hydrocarbon contamination in cartagena bay, colombia

4
Baseline Edited by Bruce J. Richardson The objective of BASELINE is to publish short communications on different aspects of pollution of the marine environment. Only those papers which clearly identify the quality of the data will be considered for publication. Contributors to Baseline should refer to ‘Baseline—The New Format and Content’ (Mar. Pollut. Bull. 42, 703–704). Hydrocarbon contamination in Cartagena Bay, Colombia C.H. Parga-Lozano, A.J. Marrugo-Gonz alez, R. Fern andez-Maestre * Facultad de Ciencias Qu imicas y Farmac euticas, Universidad de Cartagena, Zaragocilla, AA 10618 Cartagena, Colombia Abstract This study deals with the levels of aromatic and aliphatic hydrocarbon quantification in sediments and organisms in Cartagena Bay (Colombia), 1996–1997. Sediments (14 stations) and bivalves (2 stations) were monitored at different times of the year. Areas with high values were in the north with concentrations above 100 lg/g with a maximum of 1415 lg/g. Areas with low values were located toward the south, near the outlet of the Canal del Dique and Bar u Island, with values below 10 lg/g. In other areas concentrations were between 50 and 100 lg/g. A decrease in sediment concentrations of hydrocarbons has occurred since 1983, but levels in some sectors are still similar to those in polluted areas. Organisms have relatively low values (8–30 lg/g for bivalves, and 10– 40 lg/g for fish). Ó 2002 Elsevier Science Ltd. All rights reserved. Keywords: Hydrocarbons; Pollution monitoring; Cartagena Bay; Colombia; Crassostrea rhizoporae 1. Introduction Cartagena Bay is an important tourist attraction in Colombia and is an important port and trading area. This body of water has been exposed to contamination from metals, organic matter, garbage and hydrocarbons as the city has grown. Pollutants come from the Canal del Dique, the industrial area of Mamonal, and from the sewer system (Pagliardini et al., 1982). Cartagena Bay is located in the Caribbean Sea, be- tween 10°25 0 and 10°16 0 N and 75°30 0 and 75°36 0 W in the department of Bol ıvar (Colombia). It is 12 km 6 km, with an area of 72 km 2 . Its two entrances into the Caribbean Sea are restricted by the islands of Tierra- bomba and Bar u. It receives freshwater from the Canal del Dique, which also has sediments, and the area has been described as an estuary (Pagliardini et al., 1982). 2. Methodology Methods were taken from UNESCO manuals (1986), reference method number 11, used in intercalibration by the International Atomic Energy Agency (IAEA), In- ternational Oceanographic Commission (IOC), United Nations Environmental Programme (UNEP) and the Centro de Investigaciones Oceanogr aficas e hidrogr afi- cas de la Armada Nacional de Colombia (CIOH) (Armada, 1993). This methodology was adapted to the Caribbean region to apply it in the CARIPOL pro- gramme (Programa de las Naciones Unidas para el Gran Caribe) and it is being applied to later projects where levels of hydrocarbons in sediments and organ- isms are studied in this region (United Nations Envi- ronmental Programme, 1992). Sampling was carried out www.elsevier.com/locate/marpolbul Marine Pollution Bulletin 44 (2002) 71–81 * Corresponding author. E-mail address: [email protected] (R. Fern andez- Maestre).

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Page 1: Hydrocarbon contamination in Cartagena Bay, Colombia

Baseline

Edited by Bruce J. Richardson

The objective of BASELINE is to publish short communications on different aspects of pollution of the marineenvironment. Only those papers which clearly identify the quality of the data will be considered for publication.Contributors to Baseline should refer to ‘Baseline—The New Format and Content’ (Mar. Pollut. Bull. 42, 703–704).

