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PALEOLIMNOLOGICAL RECONSTRUCTIONS OF TWO COASTAL DUNE LAKES IN NORTHWEST FLORIDA USING SEDIMENT ORGANIC MATTER PROXIES By BRANDY ELIZABETH SARA FOLEY A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2018

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PALEOLIMNOLOGICAL RECONSTRUCTIONS OF TWO COASTAL DUNE LAKES IN NORTHWEST FLORIDA USING SEDIMENT ORGANIC MATTER PROXIES

By

BRANDY ELIZABETH SARA FOLEY

A THESIS PRESENTED TO THE GRADUATE SCHOOL

OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF SCIENCE

UNIVERSITY OF FLORIDA

2018

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© 2018 Brandy Elizabeth Sara Foley

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To my love, Matthew

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ACKNOWLEDGMENTS

Foremost, I would like to express my sincere gratitude to Dr. Stephens for her

continuous support, enthusiasm and generous knowledge. My sincere appreciation of

the funding and support from the Mattie Kelly Environmental Institute and

Choctawhatchee Basin Alliance of Northwest Florida State College, and Walton County.

A special thank you to Dr. Brenner and Dr. Curtis for your exceptional assistance and

dedication that helped to develop this research project.

I would also like to express my immense gratitude to my advisor, Dr. Wright, and

committee members Dr. Stephens, Dr. Reynolds and Dr. Ogram for their patience,

support and commitment to my academic success.

Finally, I must express my very profound gratitude to my parents, family and

friends for providing me with unfailing support and continuous encouragement

throughout my life and during this time researching and writing my thesis. This

accomplishment would not have been possible without them. Thank you.

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TABLE OF CONTENTS page

ACKNOWLEDGMENTS .................................................................................................. 4

LIST OF TABLES ............................................................................................................ 7

LIST OF FIGURES .......................................................................................................... 8

ABSTRACT ..................................................................................................................... 9

CHAPTER

1 REVIEW OF LITERATURE .................................................................................... 11

Coastal Dune Lakes of Northwest Florida ............................................................... 11 Global Distribution ............................................................................................ 16

Similarities to Estuaries .................................................................................... 19 Similarities to Lagoons ..................................................................................... 24 Geomorphology ................................................................................................ 26

Physicochemical Variables ............................................................................... 27 Paleolimnology ....................................................................................................... 29

Objectives ............................................................................................................... 39

2 MATERIALS AND METHODS ................................................................................ 43

Site Description ....................................................................................................... 43 Eastern Lake .............................................................................................. 43 Big Redfish Lake ........................................................................................ 44

Surface Water Chemistry Collection ....................................................................... 45 Statistical Analyses ................................................................................................. 46

Collection and Preparation of Sediment Samples ................................................... 46 Geochronology ....................................................................................................... 47 Total Phosphorus .................................................................................................... 49

Geochemistry .......................................................................................................... 49

3 RESULTS ............................................................................................................... 53

Surface Water Chemistry ........................................................................................ 53

Nutrients ........................................................................................................... 53

Eastern Lake .............................................................................................. 53 Big Redfish Lake ........................................................................................ 54

Physicochemical Variables ............................................................................... 55 Eastern Lake .............................................................................................. 55 Big Redfish Lake ........................................................................................ 55

Geochronology and Sedimentation Rates .............................................................. 56 Eastern Lake .................................................................................................... 56

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Big Redfish Lake .............................................................................................. 57

Total Phosphorus .................................................................................................... 58 Eastern Lake .................................................................................................... 58

Big Redfish Lake .............................................................................................. 59 Geochemistry .......................................................................................................... 59

Eastern Lake .................................................................................................... 59 Big Redfish Lake .............................................................................................. 60

4 DISCUSSION ......................................................................................................... 78

Surface Water Chemistry ........................................................................................ 79 Water Column Nitrogen to Phosphorus Ratios ....................................................... 89 Geochronology ....................................................................................................... 92 Sediment Total Phosphorus .................................................................................... 94

Organic Matter ........................................................................................................ 96 Paleoproductivity .................................................................................................. 101

Paleosalinity .......................................................................................................... 102

5 CONCLUSION ...................................................................................................... 111

LIST OF REFERENCES ............................................................................................. 115

BIOGRAPHICAL SKETCH .......................................................................................... 125

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LIST OF TABLES

Table page 1-1 The 15 Recognized Coastal Dune Lakes of Walton County morphometric

summary statistics (Hoyer and Canfield 2008). .................................................. 42

3-1 Eastern Lake long term summary statistics (CBA 2017) .................................... 62

3-2 Big Redfish Lake long term summary statistics (CBA 2017). ............................. 63

4-1 Trophic state classification (Forsberg and Ryding 1980). ................................. 105

4-2 Eastern and Big Redfish Lake mean long term trophic variables (CBA 2017). . 106

4-3 Surface and bottom physicochemical variables between Eastern and Big Redfish Lake..................................................................................................... 107

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LIST OF FIGURES

Figure page 1-1 Coastal Dune Lakes of Walton County (Walton Outdoors 2018). ....................... 41

2-1 Eastern Lake and catchment area ...................................................................... 51

2-2 Big Redfish Lake and catchment area ................................................................ 52

3-2 Big Redfish Lake long term trend analysis (CBA 2017) ...................................... 65

3-3 Eastern Lake Lead-210 geochronology .............................................................. 66

3-4 Eastern Lake sedimentation rate ........................................................................ 67

3-5 Big Redfish Lake geochronology ........................................................................ 68

3-6 Big Redfish Lake sedimentation rate .................................................................. 69

3-7 Eastern Lake sediment total phosphorus ........................................................... 70

3-8 Big Redfish Lake sediment total phosphorus ..................................................... 71

3-9 Eastern Lake C/N ratio ....................................................................................... 72

3-10 Eastern Lake 13C ................................................................................................ 73

3-11 Eastern Lake δ15N .............................................................................................. 74

3-12 Big Redfish Lake C/N ratio ................................................................................. 75

3-13 Big Redfish Lake δ13C ........................................................................................ 76

3-14 Big Redfish Lake δ15N ........................................................................................ 77

4-1 Organic matter origins relationships between δ13C and C/N ratio (Lamb et al., 2006). ............................................................................................................... 108

4-2 Eastern Lake sediment δ13C and C/N ratio relationship. .................................. 109

4-3 Big Redfish Lake δ13C and C/N ratio relationship. ............................................ 110

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Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science

PALEOLIMNOLOGICAL RECONSTRUCTIONS OF TWO COASTAL DUNE LAKES IN

NORTHWEST FLORIDA USING SEDIMENT ORGANIC MATTER PROXIES

By

Brandy Elizabeth Sara Foley

May 2018

Chair: Alan Wright Major: Soil and Water Sciences

Coastal dune lakes in Northwest Florida frequently exchange seawater with the

Gulf of Mexico, but remain undefined in their geomorphology and hydrologic functions

due to limited published literature. A 20-year record of surface water quality data

indicated that two coastal dune lakes, Eastern and Big Redfish Lake, exhibited

significant positive trends in nutrients and chlorophyll indicating shifts toward more

biologically productive systems. To gain an understanding of historical changes within

Eastern and Big Redfish Lake, paleolimnological analyses of sediment organic matter

were conducted. Geochemical signatures of 210Lead, total phosphorus (TP), total

carbon (TC) and total nitrogen (TN) ratios, and the stable isotopes δ13C and δ15N were

analyzed to depict historical variability of lake hydrologic conditions. Results of these

analyses reconstructed historical nutrient status, organic matter sources,

paleoproductivity and periods of marine or freshwater dominance. TP and TN exhibited

significant increases (p<0.05) towards surface sediments, indicating a change in the

lake’s nutrient balance. The TC/TN ratios demonstrated significant decreases (p<0.05)

towards surface sediments, indicating a shift to autochthonous organic matter sources.

