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A SURVEY OF SELECTED FLUOROCHEMICALS IN THE DECATUR ALABAMA AREA 2002 SAMPLING
Preparedfor: 3M
St. Paul, Minnesota Prepared by: Entrix, Inc.
John P. Giesy, Ph.D. John L. Newsted, Ph.D. East Lansing, Michigan
Project No. 178401 July, 2003
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TABLE OF CONTENTS
1 EXECUTIVE SUMMARY......................................................................................4
2 INTRODUCTION..................................................................................................... 6
3 FIELD SAMPLING..................................................................................................6 3.1 Site Description.............................................................................................................. 6 3.2 Field Sampling Logistics.............................................................................................. 8 3.3 SAMPLE COLLECTION.................................................................................................. 8
3.3.1 Water and Sediment Collection..................................................................................... 8 3.3.2 Fish Collection.................................................................................................................9 3.3.3 Fish Fillet Processing and Sample Preparation............................................................9
4 IDENTIFICATION AND QUANTIFICATION OF FLUOROCHEMICALS 11 4.1 Water Analysis.............................................................................................................11 4.2 Sediment Analysis.........................................................................................................11 4.3 Fish Fillet Analysis......................................................................................................12
5 QA/QC..................................................................................................................... 12
6 STATISTICAL ANALYSES................................................................................. 13
7 RESULTS................................................................................................................ 13 7.1 WATER QUALITY PARAMETERS.........................................................................................13 7.2 FLUOROCHEMICALS IN SURFACE W ATERS...................................................................... 14 7.3 Sediment concentrations of fluorochemicals....... .............................................. 14 7.4 Fish ...................................................................................................................................15
7.4.1 Fish Fillet concentrations ofPFOS, FOSA, PFOA, PFHS andPFBS......................16 7.5 Comparison to 2000 Decatur Monitoring Study....................................................18
7.5.1 Surface water..................................................................................................................18 7.5.2 Sediment.......................................................................................................................... 19 7.5.3 Fish................................................................................................................................. 20
REFERENCES................................................................................................................22
9 APPENDICES..........................................................................................................23 9.1 APPENDIX A .................................................................................................................. 24 9.2 APPENDIX B................................................................................................................... 25 9.3 A p p e n d ix C...................................................................................................................... 26 9.4 APPENDIX D .................................................................................................................. 35 9.5 APPENDIXE................................................................................................................... 36
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TABLES Table 1. Location and identification of sediment and water samples collected
from the Tennessee River in Alabama..............................................................8 Table 2. Sample identification and location of individual fish collected from the
Tennessee River................................................................................................ 10 Table 3. Water quality parameters for samples collected from the Tennessee
River, in the Decatur Alabama area. Values are reported as a single value ............................................................................................................... 14 Table 4. Concentration of fluorochemicals in surface waters of the Tennessee River in the Decatur, Alabama area..................................................................14 Table 5. Concentration of fluorochemicals in sediments of the Tennessee River in the Decatur, Alabama area............................................................................15 Table 6. Mean length, weight, and condition factor for fish collected from the Tennessee River (Collected on 04/15/02-04/18/02)........................................ 16 Table 7. Whole body concentrations (wet weight) of selected fluorochemicals in fish collected from the Tennessee River in the Decatur Alabama area.a.......17 Table 8. Mean concentration of fluorochemicals in surface waters of the Tennessee River near Decatur, Alabama.a...................................................... 19 Table 9. Mean fluorochemical concentrations in sediments of the Tennessee River near Decatur, Alabama........................................................................... 20 Table 10. Mean tissue fluorochemical concentrations in fish sampled from the Tennessee River near Decatur Alabama...........................................................21
FIGURES Figure 1. Tennessee River and sampling locations evaluated during study.....................7
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1 EXECUTIVE SUMMARY
A monitoring study was conducted to determine the concentrations of selected
fluorochemicals fish, water and sediments within the Tennessee River in the vicinity of
the 3M facility in Decatur Alabama. Samples were analyzed for five fluorochemicals:
perfluorooctanesulfonate
(PFOS),
perfluorooctanesulfonamide
(FOSA),
perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHS), and perfluorobutane
sulfonate (PFBS). Three primary locations were sampled during the survey. These
included a location upstream of the 3M facility (LOC-3) near river mile 307.5, a location
across the River from the 3M facility near river mile 301 (LOC-2), and a location
downstream of the 3M facility near river mile 296 (LOC-1). All surface water, sediment
and fish samples were collected according to standard procedures and analyzed for
fluorochemicals according to 3M Environmental Laboratory methods.
Conductivity and pH were greater in surface waters from the downstream location
(LOCI) when compared upstream locations (LOC-3 and LOC-2). However, these
differences were minor and fell within the range of water quality parameters measured in
the Tennessee River near Decatur, AL. Surface water concentrations of targeted
fluorochemicals were less than limits of quantitation at LOC-2 and LOC-3. In contrast,
PFOS, PFOA, PFHS and PFBS were detected in surface water collected downstream of
the 3M facility (LOC-1) but were less than 0.6 pg/L. In sediments, PFOS concentrations
ranged from 0.42 pg/kg to 3.1 pg/kg (wet weight) for LOC-3 and LOC-1, respectively.
In addition to PFOS, concentrations of FOSA, PFOA, PFHS and PFBS in sediments were
also greater at the downstream location (LOC-1) when compared to measured
concentrations at LOC-2 and LOC-3. However, due to the small sample size (N=l),
statistical analysis were not conducted to evaluate the differences between sample
locations. In general, concentrations of fluorochemicals in water and sediment were
greater downstream of the 3M facility as compared to concentrations measured across
(LOC-2) or upstream (LOC-3) of the 3M facility. In a qualitative analysis,
concentrations of fluorochemicals in river water tended to be less in 2002 as compared to
2000 in the Tennessee River. However, due to differences in sample locations and
analytical methods, no conclusions about temporal trends could be made.
