WATER QUALITY SURVEY OF STREAMS FROM RETEZAT MOUNTAINS (ROMANIA ) 1 [610264]
1
WATER QUALITY SURVEY OF STREAMS FROM RETEZAT MOUNTAINS (ROMANIA ) 1
2
Mihai -Cosmin Pascariu1,2, Tiberiu Tulucan3,4, Mircea Niculescu5, Iuliana Sebarchievici2, Mariana Nela Ștefănuț2* 3
4
1 “Vasile Goldiș” Western University of Arad, Faculty of Pharmacy, 86 Liviu Rebreanu, RO -310045, Arad, 5
Romania 6
2 National Institute of Research & Development for Electrochemistry and Condensed Matter – INCEMC 7
Timișoara, 144 Dr. Aurel Păunescu -Podeanu, RO -300569, Timișoara, Romania 8
3 “Vasile Goldiș” Western University of Arad, Izoi -Moneasa Center of Ecological Monitoring, 94 Revoluției 9
Blvd., RO -310025, Arad, Romania 10
4 Romanian Society of Geography, Arad subsidiary, 2B Vasile Conta, RO -310422, Arad, Romania 11
5 University Politehnica Timișoara, Faculty of Industrial Chemistry and Envi ronmental Engineering, 6 Vasile 12
Pârvan Blvd., RO -300223, Timișoara, Romania 13
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*Corresponding author, e -mail: [anonimizat] , tel.: +[anonimizat], fax: +[anonimizat] 15
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Abstract 17
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The Retezat Mountains , located in the Southern Carpathians , are one of the highest massifs in Romania 19
and home of the Retezat National Park , which posse sses an important biological value and which is the oldest 20
Romanian national park. In this study a number of samples from creeks located in the Southern Retezat (Piule – 21
Iorgovanul Mountains ) between 1529 and 1871 m of altitude were analyzed using the chemical methods 22
stipulated in the Romanian Pharmacopoeia to estimate their levels of some inorganic ions, including a few 23
heavy metals. Additionally, the samples were investigated using microwav e plasma – atomic emission 24
spectrometry to quantify specific elements, namely aluminium, cadmium, cobalt, chromium, copper, iron, 25
magnesium, manganese, molybdenum, nickel, lead and zinc. The measured contents were compared with the 26
European Union and Roman ian standards regarding drinking water and surface water quality. A high purity with 27
respect to the ion levels was found for the analyzed water sources, which are tributaries to the Jiul de Vest River . 28
The studied h eavy metals have been found to be in very low concentrations or under the method’s detection 29
limit. Thus, in the microbasin corresponding to the sampling points, there seems to be no heavy metal pollution 30
and, f rom this point of view, the samples comply as drinking water according to the E uropean Union and 31
Romanian recommendations. Also, no other potential sources of chemical pollution have been identified in the 32
studied perimeter during our survey. 33
34
Keywords: water chemical analysis, surface water quality , heavy metals, MP -AES, Romanian Pharma copoeia, 35
Retezat National Park 36
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INTRODUCTION 38
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The Retezat National Park (Romania , Hunedoara County ), located in th e western part of th e Southern 40
Carpathian Moun tain Range , possesses a high biological value and has thus been added to the UNESCO Man & 41
Biosphere Reserves network. The p ark includes 19 peaks above 2000 m elevati on and i t has been proposed a s a 42
model for the conservation efforts in Romania and other countries (Bytnerowicz et al. 2005). 43
While several studies from the scientific mainstream literature have dealt with the geology and 44
hydrogeology of the area ( Povară and Ponta 2010 ) or the composition of mountain lake sediments ( Catalan 45
2015; Camarero et al. 2009; Rose et al. 2009 ), studies regarding the c omposition of surface creeks seem to be 46
scarce or non -existent . 47
In this work , several springs and streams from the Southern Retezat were analyzed for the presenc e of 48
heavy metals and other ions (cations and anions). The tested cations include ammonium (NH 4+), arsenic (As3+), 49
calcium (Ca2+), iron (Fe2+/Fe3+) and other heavy metals (e.g., lead Pb2+), while the anions that were searched for 50
include halides (chloride Clˉ, bromide Brˉ, iodide Iˉ), nitrite (NO 2ˉ) and sulfate (SO 42ˉ), all of them being 51
determined according to the chemical methods stipulated in the Romanian Pharmacopoeia (1993) or by using 52
test strips. The results were supplemented by microwave plasma – atomic emission spectrometry (MP-AES) 53
determinations for some metals, i.e. aluminium, cadmium, cobalt, chromium, copper, iron, magnesium, 54
manganese, molybdenum, nickel, lead and zinc. Most of them are included in the category of h eavy metals 55
(Duffus 2002) , which are considered common pollutants of the environment, having both natural and 56
