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Particulate pollution monitoring in the Elefsis Gulf: The role of mineral magnetic studies
Volume 15/Number 6/June 1984 Lie, U. (1968). A quantitative study of benthic infauna in Puget Sound, Washington, USA, in 1963-1964. Fiskdir. Skr. Serie Havunders~kelser, 14, 237-556. Longhurst, A. R. (1959). The sampling problem in benthic ecology. Proc. N. Z. ecol. Soc., 6, 8-12. Rees, H. L. (1983). Pollution investigations off thc north-east coast of
England: community structure, growth and production of benthic macrofauna. Mar. envir. Res., 9, 61-110. Warwick, R. M., George, C. L. and Davies, J. R. (1978). Annual macrofauna production in a Venus community. Estuar. cstl. mar. Sci., 7, 215-241.
0 0 2 5 - 3 2 6 X / 8 4 $3.oo+o.oo © 1984 Pergamon Press Lid.
Marine Pollution Bulletin, Vol. 15, No. 6, pp. 229 231, 1984 Printed in Great Britain
Particulate Pollution Monitoring in the Elefsis Gulf: The Role of Mineral Magnetic Studies FRANK OLDFIELD* and MICHAEL SCOULLOS t *Department of Geography, University of Liverpool, L69 3BX, U.K. tDepartment of Chemistry, University of Athens, 13 A Navarinou str. 106 80, Athens, Greece Measurements of 'quadrature' susceptibility (Xq) at low and high frequency on seabottom sediments of the Gulf of Elefsis supplement the results derived from the study of magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) (ScouHos et al., 1979) and make possible the distinction between the background soil erosional fraction and that of anthropogenic combustion origin. New devices speed up the on-site appraisal of the impact of discharges on marine sediment quality. Scoullos etal. (1979) suggested that in marine environments where ferrimagnetic iron oxides are important components of the discharge from industrial or urban complexes, particulate pollution monitoring may be carded out using simple non-destructive measurements. They showed that magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) could be used to characterize sediment samples and filtered particulates. Subsequent results summarized by Scoullos (1981) show that not only particulate iron but also zinc concentrations are positively correlated with magnetic concentrations in the water column. Studies elsewhere have pointed to a link between these magnetic properties and heavy metal concentrations in recent ombrotrophic peats (Oldfield et ai., 1981; Jones, in press), in storm water suspended solids from an urban catchment (Revitt et al., 1982) and in contemporary atmospheric dusts (Hunt et al., 1983). At the same time a growing number of authors (summarized in Hunt et al., 1983) have confirmed that several transition metals can be strongly enriched in the magnetic fraction of emissions from industrial and automotive sources. In their original paper, Scoullos et al. used coercivity of SIRM to characterize the magnetic mineral assemblages in the effluent from the major iron and steel works in the north-east corner of the Elefsis Gulf. The results indicated that the dominant magnetic mineral was a ferrimagnetic spinel, presumably 'magnetite'. Coercivity curves failed to
distinguish between anthropogenic magnetic present in the industrial discharge from the plant and the magnetite and/or maghemite washed into the sediments of the Gulf as a result of the erosion of surface soils rich in secondary magnetic minerals (cf. Le Borgne, 1955; Mullins, 1977; Longworth et al., 1979). This constituted a significant limitation to the approach proposed, save where, as in the Elefsis Gulf, the magnetic concentrations arising from industrial sources were extremely high. The present report summarizes additional magnetic measurements designed both to address the problem of differentiating soil from industrial discharge as well as to speed up the on-site appraisal of the impact of industrial discharge on sediment quality.
Magnetic Parameters and Measurements: Quadrature Susceptibility Mullins & Tite (1973) show that the out-of-phase, 'quadrature' component of the total low field susceptibility of soil samples results almost entirely from the presence of fine grained secondary magnetic minerals with crystal diameters around 0.03-0.05 /am. Such fine
Oi
Km
:!5i.::i:~'I::"''"., ' ." IrorT &" St;Bol .
...::-.:~!::::":".'~+::i:i:::
"::::~:?i:::.