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Fish collected from LOC-1 contained quantifiable levels of PFOS, FOSA and PFOA while at LOC-2 and LOC-3, the only quantifiable fluorochemical in fish was PFOS. The least concentration of fluorochemicals were observed in fish from LOC-2 and LOC-3, across from and upstream of the 3M facility while the greatest concentrations were observed in fish collected downstream of the facility, at LOC-1. For instance, in fish fillets from LOC-3, the average concentration of PFOS was 7.6 pg/kg while FOSA, PFOA, PFHS, PFBS concentrations were <LOQ (wet weight). For fish collected at LOC-1, average fillet concentrations for PFOS, FOSA, and PFOA were 305 pg/kg, 32 pg/kg and 9.1 pg/kg (wet weight), respectively. The concentration of PFHS and PFBS were <LOQ (wet weight). While differences in the concentrations of fluorochemicals were observed between catfish and largemouth bass at the different locations, due to the among individual variability and small sample sizes these differences were not statistically significant. In addition, while fish have been sampled in the Tennessee River near the 3M facility, a comparison between the previous monitoring study could not be done due to differences in sampling locations, fish age and size, and the types of fish tissues analyzed in each of the studies. Therefore, a trend analysis was not conducted with the fish fluorochemical data
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2 INTRODUCTION Entrix, Inc. (ENTRIX) is providing a report on activities to assess the distribution of fluorochemicals in the Tennessee River in the Decatur Alabama area. The results of this study are part of a larger effort to ascertain the spatial and temporal behavior of fluorochemicals in the Tennessee River that may have been discharged from the 3M Decatur Alabama Facility. The results of the 2002 sampling season were compared qualitatively to the results the 2000 sampling season to examine any potential trends in the distribution and magnitude of the fluorochemicals in water, sediment and biota. Water, sediment, and fish were collected from three locations upstream, across and downstream of the 3M Facility. Fluorochemicals selected for evaluation in this study included: perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS) ( see Appendix A).
3 FIELD SAMPLING
3.1 Site Description The sampling locations selected as part of the 2002 sampling program were representative of areas used by recreational and commercial fishermen. At each of three locations selected for this field investigation, water, sediment, and fish samples were collected. Sampling areas consisted of a location across the River from the 3M point of discharge, a location downstream of the 3M facility, and a location upstream of the 3M facility. The Riverwalk Marina (Marina) located on the northeast side of the river at approximately river mile 305 was used for river access. The downstream sampling location (LOC-1) was in the vicinity of Fox Creek (approximately river mile 296). The sampling location across the river from the 3M facility (LOC-2) was located approximately at river mile 301 while the upstream location (LOC-3) was at river mile 307.5 (upstream of the 3M discharge, the city of Decatur, and the Highway 31 bridge) (Figure 1; see Appendix B).
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Legend
0 Water and Sediment Sample Locations Fishing Locations
O Fishing Start Point Fishing Stop Point
3M Facility
Base map from the following USGS 250K topographic map: Gadson, AL. 1977.
ENTR IX
Figure 1 Site Location Map Tennessee River Sampling Locations
3M Corporation Decatur, Alabama
Proj. No,: 178401
04/2002
3.2 Field Sampling Logistics Sampling at selected sites on the Tennessee River was initiated on April 15, 2002 by ENTRIX. Collection of water and sediment samples continued until April 16, 2002. Fish collection was initiated on April 15 and continued through April 18, 2002. Water, sediment, and fish were collected as outlined in the General Project Outline (GPO) provided by 3M.
3.3 SAMPLE COLLECTION
3.3.1 Water and Sediment Collection Water samples were collected using standard sampling protocols from a total of 3 locations (Table 1: Appendix C). At each location, water quality parameters were measured using YSI Model 63 and 95 meters. One sample was collected from each of the locations. All sampling locations were documented using TRIMLBE PRO-XRS Global Positioning Satellite technology and these locations were recorded on topographic maps. Samples were labeled, stored on ice at 4C, and delivered to the 3M Environmental Laboratory, St. Paul, MN.
Sediment samples were collected from the same locations as the water samples (Table 1). A total of 3 grab samples were collected from the Tennessee River. Sediments were collected by use of a PONAR dredge following standard protocols (Appendix C). Sediments were placed into labeled LDPE containers, stored on ice at 4C, and shipped to the 3M Environmental Laboratory, St. Paul, MN.
Table 1. Location and identification of sediment and water samples collected from
the Tennessee River in Alabama
Water
Sediment
Location
Sample
Sample
River Mile
Code
SW-01
SED-01
Downstream
296 LOC-1
SW-02
SED-02
Across River
301 LOC-2
SW-03
SED-03
Upstream
307.5
LOC-3
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3.3.2 Fish Collection Fish were collected from three locations (Figure 1). These three locations were in close proximity to where water and sediments were collected. Fish were collected using a boat mounted Smith-Root type VI-A electroshocking device. According to the GPO, a minimum of six bass (preferably largemouth) and six catfish were to be collected from each of the three sites. For this investigation, only the desired fish species caught at each of the sampling locations were retained for analysis. Collected fish were measured (total length), weighed, and immediately wrapped in aluminum foil and placed in Ziplock storage bags (Table 2). Samples were labeled, placed on ice, and shipped via overnight FedEx to the ENTRIX office in East Lansing, Michigan, and then transported immediately to freezer facilities in the Aquatic Toxicology Laboratory (ATL) at Michigan State University. Upon completion of sampling activities, the Alabama Department of Wildlife and Freshwater Fisheries was notified that sampling was complete and their required notification form was completed and mailed to them.
3.3.3 Fish Fillet Processing and Sample Preparation ENTRIX conducted the fish processing and preparation of fillets. Procedures described in the 3M GPO and the Alabama Department of Environmental Management Standard Operating Procedures Volume III were followed in fish fillet preparation (USEPA 2000) Fillets included the tissue from behind the head to the tail on both sides of each fish. Each fillet was removed from the fish and the skin removed using a fillet knife. The rib bones were either avoided during filleting or removed from each fillet so that only edible portions of the fillet remained. The carcass of each fish, the skin, and rib bones from each fillet were then wrapped in aluminum foil (dull side to fish), labeled with its sample location and ID number, placed in a pre-labeled Ziploc bag and stored at -20C. The fillet was cut into small pieces to expedite the grinding process. A hand grinder was used for the larger fish and a stainless steel blender for samples with less tissue. In all cases, the ground tissues were thoroughly mixed with stainless steel spatulas and mortar and pestle to ensure adequate homogenization. Once homogenized, the tissue was massed to the nearest hundredth gram and placed in Nalgene HPDPE containers. A label detailing the sample location, ID number, date processed, sample identity (bass or catfish) and
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mass of the tissue was placed on each container. All containers were placed in pre labeled Ziploc bags and stored in coolers at -20C. All tools and homogenizers were washed with detergent and warm water, then rinsed with methanol followed by a de ionized water rinse to avoid cross contamination between each fish sample.
