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14ATER QUALITY, CIRCULATION PATTERNS AND SEDI14FNT ANALYSTS OF THE ESTERO BAY ESTUARINE SYSTEM, 1986 COASTAL ZONE INFORMATION CENTER WATER QUALITY, CIRCULATION PATTERNS AND SEDIMENT ANALYSIS OF THE ESTERO BAY ESTUARINE SYSTEM, 1986 By Roger S. Clark Department of Community Development Lee County, Florida Lee County Board of County Commissioners Prepared under Coastal Zone Management Grant CM-123 from the Florida Department of Environmental Regulation September, 1986 N- -11 0 ri CONTENTS PAGE ABSTRACT ... ......................................................... 1 EXECUTIVE S Y ........................................................ 2 3 Purpose and Scope ......... ................... 3 Description of the Study Area ........................................ 4 Acknowledgements ...................................................... 4 PRESENTATION OF DATA ..................................................... 4 Water Column Analysis ................................................ 6 Circulation Study .................................................... 7 Bottom Sediment Analysis ............................................. 8 REFERENCES ............................................................... 9 ILLUSTRATIONS Map 1 Showing Location of Lee County, Florida ........................ 5 Figure 1 - Estero Bay Aquatic Preserve Location Map .................. 10 Figure 2 - Names Location Map ......................................... 11 Figures 3-7 Maps Showing Physical and Chemical Parameters Figure 3 - Total Nitrogen Concentrations ........................ 12 Figure 4 - Nitrite - Nitrate Concentrations ..................... 13 Figure 5 - Biochemical oxygen Demand Levels ..................... 14 Figure'6 - Average Salinity Values ..... .......... 15 Figure 7 - Average Dissolved Oxygen Concentrations .............. 16 Figures 8-9 - Maps Showing Circulation"Patterns Figure 8 - Hendry, Mullock & Spring Creek ....................... 17 Figure 9 - Estero and Imperial Rivers ........................... 18 Figures 10-27 - Maps showing Trace Metal Concentrations Figure 10 - Arsenic Concentrations January 15, 1986 ............. 19 Figure 11 - Arsenic Concentrations August 11 and 27 & September 3, 1986 ............................... 20 Figure 12 - Aluminum Concentrations January 15, 1986 ............ 21 Figure 13 - Aluminum Concentrations August 11, 27 & September 3, 1986 ............................... 22 Figure 14 - Cadmium Concentrations January 15, 1986 ............. 23 Figure 15 - Cadmium Concentrations August 11, 27 & September 3, 1986 ............................... 24 Figure 16 - Chromium Concentrations January 15, 1986 ............ 25 Figure 17 - Chromium Concentrations August 11, 27 & . September 3, 1986 ............................... 26 Figure 18 - Lead Concentrations January 15, 1986 ................ 27 Figure 19 - Lead Concentrations August 11, 27 & Sept. 3, 1986 ... 28 Figure 20 - Mercury Concentrations January 15, 1986 ............. 29 Figure 21 - Mercury Concentrations Aug. 11, 27 & Sept. 3, 1986.. 30 Figure 22 - Silver Concentrations January 15, 1986 .............. 31 Figure 23 - Silver Concentrations Aug. 11, 27 & Sept. 3, 1986 ... 32 ii PAGE ILLUSTRATIONS (CONT9D) Figure 24 - Copper Concentrations January 15, 1986 .............. 33 Figure 25 - Copper Concentrations Aug. 11, 27 & Sept. 3, 1986 ... 34 Figure 26 - Zinc Concentrations January 15, 1986 ................ 35 Figure 27 - Zinc Concentrations Aug. 11, 27 & Sept. 3, 1986 ..... 36 TABLES PAGE Table 1 - Locations and Site Numbers for Tables Two Through Five Collection Date: January 16, 1986 ................................... 37 Table 2 - Nutrients in Estero Bay Water Column Collection Date: January 16, 1986 ................... ................ 38 Table 3 - Physical/Chemical Characteristics in the Estero Bay Water Column Collection Date: January 16, 1986 ................................... 39 Table 4 - Bacteriological Data From Estero Bay Water Column Analysis Collection Date: January 16, 1986 ........... ......... 40 Table 5 - Locations and-Site Numbers For Tables Six Through Eight Collection Date: June 18 , 1986 ...................................... 41 Table 6 - Nutrients In Estero Bay Water Column Collection Date: June 18, 1986 ...................................... 42 Table 7 - Physical/Chemical Characteristics In The Estero Bay Water Column Collection Date: June 18, 1986 ....................................... 43 Table 8 - Bacteriological Data From Estero Bay Water Column Analysis Collection Date: June 18, 1986 .............. ********* ...,... ''***** 44 Table 9 - Locations and Site Numbers For Tables Ten Through Twelve Collection Dates: August 6, 1986 and August 7, 1986 ................. 45 Table 10 - * Nutrients in Estero Bay Water Column Collection Date: August 6, 1986 and August 7, 1986 ................... 46 Table 11 - Physical/Chemical Characteristics in the Estero Bay Water Column Collection Date: August 6, 1986 and August 7, 1986 .................. 47 Table 12 - Concentrations of Rhodamine Dye in Estero Bay Collection Date: July 17, 1986 ......... 48 Table 13 - Concentrations of Rhodamine Dye in Estero Bay Collection Date: July 18, 1986 ................ 51 Table 14 - Concentrations of Rhodamine Dye in Estero Bay Collection Date: July 19, 1986 ... ..... 52 Table 15 - Concentrations of Rhodamine Dye in Es tero Bay Collection Date: September 17, 1986 ................................. 53 Table 16 - Concentrations of Rhodamine Dye in Estero Bay Collection Date: September 18, 1986 ................................. 55 Table 17 - Locations and Site Numbers for Table Eighteen Collection Date: January 15, 1986 ................................... 56 Table IS - Trace Metals and Nutrients in Estero Bay Sediment Collection Date: January 15, 1986 57 Table 19 - Locations and Site Numbers for Table Twenty Collection Date: August 11, 1986 .................................... 58 Table 20 - Trace Metals and Nutrients in Estero Bay Sediment Collection Date: August 11, 1986 ..................................... 59 Table 21 - Locations and Site Numbers for Table Twenty-Two Collection Date: August 27, ...... 60 Table 22 - Trace Metals and Nutrients in Estero Bay Sediment Collection Date: August 27, 1986 .................................... 61 Table 23 - Locations and Site Numbers for Table Twenty-Four Collection Date: september 3, 1986 .................................. 62 Table 24 - Trace Metals and Nutrients in Estero Bay Sediment Collection Date: September 3, 1986 .......... ... ******' 63 Table 25 - Pesticides and PCBs in Estero Bay Sediment Composites . Collection Dates: August 11-27', 1986/September 3, 1986 .............. 64 APPENDIX - Quality Assurance and Documentation iv WATER QUALITY, CIRCULATION PATTERNS AND SEDIMENT ANALYSIS OF THE ESTERO BAY ESTUARINE SYSTEM, 1986 By: Roger S. Clark ABSTRACT The Lee County Department of Community Development conducted in 1986 analyses of physical-chemical parameters, circulation patterns and bottom sediments from Estero Bay. The major focus of this study was analyzation of bottom sediments for trace metals, nutrients, pesticides and PCBs. Baseline data for these parameters has been established by' this study. Continued data collection will be necessary to allow conclusions to be made regarding contamination of the Bay. This report presents data collected in 1986 and includes maps containing parameter levels, and tables containing the data. The purpose and scope of the study is explained and the results of the analyses are discussed. Methods of sample analysis and collection as well as quality assurance and control are also explained. EXECUTIVE SUMMARY Samples f rom selected sites were taken f rom Estero Bay by- the Lee County Environmental Laboratory in 1986. The water column was sampled for typical physiedl-chemical parameters including nutrients and dissolved oxygen. A circulation study using non-toxic dye was performed to determine the primary direction of water flow from the major tributaries through the estuary. Bottom sediments were analyzed for trace metals, nutrients, pesticides and polychlorin'ated biphenyls (PCBs). selected water column and bottom sediment parameters were compared to the recent report "Water Quality of the Charlotte Harbor Estuarine System, Florida, November 1982 through December 1984". This report, prepared by the United States Geological Survey, presents data from the first two years of this seven year study. Values for orthophosphorus, total nitrogen and nitrite-nitrate were similar in Estero Bay in 1986 to those in Charlotte Harbor in 1982-84. Values for dissolved oxygen had more bf a range than the average values reported in the USGS study. The circulation study provided a general interpretation of the effect of the Bay's tributaries on circulation within the Bay. Water from Hendry-Mullock Creeks and the Estero River appeared to flow towards Big Carlos Pass, which corroborates an earlier theory that the Bay is hydrologically divisable into two major regions. Water from Spring Creek appeared to flow north and then west towards New Pass. Water from the Imperial River appeared to flow through Fish Trap Bay _and through Hogue Channel northward. Residency of water from the tributaries appeared to be at least several days within the Bay. Comparison of bottom sediment concentrations from Estero Bay with those from Charlotte Harbor provided the general conclusions that ranges for aluminum, lead, cadmium and mercury were similar. Chromium, copper and zinc had higher levels in Estero Bay in 1986 than those in Charlotte Harbor in 1984. The concentration levels of pesticides and polychlorinated biphenyls (PCBs) were all below minimum detection limits, The variation in minimum detection limits for the data are related to the percent solids, response factors and the methodology used. The Lee County Environmental Laborato ry plans to expand the scope of the South Estero Bay (Big Hickory Pass area) monitoring program both in area covered and parameters sampled to allow continual comparisons to be made to at least some of the data contained in this study. 