 0.004
0.005 0.002
R² = 0,95
R² = 0,94 0
0
0 200 400 600 0 200 400 600

Turbidity (NTU) Turbidity (NTU)

Cu As

Total concentraƟon (mg/L)

Total concentraƟon (mg/L)

0.15
0.06
0.05
0.04 0.1
0.03
0.02 0.05
0.01 R² = 0,91 R² = 0.94
0 0
0 200 400 0 200 400 600
Turbidity (NTU) Turbidity (NTU)

Zn Sr

Total concentraƟon (mg/L)

Total concentraƟon (mg/L)

0.15 1
0.8
0.1 0.6
0.4
0.05
0.2
R² = 0,94 R² = 0,92
0 0
0 200 400 600 0 200 400 600
Turbidity (NTU) Turbidity (NTU)

Pb Ni
Total concentraƟon (mg/L)
Total concentraƟon (mg/L)

0.04 0.08

0.03 0.06

0.02 0.04

0.01 0.02
R² = 0,93
R² = 0,93
0 0
0 200 400 600 0 200 400 600
Turbidity (NTU) Turbidity (NTU)

Fig. 5. Linear regressions of total concentration of elements in water and turbidity during two December (dry, open rectangles) and May (wet, open triangles) sampling campaigns.

90 Table 3
TSS based Conc. Results from linear regressions shown in Figs. 4 and 5; Cw: concentrations of ele-
Regression based concentra on of

80 As ments in water (intercept ± standard error); Csus: concentration in suspended solids

Turbidity based Conc. (slope ± standard error); Kd is the distribution coefficient ¼ Csus/Cw.
70
dissolved metals (μg/l)

Zn
1:1-line Analyte Data analyzed Cw (mg/L) Csus (mg/kg) R2 Kd (L/kg)
60
Ni TSS based 28 ± 1.1 34 ± 2.1 0.94 1200
50 Sr* turbidity based 28 ± 1.2 34 ± 2.3 0.93 1200
Pb TSS based 5.7 ± 1.0 21 ± 1.9 0.88 3700
40
turbidity based 5.3 ± 0.8 22 ± 1.5 0.93 4300
30 Cd TSS based 3.1 ± 0.2 7.0 ± 0.4 0.95 2200
Ni turbidity based 3.0 ± 0.2 7.1 ± 0.4 0.95 2300
20 Cu TSS based 17 ± 1.5 32 ± 2.9 0.87 1900
Cu turbidity based 16 ± 1.3 33 ± 2.5 0.91 2100
10 Co
Zn TSS based 69 ± 1.9 45 ± 3.6 0.89 650
CdPb turbidity based 68 ± 1.4 47 ± 2.8 0.94 680
0
Co TSS based 12 ± 0.3 10 ± 0.7 0.93 830
0 20 40 60 80 100
turbidity based 12 ± 0.3 10 ± 0.6 0.94 860
Measured concentra on of dissolved metals (μg/l) As TSS based 78 ± 1.4 34 ± 2.6 0.91 430
turbidity based 78 ± 1.1 36 ± 2.1 0.94 450
Fig. 6. Comparison of measured (from laboratory analysis) and regression based Sr TSS based 482 ± 8.5 210 ± 16.3 0.90 440
(intercept from plots) dissolved metal concentrations; *Sr values divided by 10 to fit turbidity based 479 ± 7.8 219 ± 15.0 0.92 460
into scales shown.
 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9 7

60 particles along the lower course of the river. This finding is in

Es mated concentra on of metals in

TSS based Conc.

contrast to the strong heterogeneity of metal concentrations typi-
suspended sediments (mg/kg)