Table 2. Sample identification and location of individual fish collected from the
Tennessee River.
Sample Id
Location
Fish Type
SL01-LM01 SL01-L M 02 S L01-LM 03 SL01-LM 04 S L01-LM 05 SL01-L M 06 SL01-CAT01 SL01-CAT02 SL01-CAT03 SL01-CAT04
Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek) Downstream (Near Fox Creek)
Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Catfish Catfish Catfish Catfish
SL01-CAT05 SL01-CAT06 SL02-LMB01
Downstream (Near Fox Creek) Downstream (Near Fox Creek) Across River from 3M
Catfish Catfish Largemouth Bass
S L02-LM B 02
Across River from 3M
Largemouth Bass
S L02-LM B 03 SL02-L M B 04 SL02-LM B01 SL02-CAT01 SL02-CAT02 SL02-CAT03 SL02-CAT04 SL02-CAT05 SL02-CAT06 SL02-CAT07 SL03-LM B01 SL03-LM B 02 S L03-LM B 03 SL03-LM B 04 S L03-LM B 05 SL03-LM B 06 SL03-L M B 07 SL03-SM 01 SL03-CAT01 SL03-CAT02 SL03-CAT03 SL03-CAT04 SL03-CAT05 SL03-CAT06
Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream U pstream
Largemouth Bass Largemouth Bass Largemouth Bass Catfish Catfish Catfish Catfish Catfish Catfish Catfish Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Smallmouth Bass Catfish Catfish Catfish Catfish Catfish Catfish
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4 IDENTIFICATION AND QUANTIFICATION OF FLUOROCHEMICALS Water and sediment were collected from the Tennessee River and analyzed by the 3M Environmental Laboratory (Study No. E02-0443). The analytical methods used for the analysis of water samples were validated by the 3M Environmental Laboratory. HPLCElectrospray/Mass Spectrometry (HPLC/ES/MS) characterization of fluorochemicals was conducted at the 3M Environmental Laboratory. Summaries of each protocol are given:
4.1 Water Analysis Solid phase extraction was used to prepare the samples for HPLC/ES/MS analysis. A forty-milliliter portion of river water was passed through a preconditioned Cig SPE cartridge and the column was allowed to dry for at least 3 min. The cartridge was eluted with 2 ml of methanol into autovials. The eluate was collected for analysis by LC/MS/MS. Water extracts were analyzed by use of a Hewlett-Packard HP 1100 HPLC system coupled to a Hewlett-Packard Series 1100 API/Mass Spectrometer Detector. HPLC conditions and ES/MS methods were based on ETS-8-155.1 "Analysis of waste stream, water extracts or other systems using HPLC-Electrospray/Mass Spectrometry".
4.2 Sediment Analysis For sediment samples, a 20 g portion was extracted into 35 ml of 1% acetic acid in
capped centrifuge tubes. The samples were shaken for 60 min and then centrifuged. The
aqueous solutions then passed through pre-conditioned SPE cartridge and the eluate was
discarded. Methanol was then added to the sediment and the mixture was shaken for 30
min and centrifuged. The methanol was passed through the SPE cartridge and the eluate
was discarded. The SPE cartridge eluted with 4 ml methanol and the collected methanol
was then added to approximately 200ml of ASTM Type I water. This solution was then
passed through a new pre-conditioned SPE cartridge and the aqueous eluates were
discarded. The analytes were eluted from the SPE cartridge with 2.0 ml methanol in to
autovials for analysis. The extracts were analyzed by use of a Hewlett-Packard HP1100
HPLC system coupled to a Hewlett-Packard Series 1100 API/Mass Spectrometer
Detector. HPLC conditions and ES/MS methods were based on ETS-8-155.1 "Analysis
of waste stream, water extracts or other systems using HPLC-Electrospray/Mass
Spectrometry".
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4.3 Fish Fillet Analysis Fluorochemicals were extracted from fish fillets using a solid phase extraction (SPE) method. Briefly, 2 g homogenized fillet tissues were diluted with ASTM Type I, mixed and aliquoted in to triplicate samples. Matrix spikes were prepared for each sample and were spiked with 10 pL of a 100 pg/mL spike solution of each test substance. Acetonitrile is added to extract the fluorochemicals and to precipitate proteins that can interfere with the analysis. After mixing and centrifugation, the supernatant is then passed through a pre-conditioned Ci SPE cartridge. Finally, the analytes are eluted from the SPE cartridge with methanol into autovials. The extracts were analyzed by HPLCES/MS/MS. Details of the analytical procedure have been outlined in the 3M Environmental Laboratory (St. Paul, MN) standard operating procedures (ETS-8-231.1) for the analysis of fluorochemicals in tissues.
5 QA/QC Standard operating procedures for sample collection and preparation were maintained during the entire project. Proper QA/QC samples, as required by 3M, were collected in the field (Appendix D). Field blanks and Trip blanks were collected and shipped with the samples. Field matrix spikes and field control samples were collected at each location along with a Field duplicate. Field matrix spike solutions were prepared by collecting one liter of site water and spiking with a stock solution containing PFOS, FOSA, PFOA, PFHS and PFBS. The same procedure was followed to spike one liter of distilled water to prepare the field spike control samples. All samples were shipped under ENTRIX chain of custody forms and a field book was used to document conditions and activities. Pictures of all locations were taken to provide a visual record of the conditions of the site during the sampling events. Since the method detection limit (MDL) and lowest limit of quantification (LLOQ) are analyte and matrix specific, method and matrix blanks along with matrix spikes were used to determine accuracy and precision of the extractions and final chemical determination. Data quality objectives were also established for each sample matrix (river water, sediment, and fish). In general, the Data Quality Objectives were: (1) all samples were analyzed in triplicate and the %RSD should be < 25%, (2) matrix spikes should be 30% of expected value, (3) water blanks should be less than < % LLOQ for each analyte, and (4) extraction blanks should be < % LLOQ. Water and
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sediment concentrations were not corrected for either matrix spike recoveries or for purity of the fluorochemical standards. In addition, ambient water quality parameters, such as temperature, conductivity, salinity, pH and dissolved oxygen were measured at each location during each sampling event.
