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Microchemical Journal 88 (2008) 52 – 55

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Determination and comparison of heavy metals in selected seafood, water,

vegetation and sediments by inductively coupled plasma-optical emission
spectrometry from an industrialized and pristine waterway
in Southwest Louisiana
Michael A. Hamilton, Paul W. Rode, Mark E. Merchant, Joseph Sneddon ⁎
Department of Chemistry, McNeese State University, Lake Charles, Louisiana 70609, USA
Received 19 September 2007; accepted 27 September 2007
Available online 6 October 2007

Abstract

Samples of crab, fish, sediments, vegetation and waters were collected from a pristine (Rockefeller Wildlife Refuge) and historically polluted
(Bayou d'Inde) waterway in Southwest Louisiana. After sample preparation via microwave digestion to obtain a solution, cadmium, mercury,
nickel and lead were determined by inductively coupled plasma-optical emission spectrometry. A comparison of results showed that there was
very little difference in concentrations for the four metals between the two areas, typically in the 10 μg/g range for crabs and fish, around 0.05 μg/
mL or lower for waters, and somewhat higher for sediments and vegetation of around two to three times.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Metals; ICP-OES; Crabs; Vegetation; Fish; Sediments; Waters

1. Introduction documented and historically polluted waterway and the

second a more pristine waterway. Of particular interest was
Southwest Louisiana is one of the most productive areas in the the concentration of these metals in crabs, fish, vegetation,
continental USA for fishing, both commercial and recreational. sediments and waters. Crabs and fish are frequently caught
Because of its remoteness and nearness to water in the 1940's it and consumed by recreational fisherman, often a family
was chosen as an area for fossil fuel refining and production of tradition [2].
associated petrochemicals. None or poorly enforced environmen-
tal laws resulted in widespread pollution, particularly from heavy 2. Experimental
metals such as cadmium, mercury and lead. While the intro-
duction and enforcement of environmental laws has significantly 2.1. Sampling sites and collection
improved from the early 1970's, the possibility of heavy metal
contamination and sources of previously polluted waterways still The two areas investigated are on the heavily industrialized
exist in Southwest Louisiana [1]. and historically polluted Bayou d'Inde waterway, and the more
The object of this study was to compare the concentration pristine Rockefeller Wildlife Refuge, both located in Southwest
of selected heavy metals (cadmium, mercury, nickel, and Louisiana.
lead) in two quite different waterways: one on a well Bayou d'Inde is located approximately one mile west of the
city of Lake Charles, Louisiana. The waterway empties into
Lake Charles. Bayou d'Inde is located in the northern part of the
⁎ Corresponding author. Calcasieu Estuary, west of the city of Lake Charles in Calcasieu
E-mail address: [email protected] (J. Sneddon). Parish, Louisiana [1,2]. Bayou d'Inde's headwaters originate in
0026-265X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2007.09.004
 M.A. Hamilton et al. / Microchemical Journal 88 (2008) 52–55 53