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A combination of terrestrial C3 plants, freshwater and marine organic matter inputs were

revealed through stable isotopes δ13C and δ15N values. Paleo-productivity inferred from

stable isotopes did not correlate with increasing TP and TN, indicating that primary

productivity may not be the dominant source of organic matter in these lakes. Periods of

marine or freshwater dominance were revealed through stable isotope trends indicating

historical variability between both lakes. This research has improved our understanding

of two coastal dune lakes’ hydrologic functioning through the last century.

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CHAPTER 1 REVIEW OF LITERATURE

The purpose of this literature review is to examine the global distribution of

similar coastal waterbody subclasses to the coastal dune lakes of Northwest Florida,

examine classification designations, and compare the morphologic and hydrologic

characteristics among these systems. This information will help to bolster our

understanding of the dynamic interactions between morphologic and hydrologic

interactions of the coastal dune lakes ecosystems and may lead to innovative

management techniques.

Coastal Dune Lakes of Northwest Florida

Coastal dune lakes of Northwest Florida are referenced as unique and rare

coastal waterbodies found in select locations around the world (FNAI 2010). They are

considered distinctive due to their intermittent connections to seawater of the Gulf of

Mexico and the subsequent role this interaction has on physicochemical conditions

within the lakes. This cluster of coastal dune lakes in Northwest Florida are the only

formations that exist in the state of Florida and are considered internationally rare

formations due to intermittent connections to seawater, geological characteristics of this

region in Florida, Gulf of Mexico geomorphology and regionally distinct climate of

Northwest Florida.

Walton County recognizes 15 coastal dune lakes between Walton and Bay

County in Northwest Florida (Figure 1-1). Within this region, barrier islands have not

formed, therefore, the lakes interact directly with the Gulf of Mexico waters (Gross

2015). The lakes are located between the maritime forest and the Gulf of Mexico coast,

occurring behind the barrier sand dune system. The hydrologic functions and

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characteristics of the coastal dune lakes are unique when compared to other fresh,

estuary and marine waterbodies in the region. They are characterized by shallow,

irregularly shaped waterbodies located within three kilometers of the coastline (FNAI

2010; Hoyer and Canfield 2008). On average, coastal dune lakes have small

catchments areas of less than two square kilometers (km2) and morphometric features,

with an average surface area of 0.26 km2 and an average depth of two meters (Table 1-

1). Twelve of the fifteen recognized coastal dune lakes have an intermittent connection

to the Gulf of Mexico.

Physicochemical properties range among Northwest Florida’s coastal dune lakes

and are presumed to be strongly associated with local geologic conditions, lake

watershed and morphometry, climate, and frequency and duration of outlet connection

to seawater (Hoyer and Canfield 2008). Northwest Florida waterbodies exhibit soft

water and a high mineral content of predominantly sulfate, sodium and chloride ions

(Griffith et al., 1997). Due to geologic and watershed influences, coastal dune lakes are

considered oligotrophic waterbodies with low biological productivity and low nutrient

levels. High concentrations of humus in the form of dissolved organic matter drains from

forests and wetlands throughout lake watersheds. These contributions cause the lake

waters to be slightly acidic (Hoyer and Canfield 2008). The dominant portions of colored

dissolved organic matter give the lakes water a dark, tea color with a mean true color

value of 99 Platinum-Cobalt units (Hoyer and Canfield 2008).

Coastal dune lakes are lentic water bodies without significant surface inflow (i.e.

fluvial inputs), and receive much of their freshwater from lateral groundwater seepage

through the surrounding well-drained coastal sands, minor streams and surface water

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runoff (Hoyer and Canfield 2008). If seawater enters the lake, it is predominantly

through an outlet connection to the Gulf, however, storm overwash events, and potential

saltwater intrusion through the beach face can also be considered potential sources of

saltwater inputs (Hoyer and Canfield 2008; Browder and Dean 1998).

Seasonal climate conditions have a substantial role on lake water levels, outlet

connections and physicochemical variations. Rainfall varies throughout the State of

Florida, however, northwest Florida has one of the highest mean annual rainfall in the

state, with 60-64 inches a year (Borisova and Wade 2017). If groundwater is the

dominant source of water to coastal dune lakes, water table level fluctuations may

influence outlet connections and correlate with seasonal lake levels (Hoyer and Canfield

2008). During drier climate conditions, groundwater levels generally drop and lake

outlets do not typically connect to the Gulf of Mexico. Under these conditions lake

waters may experience stable lake levels and decreased water clarity due to saturation

of dissolved organic matter or increased clarity due low surface water inputs (Hoyer and

Canfield 2008). A wet climate can cause increased surface water runoff and potential

increases in groundwater levels, causing lake levels to rise and decreasing Secchi

depth with the addition of dissolved organic matter inputs (Hoyer and Canfield 2008).

Lake outlet connections to the Gulf of Mexico cause the lake level to drop, Secchi depth

measurements may increase due to seawater influx and stratified lake conditions can

occur within the water column (Hoyer and Canfield 2008).

The coastal dune lakes are also critical insect breeding sites which form the

basis of local food chains and are important habitat for fish, birds and mammals

inhabiting the lakes and surrounding coastal ecosystems (Griffith et al., 1997; FNAI

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2010). Lake outlet habitats are important sources of food and habitat for many migratory

and native shorebirds. Threatened species, such as the Snowy plover and

Choctawhatchee Beach Mouse, utilize shorelines and sand dune habitat of coastal

dune lakes (de Villegas 2017).

Northwest Florida coastal dune lakes exhibit intermittent connections to the Gulf

of Mexico, known as outlets or outfalls, and open to the Gulf under a variety of

conditions based on hydraulic gradient, climate, and tide. Outlet openings are typically

the result of a shift in the hydraulic gradient between the beach face and the lake water

level. Often, when lake levels reach near flood level conditions, the hydraulic gradient

becomes reduced between the lake outlet and Gulf of Mexico beach face causing lake

water to breach the separating sand berm and flow into the Gulf (Browder and Dean

1998). Strong storms, tides, waves and wind can also cause an outlet connection to

occur in the reverse, Gulf water flowing into a lake through the outlet (Hoyer and

Canfield 2008). When lake water exchanges with seawater, system shifts from a

freshwater dominant state, 0-0.5 parts per thousand (ppt), to a brackish, estuarine-like

condition of 0.5-30 ppt. Variable outlet connection factors, along with the movement of

coastal sediments play a role in the frequency and duration of the outlet connections.

Each coastal dune lake outlet status (open or closed) varies in frequency and duration

of opening (Hoyer and Canfield 2008). Outlet status may not be the only mechanism by

which salinity changes in lakes. Groundwater flow, runoff, potential subaqueous

exchange through the beach face may also impact salinity in lakes.

For example, Campbell Lake experiences outlet connections to the Gulf, but

does not display changes in lake salinity under typical outlet conditions, i.e. flow from

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the lake to the Gulf, and maintains a mean surface salinity of 0.06 ppt. This is likely the

result of lake elevation in comparison to the mean sea level (Griffith et al., 1997).

Conversely, Powell Lake has outlet connections lasting longer in duration, thus,

maintaining conditions more similar to a lagoon-state, with a mean surface salinity of

14.3 ppt. However, Powell Lake is manually opened during high water level conditions

that threaten residences and infrastructure.

All of the coastal dune lakes in Walton County have natural, unrestricted outlet

connections that move freely within their outlet sweep zone; meaning that they are not

stabilized by structural support or directed through artificial arrangements (Browder and

Dean 1998). Historically, four coastal dune lake outlets Western, Eastern, Deer and

Alligator Lake have permits to be manually maintained, or opened, by officials during

high water level events to protect infrastructure and residences.

It is hypothesized that coastal dune lakes of Northwest Florida developed from

various coastal processes, beginning as tidally influenced basins or lagoons that

became closed off by sand infilling its inlet buffering or eliminating a tidal influence

(Gross 2015; Liu and Fearn 2000; FNAI 2010). The U.S. Gulf of Mexico and Atlantic

coasts experienced a steady rise in sea level of approximately 6 millimeters/year,

relative to the land, causing sediment barriers to close off coastal water features from

the sea and a landward migration of water features (Bird 1994; Donoghue 2011).