6 STATISTICAL ANALYSES Statistical analyses were preformed with SAS (Version 8, SAS Institute, Cary NC, USA). Where relevant, General linear models (PROC GLM) were used to test for differences among locations for all analyte concentrations in fish measured in the study. If values of F tests indicated a significant difference, Tukey's HSD test for multiple comparisons was used to compare means of the different locations. All fish samples were included in the statistical analysis. For samples where fluorochemicals concentrations were less than their limit of quantitation, the limit of quantitation was substituted as a conservative estimate of the fish fluorochemical concentrations.
7 RESULTS
7.1 Water quality parameters Surface water quality parameters from each location are reported (Table 3). Dissolved oxygen, pH, conductivity, and temperature were relatively constant for the Upstream (LOC-3) and Across (LOC-2) locations. However, at the downstream location (LOC-1), pH and conductivity were slightly greater than those recorded at the other locations. These minor differences may be due to the fact that sampling locations LOC-2 and LOC3 were within or near the Tennessee River channel whereas LOC-1 was located in the mouth a small bay at the mouth of Fox Creek. As result, LOC-1 most likely was influenced by the water quality of the creek. Regardless, all values fell within historical water quality parameters measured in the Tennessee River in the Decatur Alabama area (Giesy and Newsted, 2001).
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Table 3. Water quality parameters for samples collected from the Tennessee
River, in the Decatur Alabama area. Values are reported as a single value a
Location
DO (mg/L)
Conductivity Temperature (pS) (C)
pH (s.u)
Upstream (LOC-3)
10.7
139.4
18.1 7.2
Across River (LOC-2) 9.36
138.9
21.0 7.3
Downstream (LOC-1)
-
162.3
21.8 9.4
a M eans and standard deviations could not be determined since only a single sample was collected from each location.
7.2 Fluorochemicals in Surface waters Fluorochemicals were detected in all surface waters collected from the sample locations in the Tennessee River (Table 4) (Ellefson, 2003). At LOC-2 and LOC-3, all surface water concentrations of PFOS, FOSA, PFOA, PFHS, PFBS were less than the limit of quantitation. In contrast, all targeted fluorochemicals were quantifiable in surface water collected from LOC-1, downstream of the 3M facility. However, in samples where fluorochemicals were quantified (LOC-1), the concentrations were less than 0.6 pg/L. Due to the small sample size (N=l), statistical analyses of the data was not conducted to evaluate differences among the sample locations.
Table 4. Concentration of fluorochemicals in surface waters of the Tennessee
River in the Decatur, Alabama area.a____________________________________
PFOS
FOSA
PFOA
PFHS
PFBS
Location Upstream
(Pg/L) <0.13
(Pg/L) < 0.025
(Pg/L) <0.05
(Pg/L) <0.025
(Pg/L) <0.05
(LOC-3)
Across River
<0.13
< 0.025
<0.05
<0.025
<0.05
(LOC-2) Downstream 0.49 0.025 0.55 0.20 0.08
(LOC-1)
a Since only a single sample was collected from each location, no statistics are reported.
7.3 Sediment concentrations o ffluorochemicals Fluorochemicals were detected in sediments collected from all three locations within the study site (Table 5). Least concentrations of fluorochemicals in sediment were observed
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at LOC-3, upstream of the 3M Facility while the greatest concentrations were observed in sediments collected near Fox Creek (LOC-1), downstream of the 3M facility. Sediment concentrations of PFOS, FOSA, PFOA, PFHS, and PFBS were 7.52-fold, 21.2-fold, 5.59-fold, 2.6-fold, and 1.28-fold greater at LOC-1 as compared to LOC-3, respectively. In contrast, sediment concentrations of PFOS, FOSA, PFOA, PFHS, and PFBS were only 1.10-fold, 2.07-fold, 0.38-fold, 1.00-fold, and 0.97-fold greater at the LOC-2 as compared to LOC-3, respectively. Thus, while there was insufficient data to conduct a statistical comparison among the sampling locations, these data indicate that concentrations of fluorochemicals in sediments were greater downstream of the 3M facility as compared to the upstream or across the river locations in the Tennessee River.
Table 5. Concentration of fluorochemicals in sediments of the Tennessee River in
the Decatur, Alabama area.a___________________________________________
PFOS
FOSA
PFOA
PFHS
PFBS
Location Upstream
(Pg/kg) 0.42
(Pg/kg) 0.068
(pg/kg) 0.13
(Pg/kg) <0.10
(pg/kg) 0.45
(LOC-3)
Across River
0.46
0.141
< 0.025
<0.10
0.44
(LOC-2) Downstream 3.13 1.44 0.73 0.13 0.58
(LOC-1)
a M eans and standard deviations could not be determined since only a single sample was collected
from each location. All concentrations reported on a wet w eight basis.
7.4 Fish There were no significant differences in weight, length of either fish species among locations (Table 6; see Appendix E). Smallmouth bass were not included in statistical analyses due to the fact that only one fish was collected during the study. This fish was collected at LOC-3. Condition factors were calculated for each species and are given (Table 6). Statistical analysis of the condition factors showed no significant differences between sites for either fish species. The condition factor is a measure of the overall physiological health of a fish as measured as a ratio of weight to length. Results from the statistical analysis indicate no differences in fish health between the three locations as evaluated by the condition factor.
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Table 6. Mean length, weight, and condition factor for fish collected
from the Tennessee River (Collected on 04/15/02-04/18/02).a
Sample ID
Largemouth Bass
Location Upstream (LOC-3)
Across (LOC-2)
Downstream (LOC-1)
Length
(cm)
36.3 (4.77) 35.4 (6.89) 34.5 (4.08)
Weight
(g) 639 (219) 647 (302) 591 (170)
Condition
Factor b
1.305 (0.228) 1.432 (0.208) 1.416 (0.126)
Catfish
Upstream (LOC-3)
55.1 (11.7)
2386 (1099)
1.468 (0.598)
Across (LOC-2)
56.5 (4.43)
1942 (623)
1.049 (0.103)
Downstream (LOC-1) 61.4 (7.30)
2920 (1644)
1.166 (0.192)
Smallmouth Upstream (LOC-3) Bass
32.5
563
1.640
Values are means with standard deviations (in parentheses). b Condition factor calculated as (W eight xl00)/Length3
7.4.1 Fish Fillet concentrations o fPFOS, FOSA, PFOA, PFHS and PFBS Fluorochemicals were detected in all fish fillets collected at all three locations (Table 7). The least concentrations of fluorochemicals were observed in fish collected from the upstream location (LOC-3) while the greatest concentrations were observed in fish collected from the downstream location (LOC-1). At all three locations, the concentrations of PFHS and PFBS in fish were less than the LOQ. FOSA and PFOA were detected only in fish collected from the downstream location (LOC-1), while PFOS was quantified in fish species collected from all three locations. The mean concentration of PFOS for all fish collected at LOC-1 was approximately 3.5-fold greater than that measured in fish from LOC-2 and 40-fold greater than that measured in fish from LOC-3. In the smallmouth bass collected at LOC-3, all monitored fluorochemicals were less than their limit of quantitation (LOQ).
