Evaluation of heavy metal and persistent organic pollutants input … · 2011. 9. 12. · Crisen...
Transcript of Evaluation of heavy metal and persistent organic pollutants input … · 2011. 9. 12. · Crisen...
EVALUATION OF HEAVY METAL AND PERSISTENT
ORGANIC POLLUTANTS INPUT FROM DANUBE
WATERS IN THE BLACK SEA AREA INFLUENCED BY
THE DANUBE, IN THE CONTEXT OF RECENT
CLIMATIC CHANGES AND BIOACCUMULATION
OF THESE COMPOUNDS IN BIOTA
Valentina COATU, Victoria PIESCU, Andra OROS, R. MIHNEA
National Institute for Marine Research and Development
„Grigore Antipa” Constantza
ABSTRACT
The paper presents data regarding the level of heavy metals,
organochlorine pesticides and polycyclic hydrocarbons pollution
and their bioaccumulation in organisms from Danube mouth and
Black Sea area influenced by Danube.
The distribution of heavy metal, organochlorine pesticides and
polycyclic hydrocarbons concentrations underlined the phenomena
of pollutants concentration both in water and sediments, especially
in the eastern and southern part of the Musura Bay and in Sulina
and Sfântul Gheorghe arms outfalls.
The bioaccumulation of heavy metals and organochlorine
pesticides is more obviously in mollusks when compare with fish
species, but bioaccumulation of polycyclic hydrocarbons is similar
in both categories of organisms.
KEY WORDS: organochlorine pesticides, polycyclic
hydrocarbons, heavy metals, Danube mouth, Black Sea
INTRODUCTION
Despite the efforts and the results obtained by International
Commission for the Protection of the Danube River there are still rezones of
concern regarding Danube’s ecosystem state; one of them refers to dangerous
substances which are present in concentrations that represent a risk for aquatic
environment and human health.
Recent climatic changes had as result some disasters like huge
inundations. As a consequence, there were large quantities of waters
discharged in Danube river, waters that washed out large areas with various
uses and carried along considerable quantities of pollutants. Finally, this
pollutants flows into the Black Sea.
This paper presents data on heavy metals, organochlorine pesticides
and polycyclic hydrocarbons pollution and their bioaccumulation in organisms
from Danube mouth and Black Sea area influenced by Danube in 2006 – 2007.
MATERIAL AND METHODS
Water and sediment samples were collected from Danube arms: Chilia,
Sulina and Sfântul Gheorghe, Musura Bay and Black Sea area in front of
Sulina and Sfântul Gheorghe arms (Fig. 1).
Biota was represented by mollusks and fish species collected as a result
of research expeditions from marine area influenced by Danube between Sulina
and Portita and from fishermen in Sulina and Sfântul Gheorghe.
Samples were analyzed for heavy metals, organochlorine pesticides
and polycyclic aromatic hydrocarbons.
Organic pollutants were extracted from water samples in a separation
funnel using a mixture of 7/3 hexane/dichloromethane. Sediment and biota
samples were extracted 8 hours with hexane in Soxhlet apparatus.
The extracts were concentrated to about 20 ml in a rotary evaporator;
the sulphur compounds were removed with copper powder in an ultrasonic
bath (sediment samples) and lipids were removed with sulphuric acid (biota
samples); the samples were fractionated on alumina-silica gel columns for
polycyclic aromatic hydrocarbons and on florisil columns for organochlorine
pesticides; the final concentration was done in Kuderna-Denish concentrators
and in nitrogen stream up to 1 ml.
The detection of polycyclic aromatic hydrocarbons concentration in
extracts obtained as described above was done with a Perkin-Elmer gas
chromatograph with mass selective detector and for organochlorine pesticides
with Perkin-Elmer gas chromatograph with electron capture detector.
Fig. 1 - Sampling sites for water and sediments on Chilia, Sulina and Sfântul Gheorghe arms,
Musura Bay and marine area in front of Sulina and Sfântul Gheorghe arms:
1- Chilia arm; 2 – Tulcea - Sulina arm; 3 – Crişan - Sulina arm; 4 – Sulina – Sulina arm;
5 – Murighiol - Sfântul Gheorghe arm; 6 – Musura Bay N; 7 – Musura Bay V; 8 – Musura
Bay S; 9 – Musura Bay E; 10 - Sulina discharging area S; 11- Sfântul Gheorghe dischargind
area N; 12- Sfântul Gheorghe discharging area S.