2 INTRODUCTION Previous studies in Estero Bay Aquatic Preserve have examined ecological and water column conditions (Tabb et al 1971), - (Balogh et al, 1977); productivity (Environmental Science and Engineering, Inc. , 1978); inlet and circulation dynamics (Suboceanic Consultants, Inc. , 1978), (Jones 1980)', environmental quality (SWFRPC, 1975); and long term trends in water chemistry (DER, 1980 in Estevez, 1984). These studies provide "window" views of the bay separately and when considered together open the door to an acquaintance with the Bay. Long term comprehensive studies of Bay water quality parameters coupled with effective land use planning, watershed protection and strict control of dredge and fill activities will be necessary to protect the quality of the estuary. The Estero Bay Watershed and the barrier islands adjacent to the Bay continue to develop at a rapid pace. A major decision will have to be made soon by Lee County and the DKR on what the Bay's fate is to be. This decision has been delayed while projects are proposed including ones to dredge the entire channel which parallels Estero Island and to build a nearly 2 mile bridge extending from the mainland to Black Island. The former project, proposed by private citizens, has recently received lack of funding support from the U.S. Army Corps of Engineers. The latter project has been proposed by the Lee County Board of County Commissioners who have appropriated $955,000 for Fiscal Year 1986-87 for studies on the proposed project. These types of major projects, if carried out, will make the decision on the Bay's fate harder, if not impossible to make. Meanwhile smaller projects are proposed and carried out. These include maintenance dredging, dock construction and shoreline development. Unless a decision on the Bay's fate is made soon, it will no longer be an important one to make. The Department of Natural Resources (1983) designates Estero Bay on page 3 of the Estero Bay Aquatic Preserve Management Plan as a wilderness preserve. Is Estero Bay to be protected as a wilderness preserve, a recreational boating area, a commercial fishing resource or as an aesthetic resource for Lee Countyl While these classifications or uses are not necessarily mutually exclusive, it may not be possible to accomodate all of them in the future. It may be more feasible to maximum the value of the Bay by managing and protecting it for some, but not all of these uses. Estero Bay is a dynamic ecosystem. Dynamic and carefully considered action will be necessary to protect its intrinsic values. Purpose and Scope The purpose of this report is to present data which will allow a better assessment to be made of the current health of Estero Bay. The main focus of this study was the analysis of bottom sediments for selected parameters including trace metals, pesticides and nutrients. This focus heretofore has not been undertaken for Estero Bay. Thus, the bottom sediment data serves to establish baseline concentrations. Future land use and permitting considerations can be influenced by not only this baseline data but subsequent data as well. 3 The water column and circulation pattern data also contained in this report complement the sediment data and provide a wider scope for this report. The Lee County Environmental Laboratory has been collecting data in Estero Bay since January, 1978. This sampling has been conducted primarily in South Estero Bay near Big Hickory Pass. This pass has been closed, except for brief openings following dredgings and a storm in June, 1982, since September 1976 (Suboceanic Consultants, Inc., 1978). The Lee County Environmental Laboratory plans to expand the scope of the south Estero Bay monitoring program both in area covered and parameters sampled to allow continual comparisons to be made to at least some of the data contained in this study. Description of the Study Area Estero Bay (Figures 1 and 2) is a shallow, turbid, approximately 11,300 acre sub-tropical estuary located in Lee County, Florida (Map 1). Fringing mangroves form its shoreline which is bordered to the west by a chain of barrier islands which separate it from the Gulf of Mexico. These islands include Estero Island (Fort Myers Beach), Lovers Key and Big Hickory Island and Little Hickory Island (Bonita Beach). The major passes are New Pass, Big Carlos Pass and Matanzas Pass. The Bay consists of sea grass meadows, extensive oyster bars, sandy bottoms and mangrove islands (Tabb et al, 1971). It has four main tributaries - Hendry - Mullock Creek, the Estero River, Spring Creek and the Imperial River. The entire Bay, with the exception of the area west of the channel paralleling Estero Island, is an aquatic preserve managed by the Department of Natural Resources. Acknowledgements We wish to thank Bob Repenning and Kevin Bowen, Department of Natural Resources, Estero Bay Aquatic Preserve, for assistance provided in collecting data for this study. PRESENTATION OF DATA Data is presented both in tables, and for selected parameters, in figures. The three areas for which data were included water column analysis, bottom sediment analysis and circulation patterns. Figures 3 through. 27 depict on a map of Estero Bay the approximate locat ions of sampling sites. The individual or average value for the parameter sampled has been placed next to the station location. This approach allows ease of future data comparison and makes the data visually conducive to use during review of permits and development applications. The data presented in the figures complements and relates directly to data contained in the tables. 4 ---f cc.- 314' F 2: @-l -4 Ln Q'I + -C A .L 0 L4991e@,- ' - - I .* : * - '" " , , 0 s A N C A 0 KC Ester'o Bay f C 0 Water Column Analysis The water column was sampled in the dry season (January) and the wet season (August). Parameters included physical-chemical, nutrients and fecal coliform and fecal streptococcus. Sample sites were selected by using aerial photographs, navigational charts and visual observation by boat. Sample collection methods are discussed in the Appendix. Figures 3, 4 and 10 and Tables 2 and 6 present data on nutrients collected during the dry and wet seasons. Values for orthophosphorus, total nitrogen and nitrite-nitrate are similar to those presented for Charlotte Harbor in Figures 17, 18 and 20 pps 21, 22 and 24 of the USGS report (Stoker, 1984). Figures 5-7 and Tables 3, 7 and 11 provides data on physical parameters for the dry and wet seasons. Values for dissolved oxygen had more of a range (3.1 to 10.1 milligrams per liter) than the average values depicted in Figure 10 (page 14) of the Charlotte Harbor Study (Stoker, 1984). Tables 4 and 8 provide bacteriological data collected in the dry and wet seasons. Estero Bay is presently a closed area for shellfish harvesting. The Department of Natural Resources Shellfish Environmental Assessment Section is currently monitoring the Bay for bacteriological parameters with the goal of reopening the Bay for shellfish harvesting. 6 JU Circulation Study The circulation study of the Bay was performed in two phases during the wet season. Flow meters were not used in the tributaries during the study. The @SGS doe7i3 not have stage discharge gauges for the Estero Bay tributaries but is planning to install gauges in Fall 1986 in Ten Mile Canal (which drains into Mullock Creek) and the Imperial River. The studies were performed in- phases because of the assumption that Hendry-Mullock Creeks might influence circulation in some of the same areas as the Estero River and that Spring Creek might influence circulation in some of the same areas as the Imperial River. Thus, the first phase involved Hendry-Mullock Creeks and Spring Creek and the second phase involved the Estero and Imperial Rivers. Figure 8 depicts station numbers and their location and approximate circulation patterns for about I hours after placement of the dye in the mouth of the tributaries. Sampling performed the day after dye placement and after nearly 2 complete tidal cycles showed the dye still to be present in the bay but not in measurable amounts (<0.3 mg/1) at the major passes (Big Carlos and New Pass). This indicates that water from the tributaries has a residency time in the bay of at least several days during the wet season. The results also corroborate the statement made by Tabb (1971) "that the Estero Bay system may be hydrologically divisible into two major regions by a northeast-southwest oriented line drawn through the lower portion of Julies Island." The results of the second phase of the circulation study is represented by Figure 9 which depicts station members and their locations and the approximate circulation patterns for approximately 24 hours after dye placement. Data for Estero River are inconclusive and Figure 9 represents visual observation of dye travel for several hours after it was placed in the river, but the hydrography in the Imperial River mouth area seems to influence circulation such that the water from the river has a fairly long residency in Fish Trap Bay and is conveyed via Hogue Channel north. Data do not indicate direction of circulation patterns north of Hogue Channel. Future circulation studies of Estero Bay should probably combine a combination of dye and drogues to provide better interpretation of circulation. It is suggested that the circulation patterns influenced by the passes be compared to the influences of the tributaries. 7 Bottom Sediment Analysis Sediment samples were collected during the dry and wet seasons. Samples were analyzed for trace metals, nutrients and pesticides. It appears from a study of the literature on Estero Bay that the sediment data provided in this report is the first such data collected for Estero Bay. The U.S. Army Corps of Engineers (1976 -in Estevez, 1984) analyzed nutrients-, chemical oxygen demand and total organic carbon of sediments for San Carlos Bay. Comparison of trace metal concentrations from Figures 10-27 and Tables 18, 20, 22 and 24 with Table 8 from the Charlotte Harbor USGS Study (Stoker, 1984) provided the following general conclusions. Ranges for concentrations of aluminum, lead, cadmium and mercury were similar. Chromium, copper and zinc had higher levels in Estero Bay in 1986 than those in Charlotte Harbor had in December 1982. The concentration levels of pesticides and polychlorinated biphenyls (PCBs) presented in Table 25 were all below minimum detection limits. The variation in minimum detection limits for the data are related to the percent solids, response factors and the methodology used. 8 REFERENCES Balogh, F., Gersberg, D., Johnson, W., and Loewer, B., 1978 Big Hickory, Pass - Environmental Impact Study. Environmental Laboratory, Division of Environmental Protection Services, Board of County Commissioners, Lee County 24p. Department of Environmental Regulation. 