Throughout its geological history, Northwest Florida experienced periods of flooding

from marine intrusions or exposed sandy coastlines (Coor 2013). In the Gulf of Mexico,

sea level rise gradually slowed in the middle to late Holocene epoch, approximately 6-

8,000 years ago (Blum et al., 2002: Coor 2013). Net longshore currents transported

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sediment dominated by quartz sand erosion of the Appalachian Mountains to the

Apalachicola River delta, then west along the northwest Florida Panhandle region (Coor

2013). Radiocarbon dating of organic matter found in sediment cores from two

Northwest Florida coastal dune lakes showed the lake formed during a similar section of

the mid-Holocene, roughly 5,000 years ago (Liu and Fearn 2000).

Global Distribution

The shifting nature of coastal environments pose a challenge to global

classification and the definitions used to categorize coastal waterbodies. It can be

further complicated by regionally distinct waterbody functions, such as an estuary or

lagoon, and potential subtypes like the coastal dune lakes found in Northwest Florida.

Coastal waterbodies identified as coastal dune lakes have been reported throughout the

world, however often do not intermittently connect with seawater and therefore appear

to contrast the ones in Northwest Florida (Gross 2015; Timms 1986).

Coastal dune lakes have repeatedly been examined and classified based on

physicochemical and geomorphic characteristics (Timms 1986; Gross 2015; Coor

2013). In contemporary studies, similarly functioning systems have become recognized

as Intermittently Closed and Open Lakes and Lagoons (ICOLLs), but are

interchangeably used with references such as intermittently open and closed estuaries

(Gale et al., 2006; Haines et al., 2006). In South Africa, similarly functioning systems

exist, but are predominantly fluvial dominated systems that intermittently connect to

seawater based on climate conditions, known as Temporarily Open/Closed Estuaries

(TOCEs) (Perissinotto et al., 2010; Whitfield and Bate 2007; Cooper 2001). In New

Zealand, such waterbodies are referred to as coastal lagoons and have been

distinguished using a sub-classification of either coastal lakes known as ‘Waiatuna-

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type,’ or river-mouth lagoons called ‘Hapua’ (Kirk and Lauder 2000). Within the United

States, the Pacific Northwest coast of Oregon and California, the Atlantic East coast of

North Carolina identify refer to intermittently open or closed coastal waterbodies as

simply lagoons, coastal ponds or coastal lakes (Kling 1986; Eilers et al., 1996; Klaus et

al., 2002). South American studies refer to these systems as lagoons or ICOLLs (Netto

and Fonseca 2017). The southern Baltic region has also reported comparable coastal

waterbodies as intermittently open/closed coastal lakes (Astel et al., 2016).

Internationally, studies on various coastal waterbodies that share parallels in hydrologic

functions to intermittently opened or closed waterbodies have occurred on every

continent (Tagliapietra et al., 2009). However, these waterbodies remain regionally

identified throughout the world due to the neglect of developing an internationally

recognized classification system.

On a global scale, wave dominated coastal waterbodies located on microtidal

coasts make up between 8% (Dürr et al., 2011) and 12% of the world’s coastlines

(Kennish 2015). Coastal environments are viewed as highly dynamic zones where

terrestrial ecosystems blend with marine systems (Dürr et al., 2011). It is due to these

forces, estuarine lagoons form in coastal environments and are a representation of an

ecotone between terrestrial and marine systems. Contrasting settings of these

waterbodies form on low lying coasts with limited tidal variation and have a tendency to

be wave dominated, versus tidally dominated (Kennish 2015; McSweeney et al., 2017).

Depending on the system’s dominant forces, i.e. catchment area, fluvial or tidal, a

connection to seawater exists with an intermittently opened or closed state and the

frequency and duration of its connection may be dependent on geomorphologic

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characteristics. Generally, these systems are not permanently open to the sea

(McSweeney et al., 2017).

McSweeney et al. (2017) studied the global geomorphology of intermittently

open/closed coastal waterbodies referring to them collectively as intermittently

open/closed estuaries (IOCEs). Using estuaries as the largest classification order, after

oceanic waterbodies, McSweeney et al. (2017) contended that IOCEs are a rare sub-

class of wave dominated estuaries. Distinguishing features of ICOEs are their

geomorphic characteristics (catchment and surface area), physicochemical features and

intermittent and restricted connections to seawater (Tagliapietra et al., 2009;

McSweeney et al., 2017). IOCEs predominantly exist on coastlines that exhibit a

microtidal range, less than 2 meters, and are wave versus tide dominated (Tagliapietra

et al., 2009; McSweeney et al., 2017, Roy et al., 2001). Wave dominated coasts are

driven by wave energy and longshore sediment transport which control the morphology

of the coast versus tide dominated coasts that are driven by tidal currents redistribution

of sediments (Roy et al., 1994).

Using site specific characteristics to classify coastal dune lakes alleviates

misidentification errors and provides a foundation to compare similar functioning

waterbodies with. Estuarine lagoon subtypes tend to become regionally defined

because of the latter and non-existent or grouped with larger, worldwide coastal

waterbody classification systems. A variety of terms have been used to discuss and

identify these subtypes causing a general miscommunication of which systems are

being discussed and how to refer to these systems on an international scale.

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To accurately depict the geomorphology and hydrology of coastal dune lakes in

Northwest Florida these lakes can be referred to as estuarine lagoons, encompassing

similar characteristics from both estuaries and lagoons. Estuarine lagoons have

parallels in their geologic formation, geographic locations, physicochemical

compositions, and relationship of morphometric variables.

Estuarine lagoons are referred to as geologically “young” formations with origins

establishing during the Holocene period of the Post-glacial Marine Transgression

approximately 8,000 years ago (Roy et al., 2001). Post-glacial Marine Transgression

induced episodic sea level rise that occurred worldwide (Donoghue 2011). Present day

sea levels were reached around 6,700 years ago, forming modern shorelines and

coastal features such as estuaries and lagoons (Blum et al., 2002). During this period,

the formation of coastal sand barriers at the mouth of flooded river valleys and coastal

inlets created isolated estuarine lagoon environments (Adlam 2014). Many modern

coastal waterbodies were formed during this time through sedimentation (Roy et al.,

2001). Typically, a coastal waters’ maturity is measured by its sedimentation, from an

immature unfilled state to a mature filled state (Adlam 2014). Estuarine lagoons are

considered geologically undeveloped and relatively short-lived formations with a strong

probability to disappear (FNAI 2010). However, Adlam (2014) hypothesizes that

estuarine lagoons’ geological evolutions are inhibited by local energy regimes.

Similarities to Estuaries

Estuarine lagoons can be grouped into many broad conceptual coastal

waterbody classes including estuaries, coastal lagoons, ICOLLs, TOCEs, tidal creeks,

river mouths, rias, fjords, fjards, and bahiras (Tagliapietra et al., 2009). Broad

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classification for estuarine lagoons are used to show the arrow of unique subtypes of

estuary formations (McSweeney et al., 2017; Tagliapietra et al., 2009).

One of the original definitions of estuaries was created by Pritchard in 1967, but

more recently restructured by J. H. Day to include additional unique waterbodies found

in other regions that intermittently open or close to an ocean, as well as address

variations in salinity gradients found in estuary environments (Potter et al., 2010).

According to J. H. Day (1981), “an estuary is a partially enclosed coastal body of water

which is either permanently or periodically open to the sea and within which there is a

measurable variation of salinity due to the mixture of seawater with freshwater derived

from land drainage.” Defining and classifying estuaries follows a methodology organized

by the physical processes of a system and subsequent physicochemical and ecological

characteristics (Hume et al., 2007). Broadly, estuaries are formed by the physical

variables of latitude, oceanic basins and large landmasses (Hume et al., 2007). Their

formation and function is dominated by a single or many energy sources including

waves, river and/or tides (Heap et al., 2001). These foundational forces explain the

development of different estuaries and estuary subtypes, as well as their morphologic

and hydrologic characteristics which correlate with their global geographic region (Hume

et al., 2007). Morphologic characteristics can be explained by the processes that occur

within an estuaries’ catchment and its interactions with the marine and terrestrial

environments. Hydrologic conditions of an estuary are significantly influenced by salt

and freshwater inputs, precipitation, stratification, flushing, mixing and sedimentation

(Hume et al., 2007), and these physical processes drive an estuaries behavior and help

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to distinguish them from other coastal waterbodies. However, there are always caveats

in science.