Table 1 The sampling of this project involved six locations

Sampling location on Bayou d'Inde throughout the Bayou D'Inde area. A global positioning system
Site GPS (coordinates) Samples taken (GPS) was used to establish the exact location of each site and
1 N 30° 12.289′ Water, vegetation, sediment, crab, fish shown in Table 1. The sampled substances to be tested included:
W 93° 20.566′ (1) Fish (mullet), (2) Crab (Blue Crab, Callinectes sapidus),
2 N 30° 12.102′ Water, vegetation, sediment, crab, fish (3) Vegetation, (4) Water, and (5) Sediments. The samples were
W 93° 19.7771′
collected on two different dates, 01/26/06, temperature of 20 °C,
3 N 30° 12.129′ Water, vegetation
W 93° 19.490′ samples 51–79 (water, sediments and vegetation) and 05/30/06,
4 N 30° 12.720′ Water, vegetation temperature of 33 °C, samples 1–50 (samples 42–50 from
W 93° 18.632′ sampling Site 1 of whole crab were contaminated and results not
5 N 30° 12.429′ Water, vegetation presented in this work).
W 93° 18.368′
The water samples were collected by scooping a plastic
6 N 30° 12.480′ Water, vegetation
W 93° 17.841′ container into the water in the sampling area in a 50 mL plastic
container. The soil was collecting by using a four foot PVC pipe
about 5 ft from the shoreline. The pipes were labeled and stored
the western part of Sulphur, Louisiana and flow primarily east- in cold storage room (0 °C). The vegetation was collected from
southeast through heavy commercial and industrial areas the shoreline using a catch and grab method. Flora was stored in
emptying into the Calcasieu Ship channel west of Lake Charles. Ziploc bags, labeled and stored at − 20 °C. The crabs and fish
Bayou d'Inde is a tidally influenced wetland bayou that were collected using a hybrid fish/crab trap. Fish and crabs were
flows through or adjacent to property owned by Citgo individually stored in Ziploc bags, labeled and stored at − 20 °C.
Petroleum (Citgo), OxyChem Corporation (OxyChem), Fire- The crabs collected were only found in Site 1 and 2. The other
stone Synthetic Rubber and Latex Company (Firestone), sites did not produce crabs. The fish collected were only found
Westlake Polymers Corporation (Westlake Polymers), Brown- in Site 1 and 2.
ing-Ferris Industries (BFI), Certain-Teed Products Corporation Rockefeller Wildlife Refuge is a federally protected refuge,
(Certain-Teed), and Pittsburgh Paint and Glass Industries and harbors various types of wildlife. It is located in eastern
(PPG). These facilities are all active. Cameron and western Vermilion Parishes, South of Lake
The land around Bayou d'Inde includes undeveloped Charles (approximately 40 miles) and is owned and maintained
wooded marshland, rural residential, commercial, and heavy by the State of Louisiana. This area, of approximately 76,000 ac
industrial property. Rural residential and underdeveloped borders the Gulf of Mexico for 26.5 miles and extends inland
woodland areas border the Bayou northwest and up gradient toward the Grand Chenier ridge, a stranded beach ridge, and
of the industrial area. Heavy industry dominates the middle and 6 miles from the Gulf. It is remote from industry and is regarded
southern reaches of Bayou d'Inde on both sides. Several of the as a pristine area with various wildlife studies such as alligator
industries have wastewater outfalls permitted under the research in progress. Detailed information about Rockefeller
National Pollutant Discharge Elimination System (NPDES). Refuge can be found elsewhere [3]. The samples were acquired
Permitted discharges to Bayou d'Inde include outfalls belong- from the Wildlife Employees located at Rockefeller Refuge
ing to Citgo, OxyChem, Firestone, Westlake Polymers, BFI, testing complex. The whereabouts of these samples are not
Certain-Teed, and PPG. exact. Samples are known to be caught near the middle of the
In addition, PPG discharges wastewater to Bayou d'Inde via refuge. The samples were acquired on 08/03/06. Acquisitions
the PPG Canal, which enters the bayou approximately one mile included blue crab and fish. Samples acquired were labeled 80–
upstream of the Calcasieu Ship Channel. These discharges 117.
(current and historic), storm-water runoff, and accidental re-
leases have contributed to organic and inorganic impacts to 2.2. Sample preparation
surface water, sediment, and biota within the Bayou d'Inde area
of concern. Sample preparation was similar to that described previously
Although Bayou d'Inde is not used as a drinking water [4]. A few drops of concentrated nitric acid was added to all
source, the estuary surface waters have been designated by the water samples and stored in at 4 °C prior to determination by
Louisiana Department of Environmental Quality as supporting inductively coupled plasma-optical emission spectrometry
primary contact recreation, secondary contact recreation, and (ICP-OES). The vegetation was removed from cold storage
fish and wildlife propagation. Bayou d'Inde supports recrea- and placed in a mortar and dried overnight at 70 °C in an oven.
tional fishing and has several delineated wetlands that are The sample was ground with the pestle and approximately
considered sensitive environments. Health advisories warning 0.3000 g accurately weighed into the microwave digestion tube,
of contaminated fish consumption have been issued for the and 4 mL of concentrated nitric acid and 2 mL of hydrogen
Calcasieu Estuary including Bayou d'Inde. peroxide then added. The sample was microwaved on power 3
The Bayou d'Inde area of concern has not been proposed for for 3 min, and removed and placed under a hood for 5 min. A
inclusion on the National Priorities List (NPL), but the entire microwave of a further 5 min at microwave power of 3 was
Calcasieu Estuary has been the subject of environmental studies followed by a 5 minute cool down in a hood. The microwave
dating back to the early 1970's. digestion was vented for 5 min. The contents were filtered into a
54 M.A. Hamilton et al. / Microchemical Journal 88 (2008) 52–55

25.0 mL or 50.0 mL volumetric flask and diluted with de- conditions are described in detail elsewhere [5]. Results were
ionized water. The sample was stored in a plastic container at determined in μg/mL (parts per million) and converted into μg/g
4 °C prior to determination by ICP-OES. (except waters) as follows:
Sediments were collected as previously described [4] and
involved using a four foot PVC pipe about 5 ft from the shoreline. lg=mL
50:0 mL or 25:0 mL
: ð1Þ
The pipes were labeled and stored at 0 °C. Prior to metal accurate mass of approximately 0:3000 g of sample
determination they were dried overnight at 70 °C in an oven. The
sample was ground with a pestle and approximately 0.3000 g Detection limits (signal-to-noise ratio of three) for solution
accurately weighed into the microwave digestion tube and determination of the four metals were around 0.02 μg/mL which
identical digestion as the vegetation performed. translates into detection limits of around 1.67 μg/g for solid
The blue crab was removed from cold storage and either samples using Eq. (1) with a 25.0 mL volume.
dissected or left whole. The dissected crab was opened and the
gills, meat and shell dried at 70 °C overnight. Following 2.4. Chemicals
grinding in a mortar and pestle four samples of accurately
weighed approximately 0.3000 g was prepared as the vegetation. All chemicals were reagent grade. Stock solutions of
Fish was prepared in an identical fashion to that of the blue 1000 μg/mL (ppm) were used to prepare calibration standards
crab. daily as required.