1980. Hole-In-Wall #1 (Gasparilla Island). Unpublished data, Punta Gorda, Florida. Department of Natural Resources 1983 Estero Bay Aquatic Preserve Management Plan. 118 pages. Environmental Science and Engineering, Inc. Final Report and Technical Appendix of the Productivity Study for the Estero Bay Study Area. Prepared for Southwest Florida Regional Planning Council, February, 1978 Estevez, E.D. January, 1984 (revised) Charlotte Harbor Estuarine Ecosystem Complex and the Peace River, Volume Southwest Florida Regional Planning Council. Jones, C.P. 1980. Big Hickory Pass, New Pass, and Big Carlos Pass, Glossary of Inlets Report #8. Florida Sea Grant College. 47pp. Stoker, Y.E. 1986. Water Quality of the Charlotte Harbor Estuarine System, Florida, November, 1982 through December, 1984 United States Geological Survey Open File Report 85-563. Suboceanic Consultants, Inc. 1978. Big Hickory Pass, Lee county, Florida Hydrographic Study'Naples, Florida 75+ pages Tabb, D., Alexander, T., Rehrer, R.,-Heald, E., Nov. 1971 A Preliminary Survey of Estuarine and Coastal Resources of Estero Bay and Environs, Lee County, Florida. Rosenstiel School of Marine & Atmospheric Sciences. Wilson, J.F., Jr. 1968. Flourometric Procedures for Dye Tracing. Techniques of Water Resources Investigations of the United States Geological Survey. Book 3 Chapter A12. 31 pages. 9 Crook Hurricalie muftek Bay creek"-- Nb Hall PeOney Be Y Estero Rlyer Estero Island Mound (Fort Myers Beach) lop. Black Island Lovers Ke Long Key CIO sit SprIng crook Big Hickory Island u, A CIO 408 A Ole Bonita Beach RI'Ver Little Hickory Island zmperla Figure 1. Estero Boy Aquatic Preserve Location Map 10 k: AOL ii I 23, N CARLO-$ 9 211 20 air 25 -130 ST.* 29 28 *cases..%:, Ism 11a PL.Ts US, ds% IL KOM MAN r PA 33 0 AN 31 0 a." 32 33 Z May t 00 SLAM" @Mwf KIE S2 W ... W 890.48. '01 Is tAftfis Piewr a."* 4Z atbakADO 10 9 16L.. MILT 16 .... ................. i k. 20 19 7. p.zl ..,v . . .IA . - - 21 987 30 29' 28 ......... .................... 32- 33 q, Figure 2. 34 sea Place Names Location Map 4 Ar V3 Estero Riyer Estero Island Mound (Fort Myers Beach) VI-q 4z 10 Black Island Lovers @e Long, Key CL69 to 0.62 sorhig Big Hickory Isio-nd. Explanation, 670 post 054 0.69- $1001 .. OA4 Q. $4 .. Sample site and total nitrogen concentration in milligram/liter Bonita Beach Little Hickory island 0.71 Figure 3. Concentrations at Estero@ Bay 'water quality sites, January 16, 1986', of total nitrogen 80Y Hefl 4400 -Estero Island Mound (Fort Myers Beach) Key Black Island Lovers Ke Long Key 01 0 <0 C-0: .0 Cre 10.06 Big Hickory Island A Explanation I QO 0 0.10 0%0(1 0. Sample site and nitrite-nitrate concentration in milligram/liter Bonita Beach Little Hickory Island er/d 0.10 0*03 Figure 4. Concentration at Estero Bay T_ water quality sites, January 16, 1986 of nitrite - nitrate 13. levy 0 Bay Ole Estero -Esl4ro Island Mound N, Key W (Forl Myors Beach) to* COMO Sic ck Island Lovers Key Lonq Ke 1. P4 It. .1, 11 '0': sprhig Creek Big Hickory Island Explanation 00.10 1 OA < Sample site and BOD,,- concentration in mil gram/liter A Ban(% Beach Little Kickory Island Imperial River Figure 5. Concentration*at Estero Bay water quality sites, January 16, 1986 of BOD5 .14 Crl*k say Crook B9,r -Estero Island Mound (Fort Myers Beach) Key Le. to$$ Black Island Lovers Ke Long Key 0 M3 2 7 66 lot $04,79 it Cresh Big Hickory Island 115.7 Explanation I. G%6(1 . 25.5 Sample site and salinity values in parts per thousand Bonlia Beach Little Hickory Island I 11n drial RI*Yojr 19.0 4 13.0 Figure 6. Average values at Estero , \hj Bay water quality sites, January 16, 1986 for salinity Cra Hf11 7.71 P10#70Y say Estero Rlyer -Est4ro (stand Mound (Fort Myers Beach) K4Y post Black Island Lovers Xe Long K4y 6.9 6 6.9'. r4so C.F# sk Big Hickory Island Explanation I so 47 6. d to 7.9- 9 7.9 $100 7.3 Sample site and dissolved oxygen concentration in milligram/liter Bonita Booth Little Wickory Islond 010/ 1rVer 44 .8 Figure 7.! Average concentrations at Estero Bay water quality sites, January 16, 1986, of dissolved oxygen C wk . Hurricafte A1111100k Bay dek"N HelY Bey WA 2 Estero Island d (Fort Myers Beach) ey 3 2 20 22 23 too Black Island 14 Lovers Ke 'A Long Key 017 W. C% 0 8 Creek Big Hickory Island Explanation 1 10006 17 0 Station number and location ,,@@Concentration of dye at time indicated A. Bonita Beach Little Hickory Island A Perial R Figure 8. Circulation patterns in Estero Bay as affected by Hendry, Mullock and Spring Creeks July 17 1986 17 F` creek Hurricane BO crook Hell Bar 5 Z'stero River Estero Island Mau (Fort Myers Beach) Ke 2 @17 0 1*5 C post .4 GOO Black Island Lovers Ke 25 C1 Long Key '0 23 Crook Big Hickory Island I toss A 6, D. Explanation 0 25* Station number and location 3.2 117 911 -'3@Concentration of dye at time indicated 5 Bonito Beach 9/17 5:00 14 .471 IRI.veil Little Hickory Island 3 9117 4:00 9/1 3:06 Figure 9. Circulation patterns in Estero Bay as affected by Estero and Imperial Rivers, September 17-18, 1986 18 crf Ok Sol cr*a Y Rlror Estero island (Fort Myers Beach) 0-0 Mound% '4* W12; ck Island Lovers Ke V_ Long Key @0. 7 0 .V 0.83 2 55 Big Hickory Islaind. 63 Explanation 1, FOSS Z4 7 1.09 2 Sample site and arsenic .47- concentration in milligrams/Kilogram, Sonlia Beach Little Hickory Island A IN Q.7 1. M Off Ver Figure 10. Concentrations of arsenic in Estero Bay sediments January 15, 1986 19 creek Hurricane 0 Bay 1.05 muflock V Hell PecIcney Bay V.. CL8510 rs-tdro 1.20 IS8 Estero Island 30 0.33 Mound Key (Fort Myers Beach) 0a 0 0 0 3 0 8 100 8 2AO of 014 Black Island Lovers Ke Long Key Q55 to 5 Crook Big Hickory Island Explanation A 0 1.08 095 Sample site and arsenic 09 concentration in Milligrams/Kilogram Bonita Beach 0.15 Little Hickory Island Orial /?I'Vef Figure 11. Concentration of arsenic in Estero Bay Sediments August 11, August 27 and September 3, 1986 20 cr*** fit NO# Ilk "Ir 4Werv N Estero Island Mound (Fort Myers Beach) Key Black Island Lovers Ke y Long Ke 1218 00 382 1872 Big Hickory lsl@ad 819 itplanation-, t,* 03.82 Imple site and aluminum concentration Milligrams/Kilogram Sonlia Beach N Little Hickory Island dri.471 River 23 Z964 Figure 12. Concentrations of aluminum in Estero Bay sediments January 15, 1986 21 creek Hurricane 4590 3 84al 2845 H ;% Peckney Bay 3610 3345 3390 26 Estero Island 4--J50 1415 Mound Key (Fort Myers Beach) 0 2%0 830 19 C, 2480 114 2380 680 we 4 fists @60 Sig 0 Block Island Lovers Ke Long Key ;, '0 1615 AO- 735- Spring Cree* Big Hickory Island Explanation si In. A 2720 1145 614 006a 20 4r Sample site and aluminum concentration in Milligrams/Kilogram Bonita Beach 21 890 442 Little Hickory Island Imperial 955 Figure 13. Concentration of aluminum in Estero Bay sediments August 11, August 27 and September 3, 1986 22 gay Boy ZWero, RV. Estero Island Mound (Fort Myers seach) K 014 Stock Island Lovers Ke, LonqL Key U7 Oq.73 $40f 819 Mckory lsl@*nd L88 clef Explanation 01.09 IN Sample site and cadmium concentration 'in Milligrams/Kilogram Bonita Beach Little Hickory Island R;,,Or 73 Figure 14. Concentrations of cadmium in Estero Bay sediments January 15, 1986 23 crook HUrIrIC47,70 2.5 0. 1 0 mumock VY B, Creek,-, 6 10. 1,4 Hell T. ey Bay "A 0.93 OJ7 Estero RV 0.40 093 Estero Island Mound 0667 (Fort Myers Beach) Key 0.54 7 4 OU 7. 3 OACI 44 0 0 80 Black Island'. Lovers Ke. Long Key 0 80 0, pas .54 0.13 sprI179 Crook Explanation Big: Hickory Island 9 0.93 65 Sample site and Cadmium OW-54 dPO27.A 514 concentration in Milligram/ 7 Kilogram Bonito Beach 0.80 Little Hickory Island erl 1*33 R,,Yer 4 Figure 15. Concentration of cadmium in Estero Bay sediments August 11, August 27 and September 3, 1986 croo Hell P*Okfie BaX Estero is and Mou nd (Fort Myers Beach) Key ss (lot C,o 0 Black Island Oil K Lovers Long f,*Y w '0. Y 2 Nov Cre 0 Big Hickory IsIdnd i planation 2@4 027.4 2 Sample site and chromium con- ntration in Milligram/ tlogram Bonita Beach Little Hickory islandI In erA71 0.9 Figure 16. Concentrations of chromium in Estero Bay sediments January 15, 1986 25 Creek 13 0 Hurricane 30.44 Bay Nuflock NN, PeCkfidy Bay Ila 44 17,0 20.6 E'Stdro RV Estero Islad 2 Ind ..7.95 9-8. (Fort Myers Beach) Key 117 2.6 1 4 J:2 J.5 gig Black Island Lovers Ke Long Key Cl 0 lQ3 Cw '7.48 16A Crook Big Hickory Island Explanation A. 9 8,88 1,& r Sample site and chromium Gig concentration in Milligrams/ Kilogram Bonita Beach 1 5.1 21.5 Little Hickory Island -rjalA Rl*ver 0 Figure 17. -Concentration of chromium in Estero Bay sediments August 11, August 27 and September 3, 1986 26 crook Nurflogne croo".- Nell B47y N Ester, Estero Island Mound Key (Fort Myers Beach) IVW Black Island Lovers Ka Long Key 88 10.80 5.901 46# sprIng Crook Big Hickory Isla .nd 121.3 Explanation 11.8 6 01.09 $to 01 Sample site and lead 3 concentration in Milligrams/ Kilogram Bonita Beach 41 Imperial River 13. Little Hickory Island Figure 18. Concentration of lead in Estero Bay sediments January 15, 1986 27 crde* 6. M08 Hell POCICney Bay 12 10,1 Estero NO--- 8.18 1 Estero Island 7-208 Mound 3 3.64 (Fort Myers Beach) Key 2.34 3.6 2.81 4 6.37 0 0 A. 100.9 (101 0 614 Black Island Lovers Ke -211* Long, K y 64 p oss ass .09.09 Explanation Big Hickory Island 07.28 Sample site and lead concentra- V311i A tion in Milligrams/Kilogram 6637 $to 72 Bonita Beach 4.55 9. Little Hickory Island 1h Figure 19. Concentration of lead in Estero Bay sediments August 11, August 27 and September 3, 1986 28 toy V -Estero Island Mound 40 (Fort Myers See h) 4:V Key 06,10t Block Island: Lovers Ke Long, Key 0.14 U4* 05 Explanation Big Hickory Island' 5 91.09 J! r4j; W3@ Sample site and mercury Concen- $14101, 0, tration in Milligrams/ Kilogram 5 Bonito Beach Little Hickory Island /M Orial IRi.ver <.05 Figure 20. Concentrations of mercury in Estero Bay sediments January 15, 1986 29 011 0.16 BUZ 011 Hell Pechne Y Ba y <0 8' 048'. Estero River 05 < 04#PO5 Estero Island 0427 Mound *07 (Fort Myers Beach) Key 00 1CP a@ 05 0.105 0.11 0 014 Black Island Lovers Ke LongL Key 0 '-wo.05. 