For heavy metals analyse unfiltered water samples, preserved in plastic
bottles in order to avoid contamination, were acidified to pH 1.5 – 2.0 with
HNO3 and stored at about 40C. Total metal concentrations were analysed
directly, by atomic absorption spectrometry method, using an ATI-UNICAM
939Z spectrometer, with graphite furnace and Zeeman background correction
device.
Sediments samples were oven-dried at 1050C and well homogenized (>
2 mm fraction removed). Dried sediment and biota (fresh) samples were
weighted and treated with 5 ml concentrated nitric acid 65%, HNO3 Suprapur
(Merck).
Digestion procedure was carried out in a Microwave digestion system
with built in, non-contact temperature and pressure measurement – type
Speedwave MWS – 3 (Berghof), with microwave power 1 450 W. At the
completion of this process, samples were diluted to 100 ml with deionized
water.
Trace metals concentrations were determined by graphite furnace
atomic absorption spectrometry (GF-AAS), using an SOLAAR M6 DUAL
Zeeman, Thermo Electron – UNICAM equipment.
RESULTS AND DISCUSSION
Data obtained for abiotic elements revealed a highly variability
especially for organic pollutant.
In water samples, heavy metals had concentrations between 9.98 μg/L
and 20.14 μg/L for Cu; 0.98 μg/L and 2.15 μg/L for Cd; 15.21 μg/L and 29.31
μg/L for Pb; 5.79 μg/L and 9.25 μg/Lfor Cr and 2.15 μg/L and 4.74 μg/L for
Ni. The highest levels were measured for Pb (24.72 g/L in fluvial water -
Sulina arm; 25.34 g/L in Musura Bay and 29.31 g/L in marine waters -
Sfântul Gheorghe arm discharging area S (Fig. 2).
In sediments heavy metals had concentrations between 2.03 μg/g dry
sediment and 20.14 μg/g dry sediment for Cu; 0.30 μg/g dry sediment and 2.95
μg/g dry sediment for Cd; 4.11 μg/g dry sediment and 36.96 μg/g dry sediment
for Pb; 5.32 μg/g dry sediment and 18.46 μg/g dry sediment for Cr; 2.81 μg/g
dry sediment and 46.66 μg/g dry sediment for Ni and 1.08 μg/g dry sediment
and 9.24 μg/g dry sediment for Ni. The highest levels were measured for Ni
(46.6 g/ g dry sediment in fluvial area – Sfântul Gheorghe arm; 37.87 g/g
dry sediment in Musura Bay), Cu (20.14 μg/g dry sediment in fluvial area –
Sfântul Gheorghe arm) and Pb (37.87 g/g dry sediment in fluvial area –
Sulina arm; 36.96 μg/g dry sediment in marine waters - Sfântul Gheorghe arm
discharging area) (Fig. 3).
0 10 20 30 40 50 60 70
Chilia Arm
Sulina Arm - Tulcea
Sulina Arm - Crisan
Sulina Arm - Sulina
Sf. Gheorghe Arm- Murighiol
Musura Bay - N
Musura Bay - V
Musura Bay- S
Musura Bay - E
Sulina discharge area- S
Sf. Gheorghe discharge area - N
Sf. Gheorghe discharge area- S
µg/l
Cu
Cd
Pb
Cr
Ni
Fig. 2 - Concentration of heavy metals in water samples collected from Danube
mouth and Black Sea area influenced by Danube
0 20 40 60 80 100 120
Chilia Arm
Sulina Arm - Tulcea
Sulina Arm- Sulina
Sf. Gheorghe Arm - Murighiol
Musura Bay - V
Musura Bay- S
Musura Bay- E
Sulina discharge area - S
Sf. Gheorghedischarge area - N
Sf. Gheorghe discharge area - S
µg/g d.w .
Cu
Cd
Pb
Cr
Ni
Li
Fig. 3 - Concentration of heavy metals in sediment samples collected from Danube
mouth and Black Sea area influenced by Danube
Polycyclic aromatic hydrocarbons were detected in all water samples
in concentrations between 0.11 and 1969.41 ng/L. The highest level of PAHs
was measured in southern part of Musura Bay (1520.11 ng/L Naphtalene,
1886.57 ng/L Phenanthrene, 1969.41 ng/L Anthracene and 1433.78 ng/L
Indeno(1,2,3-c,d)pyrene), and also in Sfântul Gheorghe arm discharging area
(1057.23 ng/L Naphtalene, 1542.39 ng/L Phenanthrene, 1610.17 ng/L
Anthracene) (Fig. 4).
