Water quality survey of streams from Retezat Mountains, Romania [600812]

1
Water quality survey of streams from Retezat Mountains, Romania

Mihai -Cosmin PASCARIU1,2,3, Tiberiu TULUCAN4,5, Mircea NICULESCU3,6, Mariana Nela ȘTEFĂNUȚ7*

1 “Vasile Goldiș” Western University of Arad, Faculty of Pharmacy, 86 Liviu Rebreanu, RO -310045, Arad,
ROMANIA
2 “Victor Babeș” University of Medicine and Pharmacy of Timișoara, Faculty of Medicine, 2 Eftimie Murgu Sq.,
RO-300041, Timișoara, ROMANIA
3 “Chemeia Semper” Association, 6 Giuseppe Verdi, RO -300493, Timișoara, ROMANIA
4 “Vasile Goldiș” Weste rn University of Arad, Izoi -Moneasa Center of Ecological Monitoring, 94 Revoluției
Blvd., RO -310025, Arad, ROMANIA
5 Romanian Society of Geography, Arad subsidiary, 2B Vasile Conta, RO -310422, Arad, ROMANIA
6 University Politehnica Timișoara, Faculty of In dustrial Chemistry and Environmental Engineering, 6 Vasile
Pârvan Blvd., RO -300223, Timișoara, ROMANIA
7 National Institute of Research&Development for Electrochemistry and Condensed Matter – INCEMC
Timișoara , 144 Dr. A urel Păunescu Podeanu, RO -300569, Tim ișoara, ROMANIA

* Corresponding author , e-mail: [anonimizat]

Abstract

A series of samples from creeks located in the Retezat Mountains (Romania) was analyzed using the
chemical methods stipulated in the Romanian Pharmacopoeia to establish their content of heavy metals and other
ions, both cations and anions. Additionally, the samples were investigated using microwave plasma – atomic
emission spectrometry (MP -AES) to quantify specific elements, namely aluminium, cadmium, cobalt,
chromium, co pper, iron, magnesium, manganese, molybdenum, nickel, lead and zinc. The cation levels found
were compared with the Romanian national standards regarding surface water quality. A high purity with respect
to the ion levels was found for the analyzed “Jiul d e Vest” tributaries.

Keywords: heavy metals, MP -AES, chemical analysis, Romanian Pharmacopoeia, surface water quality, Retezat
National Park

INTRODUCTION

Heavy metals (Duffus 2002) are considered common pollutants of the environment, having both natural
and anthropogenic origins. They can form highly toxic compounds which, when inhaled or ingested , affect
almost every organ and system in the body , posing a threat to both the stability of the ec osystems and the human
health (Bradl 2005) .
In this paper sev eral springs and streams from the Retezat Mountains (Romania , Hunedoara County ) were
analyzed for the presence of heavy metals and other ions (cations and anions). The tested cations include
ammonium (NH 4+), arsenic (As3+), calcium (Ca2+), iron ( Fe2+/Fe3+) and other heavy metals (e.g., lead Pb2+),
while the anions that were searched for include halides ( chloride Cl ˉ, bromides Brˉ, iodides Iˉ), nitrite (NO 2ˉ)
and sulfate (SO 42ˉ), all of them being determined according to the chemical methods stipulated in the Romanian
Pharmacopoeia (10th edition ) or by using test strips . The results were supplemented with MP -AES (mic rowave
plasma – atomic emission spectrometry) determinations for aluminium, cadmium, cobalt, chromium, copper,
iron, magnesium, manganese, molybdenum, nickel, lead and zinc.
In contrast to atomic absorption spectrometry (AAS), which is based upon the absor ption of a
characteristic radiati on, atomic emission spectrometry (AES) uses the emission of a characteristic wavelength for
the determination of the analyte element. Plasma emission spectro metry utilizes a plasma (an electrical
conducting gaseous mixture that contains a significant number of cations and electrons) as the excitation source
for atomic emission s. In MP -AES, p lasma is formed via the use of a microwave field source. AES belongs to the
most useful and commonly used techniques for the analysis of heavy metals, providing rapid and sensitive
results in a variety of sample matrices although the detection limits are higher than those of AAS (Bradl 2005 ;
Higson 2006 ).