0 40.05- SOrl,79 Crook Explanation Big Hickory island A 0 < 0.0,@ Sample site and mercury con- SIG centration in Milligrams/ Kilogram Bonita Beach @!40.05 Little Hickory Island Amper/.a/ River Figure 21. Concentration of mercury in Estero Bay sediments August 11, August 27 and September 3, 1986 30 V elk .847.V eye// R1 -Estero Island Mound (Fort Myers Beach) Key N%' LJt Voss Stock Island Lovers Key Long, X 1.09 nr O:i 4C w Cr Ok Big Hickory Island 10.5 Explanation 1,66 . .1 . .. . , I 1< 01.09 Sample site and silver concentration in Milligrams/ Kilogram Bonita Beach Little Hickory Island j perl. /?I rer e 0.5 3.5 Figure 22. Concentrations of silver in Estero Bay sediments January 15, 1986 .31 CTOO 8, Q6 JVW/Och cre VY tieff 0 @W, pec*ney Bay 1 5 0.9 . . . . . . . rstero River 0.63 Estero Island 014 0.63 Mound Key (Fort Myers Beach) <0-5 P-POO.63 Block Island Layers Ke Long Key '0 0.94 r1,7 Crook Explanation Big Hickory Island A 90.94 0405:, Sample site and silver 0.94 concentration in Milligrams/ 0. Kilogram Bonito Beach 40.5 'ICO-5 Little Hickory Island River Figure 23. Concentration of silver in Estero Bay sediments August 11, August 27 and September 3, 1986 32 crofk Bel creet'-, Hell S "6 Bay V -Estero Island Mound (Fort Myers Beach) Key 40 00096 lack Island loft Lovers Key Long Key j '0, V 1.24 2 8 , ,. -! ., . ... I Crook Big Hickory Island 18.97 3.31 Explanation V F 1 01.09 sit Sample site and copper concentration in Milligrams/ Kilogram Bonita Beach Little Hickory Island Im Orl.d/ IRI'Ver 3.3 0 Figure 24. Concentrations of copper in Estero Bay sediments January 15, 1986 3@ CPO#* 4F 6.1 4 7 A r-3 3.2 Nell Peoney Bey 4 7 V. 3J4' 4 &f0ro Myer U3 XJ4 Estero Island 1 1.95 Mound (Fort Myers Beach) 22 Key k* 2.2 163 .2.043 0.60 ap a 2.2 a 4 fo 622 014 Block Island Lovers K* Long X y 0 V4 .2,A3 ;4'1.79 A t[49# Explanation Big Hickory Island' 0 2.43 11 east, f 2.78 Sample site and copper 0. 40 concentration in Milligrams/ 8 Kilogram Bonita Beach 29 5, 1.63 Little Hickory Island "0 RI'Ver Figure 25. Concentration of copper in Estero Bay sediments August 11, August 27 and September 3, 1986 34 crook say MWOO eff'o'- HO Bvv A. &toro Rlyor -Estero Island <%, Mound (Fort Myers Beach) Vr/Z Zd 00(10 $14 Blook Island Lovers Key Long Key 0 4.84 4 Z2 fogs Crook Big Hickory Island 68.0 Oss &77 llif Explanation .21 01.09 Sample site and zinc concen- Bonita Beach tration in Milligrams/Kilogram Little Hickory Island i. RI'Vef 14.3 Figure 26. Concentrations of zinc in Estero Bay sediments January 15, 1986 35 creek Hurricafte 2 i. B17Y Afullock 7-4 Hell Pec*ney Bar 9.35 0 Estero River 10.0 Estero Island - 3440 _a, 5A8 Mound -.'5.39 (Fort Myers Beach) Key 6.W kl* .1 2 0 7.41 ....9.84 100 9 C Black Island Lovers Ke Long Key 0 % 6 -Itp 5.52 Spring Crook Explanation Big Hickory Island o 6.18 Vfast Sample site and zinc concentra- Octal gig 6A tion in Milligrams/Kilogram 2.6 Bonito Beach 6' 4.39 ./2% Little Hickory Island River 26 Figure 27. Concentration of zinc in Estero Bay sediments August 11, August 27 and September 3, 1986 36 TABLE # I LOCATIONS AND SITE NUMBERS FOR TABLES TWO THROUGH FIVE COLLECTION DATE: JANUARY 16, 1986 SITE LOCATION SITE 1 Outside New Pass 2 Inside New Pass 3 Mouth of Spring Creek 4 Spring Creek at Bonita Bay Gulf Course 5 Spring Creek at Subdivision 6 Big Hickory Bridge 7 Boat Dock in Big Hickory/Broadway Channel 8 Squaw Creek 9 Mouth of Imperial River 10 Imperial River at U.S. 41 Bridge 11 East End of Imperial River 12 Halfway Between U.S. 41 and Mouth of Imperial River 13 Hogue Channel 37 TABLE 2 NUTRIENTS IN ESTERO BAY WATER COLUMN COLLECTION DATE: JANUARY 16, 1986 TOTAL TOTAL NITRATE TOTAL ORTHO NITROGEN KJELDHAL + PHOSPHATE PHOSPHATE NITROGEN NITRITE SITE mg/l mg/l mg/1- mg/l mg/l 1 0.69 0.69- <0.01 0.06 0.02 2 0.59 0.58 0.01 0.05 0.02 3 0.56 0.54 0.02 0.08 0.08 4 0.70 0.64 0.06 0.08 0.02 5 0.62 0.62 <0.01 0.04 0.04 6 0.64 0.63 0.01 0.05 0.02 7 0.52 0.51 0.01 0.09 0.09 8 0.54 0.54 <0.01 0.07 0.04 9 0.59 0.58 0.01 0.04 0.04 10 0.71 0.61 0.10 0.06 0.06 11 0.82 0.68 .0.14 0.02 0.02 12 0.76 0.73 0.03 0.05 0.02 13 0.49 0.47 0.02 0.06 0.02 38 TABLE # 3 PHYSICAUCHEMICAL CHARACTERISTICS IN THE ESTERO BAY WATER COLUMN COLLECTION DATE: JANUARY 16, 1986 TEMPERATURE DISOLVED OXYGEN SALINITY DEGREES CENTIGRADE mg/l % SITE TOP MID BOTTOM TOP MID BOTTOM TOP MID BOTTOM 1 17 17 17 6.5. - 26 27 26 2 17 17 16 7.4 - - 27 27 27 3 18 - - 7.0 - 6.9 27 - 27 4 20 - - 6.9 - 6.5 10 18 19 5 20 - - 6.9 - 6.9 18 20 23 6 20 - - 6.8 6.9 7.2 27 27 27 7 20 - - 7.8 - 8.0 27 27 27 8 19 - 19 7.6 7.8 29 - 29 9 19 - 18 6.2 5.8 5.5 11 15 17 10 21 - - 5.2 4.8 3.1 4 23 30 11 20 - - 4.3 - 4.3 <1 - <1 12 20 - - 6.6 6.2 5.4 8 16 15 13 21 - 7.5 7.0 6.5 24 25 27 TURBIDITY CONDUCTIVITY BOD5 SITE NTU umhos/cm mg/l 1 4.5 45,000 0.1 2 4.0 44,000 <0.01 3 2.1 40,500 0.1 4 1.0 15,500 0.5 5 1.2 29,000 0.6 6 1.2 42,500 <0.01 7 1.6 43,000 <0.01 8 3.7 44,500 0.4 9 1.0 18,000 0.4 10 1.0 6,750 0.3 11 0.73 550 <0.01 12 1.0 11,500 0.8 13 1.8 40,000 <0.01 39 TABLE 4 BACTERIOLOGI CAL DATA FROM ESTERO BAY WATER COLUMN ANALYSIS COLLECTION DATE: JANUARY 16, 1986 TOTAL FECAL FECAL COLIFORM COLIFORM STREPTOCOCCUS colonies colonies colonies SITE 100 ml 100 ml 100 ml 1 10 ** 4 ** 3 2 <10 <10 <10 3 <10 10 <10 4 40 40 <10 5 <10 <10 <10 6 *NR <10 <10 7 20 40 <10 8 20 10 <10 9 20 100 10 10 10 210 10 11 <10 90 150 12 20 160 20 13 10 <10 <10 ALL SAMPLE SIZES 10 ML UNLESS NOTED. No Results- Laboratory accident Sample size 100 ml. 40 TABLE 5 LOCATIONS AND SITE NUMBERS FOR TABLES SIX THROUGH EIGHT COLLECTION DATE: JUNE 18, 1986 SITE LOCATION SITE 14 Big Carlos Pass 15 Mantanzas Pass 16 Mullock Pass 17 Spring Creek at mouth 18 New Pass 19 Imperial River at mouth 41 TABLE- 6 NUTRIENTS IN ESTERO BAY WATER COLUMN- COLLECTION DATE: JUNE 18, 1986 TOTAL TOTAL NITRATE TOTAL ORTHO NITROGEN KJELDHAL + PHOSPHATE PHOSPHATE NITROGEN NITRITE SITE Mg/l mg/l mg/l mg /1 mg/l 14 0.06 0.05 0.01 0.31 0.01 15 0.18 0.18 <0.01 0.32 0.02 16 0.37 0.37 <0.01 0.14 0.02 17 0.28 0.28 <0.01 0.33 0.01 18 0.12 0.12 <0.01 0.35 <0.01 19 0.40 0.40 <0.01 0.05 0.03 4.12. TABLE 7 PHYSICAL/CHEMICAL CHARACTERISTICS IN THE ESTERO BAY WATER COLUMN COLLECTION DATE: JUNE 18, 1986 DISOLVED OXYGEN SALINITY mg/l % SITE TOP MID BOTTOM TOP MID BOTTOM 14 5.5 8.0 9.0 30 30 31 15 4.5 6.2 7.2 29 29 30 16 3.8 3.8 3.8 32 34 36 17 4.5 4.5 4.5 30 30 30 18 6.8 7.0 7.2 28 32 31 19 5.5 5.6 5.8 19 20 22 TURBIDITY BOD5 pH SITE# NTU mg/l UNITS 14 2.3 3.1 7.8 15 3.0 2.5 7.8 16 3.1 6.9 8.0 17 3.0 2.9 7.9 18 2.1 3.8 8.0 19 2.6 1.2 7.9 43 TABLE BACTERIOLOGICAL DATA FROM ESTERO BAY WATER COLUMN ANALYSIS COLLECTION DATE: JUNE 18, 1986 TOTAL FECAL FECAL COLIFORM COLIFORM STREPTOCOCCUS colonies colonies colonies SITE looml 100 ml looml 14 <10 <1 <1 15 <10 confluent 16 16 <10 * 3 10 17 30 * 8 18 18 <10 * 20 15 19 80 * 26 <1 ALL SAMPLES SIZES 10 ML UNLESS NOTED. Sample size 106 ml. 44 TABLE # 9 LOCATIONS AND SITE NUMBERS FOR TABLES TEN THROUGH TWELVE COLLECTION DATES: August 6, 1986 and August 7, 1-986 SITE LOCATION SITE DATE 20 MULLOCK CREEK AUGUST 6, 1986 21 BIG CARLOS AUGUST 6, 1986 22 NEW PASS AUGUST 6, 1986 23 DIXON POINT AUGUST 6, 1986 24 SPRING CREEK AUGUST 6, 1986 25 ESTERO RIVER AUGUST 6, 1986 26 IMPERIAL RIVER AUGUST 7, 1986 27 IMPERIAL RIVER AT BEND AUGUST 7, 1986 28 FISH TRAP BAY AUGUST 7, 1986 45 TABLE 10 NUTRIENTS IN ESTERO BAY WATER COLUMN COLLECTION DATE: AUGUST 6, 1986 AND AUGUST 7, 1986 TOTAL TOTAL NITRATE NITROGEN KJELDHAL + NITROGEN NITRITE mg/l mg/l mg/l SITE TOP MID BOTTOM TOP MID BOTTOM TOP MID BOTTOM 20 1.46 - 1.42 - - 0.02 - 21 0.48 - 0.48 - - <0.01 - 22 0.41 - - 0.41 - - <0.01 - - 23 0.99 1.30 1.14 0.94 1.24 1.08 0.05 0.06 0.06 24 0.59 - - 0.58 - - 0.01 - - 25 0.77 - 1.01 0.77 - 1.00 <0.01 - 0.01 26 0.85 - 0.96 0.85 - 0.96 <0.01 - <0.01 27 0.62 - - 0.62 - - <0.01 - - 28 0.99 - 0.99 - - <0.01 - AMMONIA TOTAL ORTHO. mg/l PHOSPHATE PHOSPHATE SITE TOP MID BOTTOM TOP MID BOTTOM TOP MID BOTTOM 20 0.03 - 0.07 - 0.05 - 21 <0.01 - 0.03 - 0.02 - 22 <0.01 - - 0.01 - - 0.01 - - 23 0.09 0.11 0.12 0.03 0.04 0.03 0.07 0.04 0.04 24 0.07 - - 0.01 - - 0.01 - - 25 <0-.01 - <0.01 0.01 - <0.01 0.01 - 0.01 26 <0.01 - <0.01 <0.01 - 0.01 0.02 - 0.01 27 <0.01 - - 0.01 - - 0.03 - - 28 <0.01 - 0.01 - 0.01 - 46 TABLE-1 11 P-HYSICAL/CHEMICAL CHARACTERISTICS IN THE ESTERO BAY WATER COLUMN COLLECTION DATE: AUGUST 6, 1986 AND AUGUST 7. 1986 TEMPERATURE DISOLVED OXYGEN SALINITY DEGREES CENTIGRADE mg/l % SITE TOP MID BOTTOM TOP MID BOTTOM TOP MID BOTTOM 20 30 5.6 18 .21 30 5.4 31 22 30 - - 5.4 - - 31 - - 23 @o 30 30 4.2 5.2 4.6 20 20 21 24 29 - - 5.4 - - 33 - - 25 30 - 30 7.7 - 10.1 29 - 30 26 31 31 30 5.6 - 4.4 17 18 18 27 - - - 9.2 - - - - - 28 6.5 - TURBIDITY BOD5 pH NTU mg/l UNITS SITE TOP MID BOTTOM TOP MID BOTTOM TOP MID BOTTOM 20 1.7 - 0.6 - 7.7 - 21 2.7 - 3.2 - 7.9 - 22 0.5 - - 1.1 - - 8.1 - - 23 1.7 4.0 8.5 1.3 0.7 1.9 7.7 7.7 7.6 24 1.1 - - 1.9 - - 8.1 - - 25 3.4 - 2.6 1.6 - 1.5 8.0 - 8.0 26 1.9 - 1.5 2.7 - 2.5 7.8 - 7.6 27 0.9 - - 1.9 - - 7.8 - 28 2.8 - 1.6 - 7.9 - 47 TABLE -12 CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: JULY 17, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/l Station 1 12:44PM 0.3 Station 1 1:37PM 0.3 station 1 2:33PM 0.3 station 1 4:25PM 0.3 Station 2 12:43PM <0.3 Station 2 1:30PM 0.3 Station 2 2:20PM <0.3 Station 2 4:22PM <0.3 Station 3 12:39PM <0.3 Station 3 1:28PM <0.3 Station 3 2:26PM <0.3 Station 4 11:20AM <0.3 Station 4 12:07PM <0.3 Station 4 I:llpm <0.3 Station 4 2:05PM <0.3 Station 4 3:04PM 1.3 Station 4 4:21PM 1.3 Station 5 11:15AM 0.3 Station 5 12:04PM 0.3 Station 5 1:08PM. 4.3 Station 5 2:03PM 1.3 Station 5 3:02PM 1.0 Station 5 4:19PM 0.5 Station 6 11:14AM 0.3 Station 6 12:03PM 22.8 Station 6 1:06PM 3.1 Station 6 2:01PM 2.0 Station 6 3:OOPM 0.8 Station 6 4:17PM 0.5 Station 7 11:13AM <0.3 Station # 7 12:02PM 6.5 Station # 7 1:05PM 2.8 Station # 7 2:OOPM 0.8 Station # 7 2:58PM 0.5 Station 7 4:15PM 0.5 Station 8 11:12AM <0.3 Station 8 12:OOPM <0.3 Station 8 1:04PM 8.2 Station 8 1:58PM 2.0 Station 8 2:56PM 3.8 Station 8 4:12PM 2.6 Station 9 11:23AM 0.3 Station 9 12:10PM <6.3 Station 9 1:14PM <0.3 48 TABLE # 12 Corxtirxued CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: JULY 17, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/l Station 9 2:08PM 0.3 station 9 3:07PM 0.5 Station 9 4:23PM 4.0 station 10 11:33AM 0.3 Station 10 12:13PM 0.5 station 10 1:17PM 0.3 station 10 2:12PM 0.3 Station 10 3:10PM 0.3 Station 10 4:26PM 0.5 Station 11 11:28AM <0.3 Station 11 12:18PM <0.3 Station 11 1:22PM <0.3 Station 11 2:16PM <0.3 Station 11 3:16PM <0.3 Station 11 4:40PM <0.3 Station 12 11:26AM <0.3 Station 12 12:16PM <0.3 Station 12 1:20PM <0.3 Station 12 2:14PM <0.3 Station 12 3:14PM <0.3 Station 12 4:30PM <0.3 Station 13 12:OOPM <0.3 Station 13 1:00pm <0.3 Station 13 2:OOPM <0.3 Station 13 4:07PM <0.3 Station 14 3:OOPM 0.3 Station 14 