2.3. Instrumentation 2.5. Accuracy

All quantitative metal determination was performed using a Recoveries were periodically run during the sample pre-
Leeman Labs PS Series (Leeman Labs, Lowell, Massachusetts) paration and subsequent determination for all four metals
inductively coupled plasma-optical emission spectrometer resulting in values in an acceptable range of 92–95%. National
(ICP-OES). The instrument setting, wavelengths and operating Institutes of Standards & Technology (NIST) (Gaithersberg,

Table 2
Concentrations of cadmium, nickel, lead and mercury in crabs, fish, vegetation, sediments (in μg/g), and waters (μg/mL) from Bayou d'Inde and Rockefeller Wildlife
Refuge
Cd Ni Hg Pb
Bayou d'Inde
A. Sampling 1
1. Whole crabs, 1–12, Site 1 8.17 ± 0.11 (8.00–8.36) 8.09 ± 0.50 (7.44–9.31) 12.16 ± 0.86 (11.12–14.07) 4.39 ± 2.04 (1.70–6.53)
2. Whole crabs, 36–41, Site 2 4.17 ± 0.06 (4.08–4.24) 6.90 ± 1.47 (6.42–9.04) 5.91 ± 0.37 (5.84–6.46) 2.62 ± 2.09 (1.80–6.16)
3. Crab dissections, 22–28, Site 1 4.52 ± 0.89 (4.02–6.34) 12.61 ± 6.61 (6.73–24.67) 6.30 ± 0.95 (5.52–8.63) 3.46 ± 2.56 (2.00–7.91)
4. Crab dissections, 29–35, Site 2 4.20 ± 0.23 (4.07–4.15) 7.73 ± 4.94 (4.86–18.66) 6.31 ± 0.41 (5.90–7.08) 4.61 ± 2.66 (1.67–9.21)
5. Whole fish 13–21, Site 2 9.05 ± 1.67 (7.72–11.58) 9.65 ± 2.94 (5.95–14.45) 13.42 ± 2.41 (11.41–17.03) 3.68 ± 2.74 (1.70–6.16)

B. Sampling 2
6.a Vegetation 63–64, Site 1 4.46 (4.45, 4.46) 12.80 (12.48, 13.21) 6.41 (6.56, 6.25) 15.02 (14.44, 15.60)
6.b Vegetation 65–66, Site 2 4.58 (4.64, 4.51) 14.54 (12.92, 16.15) 6.69 (6.76, 6.61) 19.40 (28.12, 10.67)
6.c Vegetation 67–68, Site 3 4.26 (4.24, 4.29) 14.91 (10.28, 19.53) 6.36 (6.42, 6.30) 11.19 (10.28, 12.10)
6.d Vegetation 69–70, Site 4 4.36 (4.49, 4.22) 14.61 (17.95, 11.27) 6.25 (6.58, 5.91) 11.75 (12.10, 9.40)
6.e Vegetation 71–72, Site 5 4.77 (4.97, 4.61) 18.43 (20.79, 16.07) 6.25 (6.19, 6.32) 25.03 (28.99, 21.09)
6.f Vegetation 73–74, Site 6 4.55 (4.57, 4.53) 16.37 (16.87, 15.86) 6.14 (6.27, 5.99) 16.87 (17.44, 16.26)
6.g Sediments 75, 78, Site 1 4.40 (4.46, 4.33) 18.33 (12.60, 24.05) 6.20 (6.03, 6.37) 8.33 (6.96, 9.69)
6.h Sediments 76, 79, Site 2 (77–none) 4.38 (4.50, 4.26) 16.75 (14.99, 18.50) 6.22 (6.00, 6.43) 7.60 (6.97, 8.23)
7.a Water 51–52, Site 1 0.05 (0.05, 0.05) 0.06 (0.06, 0.06) 0.08 (0.08, 0.08) 0.03 (0.03, ⁎)
7.b Water 53–54, Site 2 0.05 (0.05, 0.05) 0.05 (0.05, 0.05) 0.07(0.07, 0.07) ⁎
⁎
7.c Water 55–56, Site 3 0.05 (0.05, 0.05) 0.06 (0.05, 0.06) 0.07 (0.07, 0.07) ⁎
⁎
7.d Water 57–58, Site 4 0.05 (0.05, 0.05) 0.06 (0.06, 0.05) 0.08 (0.08, 0.07) 0.03 (⁎, 0.03)
7.e Water 59–60, Site 5 0.05 (0.05, 0.05) 0.06 (0.05, 0.06) 0.06 (0.06, 0.06) ⁎ (⁎)
7.f Water 61–62, Site 6 0.05 (0.05, 0.05) 0.05 (0.05, 0.05) 0.08 (0.07, 0.08) 0.04 (0.04, ⁎)