::.....:..
..
""~-~::..
Fig. 1 The location of the sites of sediment coring in the Elefsis Gulf.
229
Marine Pollution Bulletin X
°o
2o
10-6
Xq %
4o
60
X
,5
,p o . . . .
30
,,
E_ 40
i
0
~
Xq %
,oo . . . .
,spo
?
,p
,,~
Core 2
°i 7
10-6
5p . . . .
Etefsis Gutf Greece
Core 3
80 Fig. 2 Down-core variations in total (low frequency) mass susceptibility (X) and in _quadrature susceptibility (Xo). X is plotted as 10 -6 GOe-~ cm 3 g-i, Xq as a percent of total susceptibility indicating the out-of-phase 'quadrature' component.
so
io
(,c)
~
tO
,o L
,oo
,
,
('~)
0 t
A
20
10 20
C
~30
30-
J
40
40 E
5(1
2A
50
2B
60
S
Elefsis Gu[f: whole core susceptibility Fig. 3 Whole-core plots of volume susceptibility (r) for the cores 2A and 2B (uncalibrated units).
crystals, whether of magnetite or maghemite, are very rarely present either in common geologic parent materials or in anthropogenic, combustion derived particulates, and they are almost exclusively restricted to the weathered part of soil profiles (Oldfield & Bartington, 1982). Quadrature susceptibility (Xq) can be measured using the Bartington Susceptibility meter coupled to a dual frequency sensor. At low frequency (1 kHz) total susceptibility is measured but at high frequency (10 kHz) only the in-phase component is recorded. The difference between the two, properly termed the frequency dependent susceptibility, correlates with the out-of-phase quadrature component (Xq) here expressed as a percent of total (i.e. low frequency) susceptibility (XLF). Quadrature susceptibility has been determined by a dual frequency Bartington Instrument sensor designed to accommodate samples of 10 ml volume.
Volume Susceptibility Measurements on Whole Cores The recently developed whole-core sensor attached to the Bartington Instruments susceptibility meter has been used to measure the volume susceptibility of two sediment cores (2A and 2B) taken close to Station 2 (Scoullos, 1979) 230
in the eastern part of the Gulf (see Fig. 1). The cores were obtained using a Mackereth (1969) minicorer. The sensor can accommodate cores of up to 7.2 cm external diameter either horizontally or vertically. Cores retaining a well preserved mud-water interface can thus be scanned without disturbance.
Results Figure 2 plots total (low frequency) mass susceptibility (X) alongside quadrature susceptibility (Xq) for two cores respectively 1.8 km (core 2) and 3.2 km (core 3) from the Elefsis iron and steel works. In both cases, the particulate discharge has given rise to a sharp increase in total susceptibility in the top 15-18 cm of the core. This increase corresponds with a steep decline in the percentage quadrature component, i.e. that proportion contributed by fine viscous grains derived from eroding soil. Limestone soils from Greece have Xq values between 10 and 15°70 of total susceptibility and this figure compares well with the values recorded in both cores below the industrial horizon. The proportional decline above this is steepest in core 2, as would be expected from its location and the higher levels of particulate discharge received.
Volume 15/Number 6/June 1984
Figure 3 shows the volume susceptibility plots for the 2A and 2B cores. The closely parallel traces both show nearsurface peaks reflecting the high industrial inputs at the site. Volume susceptibility scans of this kind can be carried out on site within minutes of core retrieval and Without any subsampling or sediment disturbance. Although values for the topmost 4 cm are depressed by declining bulk density and the proximity of overlying water, calibration can readily be achieved by means of a limited number of mass specific measurements. Conclusions The development of the dual frequency sensor and core scan loop attachments to the Bartington Instruments susceptibility meter now make possible the kind of magnetic monitoring envisaged in Scoullos et al. (1979) on a more rapid and confidently discriminating basis. Rapid scans of short cores can provide a basis for determining the recent spatial distribution patterns of particulate output from major sources such as the Elefsis iron and steel works. Quadrature susceptibility measurement on single samples can be used to distinguish industrial particulates from the 'background' erosional input to the Gulf of Elefsis resulting from soil erosion. This work was carried out in the frame of a project supported by the E.C. Environmental Research Programme and the IOC/UNESCO.