4:05PM <0.3 Station 15 2:56PM 0.3 Station 15 4:OOPM <0.3 Station 16 3:50PM <0.3 Station 19 3:35PM <0.3 Station 20 12:24PM <0.3 Station 20 1:15PM <0.3 Station 20 2:13PM <0.3 Station 20 4:12PM <0.3 Station 21 12:30PM <0.3 Station 21 1:20PM <0.3 Station 21 2:19PM <0.3 Station 21 4:15PM <0.3 Station 22 12:12PM <0.3 Station 22 1:12PM <0.3 Station 22 2:01PM <0.3 Station 22 4:10PM <0.3 S ation 22 5:02PM <0.3 t 49 TABLE # 12 - Continued CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: JULY 17, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/l Station 23 12:10PM <0.3 station 23 1:05PM <0.3 station 23 2:05PM <0.3 station 23 4:08PM <0.3 Station 23 5:OOPM <0.3 Station 25 11:24AM <0.3 Station 25 12:11PM <0.3 Station 25 1:16PM <0.3 Station 25 2:09PM <0.3 Station 25 3:08PM 0.3 Station 25 4:25PM 1.5 Mouth of Spring Creek 0.3 New Pass 3:45PM <0.3 Big Carlos Pass 12:27PM 0.3' Big Carlos Pass 1:17PM <0.3 Big Carlos Pass 2:15PM <0.3 Big Carlos Pass 4:13PM <0.3 50 TABLE 13 CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: JULY 18, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/l Station 1 3:35PM <0.3 Station 2 3:35PM <0.3 station 3 3:30PM <0.3 ation 4 4:OOPM 0.8 Station 5 4:02PM 1.3 ssttation 6 4:05PM 1.3 Station 9 3:56PM 0.3 Station 10 3:51PM 0.3 Station 11 3:OOPM <0.3 Station 12 4:16PM 0.3 Station 13 2:54PM <0.3 Station 14 2:51PM <0.3 Station 15 2:46PM 0.8 Station 16 2:41PM <0.3 Station 17 2:33PM <0.3 Station 18 2:35PM <0.3 Station 19 3:10PM <0.3 Station 20 3:14PM <0.3 Station 21 3:21PM <0.3 Station 22 3:05PM <0.3 Station 23 2:58PM <0.3 Station 25 3:53PM 0.3 Big Carlos Pass 3:17PM <0.3 New Pass 2:30PM <0.3 51 TABLE # 14 CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: JULY 19, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/1 Station 1 4:01PM <0.3 station 2 3:55PM <0.3 station 3 3:51PM <0.3 Station 4 2:OOPM 0.3 Station 5 2:03PM 0.5 Station 6 2:06PM 0.3 Station 7 2:08PM 0.5 Station 8 2:11PM 0.5 Station 10 3:19PM 0.3 Station 11 3:24PM <0.3 Station 12 1:16PM 0.3 Station 13 12:58PM <0.3 Station 14 12:52PM 0.3 Station 15 12:50PM 0.3 Station 16 12:35PM <0.3 Station 18 12:42PM <0.3 Station 20 1:37PM <0.3 Station 21 1:34PM <0.3 Station 22 1:09pm <0.3 Station 23 1:02PM <0.3 Station 25 1:30PM 0.3 Big Carlos Pass 1:40PM <0.3 New Pass 12:32PM <0.3 52 TABLE # 15 CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: SEPTEMBER 17, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/l Station 1 3:22PM 560 station 1 4:08PM 1.5 station 1 4:58PM 0.5 station 1 6:09PM 0.5 Station 1 7:18PM 0.5 Station 2 3:OOPM 0.5 Station 2 4:55PM <0.5 Station 2 5:30PM <0.5 Station 3 3:35PM 196 Station 3 4:01PM 14.0 Station 3 5:OOPM 3.5 Station 3 6:10PM 2.0 Station 3 7:17PM 1.5 Station 5 3:13PM 0.5 Station 5 4:58PM <0.5 Station 5 5:34PM <0.5 Station 6 4:22PM 0.5 Station 6 5:25PM <0.5 Station 6 6:31PM <0.5 Station 9 3:17PM <0.5 Station 9 5:02PM <0.5 Stati on 9 5:42PM <0.5 Station 12 3:21PM 0.5 Station 12 5:06PM <0.5 Station 12 5:44PM <0.5 Station 13 4:12PM <0.5 Station 13 5:11PM <0.5 Station 13 6:21PM 15.0 Station 14 4:08PM 34.0 Station 14 5:08PM 7.5 Station 14 6:18PM <0.5 Station 15 4:14PM <0.5 Station 15 5:15PM 22.0 Station 15 6:24PM 7.5 Station 16 3:25PM 0.5 Station 16 5:OOPM <0.5 Station 16 5:47PM <0.5 Station 17 3:35PM 0.5 Station 17 5:20PM <0.5 Station 17 6:OOPM <0.5 Station 19 4:03PM <0.5 Station 19 5:02PM <0.5 Station 19 6:13PM <0.5 Station 19 7:14PM <0.5 53 TABLE # 15 - Continued CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: SEPTE24BER 17, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE Ug/1 Station 20 4:28PM <0.5 station 20 5:55PM <0.5 station 20 6:38PM <0.5 station 21 4:18PM <0.5 Station 21 5:20PM <0.5 Station 21 6:27PM 14.5 station 23 5:46PM <0.5 Station 25 3:45PM 0.5 station 25 5:24PM <0.5 Station 25 6:03PM <0.5 Big Carlos Pass 3:30PM 0.5 Big Carlos Pass 5:15pm <0.5 Big Carlos Pass 6:55PM <0.5 New Pass 5:41PM <0.5 54 TABLE # 16 CONCENTRATIONS OF RHODAMINE DYE IN ESTERO BAY COLLECTION DATE: SEPTEMBER 18, 1986 INTRACID LOCATION TIME RHODAMINE WT DYE ug/1 Station 1 3:OOPM 1.5 station 2 2:25PM 0.5 station 3 3:03PM 3.5 Station 5 2:25PM <0.5 Station 6 2:49PM <0.5 Station 9 2:30PM <0.5 Station 12 2:32PM <0.5 Station 13 3:17PM 3.0 Station 14 3:11PM 3.5 Station 15 2:52PM 2.0 Station 16 2:35PM <0.5 Station 17 2:15PM <0.5 Station 19 3:06PM 3.0 Station 20 3:24PM 4.0 Station 21 2:50PM 1.5 Station 23 2:45PM <0.5 Station 25 2:20PM <0.5 Station 26 2:41PM <0.5 Big Carlos Pass 2:10PM <0.5 New Pass 3:32PM <0.5 55 TABLE 17 LOCATIONS AND SITE NUMBERS FOR TABLE EIGHTEEN COLLECTION DATE: JANUARY 15, 1986 SEDIMENT SITE LOCATION SITE 1 Outside New Pass 2 Inside New Pass 3 Mouth of Spring Creek 4 Spring Creek at Bonita Bay Gulf Course 5 Spring Creek at Subdivision 6 Big Hickory Bridge 7 Boat Dock in Big Hickory 8 Squaw Creek 9 Mouth of Imperial River 10 Imperial River at U.S. 41 Bridge 11 East End of Imperial River 12 Halfway Between U.S. 41 and Mouth of Imperial River 13 Hogue Channel 56 TABLE 18 TRACE METALS AND NUTRIENTS IN ESTERO BAY SEDIMENT' COLLECTION DATE: JANUARY 15, 1986 SITE *As Al Cd Cr Pb Hg Ag Cu Zn mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg 1 0.83 382 1.37 27.4 10.8 1.34 <0.5 2.48 4.66 2 0.77 684 0.89 5.71 4.43 <0.05 <0.5 0.83 4.84 3 1.30 1872 0.73 11.7 5.90 <0.05 <0.5 1.24 7.25 4 3.93 819 1.88 46.7 21.3 0.83 <0.5 8.97 38.0 5 0.82 1218 0.65 12.6 6.88 0.14 1.09 1.24 4.84 6 2.84 3252 1.37 21.7 13.3 0.05 1.09 3.73 9.51 7 1.09 2454 0.89 14.3 6.40 <0.05 <0.5 0.83 6.65 8 2.47 3750 1.21 27.4 11.8 0.13- 1.09 3.31 8.77 9 0.59 732 0.40 10.9 3.94 0.07 <0.5 0.83 5.12 10 0.73 2394 0.80 15.4 13.8 <0.05 <0.5 3.31 11.4 11 0.55 529 0.49 5.71 2.95 0.15 <0.5 0.83 4.15 12 1.60 2964 0.73 20.9 11.3 0.18 <0.5 6.20 14.3 13 1.47 2646 1.13 16.6 9.83 <0.05 0.72 2.48 8.21 SITE TOTAL TOTAL % SOLIDS PHOSPHORUS KJELDHAL NITROGEN mg/kg mg/kg 1 0.026 0.006 78.2 2 0.012 0.005 75.7 3 0.022 0.023 68.1 4 0.050 0.168 20.3 5 0.008 0.016 73.2 6 0.061 0.048 55.7 7 0.026 0.015 72.6 8 0.045 0.047 55.6 9 0.022 0.011 75.0 10 0.029 0.020 66.5 11 0.001 0.003 78.7 12 0.032 0.070 52.7 13 0.043 0.042 62.7 As - Arsenic Al - Aluminum Cd - Cadmium Cr - Chromium Pb - Lead Hg - Mercury Ag - Silver Cu - Copper Zn - Zinc 57 TABLE 19 LOCATIONS AND SITE NUMBERS FOR TABLE TWENTY COLLECTION DATE: AUGUST 11, 1986 SITE LOCATION SITE 29 Mouth of Spring Creek 30 Bar outside Spring Creek 31 Half Way Between Spring Creek & New Pass 32 New Pass 33 East Mound Key 34 Big Carlos Pass 35 Big Hickory 58 TABLE # 20 TRACE METALS AND NUTRIENTS IN ESTERO BAY SEDIMENT COLLECTION DATE: AUGUST 11, 1986 SITE *As Al Cd Cr Pb Hg Ag Cu Zn mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg 29 0.55 1615 0.80 10.3 3.64 <0.05 <0.5 1.30 6.31 30 0.68 1735 0.54 7.48 3.64 <0.05 <0.5 1.79 6.56 31 1.10 3330 0.93 16.4 9.09 <0.05 0.94 2.43 9.63 32 0.55 1165 0.54 7.95 3.64 <0.05 <0.5 0.98 5.52 33 1.12 2480 0.14 16.4 2.81 <0.05 <0.5 1.63 7.41 34 0.28 680 0.14 4.68 3.64 <0.05 <0.5 0.65 4.46 35 0.93 2015 0.54 11.7 7.28 <0.05 0.94 1.79 6.42 SITE TOTAL TOTAL % SOLIDS PHOSPHORUS KJELDHAL NITROGEN mg/kg mg/kg 29 0.021 0.020 67.4 30 0.016 0.030 73.2 31 0.034 0.037 68.7 32 0.015 0.035 63.5 33 0.032 0.046 77.2 34 0.017 0.014 71.3 35 0.032 0.045 78.0 As - Arsenic Al - Aluminum Cd - Cadmium Cr - Chromium Pb Lead Hg - Mercury Ag - Silver Cu - Copper Zn - Zinc 59 TABLE 21 LOCATIONS AND SITE NUMBERS FOR TABLE TWENTY-TWO COLLECTION DATE: AUGUST 27, 1986 SITE LOCATION SITE 14 COON KEY 15 STARVATION KEY 16 ESTERO 17 HORSE SHOE KEYS 18 NEEDMORE POINT 19 DIXON POINT 20 HENDRY CREEK I 21 HENDRY CREEK II 22 NORTH BRANCH MULLOCK CREEK 23 MULLOCK 24 MOUTH OF MULLOCK 25 NEEDMORE POINT II 26 BLACK KEY 27 MOUTH OF ESTERO 28 ESTERO II 60 TABLE 22 TRACE METALS AND NUTRIENTS IN ESTERO BAY SEDIMENT COLLECTION DATE: AUGUST 27, 1986 SITE *AS Al Cd Cr Pb Hg Ag Cu Zn mg/kg mg/kg mg/kg mg/kg mg/kg mg/kgmg/kg mg/kg mg/kg 14 0.78 1145 0.93 8.88 5.14 <0.05 0.94 2.43 9.84 15 1.20 3390 0.40 20.6 8.18 <0.05 0.-63 5.03 10.0 16 0.80 2040 0.54 11.7 2.34 0.09 <0.5 2.28 6.12 17 1.08 2650 0.93 14.0 7.28 <0.05 0.94 7.14 34.3 18 1.30 3610 0.93 19.2 12.73 <0.05 1.25 4.87 9.35 19 1.13 3255 0.66 15.9 9.09 0.08 0.63 3.57 8.06 20 0.73 2845 1.46 12.6 12.73 0.12 1.25 3.24 7.48 21 1.90 4590 0.80 30.4 6.08 0.16 0.63 6.17 14.5 22 1.05 3120 1.20 15.0 3.74. 0.08 0.63 4.87 9.64 23 0.43 1740 2.53 13.1 2.81 0.15 <0.5 3.57 28.92 24 0.28 770 0.54 6.54 1.82 0.27 <0.5 1.46 16.5 25 0.85 3375 0.67 17.3 10.9 0.18 0.94 3.24 8.34 26 0.60 1960 0.67 11.7 3.64 <0.05 <0.5 2.28 22.9 27 0.30 1540 0.40 7.95 2.73 0.07 <0.5 2.11 5.39 28 0.33 1415 0.67 9.82 3.64 0.27 0.63 1.95 5.68 SITE TOTAL TOTAL % SOLIDS PHOSPHORUS KJELDHAL NITROGEN mg/kg mg/kg 14 0.020 0.018 76 15 0.031 0.076 62 16 0.021 0.015 73 17 0.027 0.061 71 18 0.036 0.072 52 19 0.025 0.063 64 20 0.031 0.091 64 21 0.035 0.187 44 22 0.021 0.091 58 23 0.012 0.025 64 24 0.007 0.011 77 25 0.028 0.108 60 26 0.026 0.031 72 27 0.016 0.040 70 As- Arsenic 28 0.019 0.043 68. Al- Aluminum Cd- Cadmium Cr- Chromium Pb Lead Hg Mercury Ag Silver Cu Copper 61 Zn Zinc TABLE 23 LOCATIONS AND SITE NUMBERS FOR TABLE TWENTY-FOUR COLLECTION DATE: SEPTEMBER 3, 1986 SITE LOCATION SITE 36 Mound Key 37 Monkey Joe Key 38 Little Davis Key 39 Broadway*Channel 40 Hogue Channel 41 Mouth of the North Branch of Imperial River 42 Mouth of the Imperial River 43 Bend of the Imperial River 44 Fish Trap Bay 62 TABLE 24 TRACE METALS AND NUTRIENTS IN ESTERO BAY SEDIMENT COLLECTION DATE: SEPTEMBER 3, 1986 SITE *As Al Cd Cr Pb Hg Ag Cu Zn mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg 36 1.03 2830 0.27 12.6 7.28 <0.05 <0.5 2.43 6.18 37 1.00 2380 0.40 12.2' 6.37 <0.05 0.63 2.28 6.26 38 2.40 4060 0.80 21.5 10.9 0.11 0.63 4.22 9.49 39 0.95 2720 0.27 14.5 -6.37 <0.05 <0.5 2.28 8.71 40 2.56 4635 1.07 28.0 14.5 <0.05 0.94 5.68 12.6 41 0.55 1955 0.14 10.3 6.37 0.14 0.63 2.28 6.26 42 0.15 890 0.80 5.1 4.55 <0.05 <0.5 1.63 4.39 43 1.48 4120 1.33 21.5 14.5 <0.05 <0.5 11.0 22.0 44 0.53 2115 1.46 10.3 9.09 <0.05 0.63 2.92 6.76 SITE TOTAL TOTAL % SOLIDS PHOSPHORUS KJELDHAL NITROGEN mg/kg mg/kg 36 0.030 0.047 68 37 0.025 0.034 70 38 0.037 0.038 58 39 M31 0.035 70 40 0.019 0.128 4 9 41 0.037 0.030 73 42 0.006 0.023 76 43 0.034 0.148 36 44 0.031 0.040 71 As - Arsenic Al - Aluminum Cd - Cadmium Cr - Chromium Pb - Lead Hg - Mercury Ag - Silver Cu - Copper Zn - Zinc 63 TABLE # 25 PESTICIDES AND PCBs; IN ESTERO BAY SEDIMENT COMPOSITES COLLECTION DATES: AUGUST 11-27?1986/ SEPTEMER 3, 1986 SAMPLE I.D. MOISTURE ALDRIN CHLORDANE DDT,PP' ENDRIN % wet wt. vLg/kg jLg/kg tLg/kg vLg/kg Hendry-Mullock 32.7 <1.46 <8.19 <1.46 <1.46 Creek Composit Estero River 30.4- <1.42 <7.97 <1.42 <1.42 Composit Spring Creek 32.5 <1.47 <8.22 <1.47 <1.47 Composit Imperial River 41.1 <1.69 <9.45 <1.69 <1.69 Composit Big Carlos Pass 43.2 <1.69 <9.44 <1.69 <1.69 Composit SAMPLE I.D. LINDANE MIREX TOXAPHENE PCBS,TOTAL VL9/kg jig/kg vLg/kg jLg/kg Hendry-Mullock <1.46 <73.1 <173 <76.0 Creek Composit Estero River <1.42 <71.1 <168 <74.0 Composit Spring Creek <1.47 <73.4 <173 <76.3 Composit Imperial River <1.69 .