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Table 7. Whole body concentrations (wet weight) of selected fluorochemicals in fish
collected from the Tennessee River in the Decatur Alabama area.a
PFOS FOSA PFOA PFHS PFBS
Species
Nb
UpStream (LOC-3)
(Pgfcg)
(Pg/kg)
(Pg/kg)
(Pg/kg)
(Pg/kg)
Catfish
6
15.2
<2.5
<5.0
<2.5
<5.0
(14.0)
Largemouth Bass 7
<5.0
<5.0
<5.0
< 1.0
<2.5
Smallmouth Bass 1 <2.5
<5.0
<5.0
< 1.0
<2.5
Across (LOC-2)
Catfish
7 <2.5 <2.5 <5.0 <2.5 <5.0
Largemouth Bass 4
Downstream (LOC-1)
Catfish
6
Largemouth Bass 6
169 (255)
113 (48.1)
553 (231)
<5.0
61 (20) <5.0
<5.0
<5.0 15 (24)
a Concentrations are reported as means and standard deviations. bN um ber o f fish analyzed
< 1.0 <2.5 < 1.0
<2.5 <5.0 <2.5
PFOS concentrations were significantly greater (p <0.05) in both catfish and largemouth bass collected from LOC-1 (downstream) as compared to fish from collected from across the river (LOC-2) or upstream (LOC3) the 3M facility. There were no statistically significant differences in the concentrations of PFOS in catfish and largemouth bass collected at LOC-2 and LOC-3. Thus, while largemouth bass from LOC-2 had PFOS concentrations that were greater than those measured in fish from LOC-3, the difference in concentration was not statistically significant due to the variability in the measured concentrations in fish from LOC-2 (Coefficient of variation =152%). The relatively great variability observed at LOC-2 was due to PFOS concentrations in largemouth bass that ranged from <LOQ to 0.55 pg/kg, wet weight.
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In catfish, FOSA concentrations were significantly greater (p <0.05) in fish from LOC-1 than in catfish collected from LOC-2 or LOC-3. The mean concentrations of FOSA in catfish from LOC-3 were not statistically different from those measured in catfish from LOC-2. Concentrations of FOSA in largemouth bass were not statistically different among any of the locations. No statistically significant differences were observed in PFOA, PFHS or PFBS concentrations for either catfish or largemouth bass among the three sampling locations.
7.5 Comparison to 2000 Decatur Monitoring Study To evaluate trends in fluorochemical concentrations in the Tennessee River, data from the 2000 and 2002 sampling programs were compared (Giesy and Newsted, 2001). However, while fluorochemical concentrations in sediment and surface water can be directly compared among years, concentrations in fish could not be compared due to differences in experimental design. In 2000, the study design was intended to evaluate the distribution and magnitude of fluorochemicals in biota of the vicinity of the 3M facility and as a result fish concentrations were measured in whole body homogenates. In 2002, the objective of the study was to provide information on the potential exposure to humans consuming sport-caught fish and as a result, fish concentrations were measured only in homogenized fillets. Thus, a direct comparison of fluorochemicals in fish can not be made based on the different tissue targeted for analysis.
7.5.1 Surface water The concentration of fluorochemicals in surface waters remained relatively constant between the 2000 and 2002 sampling seasons (Table 8). For locations where a direct comparison could be made, WWTP to LOC3 and Fox Creek 1 to LOCI, the concentrations of fluorochemical in surface waters in 2002 were equal to or less than those measured in 2000. For instance, concentrations of PFOS, FOSA, PFOA and PFHS were 9%, 85%, 80% and 65% less in surface water collected at LOC-1 than that collected at Fox Creek 1, respectively. However, a direct comparison of fluorochemical concentrations between 2000 and 2002 was complicated by the fact that in 2000, the LOQs for all target analytes were approximately 2-fold less than those reported in 2002.
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This was due to the fact that different analytical methods were used in each sampling event to quantitate fluorochemicals in river water. Thus, if one used the greater LOQs from 2002, a decreasing trend in fluorochemical concentrations is observed for surface waters above and below the 3M facility in Decatur. However, due to the small sample size in 2002, a statistical comparison could not be made for surface water fluorochemical concentrations in the Tennessee River. Finally, it is important to note that all concentrations of fluorochemicals in surface water collected in 2002 were less than 1.0 pg/L (ppb).
Table 8. Mean concentration of fluorochemicals in surface waters of the Tennessee
I f J * A M M A A MB If A -A A ^ B B M A 1 a I b A W V I A ^
Year 2000 2000 2000 2000 2000
Station Guntersville WWTP Bakers Cr.-2 Fox Cr.-l Fox Cr.-2
River Mile 370 303.5 301-302 296 296
PFOS (Pg/L) <0.009 0.053
14 0.54 0.18
FOSA (bg/L) <0.004 0.016
1.2 0.17 0.055
PFOA (lig/L) <0.008 0.028
130 2.7 1.00
PFHS
(Pg/L) <0.003 0.006
4.0 0.57 0.17
2002 2002 2002
A
LOC-3 LOC-2 LOC-1
307.5 301 296
than their limit o f quantitation (LOQ).