Hunt, A., Oldfield, F. & Jones, J. M. (1984). Magnetic measurements and heavy metals in atmospheric particulates of anthropogenic origin. Water, Air, Soil Pollut., in prcss. Jones, J. M. (in press). Heavy metal magnetic mineral linkage in ombrotrophic peat. J. appl. EcoL Le Borgne, E. (1955). Susceptibilit~ magnrtique anormale du sol superficiel. Ann. Geophys., 11, 399-419. Longworth, G., Becker, L. W., Thompson, R., Oldfield, F., Dearing, J. A. & Rummery, T. A. (1979). M0ssbauer effects and magnetic studies of secondary iron oxides in soils. J. Soil Sci., 30, 93-110. Mackereth, F. J. H. (1969). A short core sampler for sub-aqueous deposits. Limnol. Oceanogr., 14, 145-151. Mullins, C. E. (1977). Magnetic susceptibility of soil and its significance in soil science: a review. J. Soil Sci., 30, 93-110. Mullins, C. E. & Tite, M. S. (1973). Magnetic viscosity, quadrature susceptibility and frequency dependence of susceptibility in singledomain assemblies of magnetite and maghemite. J. geophys. Rec., 78, 804-809. Oldfield, F. & Bartington, G. W. (1982). Sediment source identification: high and low frequency susceptibility sensors. U.K. Geophysical Assembly Abstracts. Geophys. J. R. Astr. Soc., 293. Oldfield, F., Tolonen, K. & Thompson, R. (1981). History of particulate atmospheric pollution from magnetic measurements in dated Finnish peat profiles. Ambio, 10, 185-188. Revitt, D. M., Bryan-Ellis, J. & Oldfield, F. (1981). Variations in heavy metals of stormwater pollution research. In Urban Storm Drainage, Proceedings of the II Intern. Conference on Urban Storm Drainage (B. C. Yen, ed.), pp. 49-58. Pentech Press, New York. Scoullos, M. (1979). Chemical Studies of the Gulf of Elefsis. Ph.D. Thesis, University of Liverpool. Scoullos, M. (1981). Zinc in seawater and sediments. Water, Air Soil Pollut., 16, 187-207. , Scoullos, M., Oldfield, F. & Thompson, R. (1979). Magnetic monitoring of marine particulate pollution in the Elefsis Gulf, Greece. Mar. Pollut. Bull., 10, 287-291.
OO25-326X/84 $3.00+o.1)o PergamonPressLtd.
MarinePollutionBulletin.Vol. 15, No. 6, pp. 231-233, 1984 Printedin Great Britain
Estimates of Oil Concentrations in Aegean Waters Water samples for the analysis of dissolved/dispersed hydrocarbons were collected from the depths of 1 and 10 m at six stations in Saronikos Bay in May 1980, September 1980 and March 1981. Water samples were also collected from 11 stations at the depth of 1 m in the eastern Aegean Sea in March 1980 on board the hydrographic ship of the Greek Navy, "Nautilus'. The sampling locations are shown in Fig. 1. The sampling bottle used was lowered closed and opened only at the collection depth using a device designed at the University of Gothenburg, Department of Analytical Chemistry (Fig. 2). The same 11. wide-necked brown glass bottle was used for sampling and extraction, avoiding transfer. The water samples were extracted with 10 ml of n-hexane (fluorescence grade) by stirring for 1 h on a magnetic stirrer according to the method of Anhoff et al. (1974). The emission intensity of the hexane extract was measured in an 1 cm quartz cell using a Perkin-Elmer MPF-44A fluorescence spectrophotometer. The wavelengths were those suggested for the IGOSS project,
TABLE 1 Concentrations of aromatic hydrocarbons in Kuwait crude oil equivalents at each station and depth. Values for Stations 1-6 represent averages from three cruises
Station No. l
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Depth (m)
Concentration (/Jg 1-1)
1 10 1 l0 1 10 1 10 1 10 1 10
4.1 1.6 3.2 2.4 5.3 3.2 3.4 2.1 3.5 2.5 5.6 2.3 9.9 9.2 13.7 7.9 11.1 10.6 4.0 4.5 2.9 7.4 5.5
231
England: community structure, growth and production of benthic macrofauna. Mar. envir. Res., 9, 61-110. Warwick, R. M., George, C. L. and Davies, J. R. (1978). Annual macrofauna production in a Venus community. Estuar. cstl. mar. Sci., 7, 215-241.