Hydrocarbon contamination in Cartagena Bay, Colombia

C.H. Parga-Lozano, A.J. Marrugo-Gonz�aalez, R. Fern�aandez-Maestre*

Facultad de Ciencias Qu�iimicas y Farmac�eeuticas, Universidad de Cartagena, Zaragocilla, AA 10618 Cartagena, Colombia

Abstract

This study deals with the levels of aromatic and aliphatic hydrocarbon quantification in sediments and organisms in Cartagena

Bay (Colombia), 1996–1997. Sediments (14 stations) and bivalves (2 stations) were monitored at different times of the year. Areas

with high values were in the north with concentrations above 100 lg/g with a maximum of 1415 lg/g. Areas with low values werelocated toward the south, near the outlet of the Canal del Dique and Bar�uu Island, with values below 10 lg/g. In other areasconcentrations were between 50 and 100 lg/g. A decrease in sediment concentrations of hydrocarbons has occurred since 1983, butlevels in some sectors are still similar to those in polluted areas. Organisms have relatively low values (8–30 lg/g for bivalves, and 10–40 lg/g for fish). � 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Hydrocarbons; Pollution monitoring; Cartagena Bay; Colombia; Crassostrea rhizoporae

1. Introduction

Cartagena Bay is an important tourist attraction inColombia and is an important port and trading area.This body of water has been exposed to contaminationfrom metals, organic matter, garbage and hydrocarbonsas the city has grown. Pollutants come from the Canaldel Dique, the industrial area of Mamonal, and from thesewer system (Pagliardini et al., 1982).Cartagena Bay is located in the Caribbean Sea, be-

tween 10�250 and 10�160 N and 75�300 and 75�360 W inthe department of Bol�ııvar (Colombia). It is 12 km� 6km, with an area of 72 km2. Its two entrances into theCaribbean Sea are restricted by the islands of Tierra-bomba and Bar�uu. It receives freshwater from the Canal

del Dique, which also has sediments, and the area hasbeen described as an estuary (Pagliardini et al., 1982).

2. Methodology

Methods were taken from UNESCO manuals (1986),reference method number 11, used in intercalibration bythe International Atomic Energy Agency (IAEA), In-ternational Oceanographic Commission (IOC), UnitedNations Environmental Programme (UNEP) and theCentro de Investigaciones Oceanogr�aaficas e hidrogr�aafi-cas de la Armada Nacional de Colombia (CIOH)(Armada, 1993). This methodology was adapted tothe Caribbean region to apply it in the CARIPOL pro-gramme (Programa de las Naciones Unidas para elGran Caribe) and it is being applied to later projectswhere levels of hydrocarbons in sediments and organ-isms are studied in this region (United Nations Envi-ronmental Programme, 1992). Sampling was carried out

www.elsevier.com/locate/marpolbul

Marine Pollution Bulletin 44 (2002) 71–81

*Corresponding author.

E-mail address: [email protected] (R. Fern�aandez-

Maestre).

Page 2: Hydrocarbon contamination in Cartagena Bay, Colombia

in four different times of the year to take into accountthe rainy and dry seasons.The following parameters were studied:

• Aliphatic and aromatic hydrocarbons in sediments.• Aliphatic and aromatic hydrocarbons in oysters(Crassostrea rhizophorae), living in the red mangroverhizophorae mangle, which is abundant in the area.

• Aliphatic and aromatic hydrocarbons in native fish ofthe bay, Mugil incilis, Lutjanus purpureus, Eugerressp., and Caraux sp.

2.1. Sampling, preservation, separation and analysis

All oysters, fish and sediment samples were coveredwith aluminium paper, preserved in ice, and placed inpolyethylene bags. In the laboratory and they were keptfrozen at )4 �C until analysis (Armada, 1993). Fish wereobtained from fishermen, and oysters were collectedfrom red mangrove roots.Oyster and fish samples were defrosted. From 6 to 8 g

of samples were weighed, digested in 15 ml of NaOH 6N for 24 h at 30 �C, extracted with 60 ml of ethylic ether(total volume) and separated by column chromato-graphy with 8 g of s�iilica gel and 8 g of deactivated alu-mina. The following fractions were obtained:Fraction 1: 20 ml of hexane. Aliphatics.Fraction 2: 20 ml of hexane–dichloromethane 9:1.Monoaromatics.Fraction 3: 40 ml of hexane–dichloromethane 8:2.Polyaromatics.

Fraction 1 was analysed by gas chromatography. Frac-tions 2 and 3 were analysed by fluorometry.Sediments were gathered with a Berthois cone. Wet

samples were dried off at 50 �C for 48 h. 30 g of drysample were digested in 100 ml methanol and 3 g of

KOH for 1.5 h, extracted with 50 ml of hexane (totalvolume) and separated by column chromatography with1.5 g of activated alumina at 102 �C. The followingfractions were obtained:Fraction 1: 4 ml of hexane. Aliphatics.Fraction 2: 4 ml of hexane. Aliphatics.Fraction 3: 4 ml of hexane–dichloromethane 7:3.Monoaromatics.Fraction 4: 4 ml of dichloromethane. Polyaromatics.