Fig. 4 - Concentration of polycyclic aromatic hydrocarbons in water samples
collected from Danube mouth and Black Sea area influenced by Danube
In sediments polycyclic aromatic hydrocarbons varied between 0,02
and 186.14 ng/g dry sediment. The highest values were measured in fluvial
area at Murighiol (109.8 ng/g dry sediment Nphthalene and 182.92 ng/g dry
sediment Phenanthrene); in V Musura Bay (186.14 ng/g dry sediment
Naphtalene and 327.71 ng/g dry sediment Anthracene in Sfântul Gheorghe
arm discharging area northen part (362.46 ng/g dry sediment Phenanthrene)
(Fig. 5).
Organochlorine pesticides (HCB, lindane, heptachlor, aldrin, dieldrin,
endrin, DDE, DDD, DDT) had concentrations between 1.7 ng/L and 586.73
ng/L in water and 1.7 ng/g dry sediment and 339.21 ng/g dry sediment.
Chilia
arm
Sulina
Arm
-Tulc
ea
Sulina
Arm
-Cris
an
Sulina
Arm
-Sul
ina
Sf. Ghe
orgh
e Arm
-Mur
ighio
l
Mus
ura
Bay-N
Mus
ura
Bay-V
Mus
ura
Bay-S
Mus
ura
Bay-E
Sulina
disc
harg
e ar
ea-S
Sf. Ghe
orgh
e dis
char
ge a
rea-
N
Sf.Ghe
orgh
e dis
char
ge a
rea-
S
0
200
400
600
800
1000
1200
1400
1600
1800
2000
ng/L
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Floranthene
Pyrene
Benzo[a]antracene
Crysene
benzo(k)fluoranthene
Benzo[a]pyrene
Benzo(ghi)perilen
Dibenzo[a,h]anthracene
Indeno(1,2,3-c,d)piren
Fig. 5 - Concentration of polycyclic aromatic hydrocarbons in sediment samples collected
from Danube mouth and Black Sea area influenced by Danube
The highest levels were measured for HCB, lindane and aldrin both in
water and sediments (Fig. 6 and Fig. 7). In water maximum concentrations
were measured for HCB in fluvial – Sulina arm (334.63 ng/L at Crisan site and
360.14 ng/L at Tulcea site); for lindane în marine area E Musura Bay (586.73
ng/L) and in Sulina arm discharging area (488.59) ng/L and aldrin in marine
area (112.16 ng/L - 543.61 ng/L). In sediments maximum concentrations were
measured in fluvial area on Sfantul Gheorghe arm at Murighiol site (125.22
ng/g dry sediment HCB, 124.33 ng/g dry sediment lindane and 339.21 ng/g
dry sediment aldrin) and in marine discharging area for Sfântul Gheorghe arm
(88.21 ng/g dry sediment HCB, 144.08 ng/g dry sediment lindane and 188.66
ng/g dry sediment aldrin).
Chili
a A
rm
Sulin
a A
rm-T
ulc
ea
Sulin
a A
rm-S
ulin
a
Sf. G
heorg
he A
rm-M
urighio
lM
usu
ra B
ay-
VM
usu
ra B
ay-
SM
usu
ra B
ay-
E
Sulin
a d
isch
arg
e a
rea-S
Sf. G
heorg
he d
isch
arg
e a
rea-N
Sf.G
heorg
he d
isch
arg
e a
rea-S
0
50
100
150
200
250
300
350
400
ng
/g d
.s.
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Floranthene
Pyrene
Benzo[a]antracene
Crisen
benzo(k)fluoranthene
Benzo[a]pyrene
Benzo(ghi)perilen
Dibenzo[a,h]anthracene
Indeno(1,2,3-c,d)piren
Fig. 6 - Concentration of organochlorine pesticides in water samples collected from Danube
mouth and Black Sea area influenced by Danube
Fig. 7 - Concentration of organochlorine pesticides in sediment samples collected from
Danube mouth and Black Sea area influenced by Danube
According to Romanian legislation (Order 161/2006, Dec.351/2005)
there are some values that exceeded the quality standards both in water and
sediments. These values refer to lead, HCB, lindane, aldrin, phenanthrene,
anthracene, benzo[a]pyrene and benzo(ghi)perilene in water and cadmium,
naphthalene, phenanthrene, and antracen in sediments.