50 Turbidity based Conc.

Zn cally observed in river sediments. Thus, often applied finger-
1:1-line
40 printing strategies, which use the heterogenous patterns of river
As Ni sediments for the identification of the particles’ sources (e.g. Franz
Cu
30
et al., 2013; Walling, 2013) would not be suited in this or compa-
20
Pb Sr* rable cases or would at least require a thorough proof of feasibility.
To validate the approach, the dissolved concentrations in water
10
Cd
Co Cw derived from regression data (Table 3) were compared with the
mean concentrations of dissolved metals from direct measure-
0
0 10 20 30 40 50 60 70 80 ments, both from rainy and dry seasons (Table 2). These data are in
Previously measured concentra on of metals in bed sediments (mg/kg) very close agreement which is shown in Fig. 6. The error between
independently measured and regression based dissolved concen-
Fig. 7. Comparison of metal concentrations in suspended solids (Csus) and bed sedi- trations for metals are between 0.1 e 8.5% and 0.2e8% for TSS and
ments from Nasrabadi et al. (2010a); *Sr values divided by 10 to fit into scales shown. turbidity-based test attempts, respectively.
In addition, the particulate-bound concentrations Csus derived
from regression data (Table 3) were compared with bed sediments
linear regressions; mMean ± standard deviation represents the
concentrations measured at the same locations in August 2007
average of all TSS/turbidity ratios).
(Nasrabadi et al., 2010a; for a grain size fraction < 63 mm). For most
Fig. 3 indicates the good linear correlation between TSS and
metals these data sets are in good agreement (Fig. 7). For As, Cu and
turbidity in water samples taken during the two events (May and
Co the difference in reported values is below 10%, while for Pb, Ni
December 2012). A TSS and turbidity range of 202e1212 mg/l and
and Cd the estimated difference is around 30%. For Zn and Sr
63e501 NTUs was covered, respectively. Maximum turbidity and
concentrations on suspended solids are remarkably lower than
TSS values during the rainy season were only slightly increased
concentrations in river bed sediments, 46e82 mg kg1 and
compared to the dry season although higher rate of precipitation
220e550 mg kg1, respectively (Nasrabadi et al., 2010b). Whether
and consequently increased generation of urban and agricultural
this is due to heterogeneities in sediment sampling or due to
run-offs in December would suggest increased concentrations.
different grain size distributions of suspended and river bed sedi-
However, it is noteworthy to mention that in both periods the sand
ments has to be further investigated.
mining activities in riverbanks are in progress which may insert a
Distribution coefficients (Kd) were calculated by dividing the
relatively constant TSS concentration in the base flow of the river.
Csus -values from regressions by the intercept (Cw). These metal
Metal concentrations: Total and dissolved concentrations of eight
specific Kd values reflect geochemical distributions between solid
metals are shown in Table 2. As it is seen element concentrations in
phases and dissolved concentrations and may be considered as an
samples collected during rainy season show again only slightly
alarming parameter showing the risk level of a toxic element's
higher values in comparison with the samples from the dry season
bioavailability. In particular when shifted to lower values metals
campaign, as also TSS/turbidity values are only slightly increased.
may then show an affinity to be released more easily into water
Stations 4, 5, 6 and 7 located in central parts of the study area show
phase. Whether the already relatively low Kd values for elements as
for most metals higher total concentrations (and partly also dis-
As, Co, Zn and Sr observed in this study may be related to increased
solved concentrations) of metals than the other locations. This is
risks has to be further investigated by geochemical modeling.
attributed to more intense riverbank mining activities in this sec-
Remarkably high values of As in river water up to 100 mg l1 and
tion of the study area and possibly also to other impacts which arise
thus ten times greater than published WHO guidelines of 10 ppb
from urban and industrial land use (Figs. 1 and 2).
have already been reported within the area (Nasrabadi et al., 2015).
TSS and/or turbidity - Ctot relationships: In a parallel approach TSS
and/or turbidity vs. Ctot relationships were evaluated in order to
5. Conclusions
calculate dissolved and particle-bound concentrations of
mentioned elements through linear regressions as given by Equa-
Very robust linear regressions were obtained between total
tion (2). Total element concentration versus TSS plots for each
element concentrations in water and total suspended solids and
element are shown in Fig. 5. Very good linear correlations of TSS
turbidity, respectively. Slope and intercept of these regressions
and Ctot were observed for all elements (Cd, Co, As, Pb, Cu, Ni, Sr and
correspond to the element concentrations associated with the
Zn) across all selected locations (R2 values vary from 0.87 for copper
suspended solids and the dissolved concentration in water. Both,
to 0.95 for cadmium). The same holds for linear correlations of
Csus and Cw determined form the regressions agree very well with
turbidity and Ctot.These results are plotted in Fig. 6. High values for
independently measured concentrations in sediment and water
R2 (from 0.91 for copper to 0.95 for cadmium) were achieved here.
samples. The correlations between total concentrations in water
Detailed results for TSS and turbidity based data are shown in
and TSS or turbidity hold for all sampling locations over a large
Table 3.
spatial scale as well as for wet and dry conditions indicating that
The observed correlations not only hold for the two investigated
suspended solids in the river represent an integral measure of
events but also for all locations where samples were taken. This
sediment quality in the total catchment. In the Haraz catchment
strongly suggest that at least the smaller grain size fraction of the
pollutants are mostly of geogenic origin but fluxes are likely
river sediment e which makes up the suspended particle load e
enhanced by mining activities which release particles into the river.
shows only little heterogeneity across the middle/lower part of the
Further anthropogenic pressures such as agriculture or urbaniza-
catchment which was investigated here. As already mentioned, the
tion were less important for the pollutant fluxes observed. Finally,
all season sand/gravel mining activities in the river may have
this new data set confirms earlier correlations of suspended solids
caused a continuous suspended sediment transport over years.
and turbidity over large ranges of TSS (202e1212 mg/l) and
Subsequent sedimentation and re-suspension of these fine sedi-
turbidity (63e501 NTUs). Thus turbidity measurements may serve
ment particles during distinct events might have caused the
as easy and low cost proxies not only to monitor suspended solids
observed homogenous pattern in pollutant loadings of suspended
in rivers, but also to determine fluxes of particle associated
8 T. Nasrabadi et al. / Applied Geochemistry 68 (2016) 1e9
pollutants such as heavy metals and metalloids in catchments. To
our knowledge this is the first study focusing on particle facilitated
metal transport at that scale and it would be interesting to compare
this results with data form other catchments with different geol-
ogy, hydrological dynamics and land use.
Acknowledgments
This study was possible through the fruitful collaboration be-
tween the corresponding author from University of Tehran, Iran
and the research team of WESS, Eberhardt Karls Universitaet Tue-
bingen. The connection was established by a DAAD (Deutsche
Akademische Austausch Dienst) scholarship which is highly
appreciated by the board of authors. The study was also supported
by the EU FP7 Collaborative Project GLOBAQUA (Grant Agreement
no 603629).
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