Fractions 1 and 2 were analysed by gas chromato-graphy. Fractions 2 and 3 were analysed by fluorometry.

2.2. Instrumental conditions

Spectrofluorometer (SHIMADZU RF-510): Excita-tion wavelength: 310 nm. Emission wavelength: 360 nm.Sensibility: 9.7. Gas chromatographer (HEWLETT–PACKARD 5890 SERIES II BONUS) with an FIDdetector. Injection system: SPLITLESS. Initial tem-perature: 80 �C. Initial time: 1 min. Rate: 6 �C/min.Final temperature: 270 �C. Final time: 10 min. Injectiontemperature: 250 �C. Detector temperature: 290 �C. Gasflow: 1.5 ml/min. Gas speed: 28.5 cm/s. Column: Cap-illary HP-5 of melt Silica, 30 m� 0:32 mm. Carrier gas:N2 99.99%. Auxiliary gas: N2 (30 ml/min). Detectorgases: dried air, 20% of oxygen in nitrogen (300 ml/min flow) and hydrogen 99.999% (30 ml/min flow).Attenuation: 0.A calibration curve with a chrysene standard was

used to calculate the aromatic concentrations. For re-solved n-alkanes a standard containing a homologousseries from C10 up to C32 was used. For non-resolvedaliphatics (UCM), the 200 ppm standard solution areaof C26 was used. An internal standard of C26 was used tocalculate the percentage of recovery.

Table 1

Total hydrocarbons in sediments and organisms

Station Number of data Range (lg/g) Average�S.D. Relative S.D.

1 3 2.4–13.5 6� 5 83

2 3 4.2–34.4 14� 14 99

3 1 34.7

4 4 4–30.3 13� 12 90

8 1 13.9

9 4 142.3–1415.4 544� 520 96

10 3 7.2–57.8 31� 21 67

12 3 6.1–25.6 10� 8 79

13 4 3.7–40.7 22� 14 53

15 3 3.9–50.4 22� 21 95

16 3 2.2–62.2 31� 25 79

18 2 4.2–31.3 18� 14 76

22 4 4.4–177.6 73� 67 91

23 3 25.8–1368.9 697� 671 96

Fish 5 13.3–37.1 22� 11 20

Oysters Coquito-Bar�uu 2 6.1–11.7 9� 3 31

Oysters Ca~nno del Oro 3 17.6–35.8 28� 8 27

Results in dry base. Recovery percentage: sediments 55.2% and organisms 83.7%.

72 Baseline / Marine Pollution Bulletin 44 (2002) 71–81

Page 3: Hydrocarbon contamination in Cartagena Bay, Colombia

3. Results and discussion

The results of total hydrocarbons in sediments andorganisms are shown in Table 1. The results of the de-termination of their origin are given in Fig. 2.

3.1. Hydrocarbons in sediments

Areas with high concentrations were found toward thenorth (internal bay) and southeast with average valuesbetween 73 and 700 lg/g, and a maximum of 1415 lg/g.In these areas, oil and port activities, and manipulationof fuels are continuous. Other areas have medium con-centrations ranging from 20 to 50 lg/g, with levels risingduring the year as a result of the currents that carry thehydrocarbons from areas of higher concentrations.These areas are located near the island of Tierrabombaand the two entrances of the bay (Bocachica and Boca-grande) (Fig. 1). There are areas with lower concentra-tion toward the south and southeast of the bay, rangingfrom 5 to 10 lg/g in the Canal del Dique, its outlet andnear Bar�uu. These values are lower because of the effects ofcurrents through Bocachica and because of less nauticaltraffic. Fig. 2 shows the petrogenic character of thesehydrocarbons, with predominance of odd to even num-bers of atoms of carbon n-alkanes, a pristane/phitaneratio close to 1, and complete series from C17 to C32 andunresolved complex mixtures in the chromatograms.

3.2. Hydrocarbons in organisms

Hydrocarbon concentrations in bivalves (oysters) wererelatively low (as they are in sediment concentrations in

Fig. 1. Distribution of hydrocarbon concentrations and stations in Cartagene Bay.

Fig. 2. Chromatogram, aliphatic hydrocarbons in sediments station 16.