0 0 2 5 - 3 2 6 X / 8 4 $3.oo+o.oo © 1984 Pergamon Press Lid.
Marine Pollution Bulletin, Vol. 15, No. 6, pp. 229 231, 1984 Printed in Great Britain
Particulate Pollution Monitoring in the Elefsis Gulf: The Role of Mineral Magnetic Studies FRANK OLDFIELD* and MICHAEL SCOULLOS t *Department of Geography, University of Liverpool, L69 3BX, U.K. tDepartment of Chemistry, University of Athens, 13 A Navarinou str. 106 80, Athens, Greece Measurements of 'quadrature' susceptibility (Xq) at low and high frequency on seabottom sediments of the Gulf of Elefsis supplement the results derived from the study of magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) (ScouHos et al., 1979) and make possible the distinction between the background soil erosional fraction and that of anthropogenic combustion origin. New devices speed up the on-site appraisal of the impact of discharges on marine sediment quality. Scoullos etal. (1979) suggested that in marine environments where ferrimagnetic iron oxides are important components of the discharge from industrial or urban complexes, particulate pollution monitoring may be carded out using simple non-destructive measurements. They showed that magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) could be used to characterize sediment samples and filtered particulates. Subsequent results summarized by Scoullos (1981) show that not only particulate iron but also zinc concentrations are positively correlated with magnetic concentrations in the water column. Studies elsewhere have pointed to a link between these magnetic properties and heavy metal concentrations in recent ombrotrophic peats (Oldfield et ai., 1981; Jones, in press), in storm water suspended solids from an urban catchment (Revitt et al., 1982) and in contemporary atmospheric dusts (Hunt et al., 1983). At the same time a growing number of authors (summarized in Hunt et al., 1983) have confirmed that several transition metals can be strongly enriched in the magnetic fraction of emissions from industrial and automotive sources. In their original paper, Scoullos et al. used coercivity of SIRM to characterize the magnetic mineral assemblages in the effluent from the major iron and steel works in the north-east corner of the Elefsis Gulf. The results indicated that the dominant magnetic mineral was a ferrimagnetic spinel, presumably 'magnetite'. Coercivity curves failed to
distinguish between anthropogenic magnetic present in the industrial discharge from the plant and the magnetite and/or maghemite washed into the sediments of the Gulf as a result of the erosion of surface soils rich in secondary magnetic minerals (cf. Le Borgne, 1955; Mullins, 1977; Longworth et al., 1979). This constituted a significant limitation to the approach proposed, save where, as in the Elefsis Gulf, the magnetic concentrations arising from industrial sources were extremely high. The present report summarizes additional magnetic measurements designed both to address the problem of differentiating soil from industrial discharge as well as to speed up the on-site appraisal of the impact of industrial discharge on sediment quality.
Magnetic Parameters and Measurements: Quadrature Susceptibility Mullins & Tite (1973) show that the out-of-phase, 'quadrature' component of the total low field susceptibility of soil samples results almost entirely from the presence of fine grained secondary magnetic minerals with crystal diameters around 0.03-0.05 /am. Such fine
Oi
Km
:!5i.::i:~'I::"''"., ' ." IrorT &" St;Bol .
...::-.:~!::::":".'~+::i:i:::
"::::~:?i:::.
::.....:..
..
""~-~::..
Fig. 1 The location of the sites of sediment coring in the Elefsis Gulf.
229
Marine Pollution Bulletin X
°o
2o
10-6
Xq %
4o
60
X
,5
,p o . . . .
