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Delfino CONTENTS Lead in Surface Waters ...82 Lead in Sediments ...82 Lead in Vegetation...84 Chemical Properties of Lead in Sediments ...84 Binding of Lead to Humic Substances...84 In 1

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Lead Distribution in Steele City Swamps* Shanshin Ton and Joseph J Delfino

CONTENTS

Lead in Surface Waters 82

Lead in Sediments 82

Lead in Vegetation 84

Chemical Properties of Lead in Sediments 84

Binding of Lead to Humic Substances 84

In 1970, Sapp Battery Service, Inc initiated its operations to process lead recovery from used automobile batteries The company gradually expanded its operation to process approximately 50,000 used batteries per week in 1978 Wastes from operations were dumped outside the plant and allowed

to run through adjacent wetlands, finally being discharged to Steele City Bay (Figure 6.1)

After 7 years of operation, in 1977, the first complaint about damage to cypress trees in adjoining wetlands was reported to the Florida Department of Environmental Regulation (FDER) FDER closed the site in January 1980

After the site was abandoned, EPA undertook emergency cleanup actions under provisions of the Clean Water Act, Section 311 The Sapp Battery site was included on the final National Priorities List in August 1982

After that date, EPA cooperated with FDER to conduct the Remedial Investigation/Feasi-bility Study (RI/FS) In this study, the on-site soils, groundwater, surface water, and sediments were examined

In 1985, Ecology & Environment, Inc (E&E) became involved in field investigations to further delineate the extent of the contamination Another draft feasibility study was finished by E&E in January 1987 See Appendix Table A6B.2

The analyses of lead were made from April 1989 to September 1992 Samples first collected at stations A through G (Figure 6.1) later extended further downstream in a series of sites: A, B, C, F, OF1, G, and OF2 (Figure 1.3) Descriptions of the sampling sites are given by Ton (1993) The chemical methods used are given in Appendix A6A, and Appendix A6B has a tabular listing of data

on lead in waters, sediments, vegetations, and related limnological data for April 1989 to May 1992

* Condensed by the Editor.

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LEAD IN SURFACE WATERS

Lead concentrations in surface waters decreased downstream (Figure 6.2) Concentrations

in most samples were less than those reported in earlier years (Appendix Tables A6B.2 and

A6B.3), and most concentrations were less than the 0.03 mg/l regarded as safe for recreation, fish, and wildlife

LEAD IN SEDIMENTS

Concentrations of lead in sediments also decreased downstream (Figure 6.3) For the most part, lead concentrations were highest in the surface sediments with lower concentrations 15 to 45 cm below (Figure 6.4) These results indicated that the distribution of lead in sediments corresponds

to the surface water drainage pattern Relatively low lead concentrations outside the boundary of the study area suggest that the wetland acts as a filter to retain lead (Appendix Table A6B.5)

Figure 6.1 Location of sampling sites, Jackson County, Florida (Ton, 1990).

Site Location

Florida

Sapp Battery Site West Swamp

East Swamp

County Rd 280

Steele City Bay

N

U.S Rd

231

County

Rd 276

Destruction of Cypress Community

meters

200 400 600 800

A

B

C

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LEAD DISTRIBUTION IN STEELE CITY SWAMPS 83

Figure 6.2 Concentration of lead in surface waters as a function of distance from original discharge (Station

A in Figure 6.1 ) (Ton, 1990).

Figure 6.3 Concentration of lead in upper sediments (0 to 15 cm) as a function of distance from original

discharge (Station A in Figure 6.1) (Ton, 1990).

Figure 6.4 Lead concentrations in sediment profiles at Stations A through G in Figure 6.1 (Ton, 1990).

n

n

Sampling sites A

B

0.3

0.2

0.1

0.0

Distance, m

G

n

n

n n

n

n

Sampling Sites A

B

C F

D 0

Distance, m

G

500

400 300 200 100

0

500 400 300 200 100

600

Depth 0-15 cm 15-30 cm 30-45 cm

Sampling sites A1 A2 B1 B2 C1 C2 D1 D2 F1 F2 G1 G2

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LEAD IN VEGETATION

Water lily (Nymphaea odorata) was the most popular species for the entire wetland, except site

A Leaves, stems, and roots of water lilies were separated for lead analysis Generally, concentrations

of lead in leaves and stems were slightly higher than those in roots However, high concentrations

of lead accumulated in roots were found commonly in other species (Appendix Table A6B.8)

CHEMICAL PROPERTIES OF LEAD IN SEDIMENTS

Sequential chemical extraction (Appendix A6A, Table A6A.1) was used to separate six compo-nents of lead in sediments, each followed by lead determinations Exchangeable lead was extracted with potassium nitrate solution; adsorbed lead was removed with potassium fluoride; organically bound lead with sodium phosphate; inorganic precipitated lead with EDTA; sulfide lead with nitric acid; and residual lead Results are given in Appendix A6B, Table A6B.9 and Figure 6.5

BINDING OF LEAD TO HUMIC SUBSTANCES

As already known from the literature and confirmed with the study of lead fractions (Figure 6.5), much of the lead combines with humic substances To measure the binding to the humic substances in the waters of the study area, 40 gal of surface water was collected from the control pond near the Sapp swamp in June and July 1991 A dialysis apparatus was set up (Figure 6.6) so that lead in solution on one side of a membrane could diffuse through the tiny pores, some becoming

Figure 6.5 Percentages of total sedimentary lead in each of six fractions at six stations in Figure 6.1 (Ton, 1990).

.

.

.

.

40

30

20

10

0

Organically Bound

Carbonate

Sampling Site

Sulfide

Residual

A B C D F G

Exchangeable

Adsorbed

Chemical State 50

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LEAD DISTRIBUTION IN STEELE CITY SWAMPS 85

bound by the humic substances in solution on the other side One side of the membrane had lead solution only, whereas the other side had lead solution plus that bound in the organic matter After suitable calculations were made using Scatchard graphs (Appendix Figure A6A.3), the ratio of lead bound to humic matter was found to be about 1.5 g lead per kilogram organic matter, slightly more

at higher pH, and about half the binding by a sample of humic materials (Aldrich Chemical Co., purified and freeze dried by Davis [1993])

A small amount (2.9 to 6.2%) of the organic humic molecules diffused in the other direction across the membrane, as measured with an instrument measuring the absorption of ultraviolet light The lower the pH the more diffused, suggesting an effect of pH in making the molecules more compact (already known from past publications) The humic substances from the bay diffused more than the sample of standard humic substance (less than 1%) In other words, the humic molecules from the control swamp were smaller than those in the standard humic material

Figure 6.6 Dialysis apparatus used for measuring the binding of lead by humic substances.

Dialysis Capsule Lead

Solution

Stirring Bars Pump

Stirrer

Sample of Dissolved Organics

Pump

Mf = Free Metals

Mt = Total Metals

Stirrer

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