Recently, McSweeney et al., (2017) studied global documentation and reviewed

aerial imagery of estuarine lagoon subtypes which led to one of the first comprehensive

classifications of these unique systems. Their classification system bases all coastal

waterbody subtypes on an estuary classification scheme and further designates estuary

subtypes, terming them intermittently opened/closed estuaries (IOCE) (McSweeney et

al., 2017). Their observations deduced that these types of waterbodies occur in

microtidal coastal and are wave dominated, not river or tidally dominated. General

estuary classifications often exclude IOCEs or recognize them as a rare subset of wave-

dominated systems, lumping they all together into one class (McSweeney et al., 2017).

Unlike previous studies, a geomorphic organizational approach was applied, versus site

specific ecological or physicochemical (McSweeney et al., 2017). Through this

methodology, three variations of IOCEs (estuary subtypes) were determined: drowned

river valleys, barrier estuaries, and saline coastal lakes (McSweeney et al., 2017). Each

variation of IOCEs is distinguished by its morphologic sedimentary infill and entrance

condition, used to represent the age or level of progression of the IOCEs (McSweeney

et al., 2017). Young IOCEs have limited infill and deeper basins, while mature estuaries

are typically shallow due to restricted space for sediment accumulation (McSweeney et

al., 2017). The classification suggested by McSweeney et al., (2017) assists in

differentiating between IOCE subtypes on a global scale through the use of easily

measurable marine and fluvial variables: entrance channel width, estuary perimeter,

surface area, catchment area, estuary length, beach width and tidal prism (McSweeney

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et al., 2017). As Tagliapietra et al., (2009) points out though, there can be various terms

and definitions used to describe estuaries, lagoons or similar coastal waterbodies, thus

creating an overlap in descriptions and the risk for confusion or disagreement.

The coastal waterbody subtypes found in South Africa, are referred to as

temporarily open/closed estuaries (TOCE) (Tagliapietra et al., 2009; Perissinotto et al.,

et al., 2010). Most of these estuary formations occupy a drowned river valley, yet some

have developed on coastal plains similar to the coastal dune lakes of Northwest Florida

(Whitfield 1992). TOCEs are classified into two subtypes based on the frequency of

their connection with seawater (McSweeney et al., 2017). The major drivers of the

South African TOCEs are their catchments and dominant influences on runoff and

streamflow (Perissinotto et al., et al., 2010). River inflow is reported as the most critical

factor influencing TOCE hydrology because of its role in the sedimentary and

hydrodynamic processes within individual systems (Whitfield 1992). Many TOCE are

considered perched estuaries with a minimum water level elevated above mean sea

level (MSL) (Perissinotto et al., 2010). The coastal dune lakes of Northwest Florida are

considered perched lakes in the context that they are perched over a confining surficial

freshwater layer slightly above mean sea level, creating a hydraulic gradient that exists

between the lakes and the Gulf of Mexico (Coor 2013). In both cases, a perched

estuarine lagoon allows for the system to sustain interval periods of an opened or

closed state with seawater. On a global scale, this aspect allows for unique outlet

behavior and creates dynamic hydrologic conditions that can vastly contrast other

similar systems. The subsequent physicochemical characteristics which are created

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from estuarine lagoon connection behavior is an integral component in distinguishing

them from other coastal waterbodies that are permanently open (Lill et al., 2012).

Similar estuarine lagoon features exist on the coast of Tasmania, a small

Australian state island, and in New Zealand. These features are also identified as

estuary subtypes and subclassified by their acting physical features, geomorphology

and ecological communities (Edgar et al., 2000; Lill et al., 2012). In Tasmania, it was

determined that a variety of subgroups exist here which can be organized by their

geomorphic criteria, ranging from drowned river valleys, marine inlets, river estuaries,

permanently open barred estuaries, seasonally closed barred estuaries and even

included a lagoon subgroup (Edgar et al., 2000). Within this study, however, associated

ecological biota was strongly influenced by salinity and tidal range (Edgar et al., 2000).

This finding holds pertinent meaning to the ideology behind estuarine lagoon subtype

classification. Edgar et al., (2000) concluded that physical estuarine lagoon

classification based solely on physicochemical data is meaningless unless validated

with biological data. Lill et al., (2012) also determined signification correlations between

New Zealand intermittently closed estuaries and biological community structure. This

data can provide another aspect to the ecological distinctions between estuarine

lagoons and other coastal features, along with providing another edge in the

classification of these waterbodies globally.

Estuaries have been traditionally identified by their physical processes,

geomorphology, and connection to seawater. Some focus has been directed to an

estuaries tidal influence and subsequent salinity gradient. However, the estuary

subtypes discussed can range from having diurnal tidal influence to no tidal prism. The

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unique aspects of estuarine lagoon subtypes cover a range of influencing processes

and may inspire a different perspective on subtype classification.

Similarities to Lagoons

The coastal dune lakes of Northwest Florida also share similarities with coastal

lagoons based on the nature of their outlet connection to seawater and potential

influence by tides. Similar to estuaries, coastal lagoons have historically had various

definitions used to define their attributes. One of the most widely accepted and

comprehensive definitions of coastal lagoons was developed by Kjerfve (1994). He

defines coastal lagoons as inland waterbodies, usually parallel to the coast, separated

from the ocean with one or more restricted inlets that can remain open or may be

intermittently open, and have shallow depths. Originally based on Phleger’s definition,

Kjerfve (1994) felt it was important to include a regard for the connection(s) of coastal

lagoons to the ocean and their potential to be closed off by sediment deposition from

wave action and littoral drift. Similar observations were made by McSweeney et al.,

(2017) in their research, confirming that a coast’s wave energy and sediment transport

have an important role to an estuarine lagoon’s connection with seawater. A coastal

lagoon seawater connection characteristics determine the influence of tides on the

system and subsequent salinity which can vary from a coastal freshwater lake to a

hypersaline lagoon (Kjerfve 1994).

Kjerfve distinguishes estuaries and coastal lagoons by establishing a

classification scheme based on the connection state and subsequent exchange of

seawater (Kjerfve 1994). Through Kjerfve’s classification, estuaries and coastal lagoons

were differentiated by freshwater inputs, tidal influence, dilution of saltwater and depth

(Kjerfve 1994). Focusing on coastal lagoons, he further subclassifies coastal lagoons by

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the frequency and amount of seawater exchange which he believes are the dominant

forces and functions of lagoons (Kjerfve 1994). The lagoon’s connection channel to the

sea have certain characteristics which heavily influence the tidal influence and water

level fluctuations within the lagoon (Kjerfve 1994). Due to these channel characteristics,

three geomorphic subclasses of coastal lagoons were designated as choked, restricted

or leaky lagoons (Kjerfve 1994). Choked lagoons are made up of a series of connected

oval coastal waterbody features, connected to the sea by a long narrow channel

(Kjerfve 1994). The connection channel has a role in the flushing time of the lagoon and

its intermittent stratification which characterize the lagoon’s physicochemical

characteristics (Kjerfve 1994). A restricted lagoon has two or more connection channels

which allow for increased tidal influence and vertical mixing (Kjerfve 1994). Lastly, leaky

lagoons have many connection channels to seawater allowing for a strong tidal

presence in the lagoon and higher salinities which mirror the influencing seawater.

However, variations among coastal lagoons can also be attributed to their

geomorphologic history and the influence of geological, climatic, hydrological and

ecological factors, as well as humans (Kjerfve 1994).