<84.4. <199 <87.8 Composit Big Carlos Pass <1.69 <84.3 <199 <87.7 Composit 64 APPENDIX QUALITY ASSURANCE FOR WATER QUALITY, SEDIMENT ANALYSIS AND CIRCULATION PATTMNS OF THE ESTERO BAY ESTUARINE SYSTEM, 1986 BY KEITH A. KIBBEY LEE COUNTY ENVIRONMENTAL LABORATORY DIVISION OF ENVIRONMENTAL SERVICES DEPARTMENT OF COMMUNITY DEVELOPMENT LEE COUNTY BOARD OF COUNTY COMMISSIONERS SEPTEMBER, 1986 APPENDIX PAGE 2 INDEX PAGE 1.0 QA OBJECTIVES FOR MEASUREMENT DATA A-3 1.1.1 INTRODUCTION A-3 1.1.2 ACCURACY A-3 1.1.3 PRECISION A-4 1.1.4 REPRESENTATIVENESS A-4 1.1.5 COMPLETENESS A-5 1.1.6 COMPARABILITY A-5 1.2 SAMPLING PROCEDURES A-5 1.2.1 WATER COLUMN ANALYSIS SAMPLING PROCEDURES A-5 1.2.2 FLOW STUDY SAMPLING PROCEDURES A-6 1.2.3 SEDIMENT ANALYSIS SAMPLING PROCEDURES A-7 1.2.4 SAMPLE EQUIPMENT PREPARATION A-8 1.2.5 SAMPLE PRESERVATION AND HOLDING TIMES A-9 1.2.6 SAMPLE SHIPPING A-10 1.3 LABORATORY CALIBRATION AND ANALYTICAL PROCEDURES A-10 1.3.1 WATER COLUMN ANALYSIS METHODOLOGY A-11 1.3.2 FLOW STUDY METHODOLOGY A-12 1.3.3 SEDIMENT ANALYSIS METHODOLOGY A-12 1.4 DATA REDUCTION VALIDATION AND REPORTING A-17 1.4.1 DATA VALIDATION A-18 1.5 INTERNAL QUALITY CONTROL A-18 1.5.1 FIELD QUALITY CONTROL CHECKS A-18 1.5.2 PERFORMANCE AND SYSTEM AUDITS A-18 1.5.3 PREVENTATIVE MAINTENANCE PROCEDURES A-19 1.5.4 SPECIFIC ROUTINE PROCEDURES TO ASSESS A-19 DATA PRECISION, ACCURACY AND COMPLETENESS 1.5.4.1 STATISTICAL PROCEDURES FOR PRECISION A-19 1.5.4.2 STATISTICAL PROCEDURES FOR ACCURACY A-20 1.5.4.3 COMPLETENESS A-22 1.5.4.4 CONTROL CHARTS A-22 1.6 QUALITY ASSURANCE RESULTS A-22 APPENDIX PAGE 3 ESTERO BAY QUALITY ASSURANCE AND QUALITY CONTROL 1.0 Q_A OBJECTIVES FOR MEASUREMENT DATA 1.1.1 INTRODUCTION The purpose of this section is to provide qualitative and quanti- tative information that defines the quality of data collected to meet the goals of this estuary study. The Lee County Environmental Laboratory is certified by Florida DHRS6(laboratory ID # 44031) and approved by the Florida DER labatory no. EL 0028. The primary goal of the sampling and analytical activities of the program was to determine the water and sediment quality in Estero Bay. The data generated will provide a "moment in time" perspec- tive of the condition of the bay during both the dry and rainy seasons at the instant of sampling. Thus, the data collected will be used to formulate future monitoring activities and actions. The goal of the reliability of the Program data was at the 95% confidence level. A goal of +/-10% for sampling precision was also established. Sampling precision will be evaluated using duplicate lab and field samples. The duplicate sample results helped to establish precision among different samples collected from the same site. 1.1.2 ACCURACY Accuracy can be defined as how closely the observed values conform to the true value. This was accomplished by the recovery of analyte on spiked samples. These samples were prepared on a site specific basis to mimic the expected composition of the environment as closely as possible. The accuracy for quantitative analyses is expressed in terms of percent recovery of the analyte. Percent recovery of analyte is determined as follows: % Analyte Recovery 100 C A + B Where A = initial concentration of analyte in sample B = quantity of analyte added to sample for spiking C = final concentration of analyte in spiked sample APPENDIX PAGE 4 The analyte recovered data was compared to that generated in prior monitoring samples taken in the area of Lee County that have approximately the same matrix composition. 1.1.3 PRECISION Precision measures the replicability and repeatability of results obtained from analyzing environmental samples. The analytical precision was monitored using results fr om laboratory and field duplicate samples. Precision limits for each compound have been determined over the course of the program and average precision goals established. The precision is to be determined using the Industrial Coeffi- cient (IC) and laboratory data which are used to establish Warning Limits for each analyte. The IC is calculated as fol- lows: A - B A + B IC = Industrial Coefficient A = First Duplicate Value B = Second Duplicate Value Warning Limits have established for each analyte to be tested in prior laboratory studies and will serve as a guide of Precision. 1.1.4 REPRESENTATIVENESS The representativeness was ensured in two ways. First, all sampling was done in accordance with procedures as outlined in the Sampling Section of this report. These guidelines have been developed to ensure the consistency in sampling efforts and to help ensure that proper sampling and sample handling procedures are followed and proper equipment is used. Additionally the monitoring was evaluated to determine if sample sites were adequate for determination of water and sediment quality in Estero Bay. Before sampling activities were undertak- en the monitoring was thoroughly evaluated to ensure that moni- toring sites had been properly spaced and designed. Properly selected monitoring sites provided data that was representative of Estero Bay. APPENDIX PAGE 5 1.1.5 COMPLETENESS The completeness of the program was monitored by both qualitative and quantitative means. A qualitative assessment was made by comparing the objectives and procedures presented in the Project Plan, This assessment will determine on a qualitative level which objectives were met or not met. Completeness was defined as thetotal number of samples taken for which acceptable analytical data are generated divided by the total number of samples collected multiplied by 100. The com- pleteness goal for this Program is 95%. Site assessment planning is incorporating this figure to ensure that the Program is meeting objectives. 1.1.6 COMPARABILITY Data generated during this Program used established and accepted analytical and sampling methods. Conformance' with the develop- ment of precision and accuracy quality indicators ensured that the data generated-under this Program was consistent and compara- ble with data generated under similar Programs. These quality indicators also ensure comparability of data with data generated in the past or in the future using acceptable sampling and analysis methods and appropriate quality indicators. 1.2 SAMPLING PROCEDURES .1.2.1 WATER COLUMN ANALYSIS SAMPLING PROCEDURES Water column samples were taken in both dry and wet seasons to provide an overall yearly variation. 1.2.1.1 WATER COLUMN SAMPLE SITE SELECTION The sites were chosen to obtain data on the quality of water entering and exiting Estero Bay. Sample sites were selected by use of aerial photographs, navigational charts, and visual observation by boat. 1.2.1.2 WATER COLUMN SAMPLE COLLECTION Surface samples were collected one foot below surface; middle samples were collected halfway between top and bottom; and bottom samples were collected one foot from bottom, by grab sampling using a Wildco Model 1282 sampler. Sample containers were labeled with a permanent water proof marker denoting sample site, date, time, preservatives added, and parameter for analysis. All samples were placed on ice after collection and transported to the laboratory as soon as possible. APPENDIX PAGE 6 1.2.1.3 WATER COLUMN SAMPLE CONTAINERS Sample containers must meet specific criteria for proper analyti- cal results. The use of properly constructed and prepared containers is outlined below. GENERAL PARAMETERS (nutrients, turbidity and pH) Samples were placed in a new plastic disposable liter bottles. Bottles were cared for as follows: Disposable containers are for a single time use and were not reused. They remained in their original shipping container which was a clean dust free environment. When a carton of sample containers were opened the sample containers were sealed with the appropriate lids. When the container for the sample container lids were opened, the lids were transferred to a plastic bag that was sealed to reduce contamination from dust and other contami- nants. Sample containers were rinsed with the sample before filling. BIOCHEMICAL OXYGEN DEMAND Clean 300 ml BOD bottle, Wheaton 1180011 or equivalent prepared by cleaning with detergent, rinsing once with tap water and twice with laboratory pure water and allowed to drain. BACTERIOLOGICAL Six ounce glass bottles prepared in accordance with section 903.15, Standard Methods for the Examination of Water and Wastewater, 16th Edition, 1985. DISSOLVED OXYGEN (Winkler) Clean 300 ml BOD bottle, Wheaton 1180011 or equivalent prepared by cleaning with detergent, rinsing once with tap water and twice with laboratory pure water and allowed to drain. Manganous Sulfate, and Alkaline Azide solutions. 1.2.2 FLOW STUDY SAMPLING PROCEDURES Intracid Rhodamine WT dye 20% was applied to the four tributaries of Estero Bay in two intervals. First dye was applied to the Hendry, Mullock Creek mouth, and the mouth of Spring Creek. The second dye application was to the mouths of the Estero River, and Imperial River. The dye was applied at high tide to allow the dye to be traced through the bay with the recessing tide. The dates and quantities of dye are as follows: APPENDIX PAGE 7 LOCATION DATE AMOUNT OF DYE Hendry, Mullock Creek July 17, 1986 10 gal Spring Creek July 17, 1986 2 gal Estero River September 17, 1986 5 gal Imperial River September 17, 1986 10 gal 1.2.2.1 FLOW STUDY SITE SELECTION Sample sites were selected to allow following of the dye on an outgoing tide through the bay to the passes. Each sample site was marked with a buoy so that they could easily be returned to for subsequent samplings. 1.2.2.2 FLOW STUDY SAMPLE COLLECTION After the dye was dispersed, surface grab samples were collected on an hourly basis until tidal change or dusk. Samples were also collected after 24 hours, and during the first application after 48 hours. The sample containers were first rinsed with sample, and then filled. Samples were taken approximately one foot below the surface. Sample containers were labeled with permanent water proof markers with the sample location, day, time, and parameters for analysis. 