anthropogenic origins. Heavy metals can form highly toxic compounds which, when inhaled or ingested, can 57
have an impact on almost every organ and system in a living organism, posin g a danger to the stability of the 58
ecosystems and also a risk for the human health (Bradl et al. 2005). 59
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2
STUDY AREA 1
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The studied area (Fig. 1 ) belongs to the southern part of the Retezat Mountains (Bytnerowicz et al. 2005) , 3
also known as Southern Rete zat (Retezatul Sudic , in Romanian). The researched space is located on the southern 4
slope of the Piule -Iorgovanu Mountains (Ardelean 2010 ; Povară and Ponta 2010 ), between 1529 and 1871 m of 5
altitude. The stream water samples were collected from point sources located in the uppe r part of the Jiul de Vest 6
River basin (Iordache et al. 2015; Ujvári 1972) , upstream from Câmpu Mielului , from its left tributaries Scorota 7
cu Apă and Scorota Seacă . The sampling points were allocated by considering the short lengths of the active 8
sections that form their higher b asin. The microbasins corresponding to the sampling points contain active 9
segments with lengths which vary between 100 and 500 m, while the flow of the studied creeks is usually 10
between 2 and 5 L/s. Also, the allocatio n of the sampling points regarded their relative position to the Scorota 11
sheepfold : near the sheepfold, which is also the lowest part of the grazing area, and in the higher limit of this 12
area, with ~100 m steps between the two altitudes. 13
From geological point of view , we mention the presence in the region of sedimentary rocks , like quartz 14
sandstones, marl and marl -limestones, with patc hes of schists and limestones. Soils are represented by humus – 15
iron-illuvial podzols, humus -silicate soils, brown podzols and brown acidic soils. These mountains are 16
characterized by a rich flora and fauna. S ubalpine meadows (grassland) predominate, being in contact with the 17
upper limit of the coniferous domain , composed mainly of Norway spruce (Picea abies ). Carex and Festuca 18
meadows alternate with mountain pine, juniper shrubs and dwarf shrubs composed of Vaccinium vitis -idaea and 19
Vaccinium myrtillus (Bytn erowicz et al. 2005; Kern and Popa 2009 ; Mâciu et al. 1982 ; Tulucan et al. 1999 ), as 20
can be seen in Fig 2 . The clim ate is continental and typical for high mountain areas (Povară and Ponta 2010 ). In 21
the last week of October, prior to sampling, weather was generally stable, with clear sky or passing cirrostratus 22
clouds, with constant atmospheric pressure and with slightly negative temperatures at night. There was no recor d 23
of rainfall or snowfall that could have produce d signs of indirect contamination. 24
The list of analyzed samples, together with time, location and on -site measured parameters, are given in 25
Table 1 . Samples 1 -3 come from springs which originate in detr ital sediments from non -karst rocks (sandstones). 26
Sample 4 comes from a spring localized in non -calcareous detrital rocks. Samples 5 and 6 were collected near 27
Scorota sheepfold from two creeks that flow over Holocene detrital deposits. The springs are loca ted in the river 28
bed deposits or at the base of the erosion regressive step. Although they can be classified as slope springs, they 29
are not generated by an obvious stream (concentrated hydrographic network). Instead , they constitute some 30
emergences at the c ontacts between superficial deposits of consolidated sedimentary rocks, which are fixed in 31
place by soils and vegetation. The catchment is located in the Festuca meadows perimeter. Sampling sites 32
corresponding to samples 1 -3, 5 and 6 are located in the jun iper floor, where juniper clusters alternate with 33
Festuca meadows. For samples 2 and 3, t he measurements were taken near a confluence of two rivulets , 34
tributar ies of Scorota cu Apă stream: sample 2 comes from the right tributary, while sample 3 comes from the 35
left tributary. Regarding the highest measured point, corresponding to sample 4, the sampling was done in a 36
ravine with the mountainsides heav ily eroded by the ra in erosion (Fig. 2 , right ). 37
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METHODS 39
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Sampling and in situ measurements 41
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Geographic coordinates and altitudes were established using a Magellan Meridian Platinum Mapping 43
GPS receiver, while air temper ature and pressure were recorded with a portable Auriol weather station. 44
Sample temperature, pH and electrical conductivity (EC) were registered with a portable Hanna HI 98130 45
Combo pH&EC measuring device. Nitrites and sulfates were measured in situ using Merck test strips 46
(Merckoquant® Nitrit -Test and Merckoquant® Sulfat -Test) . 47