In a study conducted by Haines et al., (2006), ICOLLs were classified by their

morphometric variables, such as surface area, volume, shape, tidal prism, catchment

area and Entrance Closure Index (ECI). Haines et al., (2006), based their analyses on

the ICOLLs morphometry and its direct influence on the hydrodynamics and subsequent

physicochemical nature (Haines et al., 2006). It is thought that these resemblances

would be observed in the coastal dune lakes of Northwest Florida if a comprehensive

morphometric analysis was conducted. Morphometric characteristics can also provide

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an estimation of the evolutional state of an ICOLLs geomorphology which may correlate

with its sensitivity to external inputs (Haines et al., 2006). It was determined for New

South Wales, Australian ICOLLs that systems with smaller waterbody volume to

catchment area were more geomorphologically evolved and more vulnerable to external

activities (Haines et al., 2006).

According to Bird (2008), coastal lagoons with restricted or intermittently

opened/closed connections may resemble inland lakes versus traditional coastal

lagoons features. However, saline lakes are recognized largely as coastal lagoons

which can encompass a broad range of estuarine characteristics. It is challenging to

develop a comprehensive term that can be used to define and distinguish estuarine

lagoons throughout the world (Tagliapietra et al., 2009). However, the variability that is

observed within regions and throughout the world has some consistencies among

coastal lagoons in their functional operations.

Geomorphology

Geomorphologic variables have been referred to as the distinguishing features of

estuarine lagoons from other traditional coastal waterbodies. The morphometric

relationship between waterbody and catchment area are the two major drivers of

physical, chemical and biological aspects of an estuarine lagoon system (McSweeney

et al., 2017). These morphometric variables have a substantial control over the state of

the connection, or disconnection, to seawater (McSweeney et al., 2017). An estuarine

lagoon system with a large catchment area is directly correlated to seawater

connections on an annual basis (McSweeney et al., 2017). Geomorphologic

characteristics, such as connection channel width, tidal prism, waterbody area and

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volume, and catchment size drives the frequency, duration, and state of estuarine

lagoon connection to seawater (McSweeney et al., 2017).

According to Elliott and Whitfield (2011), hydromorphology characteristics have

an influence on circulation, tidal prism and biota communities. An estuarine lagoon

system can have varying degrees of circulation and residence time. The influence of

freshwater and seawater inputs are the source of a system’s flushing rate and residence

time (Elliott and Whitfield 2011). These inputs impact the tidal prism of a system and

cause vertical and horizontal gradients within the system (Elliott and Whitfield 2011).

Salinity is the primary factor in ecosystem functions of estuarine lagoons as it

influences the presence and distribution of floral and faunal communities within a

system and impacts the ability to retain nutrients (Elliott and Whitfield 2011). Ecological

conditions, specifically salinity and temperature, are important in the geomorphological

evolution of coastal lagoons as they control the extent to which vegetation can colonize

shorelines, impeding erosion, promoting patterns of sedimentation and generating

organic deposits (Bird 1995). These conditions are then superimposed to the sediments

and geology of system. The dynamic nature of estuarine lagoon systems provides a

habitat only inhabitable to organisms that can tolerant a range of changes in

hydromorphologic variables, namely temperature and salinity (Elliott and Whitfield

2011). Consequently, the organisms of estuarine lagoons and other coastal waterbodies

are capable of absorbing natural and anthropogenic pressures more effectively than

other aquatic ecosystems (Elliott and Whitfield 2011).

Physicochemical Variables

Physicochemical variations occurring from interactions of freshwater and marine

waters have a strong correlation to an estuarine lagoon’s morphometry and subsequent

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hydromorphologic conditions (Kennish 2015). These physical influences on the

estuarine lagoon generally control the connection state of the system and subsequently

have a large impact to the physicochemical conditions of the waterbody as an influx of

seawater can alter salinity, temperature, nutrients, primary productivity, species

presence and habitat availability (Perissinotto et al., 2010; Lill et al., 2011).

The physicochemical variables have been determined as a defining characteristic

of estuarine lagoons from other coastal waterbodies (Tagliapietra et al., 2009).

Physicochemical variables such as salinity, temperatures, dissolved oxygen, pH,

nutrients and organic matter are strongly influenced by inputs from both marine and

terrestrial environments (Tagliapietra et al., 2009). There are a number of functional

differences among the coastal dune lakes of Northwest Florida. Some coastal dune

lakes may be more true to traditional coastal lakes while others to more similar to

estuaries. However, limited literature on these systems exists demonstrating the many

information gaps that exist in our incomplete understanding of them, especially for the

coastal dune lakes of Northwest Florida.

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Paleolimnology

Past environmental and hydrologic data can be reconstructed and interpreted

through the use of paleolimnology techniques applied to organic matter proxies (Birks

and Birks 2006; Gu et al., 1996). Aquatic environments, especially coastal systems, are

in a constant state of change due to internal and external influences, so long-term

observational data are critical to the best management practices of a waterbody.

However, many current observed data records are limited, intermittent or aren’t

available in an “ecologically relevant time frame” (Birks and Birks 2006; Smol 2008).

Water residence time and geomorphology (lake shape and bathymetry) can assist in

interpreting the physical historical changes of a waterbody (Cohen 2003). However,

sediments provide the most robust archives of historical changes since they persist

longer than the other archive sources (Cohen 2003). The composition of a waterbody’s

sediments can reveal many aspects about a waterbody and conditions of its watershed,

as well as insight to the environmental conditions that existed at the time of

accumulation (Routh et al., 2004). Paleolimnology is a multidisciplinary science that is

used to reconstruct past environmental conditions of inland waters through sediment

characteristics, known as proxies, and this application has been successful for fresh

and marine waters (Cooper 2001; Smol 2008; Tibby and Taffs 2011; Brenner et al.,

1993; Gu et al., 1996). Sediment proxies provide high-resolution chronologies of

environmental conditions within a waterbody, as well as its surrounding catchment.

They reveal patterns and changes that characterize variations in climate (temperature

and precipitation), hydrologic variability or anthropogenic influences (Birks and Birks

2006). Sediment proxies depict water conditions and catchment characteristics,

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specifically changes in vegetation and land use (Birks and Birks 2006). Aquatic primary

productivity heavily influences or may control organic matter that accumulates in a

waterbody and offers implications to the historical conditions of biological productivity, or

trophic state conditions (Brenner et al., 1999; Gu et al., 1996). Environmental conditions

leave numerous geochemical signals in sediment records that can be used to interpret

paleoenvironmental changes (Routh et al., 2004), and these signals can be measured

through a variety of proxies, both biological and physical. Stable isotope signatures

(δ13C and δ15N) and total carbon and total nitrogen (C/N) ratios are some of the most

common and effective geochemical sediment proxies. Most methodologies suggest

using a variety of proxies to interpret environmental changes due to complex ecological

interactions that cannot be deduced by single proxy analyses (Brenner et al., 1999;

Birks and Birks 2006; Cohen 2003).

Preserved proxies found in aquatic sediments provide significant information on

the organic matter inputs, waterbody productivity dynamics and watershed land use

conditions (Das et al., 2008) as these aquatic systems are influenced by and exposed to

many external and internal forces (Cohen 2003). These stimuli range from macro

(climate, geology, vegetation) to micro (element cycles, biota) interactions, as well as,

anthropogenic impacts (Cohen 2003). The organic matter found in sediments

represents a small, but important fragment of sediments (Meyers and Teranes 2001).

Determining the origin and quantities of organic matter in sedimentary records can

provide critical information when reconstructing past conditions of a waterbody (Meyers

and Teranes 2001). Environmental changes in a watershed and the water affect how

much and what kind of organic matter is delivered to the aquatic system and initiate

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series of geochemical processes that can leave a decipherable record in the sediments

(Routh et al., 2004; Das et al., 2008). Plants (aquatic and terrestrial) are the primary

source of organic matter to a waterbody (Meyers and Teranes 2001). Plants can be

divided into two distinct biochemical categories: vascular and non-vascular (Meyers and

Teranes 2001). Vascular plants (i.e. macrophytes, grasses, trees) contain carbon rich

cellulose and lignin, while non-vascular plants contain little to no carbon rich fractions

(i.e. phytoplankton) (Meyers and Teranes 2001). These biochemical and structural

differences leave behind different geochemical fossils in the sediment organic matter

which can be used to differentiate the origins of organic matter (Meyers and Teranes

2001).