Pr/Ph: pristane/phitane ratio; IPC: ratio of odd number of n-alkanes/

even number of n-alkanes, of atoms of carbon.

Fig. 3. Chromatogram, aliphatic hydrocarbons in C. rhizophorae,

Ca~nno del Oro, Pr/Ph: pristane/phitane ratio; IPC: ratio odd number ofn-alkanes/even number of n-alkanes, of atoms of carbon.

Baseline / Marine Pollution Bulletin 44 (2002) 71–81 73

Page 4: Hydrocarbon contamination in Cartagena Bay, Colombia

the areas where they were gathered) and, as in fish, thepetrogenic influence was high (Table 1 and Fig. 3).Fish are not good indicators of contamination be-

cause of the distances they travel but they give an ideaabout the general state of the bay. The levels in fish werelow (Table 1), similar to those obtained in only mildlypolluted places. Petrogenic influences are noticed with apredominance of odd number to even numbers of atomsof carbon n-alkanes, a pristane/phitane ratio near 1 andunresolved complex mixtures in the chromatograms.

4. Conclusions

The only previous study in 1983 (Garay, 1983) andthis one show that contamination has diminished in thelast few years. This is due to the coordinated action ofthe environmental authorities of the city, the com-munity, the industries of Mamonal and the shipping

industry (Fig. 4). However, high hydrocarbon concen-trations in sediments are found toward the north andsoutheast, some of which are as high as those seen insome of the most contaminated sites in the world.Hydrocarbons continue to be released though on asmaller scale: while 3000 barrels were spilled in 1983only 42 barrels were spilled in 1996 (Capitan�ııa delPuerto, 1996). It is clear that, in spite of the fallinglevels of hydrocarbons, the petrogenic character of thecontaminants shows human influence. We suggest car-rying out a study in sites with higher hydrocarboncontamination of the bay but with different layers ofsediments.

Acknowledgements

The authors wish to thank the IAEA for the stan-dards and the CIOH for the technical support.

References

Armada Nacional de Colombia, 1993. Manual de T�eecnicas Anal�ııticas

de Par�aametros Fisicoqu�ıımicos de contaminantes Marinos, Di-

recci�oon General Mar�iitima, C.C.O., Fundaci�oon Mamonal, CIOH,

Cartagena D.T. y C.

Capitan�ııa de puerto (Cartagena), 1996. Informe 1989–1996.

Garay, J., 1983. Concentraci�oon y Composici�oon de Hidrocarburos

Derivados del Petr�ooleo en Aguas Sedimentos y Peces de la Bah�ııa de

Cartagena. Bolet�ıın Cient�ııfico del CIOH 6, 41–62.

Pagliardini, J., G�oomez, M., Gutierrez, H., Zapata, S., Jurado, A.,

Garay, J., Vernette, G., 1982. S�ııntesis del Proyecto Bah�ııa de

Cartagena. Bolet�ıın Cientifico del CIOH 4, 49–110.

United Nations Environmental Programme, 1992. Determination of

petroleum hydrocarbons in sediments. Reference methods for

Marine Pollution Studies.

Subcellular distribution of heavy metals in livers and kidneys ofStenella coeruleoalba and Tursiops truncatus

from the Mediterranean Sea

M.M. Storelli, G.O. Marcotrigiano*

Pharmacological-Biological Department, Chemistry and Biochemistry Section, Veterinary Medicine Faculty,

University of Bari, Strada prov. le per Casamassima, km 3, 70010 Valenzano, Bari, Italy

Metallothioneins (MTs) are an important class of cy-tosolic proteins characterised by low molecular weight, a

high cysteine content (>30%), and remarkable heatstability. They were discovered in the equine renal cortexby Margoshes and Vallee (1957) as a cadmium bindingprotein. Although the role of MTs in living organisms isnot completely understood, it is now known that theinduction of MT is closely related to exposure to metals,and therefore one of the possible roles of MTs could

0025-326X/02/$ - see front matter � 2002 Elsevier Science Ltd. All rights reserved.

PII: S0025-326X(01 )00201 -6

Fig. 4. Comparison of hydrocarbon concentrations in 1983 and 1996–

1997 in Cartagena Bay.

* Corresponding author. Tel.: +39-080-5443866-7; fax: +39-080-

5443863.

E-mail address: [email protected] (G.O. Mar-

cotrigiano).

74 Baseline / Marine Pollution Bulletin 44 (2002) 71–81