As for biota heavy metals concentrations varied between 0,01 μg/g
tissue and 28.89 μg/g tissue in mollusks whole body. The highest levels were
measured for copper (21.95 μg/g tissue for Rapana sampled in Portiţa site and
28.89 μg/g tissue for Rapana sampled in Zaton site). The others metals had
concentrations less than 4 μg/g tissue (Fig. 8). In fish muscle heavy metals
concentrations varied between 0.03 μg/g tissue and 2.19 μg/g tissue. The
highest concentrations were measured for copper and chromium (Fig. 9).
0 5 10 15 20 25 30 35
Mytilus - Sulina 30m
Mytilus-Mila9 30m
Mytilus-Portita 10m
Mytilus-Zaton 20m
Scapharca - Sulina 10m
Mya- Sf. Ghe. 30m
Mya - Perisor 20m
Rapana - Portita 10 m
Rapana - Zaton 10 m
ug/g tissue
Cu Cd Pb Ni Cr
Fig. 8 - Concentration of heavy metals in mollusk tissue collected from Black Sea
area influenced by Danube
Organochlorine pesticides found in biota were HCB, lindane,
heptachlor, aldrin, DDE, DDD and DDT. Their concentrations varied between
0.02 μg/g tissue and 2.42 μg/g tissue in mollusks whole body and 0.009 μg/g
tissue and 0.944 μg/g tissue in fish. The highest levels were measured in
mollusks (> 1 μg/g tissue for lindane, heptachlor, DDD and DDT) (Fig. 10). In
fish the biggest concentrations were measured for DDT: between 0.42 μg/g
tissue and 0.944 μg/g tissue, especially for marine species (Fig. 11).
0 2 4 6 8 10 12
Exos lucius (Sulina)
Cyprinus carpio (Sulina)
Carassius auratus (Sulina)
Abramis brama danubii (Sulina)
Silurus glanis(Sulina)
Perca fluviatilis (Sf.Ghe.)
Rutilus pigus (Sf. Ghe.)
Scardinius erytrophtalmus (Sf. Ghe.)
Salmo trutta labrax (Sulina)
Trachurus mediterraneus ponticus (Sf. Ghe.)
Neogobius melonostomus (Sf. Ghe.)
Sprattus sprattus (Sf. Ghe.)
Alosa caspia nordmanni (Sf. Ghe.)
Engraulis encrasicolus(Sf. Ghe.)
Merlangius merlangus euxinus(Sf. Ghe.)
ug/g tissueCu Cd Pb Ni Cr
Fig. 9 - Concentration of heavy metals in fish tissue collected from Danube mouth
and Black Sea area influenced by Danube
Fig. 10 - Concentration of organochlorine pesticides in mollusk tissue collected
from Black Sea area influenced by Danube
0 1 2 3 4 5 6 7
Mytilus - Sulina 30m
Mytilus-Mila9 30m
Mytilus-Portita 10m
Mytilus-Zaton 20m
Scapharca - Sulina 10m
Mya- Sf. Ghe. 30m
Mya - Perisor 20m
Rapana - Portita 10 m
Rapana - Zaton 10 m
ug/tesut
HCB Lindan Heptaclor Aldrin Dieldrin Endrin DDE DDD DDT
Fig. 11 - Concentration of organochlorine pesticides in fish tissue collected from
Danube mouth and Black Sea area influenced by Danube
Fig. 12 - Concentration of polycyclic aromatic hydrocarbons in fish tissue collected from
Danube mouth and Black Sea area influenced by Danube
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2
Exos lucius (Sulina)
Cyprinus carpio (Sulina)
Carassius auratus (Sulina)
Abramis brama danubii (Sulina)
Silurus glanis (Sulina)
Perca fluviatilis (Sf.Ghe.)
Rutilus pigus (Sf. Ghe.)
Scardinius erytrophtalmus (Sf. Ghe.)