Organic matter plays an important role in sediment processes and sources due

to its interactions with biota, nutrient cycles and geochemical processes as sources of

organic matter are strongly environment-dependent (Lamb et al., 2006; Routh et al.,

2004). Sediment organic matter reflects not only its sources but also the forming factors

and influences of processes that have altered and degraded the original material

(Meyers and Teranes 2001). Coastal and freshwater sediments receive organic matter

from both autochthonous, phytoplankton and other photosynthetic organism produced

organic matter, and allochthonous, primarily vascular plants and soil organic matter

transported from watershed, sources (Toming et al., 2013). Autochthonous sourced

organic matter is predominantly made up of nonhumic substances which are labile and

easily utilized or degraded by microorganisms (Toming et al., 2013). Allochthonous

derived organic matter consists of mostly humic substances that are resistant to

decomposition and have a brownish color (Toming et al., 2013). Aquatic systems that

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do not endure regular flushing through fresh or marine water processes, such as

lagoons or isolation basins, are dominated by autochthonous sources of carbon and

control the supply of organic matter to the sediments (Lamb et al., 2006). For regularly

flushed systems, a balance is typically experienced between autochthonous and

allochthonous organic matter sources (Lamb et al., 2006). Changes in the organic

matter sources can influence primary productivity (autochthonous) and affect

sedimentation rates (Routh et al., 2004). Terrestrial vegetation contains more refractory

components, such as lignin, hemicellulose, cellulose, and less labile fractions, i.e.

protein, than aquatic plants (phytoplankton and photosynthetic micro-organisms) (Khan

et al., 2015; Meyers and Teranes 2001). Refractory structural components are nitrogen

poor and provide C3 terrestrial plants with high C/N (weight percent) ratios of greater

than 18 (Lamb et 2006; Khan et al., 2015; Meyers and Teranes 2001), but C4 vegetation

have C/N ratios greater than 30 (Lamb et al., 2006). Aquatic plants contain higher levels

of nitrogen and less lignin and cellulose portions, generally displaying lower C/N ratios

of 4 to 6 and less than 10, phytoplankton have a C/N range of 6 to 8 (Lamb et al., 2006;

Khan et al., 2015; Meyers and Teranes 2001). Elevated C/N ratios (> 20) indicate

terrestrial vegetation as the dominant organic matter source while lower C/N values (4

to 6, > 10) indicate dominant aquatic organic matter sources (Meyers and Teranes

2001; Lamb et al., 2006; Khan et al., 2015). C/N ratios of 13 to 14 suggest equal

contributions of aquatic and terrestrial plant organic matter, which is projected for most

lake systems (Meyers and Teranes 2001). Organic matter, from either aquatic or

terrestrial sources, undergoes diagenesis as it sinks through the water column and is

deposited into the sediments and may continue into sub-bottom depths (Meyers 1994).

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However, various articles report that the organic matter source signatures are

accurately preserved and undergo little further change (Meyers 1994; Routh et al.,

2004). These general observations of organic matter C/N ratios can be utilized to

determine the terrestrial and aquatic organic matter source contributions to a waterbody

system.

Carbon isotopes are widely used as indicators of organic matter sources (Meyers

and Teranes 1999; Routh et al., 2004). Both algae (phytoplankton and photosynthetic

microorganisms) and vascular plants create organic matter with a carbon signature and

can be distinguished by their carbon compositions (δ13C) and carbon to nitrogen (C/N)

ratios (Meyers and Teranes 2001). Organic matter origins become easily visualized

when stable isotope δ13C measurements are plotted against C/N ratios (Routh et al.,

2004). Terrestrial plants can be categorized into C3, C4, and crassulacean acid

metabolisms (CAM) photosynthesizing groups based on the carbon fixation pathways

used during photosynthesis (Hobbie and Werner 2003). These pathways are reflected

in the δ13C isotopic concentrations and C/N ratios in plant tissues and translated into the

sediment organic matter they produce (Hobbie and Werner 2003; Khan et al., 2015;

Lamb et al., 2006). C3 pathway plants are the most common type of terrestrial

vegetation and dominate in temperate forests, freshwater aquatic and wetland

environments (Khan et al., 2015). During photosynthesis, C3 plants favor δ12C isotopes

and discriminate against heavier 13C isotopes, resulting in more negative δ13C

concentrations in organic matter, approximately -32‰ to -21‰ (Khan et al., 2015; Lamb

et al., 2006). C4 plants commonly discriminate less against heavier δ13C isotopes and

display low δ13C concentrations in organic matter, with a range of -17‰ to -9‰ (Khan et

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al., 2015; Lamb et al., 2006). CAM plants have a wide range of δ13C concentrations, -

28‰ to -10‰, but tend to have similar ranges to that of C4 plants (Khan et al., 2015). C4

and CAM plants are common in water-stressed environments, usually occurring in arid

locations (Khan et al., 2015). These types of plants can also easily adapt to saline and

intertidal environments (Khan et al., 2015; Lamb et al., 2006). Algae, phytoplankton and

other aquatic photosynthetic microorganisms, utilize a C3 pathway distinguishable from

terrestrial C3 plants (Lamb et al., 2006; Meyers and Teranes 2001; Khan et al., 2015). In

aquatic environments algae display a range of δ13C concentrations, -30‰ to -18‰

(Khan et al., 2015; Lamb et al., 2006). Variations in δ13C occur between freshwater and

marine algae, generally freshwater algae have a δ13C range of -30‰ to -26‰ and

marine algae have a range of -23‰ to -16‰ (Khan et al., 2015; Lamb et al., 2006).

In addition to inferences of organic matter sources, stable isotope δ13C

measurements provide paleoproductivity and changes in nutrient sources to a

waterbody (Lamb et al., 2006; Meyers and Teranes 2001; Brenner et al., 1999). The

concentrations of sediment δ13C values are significantly determined by the rate of

carbon uptake during algal productivity and the composition of dissolved inorganic

carbon (DIC) (Brenner et al., 1999; Meyers and Teranes 2001). Aquatic plant δ13C is

controlled by whether the plant utilizes bicarbonate or dissolved carbon dioxide (Lamb

et al., 2006). Dissolved carbon dioxide has lower δ13C values than bicarbonate and

aquatic algae will preferentially take up carbon sources with lower concentrations until

the source is exhausted (Lamb et al., 2006). Algae preferentially uptake δ12C, a lighter

carbon isotope, causing the organic matter they produce to have higher δ12C

concentrations than the δ13C / δ12C ratio of DIC of the water column (Meyers and

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Teranes 2001; Routh et al., 2004). Algal produced organic matter removes δ12C from

the water column DIC pool and during periods of increased productivity, the δ12C DIC

pools are depleted and the remaining δ13C values increase in the water column (Routh

et al., 2004; Brenner et al., 1999; Meyers and Teranes 2001). Due to limited labile forms

of δ12C, algae in these conditions consume the remaining δ13C isotopes, causing

elevated δ13C concentrations in sediment organic matter (Meyers and Teranes 2001).

When a waterbody moves towards a hypereutrophic state, its sediments may

experience longer periods of anoxia and increased methanogenic processes that

produce heavier δ13C carbon dioxide to the water column (Brenner et al., 1999). Shifts

in paleoproductivity can be reflected in the variations of δ13C changes, i.e. increases in

sediment organic matter δ13C can indicate periods of increased productivity due to

increases in nutrients (Meyers and Teranes 2001; Brenner et al., 1999; Gu et al., 1996).

This association of δ13C concentrations in sediment organic matter and

paleoproductivity is not always applicable. Variations in pH, temperature, nutrient

sources, productivity rates and the Suess effect can have an influence on the dominant

carbon isotope created in organic matter (Meyers and Teranes 2001; Routh et al.,

2004).