1.2.2.3 FLOW STUDY SAMPLE CONTAINERS New plastic disposable one liter containers were used for the flow study and were cared-for in the same manner as for "general parameters" in the water column sample container section. Sample containers were also rinsed with the sample before filling. 1.2.3 SEDIMENT ANALYSIS SAMPLING PROCEDURES Initial sediment analysis were collected in January, 1986, to test sampling methods, laboratory methods and procedures. Since these analysis were performed with little difficulty they have been included in this report. 1.2.3.1 SEDIMENT ANALYSIS SITE SELECTION Sediment sites were selected by use of the salinity gradient, aerial photographs and the results of the flow study. An emphasis was placed on areas around the 10-15% salinity line. APPENDIX PAGE 8 1.2.3.2 SEDIMENT ANALYSIS SAMPLE COLLECTION Sediment grab samples were collected by scooping up the top layer (approximately one inch) of sediment with a polyethylene scoop. In water depths greater than 2.5 feet, samples were collected by diving and then scooped up in the same manner. Samples were brought up to the surface in a manner so to minimize sample loss, and placed in proper containers. Sample containers were then labeled with the sample location, date, time and type of sample, with waterproof markers. All samples were pl aced on ice and transported to the laboratory. 1.2.3.3 SEDIMENT ANALYSIS SAMPLE CONTAINERS Once samples were out of the water the samples for nutrients and metals were placed in new plastic 1 liter bottles, prepared in the same manner as the water column general parameters. The samples for pe*sticides were placed in borosilicate glass bottles which had been rinsed with methyl alcohol, baked in an oven and sealed with a teflon lined cap. 1.2.4 SAMPLE EQUIPMENT PREPARATION Without proper sample container preparation the potential of contamination is at risk. Special procedures were followed in order to ensure the quality of each sample container. To ensure that samples are collected and transported with minimal contami- nation the greatest of care was used when preparing the sample containers for the samples. This ensured that the sample was not contaminated with material that had deposited residue in a container that could interfere with the analysis or promote erroneous results. 1.2.4.1 ICE CHESTS AND SHIPPING CONTAINERS All ice chests and reusable shipping containers were washed with mild detergent (interior and exterior) and rinsed with tap water and air dried before storage. 1.2.4.2 VEHICLES AND BOATS All vehicles used by laboratory personnel were washed (when possible) at the end of each field trip. This routine mainte- nance minimizes any chances of contamination of samples or equipment due to contaminated vehicles. APPENDIX PAGE 9 When the vehicles are used in conjunction with hazardous waste site sampling, or studies where pesticides, herbicides, organic materials or other toxic materials are known or suspect to be present, a thorough interior and exterior cleaning is performed at the conclusion of such events. 1.2.4.3 SAMPLERS The Wildco model 1282 sampler is used to sample surface waters for a variety of analytes. Therefore it was thoroughly cleaned before sampling, between sample sites, and upon return to the laboratory. The polyethylene scoop used for sediment samples was thoroughly rinsed between samples and thoroughly cleaned in the laboratory before use in the field. 1.2.5 SAMPLE PRESERVATION AND HOLDING TIMES The method used to preserve samples is very critical to the stability of the analyte. For this reason very rigorous sample holding times and preservation methods were used to ensure the validity of data. A tabular summary of the sample holding requirements and holding times is provided below. The Lee County Environmental Laboratory follows the recommended storage time when possible and disposes of any samples which exceed maximum regulation times. SAMPLE PRESERVATION METHODS AND HOLDING TIMES Determination Container Preservation Maximum Storage BOD P,G Refrigeration *6 hr 48 hr Conductivity P,G Refrigeration *28 day 28 day Metals, general P(A),G(A) Add HNO <2 6 mos 3 6 mos Mercury P(A),G(A) HNO <2 and 28 day reirigerate 28 day Ammonia P,G Test ASAP or 7 day H SO <2 28 day r9frfgerate Nitrate P,G Add H SO <2 48 hr refrigehte 48 hr Nitrate + Nitrite P,G Test ASAP or none refrigerate 28 day Nitrite P,G Test ASAP or, none refrigerate 48 hr Nitrogen P,G Refrigerate 7 day Organic Kjeldahl w/H2so4 <2 28 day APPENDIX PAGE 10 organic Compounds Pesticides G(S),TFE- Refrigerate: 7 day line cap add Na 2S 0 7 day Oxygen Dissolved G,BOD bottle if Cl 2 PKient Electrode Test ASAP 0.5 hr 1.0 hr Winkler After acidif- 8 hr ication 8 hr pH P,G Test ASAP 2 hr 2 hr Phosphate G(A) Refrigerate 48 hr 48 hr Salinity G, wax seal Test ASAP 6 mos or seal none Temperature P,G Test Immediately Turbidity P,G Store in Dark * 24 hrs * 48 hrs P = Plastic (polyethylene or equivalent) G = Glass G(A) or P(A) = rinsed with 1+1 HNO 3 G(B) = Glass borosilicate G(S) = Glass, rinsed with organic solvents Recommended Storage Time Regulatory Storage Time 1.2.6 SAMPLE SHIPPING The holding times for certain analytes is critical and for this reason the carrier used to carry samples was selected to deliver the samples within 24 hours to the contract laboratory. The transport time to the Environmental Laboratory was the same day and processing began the same day or within 24 hours. 1.3 LABORATORY CALIBRATION AND ANALYTICAL PROCEDURES The section consists of three sub-sections: the procedures used in the water column analysis; the procedures used in the Flow study; the procedures used in the sediment analysis. APPENDIX PAGE 11 1.3.1 WATER COLUMN ANALYSIS METHODOLOGY Ammonia (EPA method 350.1 Colorimetric, Automated Phenate) Total Phosphate (Ultramicro Semi-automated Method for.the Simultaneous Determination of Total Phosphorus and Total Kjeldahl Nitrogen in Wastewaters by Jirka, et al of the U.S. EPA, Chicago Ill.) Ortho Phosphate (Method 424 E, Standard Methods for the Examination of Water and Wastewater, 15th Edition, 1980.) Total Nitrogen (TKN + NO X) Total Kjeldahl Nitrogen (Ultramicro Semi-automated Method for the Simultaneous Determination of Total Phosphorus and Total Kjeldahl Nitrogen in Wastewaters by Jirka, et al of the U.S. EPA, Chicago Ill.) NOX (EPA Method 353.2 Colorimetric, Automated, Cadmium Reduction) pH (EPA Method 150.1 Electrometric) Biochemical Oxygen Demand (EPA Method 405.1 Probe Method) Dissolved oxygen (EPA Method 360.1 Probe Method) (EPA Method 360.2 Winkler Method) Turbidity (EPA Method 180.1 Nephelometric) Salinity (Method 210 A, Standard Methods for the Examination of Water and Wastewater, 16th Edition, 1985) APPENDIX PAGE 12 Conductivity (EPA Method 180.1 Nephelometric) Temperature AEPA Method 170.1 Thermometric) Total Coliform (Method 909 A, Standard Meth ods for the Examination of Water and Wastewater, 16th Edition, 1985) Fecal Coliform (Method 909 C, Standard Methods for the Examination of Water and Wastewater, 16th Edition, 1985) Fecal Streptococcus (Method 910 B, Standard Methods for the Examination of Water and Wastewater, 16th Edition, 1985) 1.3.2 FLOW STUDY METHODOLOGY Techniques of Water-Resources Investigations of the United States Geological Survey, chapter A12, Fluorometric Procedures for Dye Tracing by James F. Wilson, Jr. Testing was performed on a Turner Fluorometer. Standards were prepared from Bay water to counteract the interference of Phosphates in water. 1.3.3 SEDIMENT ANALYSIS METHODOLOGY 1.3.3.1 % SOLIDS IN SEDIMENT Ten grams of sediment is placed in a tared foil pan and weighed on an analytical balan8e. The sample is then placed in an convection oven at 105 C for 18 hours. Cool the sample in a desiccator for 1 hour and then weigh on an analytical balance The % solids is then determined. 1A.3.2 TOTAL PHOSPHORUS IN SEDIMENT Total Phosphorus in Sludge and Bottom Sediments (oxidizable and Hydrolyzable by Sulfuric Acid-persulfate Digestion-Autoclave) APPENDIX PAGE 13 A. Sample Preparation: 1. A sample of the sludge or sediment is dried at 105 C for 18 hours. A percent solids is determined. ( see section 1.3.3.1 2. Grind the dried sample with a mortar and pestle to a fine powder-discard rocks and foreign material. B. Digestion Reagents: 1. Sulfuric Acid (H SO4 )- Add 25 ml concentrated H2so4 to distilled water ind dilute to 1 liter. 2. Potassium Persulfate (K S 0 )- Dissolve 4 gm K 2S2 08 in distilled water and dilati to 1 liter; C. Digestion Procedure * : 1. Accurately weigh 0.1 g dried sample into a 50 ml erlenmeyer flask and add 5 ml P0 4 free water. 2. Add 5 ml of the sulfuric acid reagent (25 mg/1) and 10 ml of the K2S208 reagent (4 g/1). 3. Cover the flas s with aluminum foil and autoclave for 30 minutes at 2506F and 15 psig. Note - A set of standards (0.5, 1.0, 2.0, 4.Of 6.0, 8.0, 10, 15, and 20 mg/l PO 4 as P) are digested in the same manner as the samples. 5 ml of the standard is added to the 50 ml erlenmeyer flask and repeat steps 2 and 3. Prepare a blank by using 5 ml deionized water and repeating steps 2 and 3. All glassware used in this analysis should be washed with 1:1 HCL and rinsed with deionized water to remove phos- phorus. This glassware should be used only for the determination of phosphorus. Do not use commercial detergents. D. Analysis: 1. After digestion phosphorus is determined by the Automated Single Reagent Method, Method for Chemical Analysis of Water and Wastes, EPA, 1979, Method 365.1. 2. The Technicon wash water is 6.2-ml H 2so4 per liter. APPENDIX PAGE 14 E. Calculation: 1. Dry Weight Basis: ug/ml P (from standard curve) X 5 ml X 1000 mg mg/kg P gm sample 1000 Kg 2. Wet Weight Basis: mg/kg P (Dry wt) X % Solids(decimal fraction-)= mg/Kg P(Wet Wt) References: Standard Methods, 13th edition, 1971. 1.3.3.3 TOTAL KJELDAHL NITROGEN IN SEDIMENT Total Kjeldahl Nitrogen (TKN) or Organic Nitrogen in Sediment. A. Sample Preparation 1. To determine TKN only, use wet, settled sludge or sediment samples for the analysis. B. Reagents 1. Digestion solution: Dissolve 134 g potassium sulfate, (K SY, in 650 ml ammonia-free water and 200 ml conc. suifu ic acid (H S04@. With stirring, add a solution of 2.0 g red merLri@ o ide, (HgO), dissolved in 25 ml 6N H2soV Dilute to 1 liter with ammonia-free water. 