2
STUDY AREA

The sample area belongs to the southern part of the Retezat Mountai ns, also known as the Southern
Retezat ( Retezatul Sudic , in Romanian). The researched space is located on the southern slope of the Piule –
Iorgovanul Mountains, between 1529 -1871 m of altitude. The stream water samples were collected from point
sources loca ted in the upper part of “Jiul de Vest” River basin (Ujvári 1972) , upstream from “Câmpu Mielului”
(Fig.1 ).
From geological point of view we mention the presence of sedimentary rocks : quartz sandstones, marl
and marl -limestones, with patches of schists and limestones. Soils are represented by humus -iron-illuvial
podzols, humus -silicate soils, brown podzols and brown acidic soils. In terms of flora, subalpine meadows
predominate, which are in contact with the upper limit of the coniferous domain. Carex and Festuca meadows
alternate with mountain pine , juniper shrubs and dwarf shrubs composed of Vaccinium vitis -idaea and
Vaccinium myrtillus (Mâciu et al. 1982 ).
Weather was generally stable, with clear sky or passing cirrostratus clouds, with constant atmospheri c
pressure and with slightly negative temperatures at night . There was no rainfall in the previous days to produce
signs of indirect contamination.

METHODS

Sampling

Geographic coordinates and altitudes were e stablished using a Magellan Meridian Platinum Mapping
GPS receiver, while air temperature and pressure were recorded with a portable Auriol weather station.
Sample temperature, pH and electrical conductivity (EC) were registered with a portable Hanna HI 98 130
Combo pH&EC measuring device. Nitrites and sulfates were measured in situ using Merck test strips
(Merckoquant® Nitrit -Test and Merckoquant® Sulfat -Test) .
Heavy metal content of solutions may change between sampling and analysis due to adsorption effec ts on
the container walls or by contamination due to extraction of heavy metals already contained in the material of the
storage units . To prevent these contaminations thoroughly cleaned plastic recipients were used, taking some
special precautions (Bradl 2005, Ogoyi et al. 2011) . Thus, the recipients were prepared in the laboratory by
protracted soaking with 2M nitric acid followed by rinsing with double distilled water . They were also
condition ed in situ with several aliquots of the water to be sampled. After completing this protocol a volume of
350 mL of water was collected. Also, to avoid the loss of elements by adsorption on the wall of the storage
recipients, the samples were stabilized by acidification to pH~1 by adding 20 mL of 10% nitric acid. All
glassware needed for analysis was washed with 2M nitric acid and thoroughly rinsed with double distilled water
just prior of being used (Pascariu et al. 2013) .

Laboratory analysis

Preliminary analyses were performed on filtrated samples the day after they were collected according to
the general procedures stated by the Romanian Pharmacopoeia (10th edition ). A blank solution (350 mL double
distilled water with 20 mL 10% nitric acid) was also prepared in a n identical plastic container and tested for
comparis on. The following aqueous reagents were used: Nessler ’s reagent (potassium tetraiodomercurate(II),
K2HgI 4, and potassium hydroxide, KOH) for ammonium, sodium hypophosphite (NaH 2PO 2) in hydrochloric acid
(HCl) for arsenic, ammonium oxalate ((NH 4)2C2O4) for calcium, silver(I) nitrate (AgNO 3) for chloride,
potassium hexacyanoferrate(II) (K 4[Fe(CN) 6]) for iron, sodium sulfide (Na 2S) for heavy metals (e.g., lead) and
barium chloride (BaCl 2) for sulfates . The chemical reactions that use these reagents are stated to have the
following detection limits: 0.3 ppm for ammonium, 1 ppm for arsenic, 3.5 ppm for calcium, 0.5 ppm for
chlorides, 0.5 ppm for iron, 0.5 ppm for lead and 3 ppm for sulfates (Pascariu et al. 2013) .
For MP -AES , an Agilent 4100 (Fig.2 ) with web -integrated Agilent MP Expert software was used. The
instrument was adjusted using as calibration standard the provided Wavelength Calibration Concentrate for ICP –
OES & MP -AES (Al, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Se , Sr, Zn 50 mg/L, K 500 mg/L) and also an
AAS standard solution for Ca, Fe and Mg . The following wavelengths (in nm) were measured: Al 396.152, Cd
228.802, Co 340.512, Cr 425.433, Cu 324.754, Fe 259.940, Mn 403.076, Mg 285.213, Mo 379.825, Ni 352.454,
Pb 405.781, Zn 213.857.