Stable isotope δ15N is another sediment proxy used to identify organic matter

sources and paleo-productivity, however, alone can be more challenging to interpret

than carbon isotopes (Routh et al., 2004). The nitrogen cycle is dynamic and nitrogen

isotope measurements may be more convoluted in their sources and influences (Talbot

2001; Meyers and Teranes 2001). In addition, other factors can influence nitrogen

concentrations in the natural environment, i.e. agricultural and industrial practices, as

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well as anthropogenic and natural atmospheric nitrogen fallout (Talbot 2001). These

external influences can affect internal aquatic primary productivity and subsequent

nitrogen isotope composition of sediment organic matter (Talbot 2001).

Dissolved inorganic nitrogen (DIN) in the forms of ammonium, nitrate and nitrite

are important aquatic nitrogen pools used during primary production (Meyers and

Teranes 2001; Talbot 2001). The primary producers that utilize these labile forms of

nitrogen typically dominate aquatic systems. However, nitrogen fixing bacteria, most

commonly cyanobacteria, utilize atmospheric nitrogen (N2) when the latter forms of

nitrogen are exhausted (Talbot 2001). These two forms of primary producer’s utilization

of nitrogen and the nitrogen isotope signatures that subsequently remain can be used to

roughly distinguish between organic matter sources within an aquatic system (Talbot

2001; Meyers and Teranes 2001). Like carbon stable isotopes, nitrogen organic matter

sources can be inferred through the differences between δ15N and δ14N and the

availability of inorganic nitrogen pools to plants both in aquatic and terrestrial

environments (Meyers and Teranes 2001; Routh et al., 2004). Algae utilize the more

labile forms of DIN (ammonium, nitrite and nitrate) favoring the δ14N over the heavier

δ15N isotope and produce organic matter with a lower δ15N concentration (Meyers and

Teranes 2001). As DIN nitrogen pools are spent, δ15N isotopes gradually increase and

when they are utilized for primary production it is reflected in increased δ15N

concentrations of sediment organic matter. In general, studies show an average range

of δ15N concentrations in organic matter of approximately -5‰ to 20‰ (Talbot 2001;

Meyers and Teranes 2001). Typically, DIN display larger values of δ15N than

atmospheric nitrogen (N2) and are reflected in the aquatic sediment organic matter

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(Meyers and Ishiwatari 1993; Meyers and Teranes 2001; Routh et al., 2004).

Autochthonous organic matter produced in an aquatic environment tends to have higher

δ15N signatures (Gu et al., 1996). Algae and aquatic C3 plants utilize DIN to produce an

approximate range of 7‰ and 10‰ of δ15N concentration in sediment organic matter,

whereas, allochthonous organic matter resulting from C3 terrestrial plants typically have

a δ15N concentration of roughly 0.4‰ (Meyers and Teranes 2001; Routh et al., 2004;

Gu et al., 1996). Terrestrial C3 plants and nitrogen fixing bacteria utilize atmospheric

nitrogen (N2), no nitrogen fractionation occurs, resulting in δ15N-depleted organic matter

with values near 0.4‰, but N-fixing bacteria have a range of -1‰ to 3‰ (Meyers and

Teranes 2001; Routh et al., 2004; Gu et al., 1996). A parallel exists in the variations of

δ15N and DIN availability and primary producer utilization of nitrogen pools (Talbot

2001). However, other external influences such as land use changes, changes in

organic matter sources and anthropogenic practices can affect the nitrogen isotopes

signatures in organic matter (Meyers and Teranes 2001; Routh et al., 2004; Talbot

2001).

The measurements of sediment δ15N can also provide an indication of the past

biological productivity, or trophic state, of a waterbody. In general, δ15N and δ13C

concentrations increase in autochthonous produced organic matter as the trophic state

increases from oligotrophic to eutrophic (Torres et al., 2012). Brenner et al., (1999)

found that δ15N concentrations decreased in hypereutrophic (extreme biological

productivity) Florida lakes and attributed this to nitrogen fixing bacteria. Yet, not all

eutrophic and hypereutrophic lakes are dominated by nitrogen-fixing microorganisms

(Gu et al., 1996). Therefore, low δ15N concentrations are not always attributed to

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nitrogen-fixing bacteria but can be associated with low or high levels of aquatic

biological productivity (Gu et al., 1996). The conclusions of Gu et al., (1996)

demonstrates that primary productivity controls the δ15N concentrations through algal

consumption of labile nitrogen (nitrate, ammonium, nitrite) when there are sufficient

supplies of nitrogen to a waterbody and/or nitrogen-fixing bacteria in further eutrophic

lakes that are nitrogen limited. When stable isotope δ15N measurements are reviewed in

conjunction with other proxies, such as δ13C and C/N ratios, it can provide a more

comprehensive interpretation of past environmental conditions (Talbot 2001). Larger

δ15N values in sediment organic matter are displayed when there are more negative

δ13C values, indicating a decrease in productivity resulting from limited nitrate

availability (Routh et al., 2004). Reduced values of δ15N in sediment organic matter can

result from increased availability of DIN, usually stimulating primary productivity in lakes

(Routh et al., 2004).

Additional factors can play a role in the nitrogen isotopic signature of sediment

organic matter. The limiting nutrient of a system controls the level of productivity in a

waterbody and in lakes, phosphorus is often the limiting nutrient (Meyers and Teranes

2001). When phosphorus levels are depleted, only a small fragment of nitrogen is used

resulting in an insignificant alteration to the isotopic signature of DIN (Meyers and

Teranes 2001). Therefore, measurements of the nitrogen isotope signatures would

show no change and could adversely impact paleolimnological interpretations.

Fluctuations of algal species can affect the nitrogen cycle within the water column and

cause incorrect interpretations of nitrogen isotope concentrations and paleoproductivity

(Meyers and Teranes 2001; Routh et al., 2004). The use of stables isotope signatures

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from bulk sediment organic matter to study past environmental conditions is based on

the assumptions that sediment organic matter originates from primary productivity in the

water column and that the isotopic ratios reflect the organic matter produced in the

water column (Gu et al., 2011). Therefore, stable isotopic composition of sediments can

be used as a function of nutrient driven productivity or trophic state of a waterbody (Gu

et al., 2011; Meyers and Teranes 2001; Lamb et al., 2006). Changes in the amounts

and kinds of biota (within lake and watershed) reflect changes in climate and other

environmental factors and can be inferred through stable isotope analyses (Meyers and

Teranes 2001).

Objectives

Kendall Tau statistical analyses of contemporary water quality data indicated that

two coastal dune lakes, Eastern and Big Redfish Lake, are shifting to more biologically

productive states. In order to examine these changes beyond contemporary data

collection, the historical environment of both lakes was reconstructed using

paleolimnological analyses of sediment organic matter collected from surface-sediment

interface cores. Geochemical analyses of 210Lead, total phosphorus (TP), total carbon

(TC), total nitrogen (TN), stable isotopes δ13C and δ15N were used to reconstruct and

study hydrologic variability within these two lakes.

The core objectives of this project were to i) determine historic lake nutrient

conditions through sediment accumulation of TP and TN, ii) assess sources of organic

matter by analyzing C/N ratios and stable isotope δ13C and δ15N values, iii) infer lake

paleoproductivity by assessing stable isotope δ13C and δ15N values and correlations to

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nutrient changes and iv) infer periods of marine or freshwater dominant conditions

through analysis of C/N ratios and concurrent stable isotope δ13C and δ15N values.

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Figure 1-1. Coastal Dune Lakes of Walton County (Walton Outdoors 2018).

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Table 1-1. The 15 Recognized Coastal Dune Lakes of Walton County morphometric summary statistics (Hoyer and Canfield 2008).

Lake Watershed Area (km2)

Lake Surface Area (km2)

Mean Depth (meters)

Allen 0.71 0.07 1.1

Alligator 0.38 0.06 1.5

Big Redfish 1.19 0.09 1.6

Camp Creek 2.13 0.23 1.6

Campbell 0.08 0.44 3.5

Deer 1.38 0.17 2.8

Draper 1.93 0.11 1.4

Eastern 1.54 0.25 2.1

Eastern North* . . 1.5

Fuller 0.43 0.2 1.7

Grayton* . . .