<0.13 <0.13 0.49
< 0.025 < 0.025 0.025
<0.05 <0.05 0.55
< 0.025 < 0.025
0.20
7.5.2 Sediment Concentrations of fluorochemicals in sediments upstream of the 3M facility (LOC3, WWTP and LOC2) did not differ greatly between the 2000 and 2002 sampling events. PFOS and FOSA concentrations at LOC-3 were approximately 0.42 -fold less than those measured at WWTP. In contrast, sediment PFOA concentrations at LOC-3 were 1.4-fold greater than those measured at WWTP. While differences in sediment fluorochemical concentrations of FOSA, PFOA and PFHS were observed between the three upstream sites (WWTP, LOC-3 and LOC-2), these differences were less than 1.5-fold and most likely are indicative of the natural variability in fluorochemical concentrations in the Tennessee River in the Decatur Alabama area. However, downstream of the 3M facility,
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concentrations of fluorochemicals in sediments were more variable. The mean concentration of PFOS and FOSA was approximately 2-fold greater at LOC-1 than that measured at Fox Creek 2 but were similar to those measured at Fox Creek 1. In contrast, no trend was evident for concentrations of PFOA or PFHS in sediment among these three down stream locations. Overall, the temporal differences in sediment fluorochemical concentrations did not differ greatly and due to the small sample size in 2002 (1 sample per location), a trend in fluorochemical concentrations could not be statistically evaluated upstream or downstream of the 3M facility.
Table 9. Mean fluorochemical concentrations in sediments of the Tennessee River near
Decatur, Alabama.a______________________________________________________
River
PFOS
FOSA
PFOA
PFHS
Year Station 2000 Guntersville
Mile (gg/kg) (gg/kg) (gg/kg) (gg/kg) 370 0.18 0.08 0.08 <0.20
2000 WWTP
303.5
0.98
0.15
0.09
0.08
2000 Bakers Cr.-2 301-302
192
54.1
238
11.5
2000 Fox Cr.-l
296 2.58 1.70 1.81 0.22
2000 Fox Cr.-2
296 0.93 0.44 0.80 <0.20
2002 2002 2002
LOC-3 LOC-2 LOC-1
307.5
0.42
0.068
0.13 <0.10
301
0.46
0.14
<0.25
<0.10
296 3.13 1.44 0.73 0.13
A A ll surface water concentrations reported as m ean value. Concentrations given as less than (<) are less than their lim it o f quantitation (LOQ). All data reported on a wet weight basis.
7.5.3 Fish
Concentrations of fluorochemicals were less in fish collected upstream of the 3M facility as compared to fish collected at the two downstream locations. However, comparisons between sampling events is difficult due to differences in the tissue type analyzed each year and to the fact that fish were collected from different locations in the Tennessee River. Taking these differences into consideration, the mean concentration of PFOS was less in fish collected from Guntersville, LOC-3 and LOC-2 than that observed in fish from the Outfall or LOC-1. This same trend was also observed for FOSA, PFOA and PFHS where concentrations in fish downstream of the 3M facility were greater than those measured in fish upstream of the facility. The statistical significance of these differences
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can not be determined due to the fact that whole body homogenates were analyzed in 2000 while fillet homogenates were analyzed in 2002. Finally, for both 2000 and 2002, concentrations of fluorochemicals were different between species sampled at all locations. For PFOS, the concentrations in largemouth bass were greater than those measured in catfish. However, for FOSA, PFOA and PFHS no species differences could be discerned due to variability in the data and due to the small sample size.
Table 10. Mean tissue fluorochemical concentrations in fish sampled from the
Tennessee River near Decatur Alabama.
PFOS
FOSA
PFOA
PFHS
Species
Location
Largemouth Bass Guntersvillea
(Pg/kg) 230
(Pg/kg) 8.8
(pg/kg) <8.0
(pg/kg) <7.5
LOC-3 b
<5.0
<5.0
<5.0
< 1.0
LOC-2 b
170
<5.0
<5.0
< 1.0
Outfalla
NQ
560
<8.0
<7.5
LOC-1 b
550 <5.0
15 < 1.0
Catfish
Guntersvillea LOC-3 b LOC-2 b Outfalla LOC-1 b
<7.5 <5.0 <2.5 1200 110
<7.5 <2.5 <2.5 NQ
61
<8.0 <5.0 <5.0 120 <5.0
<7.5 <2.5 <2.5
11 <2.5
a Fish collected in 2000. All values denoted with (<) are reported as less than their lim it o f quantitation. b Fish collected in 2002. All values denoted w ith (<) are reported as less than their lim it o f quantitation. NQ is not quantified due to data m eeting quality control criteria. All data reported on a wet weight basis.
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8 REFERENCES Ellefson, M.E. 2003. Tennessee River Valley Samples. 3M Environmental Laboratory
Study No. E02-0443. p. 276. Giesy, J.P. and J.L. Newsted. 2001. Selected fluorochemicals in the Decatur Alabama
Area. Report to 3M. Regan, W.K., 2002. Solid phase extraction and analysis of fluorochemical compounds
from biological matrices. 3M Environmental Laboratory Method, Number ETS-8231.1. US EPA. 2000. Guidance for Assessing Chemical Contaminant Data for Use in Fish Advisories. Volume 1: Fish Sampling and Analysis, 3rd Edition. United States Environmental Protection Agency, Office of Water. EPA 823-B-00-007.
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9 APPENDICES
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9.1 APPENDIXA
Selected Perfluorocarbons monitored in water, sediment and fish Collected from the Tennessee River, Decatur Alabama.