3
RESULTS AND DISCUSSION

At the sampling sites the springs are located in the river bed deposits or at the base of the erosion
regressive step. Although they can be classified as slope springs, they are not generated by an obvious stream
(concentrated hydrographic network) . Instead they constitute some emergences at the contacts between
superficial deposits of consolidated sedimentary rocks, which are fixed by soils and vegetation.

Some of the sampling s ites are shown in Fig.3 , while the list of analyzed samples, together with time,
location and on -site measured parameters, are given in Table 1 . Samples 1 -3 come from springs which originate
in detrital sediments from non -karst rocks (sandstones). Sample 4 comes from a spring localized in non –
calcareous detrital rocks. Samples 5 and 6 were collected near Scorota sheepfold from two creek s that flow over
Holocene detrital deposits.
The in-situ tests using test strips did not indicate the presence of nitrites or sulfates ( nitrite ion
concentration less than 1 mg/L, sulfate ion concentration less than 200 mg/L , according to test strips
instructions ). Also, the very low measured EC indicates that the total dissolved solids (TDS) must be under 10
ppm (Lenntech 201 5).

Table 1 Sampling parameters

Parameter / Sample 1 2 3 4 5a 6a
Date (month/day/year) 11/01/2014 11/01/2014 11/01/2014 11/01/2014 11/02/2014 11/02/2014
Time (UTC+2 hours) 12:00 13:00 13:10 16:00 09:00 09:10
Geographic
coordinates 45°17’57’’N
22°53’23 ’’E 45°17’55’’N
22°52’57’’E 45°17’55’’N
22°52’57’’E 45°17’57’’N
22°52’30’’E 45°17’53’’N
22°53’33’’E 45°17’53’’N
22°53’35’’E
Altitude [ m] 1620 1759 1759 1871 1533 1529
Air pressure [ mbar ] 842.8 828.3 828.3 817.6 -b -b
Air temperature [ °C] 25 22 22 15 -b -b
Sample temperature [ °C] 4.8 5.4 5.9 4.9 5.0 4.0
pH (pH units ) 8.40 7.92 8.02 8.00 8.13 8.18
EC [mS/cm] 0.01 0.00 0.00 0.00 0.00 0.00
a geographic coordinates and altitude were established using Google Earth software ;
b not measured.

The preliminary chemical analyses were performed in the laboratory using the procedures outlined in the
Romanian Pharmacopoeia (10th edition). The samples were tested for the presence of ammonium, arsenic,
calcium, chlorides, iron, heavy metals (lead) and sulfates. Excep t for a very faint opalescence obtained when
sample 1 was tested for calcium, all these tests were negative, an observation that supports the very low
measured EC for all samples ( Table 1 ).
MP-AES results are summarized in Table 2 .

Table 2 MP-AES cation content results , in mg/L

Sample Concentration
Al Cd Co Cr Cu Fe Mg Mn Mo Ni Pb Zn
1 * * 0.03 * * 1.61 0.53 * 0.03 * 0.01 *
2 * * 0.03 * * 0.05 1.10 * 0.02 * 0.01 *
3 * * 0.02 * * 0.13 1.84 * 0.02 * * *
4 0.01 * 0.02 * * 0.08 0.18 * 0.02 * * *
5 0.01 * 0.02 * * 0.14 0.88 * 0.02 * * *
6 * * 0.02 * * 0.05 0.54 * 0.02 * * *
*under detection limit .

The drinking water standards from WHO (2011 ), EU (1998) and Romanian “Law no. 311 from June 28,
2004” (2004) are given in Table 3 for comparison with the analyzed samples .