30
,,
E_ 40
i
0
~
Xq %
,oo . . . .
,spo
?
,p
,,~
Core 2
°i 7
10-6
5p . . . .
Etefsis Gutf Greece
Core 3
80 Fig. 2 Down-core variations in total (low frequency) mass susceptibility (X) and in _quadrature susceptibility (Xo). X is plotted as 10 -6 GOe-~ cm 3 g-i, Xq as a percent of total susceptibility indicating the out-of-phase 'quadrature' component.
so
io
(,c)
~
tO
,o L
,oo
,
,
('~)
0 t
A
20
10 20
C
~30
30-
J
40
40 E
5(1
2A
50
2B
60
S
Elefsis Gu[f: whole core susceptibility Fig. 3 Whole-core plots of volume susceptibility (r) for the cores 2A and 2B (uncalibrated units).
crystals, whether of magnetite or maghemite, are very rarely present either in common geologic parent materials or in anthropogenic, combustion derived particulates, and they are almost exclusively restricted to the weathered part of soil profiles (Oldfield & Bartington, 1982). Quadrature susceptibility (Xq) can be measured using the Bartington Susceptibility meter coupled to a dual frequency sensor. At low frequency (1 kHz) total susceptibility is measured but at high frequency (10 kHz) only the in-phase component is recorded. The difference between the two, properly termed the frequency dependent susceptibility, correlates with the out-of-phase quadrature component (Xq) here expressed as a percent of total (i.e. low frequency) susceptibility (XLF). Quadrature susceptibility has been determined by a dual frequency Bartington Instrument sensor designed to accommodate samples of 10 ml volume.
Volume Susceptibility Measurements on Whole Cores The recently developed whole-core sensor attached to the Bartington Instruments susceptibility meter has been used to measure the volume susceptibility of two sediment cores (2A and 2B) taken close to Station 2 (Scoullos, 1979) 230
in the eastern part of the Gulf (see Fig. 1). The cores were obtained using a Mackereth (1969) minicorer. The sensor can accommodate cores of up to 7.2 cm external diameter either horizontally or vertically. Cores retaining a well preserved mud-water interface can thus be scanned without disturbance.
Results Figure 2 plots total (low frequency) mass susceptibility (X) alongside quadrature susceptibility (Xq) for two cores respectively 1.8 km (core 2) and 3.2 km (core 3) from the Elefsis iron and steel works. In both cases, the particulate discharge has given rise to a sharp increase in total susceptibility in the top 15-18 cm of the core. This increase corresponds with a steep decline in the percentage quadrature component, i.e. that proportion contributed by fine viscous grains derived from eroding soil. Limestone soils from Greece have Xq values between 10 and 15°70 of total susceptibility and this figure compares well with the values recorded in both cores below the industrial horizon. The proportional decline above this is steepest in core 2, as would be expected from its location and the higher levels of particulate discharge received.
Volume 15/Number 6/June 1984
Figure 3 shows the volume susceptibility plots for the 2A and 2B cores. The closely parallel traces both show nearsurface peaks reflecting the high industrial inputs at the site. Volume susceptibility scans of this kind can be carried out on site within minutes of core retrieval and Without any subsampling or sediment disturbance. Although values for the topmost 4 cm are depressed by declining bulk density and the proximity of overlying water, calibration can readily be achieved by means of a limited number of mass specific measurements. Conclusions The development of the dual frequency sensor and core scan loop attachments to the Bartington Instruments susceptibility meter now make possible the kind of magnetic monitoring envisaged in Scoullos et al. (1979) on a more rapid and confidently discriminating basis. Rapid scans of short cores can provide a basis for determining the recent spatial distribution patterns of particulate output from major sources such as the Elefsis iron and steel works. Quadrature susceptibility measurement on single samples can be used to distinguish industrial particulates from the 'background' erosional input to the Gulf of Elefsis resulting from soil erosion. This work was carried out in the frame of a project supported by the E.C. Environmental Research Programme and the IOC/UNESCO.