Salmo trutta labrax (Sulina)
Trachurus mediterraneus ponticus (Sf. Ghe.)
Neogobius melonostomus (Sf. Ghe.)
Sprattus sprattus (Sf. Ghe.)
Alosa caspia nordmanni (Sf. Ghe.)
Engraulis encrasicolus(Sf. Ghe.)
Merlangius merlangus euxinus(Sf. Ghe.)
ug/g tissue
HCB Lindane Heptachlor Aldrin Dieldrin Endrin p,p'DDE p,p'DDD p,p'DDT
0 0,2 0,4 0,6 0,8 1 1,2
Exos lucius (Sulina)
Cyprinus carpio (Sulina)
Carassius auratus (Sulina)
Abramis brama danubii (Sulina)
Silurus glanis (Sulina)
Perca fluviatilis (Sf.Ghe.)
Rutilus pigus (Sf. Ghe.)
Scardinius erytrophtalmus (Sf. Ghe.)
Salmo trutta labrax (Sulina)
Trachurus mediterraneus ponticus (Sf. Ghe.)
Neogobius melonostomus (Sf. Ghe.)
Sprattus sprattus (Sf. Ghe.)
Alosa caspia nordmanni (Sf. Ghe.)
Engraulis encrasicolus(Sf. Ghe.)
Merlangius merlangus euxinus(Sf. Ghe.)
ug/g tissue
Naphthalene Acenaphthene Acenaphthylene Fluorene Phenanthrene
Floranthene Pyrene Crysene Anthracene Benzo[a]antracene
Fig. 13 - Concentration of polycyclic aromatic hydrocarbons in mollusk tissue collected from
Danube mouth and Black Sea area influenced by Danube
According to Romanian legislation (Order 97/7 Oct.2005; Order 23/1
Febr.2007, Normes/16 Dec.1998) there are some values that exceeded the
quality standards for biota. These values refer to lead in some marine fish
species, cadmium in many fresh water fish species, lindane, heptachlor and
DDT in molluscs whole body sampled from Mila 9 30m, Portiţa 10m and
Sfântul Gheorghe 30m sites, endrin in some fresh water fish species and DDT
in some marine fish species.
CONCLUSIONS
1. The distribution of heavy metals, organochlorine pesticides and
polycyclic aromatic hydrocarbons in abiotic elements underlined the
accumulation of pollutants in eastern and southern part of Musura Bay and in
discharging marin area of Sulina and Sfântul Gheorghe arms.
2. The bioaccumulation of heavy metals and organochlorine
pesticides is higher in mollusks than fish tissue, most probably because of
biotope mollusk’s “fidelity”.
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Mytilus-Portita 10m
Mytilus-Zaton 20m
Scapharca - Sulina 10m
Mya- Sf. Ghe. 30m
Mya - Perisor 20m
Rapana - Portita 10 m
ug/g tissueNaphthalene Acenaphthene Acenaphthylene Fluorene Phenanthrene
Floranthene Pyrene Crysene Anthracene Benzo[a]antracene
3. The bioaccumulation of polycyclic aromatic hydrocarbons is
less obviously. Their concentration in tissue is smaller than for the others
pollutants and the levels are similar in mollusks and fish.
BIBLIOGRAPHY :
***, 1998 - Norma igienico - sanitarǎ din 16 decembrie 1998 pentru alimente.
***, 2005 - Hotararea nr. 351/2005 privind aprobarea Programului de
eliminare treptata a evacuarilor, emisiilor şi pierderilor de substanţe
prioritar periculoase.
***, 2005 - Ordinul nr. 97 din 7 octombrie 2005 privind aprobarea Normei
sanitare veterinare şi pentru siguranţa alimentelor privind anumiţi
contaminanţi din alimentele de origine animală şi nonanimală.
***, 2006 - Ordinul ministrului mediului şi gospodǎririi apelor nr. 161/2006
pentru aprobarea Normativului privind clasificarea calitatii apelor de
suprafaţǎ în vederea stabilirii stǎrii ecologice a corpurilor de apǎ.
***, 2007 - Ordinul nr.23 din 1 februarie 2007 privind aprobarea Normei
sanitare veterinare şi pentru siguranţa alimentelor privind stabilirea
limitelor maxime de reziduuri de pesticide din conţinutul sau de pe
suprafaţa produselor alimentare de origine animală.