We have generally followed ISO 5667 -3 guidelines for sampling. To prevent contaminations , thoroughly 48
cleaned plastic recipients were used (Bradl et al. 2005; Ogoyi et al. 2011) , prepared in the laboratory by 49
protracted soaking with 2 M nitric acid followed by rinsing with double distilled water . They were also 50
condition ed in situ with several aliquots of the water to be sampl ed. After completing this protocol a volume of 51
350 mL of water was collected. To avoid the loss of elements by adsorption on the wall s of the storage 52
recipients, the samples were stabilized by acidification to pH ~ 1 by adding 20 mL of 10% nitric acid (Pascariu et 53
al. 2013) . 54
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Laboratory analysis 56
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All glassware needed for analysis was washed with 2 M nitric acid and thoroughly rinsed with double 58
distilled water just prior of being used . Preliminary analyses were performed on filtrated samples the day after 59
they were collected according to the general procedures stated by the Romanian Pharmacopoeia (1993 ). A blank 60
3
solution (350 mL double distilled water with 20 mL 10% nitric acid) was also prepared in a n identical plastic 1
container and tested for comparison. The following aqueous reagents were used: Nessler ’s reagent (potassium 2
tetraiodomercurate(II), K 2HgI 4, and potassium hydroxide, KOH) for ammonium, sodium hypophosphite 3
(NaH 2PO 2) in hydrochloric acid (HCl) for arsenic, ammonium oxalate ((NH 4)2C2O4) for calci um, silver(I) nitrate 4
(AgNO 3) for halides, potassium hexacyanoferrate(II) (K 4[Fe(CN) 6]) for iron, sodium sulfide (Na 2S) for heavy 5
metals (e.g., lead) and barium chloride (BaCl 2) for sulfates . The chemical reactions that use these reagents are 6
stated to hav e the following detection limits: 0.3 ppm for ammonium, 1 ppm for arsenic, 3.5 ppm for calcium, 0.5 7
ppm for chlorides, 0.5 ppm for iron, 0.5 ppm for lead and 3 ppm for sulfates (Romanian Pharmacopoeia 1993 ). 8
For MP -AES , an Agilent 4100 with web -integrated Agilent MP Expert software was used. The 9
instrument was adjusted using as calibration standard the provided Wavelength Calibration Concentrate for ICP – 10
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 11
AAS standard solution for Ca, Fe and Mg . The following wavelengths (in nm) were measured: Al 396.152, Cd 12
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, 13
Pb 405.781, and Zn 213.857. In contrast to atomic absorption spectrometry (AAS), which is based upon the 14
absorption of a characteristic radiation, atomic emission spectrometry (AES) uses the emission of a characteristic 15
wavelength for the determination of the analyte element. Plasma emission spectrometry utilizes a plasma as the 16
excitation source for atomic emissions , which, in MP -AES, is formed via the use of a microwave field source. 17
AES belongs to the most useful and commonly used techniques for the analysis of heavy metals, providing rapid 18
and sensitive results in a variety of sample matrices , although the detection limits are higher than those of AAS 19
(Bradl et al. 2005; Higson 2006). 20
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RESULTS AND DISC USSION 22
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Owing to the location of the sampling points and the time the samples were acquired, we can confidently 24
state that the samples were not affected by any subterranean contributions, nor by any atmospheric 25
precipitations. The surface flow was not infl uenced by the meteorological parameters regarding the weather 26
conditions prior to the sampling period , and we did not find evidence of any disturbances, either geological or 27
hydrogeological. Also, due to the fact that the sampling was performed at the begi nning of November, any 28
organic pollution that might have appeared because of grazing should have been washed by precipitations in the 29
two months that have passed since the ending of the grazing period . 30
The in situ tests using test strips did not indicate t he presence of nitrites or sulfates (nitrite ion 31
concentration less than 1 mg/L, sulfate ion concentration less than 200 mg/L, according to test strips 32
instructions). Also, the very low measured EC indicates that the total dissolved solids (TDS) must be un der 10 33
ppm (Lenntech 2016). 34
The preliminary chemical analyses were performed in the laboratory using the procedures outlined in the 35
Romanian Pharmacopoeia ( 1993 ). The samples were tested for the presence of ammonium, arsenic, calcium, 36
halides (chloride , bromide, and iodide) , iron, heavy metals ( e.g., lead) and sulfates. Except for a very faint 37
opalescence obtained when sample 1 was tested for calcium, all these tests were negative, an observation that 38