Chemical Name: Molecular structure: Molecular ion:
Perfluorooctane Sulfonate CgFnSCV 499
O
c 8f 17s--o o
PFOS
Chemical Name: Molecular structure: Molecular ion:
Perfluorooctane sulfonamide C8F17S 0 2NH2 498
\
C8Fi7^-- NH2 o
FOSA
Chemical Name: Molecular structure: Molecular ion:
Perfluorooctanoate C7F15C 0 0 ` 413
Chemical Name: Molecular structure: Molecular ion:
Perfluorohexanesulfonate C6F 13SO3' 399
Chemical Name: Molecular structure: Molecular ion:
Perfluorobutanesulfonate C4F9SO3'
1 Q7F15CO
PFOA
C6Fi3^--o O
PFHS
PFff01737
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9.2 APPENDIX B Water, sediment and fish sampling locations for the 2002, 3M Tennessee River Project
Water and Sediment
Downstream- Sample Location 1 Across 3M- Sample Location 2 Upstream- Sample Location 3
Easting
490208 498946 505470
Northing
3836096 38357705 3827825
Fish Locations
Easting
Downstream start Downstream end Across 3M start Across 3M end Upstream start (a) Upstream end (a) Upstream start (b) Upstream end (b)
490601 491386 499043 498483 505306 504900 505466 506967
Coordinate System- UTM- Zone 16 North-NAD 1927
Northing
3836210 3834205 3836283 3836387 3827660 3824585 3828685 3827705
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9.3 Appendix C
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W ater Sampling Standard Operating Procedure
3M D ecatur Sampling Trip
1.0 PU R PO SE The purpose o f this Standard Operating Procedure (SOP) is to provide details for the collection o f water using a MasterFlex peristaltic pump or some comparable u n it This SOP outlines the general procedures for collection o f water samples. Specific sampling details should be outlined in the site-specific work plan and quality assurance project plan for each individual project. SCOPE Water samples collected under this SOP are to be taken with a MasterFlex tubing pump or some comparable unit. These samplers are fairly simple devices that consist o f a peristaltic pump and tubing appropriate for the specific project. The tubing fits within a groove within the pump head. Several rollers are designed within the pump head to role over the tube in a clockwise fashion. As the rollers move over the tube they create a vacuum that draws the water up through the tubing and dispels it on the other side. These units are optimal for surface water sampling in cases where it is important that only the selected tubing comes in contact with the sample. No portion of the pump comes in contact with the sample. A new portion o f pre-cleaned tubing can be used with each sample to minimize any risk o f contamination.
E Q U IPM E N T Equipment and supplies needed may include, but are not limited to the following:
One boat or sampling barge for the purpose of collecting in situ parameters and surface water samples
Direct-read and properly calibrated water quality sampling instruments capable of recording temperature, DO, pH, conductivity, and salinity (YSI Models 63 and 95)
' MasterFlex tubing pump or some comparable unit
Sample containers and coolers with wet ice for sample storage
Field data sheets, COC forms, and related materials
Items needed to document data collection activities and to label sample jars for shipment, including: camera, film, field notebook, pens, sample labels, custody seals
Personal Protective Equipment PPE as required by the site Health and Safety Officer,
' Decontamination equipment
Prior to the collection o f surface water samples, direct-read field meters will be deployed to measure the water quality parameters at each sample station. The direct read instruments will be calibrated each day. Suggested parameters targeted for measurement at each sampling station may include but are not limited to:
Water depth (m)
Temperature (C)
Dissolved oxygen (mg/L)
Conductivity (pmhos/cm)
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Salinity ("Ax,)
pH (s.u.)
In some instances, the collection o f additional water quality parameters may be warranted or required. Water quality meters to collect additional parameters will be added as needed.
PROCEDURES 1. Obtain the sample location information from either the scope-of-work, work outline, or the
Work Plan. This may be in the form o f an actual coordinate or a description o f the general sampling location. 2. Position the sampling barge or boat over the selected sample location. The field crew should always work from the most downstream location to the most upstream location unless otherwise directed. 3. Once you arrive at the proper location measure and record depth o f water and record sample location identification as identified on the sampling log. 4. Make sure that all data sheets correspond to the correct sampling location. 5. Measure the sampling location using the best available technology (e.g., global positioning satellite system) and record sample coordinates on the sampling log.
6. After warm-up and calibration o f the field meters, water quality parameters will be measured and recorded. The depth o f readings should reflect the depth at which water samples are collected and any other requirements o f the site specific work plan.
7. W ater samples will then be collected using an appropriate pump with pre-cleaned tubing.
8. The specific type and size o f tubing for sampling should be obtained. The length o f this tubing depends on the depth o f sample to be collected.
9. Weave the tubing through the designated slot on the pump. Make sure that the peristaltic head is correctly situated.
10. Lower the end o f the tube into the water to the desired depth. Turn the pump on and wait for it to prime itself.
11. Run water through the tube until you have completed at least three volume additions o f the tubing (calculated by taking the radius o f the tubing and the length - Ilr2!).
12. Once approximately three volume additions have run through the tubing, begin collecting your sample.
13. Sample containers will be sealed with the appropriate caps, labeled, and placed on wet ice in an insulated container or cooler.
14. Appropriate COC documentation will accompany the samples as required by the projectspecific QAPP.
15. After collection o f the sample, remove the tubing and discard. Obtain a new section o f tubing and navigate to the next sampling location.
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Sediment and Soil Sampling Petite Ponar or Eckman Dredge Standard Operating Procedure For the 3M Decatur Sampling Trip
1 0 PURPOSE
The purpose of this Standard Operating Procedure (SOP) is to provide details for the collection o f surface sediments using either a Petite Ponar or Eckman Dredge. Procedures outlined below detail the general methods required to collect surface sediment samples using either o f these sampling devices. Although die details o f sample collection will be influenced by site-specific conditions, certain aspects o f sample collection can be standardized. These procedures give descriptions of equipment, field procedures, and documentation necessary to collect sediments using either o f these methods.
2.0 SCOPE
Petite Ponar The Petite Ponar is widely used in both fresh and salt waters for collecting sediments from soft to relatively hard bottoms. It is especially useful in sand, gravel, consolidated marl or clay bottoms where standard dredges will not work. The Ponar is a self-closing sampler that releases when the unit comes in contact with the sediment The sample area with this unit is 15 x 15 cm and the unit weight is approximately 55 kg.
Eckman Dredge The Eckman Dredge is designed to collect samples in soft, finely divided littoral bottoms. In systems that have high amounts o f debris or rocky bottoms, these units typically will not work well. The unit is typically lowered to the bottom via a rope and a messenger is sent down the line to release the spring-loaded doors. The doors are designed to close tight, encompassing a 15 x 15 cm area o f sediment.
*
This SOP will cover the equipment required to collect sediment samples using either of these sampling devices and the specific procedures that are followed.
3.0 EQUIPMENT
Equipment and supplies needed may include, but are not limited to the following:
Petite Ponar and Eckman Dredge Stable boat or platform barge Stainless steel mixing containers Stainless steel spoons for homogenizing sediments Sample containers (project specific) and coolers with wet ice for sample storage Field data sheets (water quality/chemistry, general data sheets) Chain-of-custody forms
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- Items needed to document data collection activities and to label sample containers for shipment, including: camera, film, field notebook, pens (write in the rain and Sharpie), sample labels, custody seals
Personal protection equipment as required by the site Health and Safety Officer, including organic vapor meters (OVMs)
Decontamination equipment specific for the project
4.0 SAMPLE COLLECTION PROCEDURE
Surface sediment collection using the Ponar or Dredge samplers will involve the following procedures:
1. Obtain the sample location information from either the scope-of-woik, work outline, or the Work Plan. This may be in the form o f an actual coordinate or a description o f the general sampling location.