Hunt, A., Oldfield, F. & Jones, J. M. (1984). Magnetic measurements and heavy metals in atmospheric particulates of anthropogenic origin. Water, Air, Soil Pollut., in prcss. Jones, J. M. (in press). Heavy metal magnetic mineral linkage in ombrotrophic peat. J. appl. EcoL Le Borgne, E. (1955). Susceptibilit~ magnrtique anormale du sol superficiel. Ann. Geophys., 11, 399-419. Longworth, G., Becker, L. W., Thompson, R., Oldfield, F., Dearing, J. A. & Rummery, T. A. (1979). M0ssbauer effects and magnetic studies of secondary iron oxides in soils. J. Soil Sci., 30, 93-110. Mackereth, F. J. H. (1969). A short core sampler for sub-aqueous deposits. Limnol. Oceanogr., 14, 145-151. Mullins, C. E. (1977). Magnetic susceptibility of soil and its significance in soil science: a review. J. Soil Sci., 30, 93-110. Mullins, C. E. & Tite, M. S. (1973). Magnetic viscosity, quadrature susceptibility and frequency dependence of susceptibility in singledomain assemblies of magnetite and maghemite. J. geophys. Rec., 78, 804-809. Oldfield, F. & Bartington, G. W. (1982). Sediment source identification: high and low frequency susceptibility sensors. U.K. Geophysical Assembly Abstracts. Geophys. J. R. Astr. Soc., 293. Oldfield, F., Tolonen, K. & Thompson, R. (1981). History of particulate atmospheric pollution from magnetic measurements in dated Finnish peat profiles. Ambio, 10, 185-188. Revitt, D. M., Bryan-Ellis, J. & Oldfield, F. (1981). Variations in heavy metals of stormwater pollution research. In Urban Storm Drainage, Proceedings of the II Intern. Conference on Urban Storm Drainage (B. C. Yen, ed.), pp. 49-58. Pentech Press, New York. Scoullos, M. (1979). Chemical Studies of the Gulf of Elefsis. Ph.D. Thesis, University of Liverpool. Scoullos, M. (1981). Zinc in seawater and sediments. Water, Air Soil Pollut., 16, 187-207. , Scoullos, M., Oldfield, F. & Thompson, R. (1979). Magnetic monitoring of marine particulate pollution in the Elefsis Gulf, Greece. Mar. Pollut. Bull., 10, 287-291.
OO25-326X/84 $3.00+o.1)o PergamonPressLtd.
MarinePollutionBulletin.Vol. 15, No. 6, pp. 231-233, 1984 Printedin Great Britain
Estimates of Oil Concentrations in Aegean Waters Water samples for the analysis of dissolved/dispersed hydrocarbons were collected from the depths of 1 and 10 m at six stations in Saronikos Bay in May 1980, September 1980 and March 1981. Water samples were also collected from 11 stations at the depth of 1 m in the eastern Aegean Sea in March 1980 on board the hydrographic ship of the Greek Navy, "Nautilus'. The sampling locations are shown in Fig. 1. The sampling bottle used was lowered closed and opened only at the collection depth using a device designed at the University of Gothenburg, Department of Analytical Chemistry (Fig. 2). The same 11. wide-necked brown glass bottle was used for sampling and extraction, avoiding transfer. The water samples were extracted with 10 ml of n-hexane (fluorescence grade) by stirring for 1 h on a magnetic stirrer according to the method of Anhoff et al. (1974). The emission intensity of the hexane extract was measured in an 1 cm quartz cell using a Perkin-Elmer MPF-44A fluorescence spectrophotometer. The wavelengths were those suggested for the IGOSS project,
TABLE 1 Concentrations of aromatic hydrocarbons in Kuwait crude oil equivalents at each station and depth. Values for Stations 1-6 represent averages from three cruises
Station No. l
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Depth (m)
Concentration (/Jg 1-1)
1 10 1 l0 1 10 1 10 1 10 1 10
4.1 1.6 3.2 2.4 5.3 3.2 3.4 2.1 3.5 2.5 5.6 2.3 9.9 9.2 13.7 7.9 11.1 10.6 4.0 4.5 2.9 7.4 5.5
231