2. Sodium hydroxide-thiosulfate solution: Dissolve 500 g NaOH and 25 g NaS 0 5H 0 in ammonia-free water and dilute to 1 liter. 2 3* 2 3. 2% Boric Acid Solution: Dissolve 20 g boric acid,H3BO3 in ammonia-free water and dilute to 1 liter. APPENDIX PAGE 15 C. Procedure 1. Take the residue in solution from the ammonia analysis, if available. Otherwise, weigh enough wet sample to give 0.1 to 0.2 g sample on a dry weight basis, place in micro- kjeldahl flask and add 50 ml ammonia-free water ( used 1-g wet sample). 2. Add 8 ml of acid-sulfate-mercury digestion solution and digest until SO fumes evolve. (If bumping is a problem add 2 or 3 Hengar selenized granules). Continue the digestion for 25-30 minutes after the evolution of the fumes. The solution should be colorless to pale yellow at this point. Cool to room temperature and stopper if not distilled immediately. 3. Steam out the distillation apparatus before use by placing 10 ml ammonia-free water and 10 ml hydroxide-thiosulfate solution in the flask. Steam out for 5-10 minutes. Samples maybe distilled consecutively after initial steam out. 4. Add 10 ml ammonia-free water prior to distillation. 5. Place a 50 ml Nessler tube containing 5 ml of 2% boric acid under the condenser with the tip of the condenser below the surface of the acid. 6. Place the kjeldahl flask on the distilling apparatus, add 10 ml hydroxide-thiosulfate solution and start steam into the flask by placing the stopper on the steam generator. Collect 35-40 ml of distillate. 7. Lower the receiving tube below the tip of the condenser and remove the stopper from the steam generator. Allow the condensate remaining in the condenser to drain into the receiving tube. Dilute to 50 ml with ammonia-free water. D. Analysis 1. After distillation the ammonia is determined by the automated procedure, Methods for Chemical Analysis of Water and Wastes, EPA, 1979, Method 350.1. Technicon's wash water is 0.2% boric acid. APPENDIX PAGE 16 E.. calculations: Dry-weight basis: mg N found X mls mg/kg (% solids)(g used) digestate": Wet weight basis: mg/kg (dry weight X % solids (decimal fraction) mg/kg N (wet weight) References: Standard Methods, 13th edition, 1971 Methods for Chemical Analysis of Water and Wastes, EPA, 1979. 1.3.3.4 METALS IN SEDIMENT In order to process a sediment sample in the laboratory for metal analysis a standard procedure of analysis must be followed. This includes the digestion, instrument setup, materials, re- agents, supplies, and other pertinent information. This is typically covered in the Methods for Chemical Analysis of Water and Wastes, U.S.E.P.A.- 600/4-79-020. The instrumentation used in metal analysis is calibrated with the frequency 'and in the manner prescribed in the EPA reference 600/4-79-020. 1. Sediment Digestion for Metals 0.5 to 1.0g of sediment is weighed out into a teflon capped teflon digestion vial. (5ml of 48% HF) and 10 ml conc. HNO are added and slowly heated to dryness (6-8 hours). 5 ml 01 conc. HNO is added and the vials ate allowed to sit for two hours. Biakers are then capped and digested on low heat for 48 hours. Caps are removed and nitric acid is then taken off (to near dryness) and five additional ml of HNO and I ml of perchloric acid are added. The vials are heatea until the white perchloric acid fumes subside. If necessary, additional increments of HNO and perchloric acid are added to complete digestion. The Aediment is then brought up with 1 ml conc. HNO 3,y Dilute to final volume of 25 ml with DI water. Analyze atomic absorption. APPENDIX '-PAGE 17 2. Specific Methods for Analysis after digestion. Arsenic (EPA Method 206.3 AA-Hydride) Aluminum (EPA Method 202.1 AA-Flame) Cadmium (EPA Method 213.2 AA-Furnace) Chromium (EPA Method 218.3 AA-Furnace) Lead (EPA Method 239.2 AA-Furnace) Mercury (EPA Method 245.5 cold vapor) Silver (EPA Method 272.2 AA-Furnace) Copper (EPA Method 220.1 AA-Furnace) Zinc (EPA Method 289.1 AA-Furnace) 3. Calculations After the concentration of the digestion solution the following equation is used to convert from ug/l to mg/Kg jig/ml x dilution ppm = mg/Kg sample wt. (g) 1.3.3.5 ORGANICS IN SEDIMENT organic analysis were performed by Environmental Science and Engineering, Inc. (ESE) of Gainseville, Florida. Mr. Jeff D. Shamis was the project coordinator for ESE. The samples were analyzed in accordance with procedures specified in EPA Method 8080, Test Methods for Evaluating Solid Waste, SW-846, Julyf 1982. ESE is certified by The Florida DHRS (certification number 82138) and is excepted by The Florida DER (Lab # EL 0024). 1.4 'DATA REDUCTION VALIDATION AND REPORTING The analytical methods used for each analyte typically illustrate the procedure for collecting, calculating, and reducing the test data to a useable form. This is outlined in the prior section of this document. APPENDIX -.-,.PAGE 18 1.4.1 DATA VALIDATION This section describes the methods by which the data was inter- preted, validated, and reported. Procedures are indicated by major measurement parameters for sampling, analysis and overall program evaluations. The overall data flow for sampling and analysis is shown in Figure 2 of this document. The significance of outliers was used to quantify and improve the the relative significance of the data generated. 1.5 INTERNAL QUALITY CONTROL This section is to outline the methods of quality control used in the laboratory. This typically includes the use of spiked samples, duplicate samples, and replicate samples. Spikes and blanks are used to check the analytical accuracy and the dupli- cate analysis is used to establish the analytical precision. Inorganic matrix spikes and duplicate analyses were performed at a frequency of one per analytical batch or one per twenty sam- ples, whichever frequency is greater. 1.5.1 FIELD QUALITY CONTROL CHECKS The following quality control checks are to be used for sampling operations: 1. Trip blanks 2. Field duplicates The above was performed at a frequency of not less than one per sample event or one per twenty samples, whichever was more frequent. This was used to establish the precision and accuracy of the field collection procedures. 1.5.2 PERFORMANCE AND SYSTEM AUDITS This auditing procedure is typically carried out by the laborato- ry's participation in both the DER performance audit sample program, the DHRS Laboratory Certification Program, and EPA quality assurance proficiency samples. This in addition to the PE check samples that are routine run by the laboratory using EPA known samples that are procured from the USEPA. This allows the laboratory to compare routine test data with that of that regula- tory agencies and other laboratories that participate in these programs. APPENDIX '.PAGE 19 1.5.3 PREVENTATIVE MAINTENANCE PROCEDURES Maintenance schedules for all sampling and analytical equipment will be in accordance with the-recommendations of the equipment manufacturers. Routine operations, such as septum replacement, oil change, etc. was performed by laboratory personnel as re- quired. Specialized inspection and maintenance of major equip- ment items was performed by factory representatives. 1.5.4 SPECIFIC ROUTINE PROCEDURES TO ASSESS DATA PRECISION, ACCURACY AND COMPLETENESS 1.5.4.1 STATISTICAL PROCEDURES FOR PRECISION Precision is a measure of the mutual agreement among individual measurements of the same parameter under prescribed, similar conditions. Replicability is the variability (within batch) among repeated independent determinations of the same measurement parameter by a laboratory at the same time under identical conditions. The following statistical procedures were used to calculate the precision attributes for this program: Replicability Xi1 xi2 data pair xi average of replicate pair xa arithmetic mean of all replicate pair averages s(xa the standard deviation of the replicate pair averages k = the number of replicate pair sets N = number of samples averaged Ri 1xi 1 - xi21 N R E R i=l N APPENDIX PAGE 20 xi X i1+ xi2 2 k x E x a i i=l k k 2 2 S(xa) E xi xa) i=l k S(x a) /s(xa) 1.5.4.2 STATISTICAL PROCEDURES FOR ACCURACY Accuracy is the degree of agreement between the true value of a parameter being measured and the average of observations made according to the test method. The following statistical proce- dures were used for accuracy determinations: Ai = percent of accuracy Oi = observed concentration Ti = true concentration N = number of check samples measured = average accuracy A = Oi x 100 i - Ti APPENDIX PAGE 21 N E A N N sA E (Ai N-1 sA 4(sA2 Recovery is an attribute related to accuracy which applies to analysis of performance using spiked performance evaluation samples. Statistical procedures'for analysis of recovery of recovery are as follows: Ri = analyte recovery (percent) 0i = observed values Bi = background values Ti = true values N = number of samples = average recovery SR = Standard deviation of recoveries R (0i Bi) T x 100 N R E R N N sR2 E (R 2 N-1 sR ,,/(SR2 APPENDIX PAGE 22 1.5.4.3 COMPLETENESS Completeness was evaluated by comparing the number of samples acquired for analysis to the number of samples analyzed. Completeness, % = Number of samples analyzed x (100) Number of samples acquired 1.5.4.4 CONTROL CHARTS Program and laboratory performance with respect to precision and accuracy was compared to existing control charts for safe drink- ing water. Means and standard deviations were calculated using the procedures outlined above for central lines and control limits respectively. Warning and control limits for means was established at 2s and 3s respectively. 1.6 QUALITY ASSURANCE RESULTS Parameter Average Average Accuracy Precision METALS IN SEDIMENT (% Recovery) IC Arsenic 90.7 0.05 Aluminum 95.7 0.04 Cadmium 89.7 0.02 Chromium 90.7 0.05 Lead 89.3 0.08 Mercury 91.8 0.00 Silver 90.0 0.21 Copper 97.3 0.07 Zinc 95.0 0.03 FLOW STUDY Rhodamine WT Dye 95.7 0.03 WATER COLUMN Ammonia Nitrogen 100.9 0.05 Nitrite Nitrogen 104.5 0.13 Nitrate Nitrogen 102.7 0.06 Total-Phosphate 96.7 0.24 Total Kjeldahl 104.6 0.39 COMPLETENESS 99% 7 P(j'j%:v; @-p 4-j"! :;,:l NnAV v itvq @C 7- N ZL vu) The follow i ng data represent the complete summary of qc k-un for -A-.e, -Only ra-presevit'ative analyt*s are r-,:),,j 4C. i ne I -i c on ro 1.1 edi STORET-iMiETHOD 71-4 .20*1 QC SL,,immary Report Fol, Sa;,,,Ple, list LCEUM ..atar Na-f(ia-. 0ISRURE, 'WE -WT .4 EirAITC-14 A*.',IALYST I A R P", F. E TCAtRTER ANALYSlS CATE: 09/08.18E, F. E-- IPL . 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