2. Position the sampling barge or boat over the selected sample location. When sampling sediments, the field crew should always work from the most downstream location to the most upstream location unless otherwise directed.
3. When sampling sediments in deep waters, attempt to set the barge in place with either a two to three point tie down (e.g., spud poles). This will provide some stability for the platfoim and ensure that the platform does not drift while sampling.
4. Once you arrive at the proper location measure and record depth of water and record sample location identification as identified on the sampling log.
5. Make sure that all data sheets correspond to the correct sampling location.
6. Measure the sampling location using the best available technology (e.g., global positioning satellite system) and record sample coordinates on the sampling log.
7. Obtain the decontaminated dredge or ponar (depends on the sediment/substrate type).
8. Make sure that the dredge or ponar are in the open position and slowly lower them over the side o f the boat. This is to prevent the units from premature closure. Once the units are slightly submerged, release them and let them fall to the bottom of the system you are sampling in. The weight o f the units should force them into the sediment bottom.
9. If using the Eckman Dredge, make sure that the unit is upright on the bottom (tug lightly on the line). Pull the line taut and release the messenger. Once the messenger releases the doors, pull the unit off the bottom and slowly through the water to the boat.
10. For the Ponar, the force of the unit hitting the sediment should cause the pin holding the doors open to release. Therefore when you pull the line holding the unit, the doors will close (collecting the sample).
11. Once the unit is in the boat, place all the contents into one o f the decontaminated stainless steel mixing containers. Use a decontaminated, stainless steel spoon to homogenize the sediment.
12. Once homogenized, use the stainless steel spoon to place sufficient sample volumes into the proper sample containers. It is critical that the sample label for this sample be placed on the container. At a minimum, this label should contain the sample ID, date, time collected, initials o f the persons collecting, and type o f analysis for this sample.
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13. Collect the appropriate QA/QC samples as outlined in the QAPP attached to the project specific work plan.
14. Complete the chain-of-custody form. 15. Place all samples in the proper sample shipping/storage container, which should contain
sufficient wet ice to keep the samples at a temperature o f 4*C until receipt by the laboratory.
Slight m odifications may be required in the field, depending upon the type o f sample that is being collected. The field crew w ill always have a working knowledge o f the equipment prior to sampling, and w ill be fam iliar w ith the specific requirem ents o f the project Any m odifications or changes that are needed for sampling specific systems should be documented in field data sheets and reflected in the final report.
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9.4 APPENDIXD
QA/QC samples for the 2002,3M Tennessee River sampling effort
Sample ID FB01 FB02 SW01-DUP SWOl-Low SWOl-Med FSCOl-Low FSCOl-Med SW02-DUP SW02-Low SW02-Med FSC02-Low FSC02-Med SW03-DUP SW03-Low SW03-Med Trip Blank #1 Trip Blank #2
Media Air
Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water
Location Tennessee River Tennessee River Downstream near Fox Creek Downstream near Fox Creek Downstream near Fox Creek Downstream near Fox Creek Downstream near Fox Creek Across River from 3M Across River from 3M Across River from 3M Across River from 3M Across River from 3M
Upstream Upstream Upstream
-
-
River Mile
-
-
296 296 296 296 296 301 301 301 301 301 307.5 307.5 307.5
-
-
Date 4/15/02 4/15/02 4/15/02 4/15/02 4/15/02 4/15/02 4/15/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02
-
-
Time 14:30 14:30 14:45 14:45 14:45 14:45 14:45 10:20 10:20 10:20 10:20 10:20 8:00 8:00 8:00
-
-
Description Field Blank-Empty Field Blank-Filled Field Duplicate Field Matrix Spike-20 ppb Field Matrix Spike-20 ppm Field Control Sample-20 ppb Field Control Sample-10 ppm Field Duplicate Field Matrix Spike-20 ppb Field Matrix Spike-20 ppm Field Control Sample-20 ppb Field Control Sample-10 ppm Field Duplicate Field Matrix Spike- 20 ppb Field Matrix Spike- 20 ppm Shipped with water samples Shipped with sediment samples
C C
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9.5 APPENDIXE Fish collection information for the 2002 3M Tennessee River sampling effort
Sample ID SL01-LM01 SL01-LM02 SL01-LM03 SL01-LM04 SL01-LM05 SL01-LM06 SL01-CAT01 SL01-CAT02 SL01-CAT03 SL01-CAT04 SL01-CAT05 SL01-CAT06 SL02-LM01 SL02-LM02 SL02-LM03 SL02-LM04 SL02-CAT01 SL02-CAT02 SL02-CAT03 SL02-CAT04 SL02-CAT05 SL02-CAT06 SL02-CAT07 SL03-LM01 SL03-LM02 SL03-LM03 SL03-LM04 SL03-LM05 SL03-LM06 SL03-LM07 SL03-SM01 SL03-CAT01 SL03-CAT02 SL03-CAT03 SL03-CAT04 SL03-CAT05 SL03-CAT06
Location Downstream Downstream Downstream Downstream Downstream Downstream Downstream Downstream Downstream Downstream Downstream Downstream Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Across from 3M Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream Upstream
Date Collected 4/15/02 4/15/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/16/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/18/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/17/02 4/18/02 4/18/02 4/18/02 4/18/02
Fish Type Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Catfish Catfish Catfish Catfish Catfish Catfish Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Catfish Catfish Catfish Catfish Catfish Catfish Catfish Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Largemouth Bass Catfish Catfish Catfish Catfish Catfish Catfish
Length (cm) 41 36 31.4 33.2 44.5 31.2 61 62.5 62.1 74.1 55 53.5 30 45.5 33 33 57 51 59.5 57.5 64 53.5 53 30.5 36.5 38 41.2 29.7 36 42 32.5 32.2 57 64.2 61.5 55 60.5
Weight
(g) 872 619 450 535 1181 478 2222 3150 2785 6047 1744 1575 450 1097 506 535 2138 1387 2025 1800 3206 1519 1519 450 760 675 956 281 619 731 563 816 3516 3769 2081 1856 2278
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