b. Rockefeller Refuge
A. Sampling 2
1.Whole crabs 80–95 8.31 ± 0.36 (8.08–9.60) 8.58 ± 1.29 (6.32–10.68) 11.49 ± 0.39 (10.37–12.07) 6.76 ± 3.26 (2.42–11.06)
2. Crab dissections, 96–101A, 101B, 106A 4.09 ± 0.22 (3.83–4.65) 4.27 ± 2.73 (2.54–11.61) 5.56 ± 0.29 (5.47–6.02) 3.29 ± 2.14 (1.77–6.56)
3. Whole fish 106B–117 8.19 ± 0.16 (7.96–8.58) 8.14 ± 1.04 (6.58–10.22) 11.44 ± 0.32 (10.39–12.36) 7.89 ± 3.43 (1.77–12.12)
⁎Less than detection limit.
 M.A. Hamilton et al. / Microchemical Journal 88 (2008) 52–55 55

Maryland) — Standard Reference Material, SRM-1577b bovine studies dating back to the 1970's and earlier. Alternatively it is
liver was used. Results for cadmium and lead were statistically possible that Rockefeller Wildlife Refuge is not immune or
acceptable to the standard. The concentration of the NIST-SRM- isolated from metal pollution. A potential factor in this area was
1577b for mercury is 0.004 μg/g and was not detected by the ICP- the presence of Hurricane Rita in late September 2005 which
OES instrumentation. There was no certified value for nickel. affected much of Southwest Louisiana and in particular
Quality assurance/quality control (QA/QC) was used as described Cameron Parish which could upset the fragile balance between
previously [4]. pristine and more industrialized areas.
This field study provides useful information and a baseline
3. Results and discussion for future and continued studies on the metal concentrations
in crabs, fish, vegetation, waters, and sediments in Southwest
The results of this study are summarized in Table 2. Each Louisiana. The work is a continuation of previous studies [6].
sample (numbers 1–117, except 42–50) was determined three
times with a relative standard deviation (RSD) of better than Acknowledgements
0.5% in all cases (results not shown). The results of each
sampling sub-area, i.e., whole crabs, etc. were pooled with the This work was supported, in part, by Merck undergraduate
mean, ± standard deviation and range presented for each pooled research program awarded to McNeese State University for
sample. 2005–2007 and provided stipends for two of the authors (MAH
In general, there was no statistical difference in concentra- and PWR). Partial support from Environmental Protection
tions for the four metals between the two sampling sites for Agency, EPA-R-82958401-1 is gratefully acknowledged.
whole crab, crab dissections or fish. In general, concentrations
for cadmium, mercury and nickel were around 10 μg/g or lower References
and for lead were about a factor of two lower than the other
three metals. For vegetation the concentrations of lead and [1] J.N. Beck, J. Sneddon, Use of atomic absorption spectrometry for the
nickel were significantly higher than that of cadmium and determination of metals in sediments and soils in Southwest Louisiana,
Microchemical Journal 66 (1–3) (2000) 73–113.
mercury. In sediments the concentrations of all four metals was
[2] J. Sneddon, P.W. Rode, M.A. Hamilton, S. Pingeli, J.P. Hagen, Deter-
comparable and below 10 μg/g. In waters the concentrations of mination of metals in seafood, Applied Spectroscopy Reviews 42 (1) (2007)
all four metals was in the very low sub-ppm range. 1–16.
[3] http://www.wlf.louisiana.gov/experience/wmas/refuges/rockefeller.cfm.
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Results from this field study show that there are small 41 (1) (2006) 23–42.
differences (in most cases less than a factor of 2) for the metals [5] J. Sneddon, C. Hardaway, K.K. Bobbadi, J.N. Beck, A study of a crude oil
(cadmium, lead, nickel, and mercury) determined in crabs, fish, spill for selected metal concentrations remediated by a controlled burning in
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[6] J. Sneddon, in: S. Caroli (Ed.), Use of spectrochemical methods for the
potentially polluted waterway (Bayou d'Inde) and the more
determination of metals in fish and other seafood in Louisiana, from the
pristine waterway (Rockefeller Wildlife Refuge). It is possible Determination of chemical elements in food: applications for atomic and
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