4
Table 3 Drinking water standards comparative table ; all values are in units of mg/L unless stated otherwise
(World Health Organization 2011; European Unio n 1998; Romanian Government 2004 )

Parameter WHO standards
2011 EU standards
1998 Romanian l aw
no. 311 /2004
pH [pH units ] No guidelined 6.5-9.5 6.5-9.5
EC [mS/cm ] Not mentioned 2.500 2.500
TDS No guidelineb,c Not mentioned Not mentioned
Temperature [°C] No guidelineg Not mentioned Not mentioned
Aluminium ( Al3+) No guideline 0.200 0.200
Ammonia /ammonium (NH 3+NH 4+) No guidelineb 0.50 0.50
Cadmium ( Cd2+) 0.003 0.005 0 0.0050
Calcium (Ca2+) Not mentionedh Not mentioned Not mentioned
Chromium (Cr3++Cr6+) 0.050 0.050 0.050
Cobalt (Co2++Co3+) Not mentioned Not mentioned Not mentioned
Copper (Cu2+) 2.000 2.0 0.1a
Iron (Fe2++Fe3+) No guidelineb 0.200 0.200
Lead (Pb2+) 0.010 0.010 0.010
Manganese (Mnx+) No guidelineb 0.050 0.050
Magnesium (Mg2+) Not ment ionedh Not mentioned Not mentioned
Molybdenum (Mox+) No guidelineb Not mentioned Not mentioned
Nickel (Ni2+) 0.070 0.020 0.020
Zinc (Zn2+) No guidelineb Not mentioned 5.000
Chloride (Cl ˉ) No guidelineb,e 250 250
Nitrite (NO 2ˉ) 3.000 0.50 0.50
Sulfate (SO 42ˉ) No guidelineb,f 250 250
a is allowed as 2 .0 mg/L if the distribution piping material contains copper ;
b no guideline, because it is not of health concern at levels found in drinki ng-water ;
c desirable: less than 600 mg/L;
d desirable: 6.5 -8.5;
e desirable: less than 250 mg/L;
f desirable: less than 500 mg/L;
g cool water is preferred;
h included in both water hardness and TDS, which are not of health concern at levels found in drin king-water.

As can be seen, except for an increased iron content in sample 1, the s tudied streams seem to be within
the limits specified for drinking water by all specified standards.
The Romanian environmental legislation regarding surface water quality is stipulated in “Ordin nr. 161
din 16 februarie 2006” (Romanian Government 2006), summarized for the considered ions in Table 4.

Table 4 Surface w ater quality classes depending on cation content , as stated in Romanian “Ord er no. 161 from
Februar y 16, 2006” ; units are in mg/L , unless stated otherwise

Parameter Order no. 161 (2006 )
I II III IV V
pH [pH units ] 6.5 – 8.5
EC [mS/cm ] No guideline
TDS Not mentioned
Temperature [ °C] No guideline
Aluminium (Al3+) Not mentioned
Cadmium (Cdx+) 0.0005 0.001 0.002 0.005 >0.005
Chromium, total (Cr3++Cr6+) 0.025 0.050 0.100 0.250 >0.250
Calcium (Ca2+) 50 100 200 300 >300
Cobalt (Co3+) 0.010 0.020 0.050 0.100 >0.100
Copper (Cu2+) 0.020 0.030 0.050 0.100 >0.100
Iron, total (Fe2++Fe3+) 0.3 0.5 1.0 2 >2
Lead (Pbx+) 0.005 0.010 0.025 0.050 >0.050
Magnesium (Mg2+) 12 50 100 200 >200

5
Manganese, total (Mn2++Mn7+) 0.05 0.1 0.3 1 >1
Nickel (Nix+) 0.010 0.025 0.050 0.100 >0.100
Zinc (Zn2+) 0.100 0.200 0.500 1.000 >1.000
Chloride (Cl ˉ) 25 50 250 300 >300
Sulfate (SO 42ˉ) 60 120 250 300 >300

According to Table 4 , the last four sampled streams seem to belong to class I . Except ion could be the
stream that provided the first sample which could belong to class IV according to the iron content , but this could
also be owned to the fact that th e samples were not filtrated when collected. Also, according to the lead content,
the streams that provided the first two samples could belong to class II or III, but these low measured lead levels
may better be accounted for by the MP-AES precision limit.