supports the very low measured EC for all samples ( Table 1). 39
MP-AES results are summarized in Table 2 , while the drinking water standards from E U (1998) and 40
Romanian “Law no. 311 from June 28, 2004 ” (Romanian Government 2004) are given in Table 3 for comparison 41
with the analyzed samples . As can be seen, except for a somewhat increased iron content in sample 1 (probably 42
due to the humus -iron-illuvial podzols, which are present in the area) , the s tudied streams seem to be within the 43
limits specified for drinking water (Brad et al. 2015) by all specified standards. 44
The R omanian environmental legislation regarding surface water quality , stipulated in “ Order no. 161 45
from Februar y 16, 2006 ” (Romanian Government 2006), is summarized for the considered ions in Table 4 . 46
According to Table 4 , the last four sampled streams seem to belong to class I . An e xcept ion could be the stream 47
that provided the first sample which could belong to class IV according to the iron content . Also, according to 48
the lead content, the streams that provided the first two samples could belong to class II or III, but these low 49
measured lead levels may more realistically be accounted for by the MP-AES precision limit. 50
Our findings support the previous studies which state that the Retezat Mountains are among the least 51
contaminated regions in Europe (Catalan 2015 , Catalan et al. 2009 ). 52
53
CONCLUSION S 54
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A modern physical -chemical method, namely MP -AES, alongside some classic al analytic al procedures 56
also applied in the Romanian Pharmacopoeia , were used to analyze a few springs and creeks from the Retezat 57
National Park . Fortunately, for all tested samples, heavy metals were at very low levels or under the detection 58
limit for the chemic al reactions employed and the MP-AES method applied. From this point of view, the samples 59
comply as drinking water according to the EU and Romanian recom mendations . The average water temperature 60
4
was 5.0 °C, the mean pH value was 8.11, while the measured EC value was around or below 10 μS/cm for all 1
samples , the later also confirming the very small ion content present in the analyzed mountain streams . In the 2
microbasin corresponding to the sampling points, there seems to be no heavy metal pollution. Also, no other 3
potential sources of c hemical pollution was recorded in the studied perimeter during our survey. 4
5
Acknowledgements 6
7
Part of this paper was presented at The 17th DKMT Euroregional Conference on Environment and Health , 8
June 5 -6, 2015, Szeged, Hungary. Some of the research w as done at the C enter of Genomic Medicine of the 9
“Victor Babeș” University of Medicine and Pharmacy of Timișoara, POSCCE 185/48749, contract 10
677/09.04.2015. 11
12
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Fig. 1 Locati on of the sampling points (Google Earth 2015) 5
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Fig. 2 Surroundings of the sampling sites 3
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Table 1 Sampling parameters 1
2
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 [μS/cm ] ~ 10 < 10 < 10 < 10 < 10 < 10
a geographic coordin ates and altitude were established using Google Earth (2015) software; 3
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Table 2 MP-AES cation content results, in mg/L 1
2
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 (< 0.0 05 mg/L) . 3
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Table 3 Drinking water stand ards comparative table; all values are in units of mg/L unless stated otherwise 1
(European Union 1998; Romanian Government 2004) 2
3
Parameter EU standards
1998 Romanian law
no. 311/2004
pH [pH units ] 6.5-9.5 6.5-9.5
EC [mS/cm ] 2.500 2.500
TDS # #
Temperat ure [°C] # #
Aluminium (Al3+) 0.200 0.200
Ammonia/ammonium (NH 3+NH 4+) 0.50 0.50
Cadmium (Cd2+) 0.0050 0.0050
Calcium (Ca2+) # #
Chromium (Cr3++Cr6+) 0.050 0.050
Cobalt (Co2++Co3+) # #
Copper (Cu2+) 2.0 0.1*
Iron (Fe2++Fe3+) 0.200 0.200
Lead (Pb2+) 0.010 0.010
Manganese (Mnx+) 0.050 0.050
Magnesium (Mg2+) # #
Molybdenum (Mox+) # #
Nickel (Ni2+) 0.020 0.020
Zinc (Zn2+) # 5.000
Chloride (Clˉ) 250 250
Nitrite (NO 2ˉ) 0.50 0.50
Sulfate (SO 42ˉ) 250 250
# not mentioned; 4
* is allowed as 2.0 mg/L if the distribution piping material contains copper. 5
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Table 4 Surface water quality classes depending on cation content, as stated in Romanian “ Order no. 161 from 1
February 16, 2006 ”; units are in mg/L , unless stated otherwise 2
3
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
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 (Clˉ) 25 50 250 300 >300
Sulfate (SO 42ˉ) 60 120 250 300 >300
4
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