CONCLUSION S

A modern physical -chemical method, namely MP -AES, alongside some classic analytic al procedures also
applied in the Romanian Pharmacopoeia, were used to analyze a few springs and creeks from the Retezat
Mountains. Fortunately, for all tested samples, heavy metals were at very low levels or under the detection limit
for the chemic al reactions employed and also under the sensitivity of the MP-AES method applied. From this
point of view, the samples comply as drinking water according to the WHO , EU and Romanian
recom mendations . The average water temperature was 5.0°C, the mean pH value was 8.11, while the measured
EC value was about 0.00 mS/cm for all samples , the later also being an argument for the very small ion content
present in the analyzed mountain streams .

Acknowledgement

Part of this paper was presented at The 17th DKMT Euroregional Conference on Environment and Health,
June 5 -6, 2015, Szeged, Hungary. Some of research was done at the Center of Genom ic Medicine of the “Victor
Babe ș” University o f Medicine and Pharmacy of Timiș oara, POSCCE 185/48749, contract 677/09.04.2015.

References

Bradl, H., Kim, C., Kramar, U., S tüben, D. 2005. Interactions of Heavy Metals. In: Bradl , H.B. (ed.) Heavy
Metals in the E nvironment : origin, inter action and r emediation . Elsevier Academic Press, Amsterdam ,
28-164.
Duffus , J.H. 2002. “Heavy metals” – a meaningless term? (IUPAC Technical Report) . Pure Appl. Chem. 74(5),
793-807.
European Union. 1998. Council Directive 98/83/EC of 3 November 1998 on th e quality of water intended for
human consumption, downloaded from http://eur -lex.europa.eu/legal –
content/EN/TXT/?uri=URISERV:l28079 , accessed July 12, 2015.
Higson, S. 2006. Analytical Chemistry. Oxford University Press, New York, 201.
Lenntech: Conductiv ity convertor , http://www.lenntech.com/calculators/conductivity/tds -engels.htm ( accessed
July 12, 2015).
Mâciu, M., Chioreanu, A., Vacaru, V., Posea, G., Ielenicz, M., Pătroescu, M., Velcea, I., Pișota, I. 1982.
Enciclopedia Geografică a României (Romania’ s Geographic Encyclopedia). “Editura Științifică și
Enciclopedică” Publisher, Bucharest, 1982 (in Romanian).
Ogoyi , D.O., Mwita , C.J., Nguu , E.K., Shiundu , P.M. 2011. Determination of heavy metal content in water,
sediment and microalgae from Lake Victoria , East Africa . The Open Environmental Engineering Journal
4, 156 -161.
Pascariu , M.C., Ciobotaru , A.L., Tulucan , T., Ștefănuț , M.N., Cătă , A., Fițigău , I.F., Ienașcu , I. 2013. Romanian
Pharmacopoeia versus atomic spectrometry as analysis tools for heavy met al content in some water
sources from the western and south -western part of Romania . Jurnal Medical Aradean (Arad Medical
Journal) XVI(1-4), 91-99.
Romanian Government, Law no. 311 from June 28, 2004 , downloaded from
http://www.rowater.ro/dacrisuri/Documen te%20Repository/Legislatie/gospodarirea%20apelor/LEGE%20
311_28.06.2004.pdf , accessed July 12, 2014 . (in Romanian).
Romanian Government, Order no. 161 from Februar y 16, 2006 , downloaded from
http://www.rowater.ro/dacrisuri/Documente%20Repository/Legislatie/gospodarirea%20apelor/ORD.%20
161_16.02.2006.pdf , accessed July 12, 2014. (in Romanian) .
Romanian Pharmacopoeia, 10th edition. 1993.

6
Ujvári , I. 1972. The Geography of Romanian Waters ( Geograf ia apelor României ). “Editura Științi fică”
Publisher, Bucharest , 591 p . (in Romanian ).
World Health Organization. 2011. Guidelines for Drinking -water Quality, 4th edition. WHO, 564 p., downloaded
from http://www.who.int/water_sanitation_health/publications/2011/dwq_guidelines/en/ , accessed July
12, 2015.

Fig.1 Surroundings of the sampling sites

Fig.2 Agilent 4100 microwave plasma – atomic emission spectrometer

7

Fig.3 Some analyzed mountain streams : (a) sample 6; (b) sample 5; (c) sample 1