Little Redfish . 0.05 1.8

Morris 0.87 0.32 3.1

Oyster 0.56 0.09 1.7

Powell 7.3 1.04 2

Stallworth 0.86 0.05 1.5

Western 2.75 0.69 5.2

Western Northeast* . . 1.7

Lakes listed with an asterisk symbol represent lakes portions that have data measurements collected independently of main lake body for water quality monitoring purposes. Eastern North is the northern portion of Eastern Lake and is delineated by Scenic Highway 30A; Grayton is the west lobe of Western Lake and Western Northeast is the upper northeast portion of Western Lake.

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CHAPTER 2 MATERIALS AND METHODS

Site Description

Walton County coastal dune lakes are located along the coastal mainland of

Florida. This region of the Gulf Coast is unusual from surrounding coastlines in

Northwest Florida because it lacks protective offshore barrier islands (Gross 2015). This

portion of the Gulf of Mexico has one of the smallest tidal ranges, approximately 0.1 to

0.3 meters (U.S. Department of Interior 2001). The coastal dune lakes of Northwest

Florida reside in the Gulf Coast Lowlands Lake Region which characterizes waterbody

hydrology as acidic, soft water that contains high concentrations of dissolved organic

carbons, elevated levels of sulfate, sodium, and chloride ions and low nutrients (CBA

2017; Hoyer and Canfield 2008, Griffith et al., 1997). Coastal dune lake substrate is

primarily composed of sand with organic sediment deposits (FNAI 2010; Hoyer and

Canfield 2008). Previous research has identified some coastal dune lakes exhibiting a

microtidal influence during outlet connections (Coor 2013; Bhadha and Jawitz 2008).

Eastern Lake Eastern Lake (Figure 2-1) is one of the 15 recognized coastal dune lakes in Walton

County, Florida (N 30.312048, -86.093230) and has an irregular surface area of 25.4

hectares and a catchment area of 154 hectares (Hoyer and Canfield 2008). Eastern

lake is considered a shallow lake with an average depth of 2.1 meters (Hoyer and

Canfield 2008). Intermittently, the lake water naturally breaches through the beach sand

berm within its relic sweep area where the dunes are not as mature as surrounding

dunes and connects to the Gulf of Mexico through its outlet. The sweep area is the

historical measurement through aerial and survey data of the length of shoreline

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identified as being influenced by all previous locations of the outlet channel (Browder

and Dean 1996). During outlet connections to seawater, the lake can potentially be

micro-tidally influenced (Bhadha and Jawitz 2008). Eastern Lake naturally breaches the

sand berm separating it from the Gulf of Mexico during high water levels or strong storm

events and can be manually opened by Walton County officials when it reaches a

designated flood threshold to protect residences and infrastructure. Eastern Lake is

intersected by Florida Scenic Highway 30-A subdividing the lake into two sections and

connecting them through a narrow open-water bridge.

Residential and commercial land use dominate Eastern Lake’s shoreline and

southern watershed area. Northern portions of the watershed consist of freshwater

forested/shrub wetlands and is preserved in the Point Washington State Forest,

consisting of Sandhill, basin swamps, Titi drains, wet flatwoods, wet prairies and

cypress swamps (Greene 2011). The lake’s intermittent connection with saltwater forms

an estuary-like environment in the lake, where fresh and marine flora and fauna coexist.

Emergent salt- and freshwater marsh plants exist interspersed along the lake shoreline,

and relic sand dunes and dune vegetation occur along the southern portion of the lake

near the outlet.

Big Redfish Lake

Big Redfish Lake (Figure 2-2) is one of 15 recognized coastal dune lakes in

Walton County, Florida (N 30.338853, W -86.195428) and has a surface area of 9.22

hectares and a watershed of 119 hectares (Hoyer and Canfield 2008), with an average

lake depth of 1.58 meters (Hoyer and Canfield 2008). Big Redfish Lake has a natural,

intermittent connection to the Gulf of Mexico through a restricted outlet. The lake is

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intersected by Florida Scenic Highway 30-A at its northern section and is connected to

the upper portion through culverts under the highway.

Its southern watershed region consists of residential development, while the

northern region is made up of freshwater forested/shrub wetlands, basin swamps, wet

flatwoods, wet prairies and cypress swamps in Point Washington State Forest and

Florida State Park (Greene 2011). Fringing and emergent salt- and freshwater

vegetation, such as S. alterniflora and Phragmites australis, occur along the lake’s

shoreline (Hoyer and Canfield 2008). Barrier sand dunes and dune vegetation occur

along the southern portion of the lake watershed.

Surface Water Chemistry Collection

Big Redfish Lake and Eastern Lake have three water quality monitoring stations

on each lake, sampled monthly by CBA citizen scientists. At each station, two water

samples were collected, and Secchi disk depth measurements and datasonde

physicochemical variables recorded. Open water surface samples were collected at 0.5

m with a 250-mL, acid-cleaned, triple-rinsed Nalgene bottle. The large, 1000-mL

Nalgene bottle is filtered within 48 hours post field collection through a Gelman 47mm

Type A-E glass fiber filter (CBA 2017). The filter is preserved in a filter label and frozen

until collected by Florida LAKEWATCH coordinators quarterly (CBA 2017). The 250-mL

Nalgene bottle is frozen on site and collected quarterly by the Florida LAKEWATCH

personnel. Florida LAKEWATCH laboratory in Gainesville, Florida analyzed water

samples and filters for total phosphorus (TP) (µg/L) and total nitrogen (TN) (µg/L), True

Color (Platinum-Cobalt Units), conductivity (µS/cm) and total chlorophyll (Canfield et al.,

2002; CBA 2017). All water samples and filters were analyzed within three months and

data results provided to CBA and state agencies. Secchi disk depth (water clarity) and

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water column depth are collected at each station and data is submitted to

LAKEWATCH. Datasonde equipment collected surface and bottom chemical variables

at each station with variables including temperature, dissolved oxygen, pH, salinity, and

turbidity.

Statistical Analyses

Data was compiled into an annual water chemistry report by CBA and the Mattie

Kelly Environmental Institute. Using the Kendall-Tau trend analysis on monthly water

quality data collection (CBA 2017). All surface water quality variables have a grand

mean calculated in JMP software, with means processed in R software using Kendall

Tau trend analysis. The results from these analyses show annual and intra-annual

variance of each coastal dune lake (CBA 2017). In addition, geochemical variables were

assessed using Kendall-Tau trend analysis and processed in R software to determine if

significant trend occurred within the data set.

Collection and Preparation of Sediment Samples

Surface sediment-water interface cores collected from two coastal dune lakes in

Walton County, Florida were dated using 210Pb,137Cs, and 226Ra isotope signatures and

analyzed for total phosphorus (TP), total carbon (TC) and total nitrogen (TN)

concentrations, stable isotopes (δ13C and δ15N). The site locations were chosen to

represent depositional environments in the deep, centrally located sites using

LAKEWATCH bathymetric maps as reference (Hoyer and Canfield 2008).

Sediment-water interface cores were recovered with a large-volume (~1 meter)

manual piston corer to avoid disturbing lake sediment. Polycarbonate tubes with a 3-

inch inner diameter were used to collect the cores which were sealed on both ends and

held in a vertical position to maintain sediment integrity and avoid mixing of sediments.

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A 75-centimeter surface sediment-water interface core (N 30.310550, W -86.092667)

was collected from Eastern Lake on May 4, 2017. A 95-centimeter surface sediment-

water interface core (N 30.337585, W -86.191956) was recovered from Big Redfish

Lake. Sediment core locations were stored with a Garmin etrex 10 geographic

positioning system unit. The sediment cores were extruded vertically and subsampled at

2-cm intervals using clean, plastic spatulas. A total of 38 sediment samples were

obtained from the Eastern Lake core and 46 sediment samples were obtained from Big

Redfish Lake. Core subsections were labeled and kept in individual one-gallon ziplock

sealed bags in a refrigerated cooler at 2 to 7 degrees Celsius. Preparation of

subsamples were conducted at the Mattie Kelly Environmental Institute of Northwest

Florida State College laboratory. Subsamples were weighed using a Unibloc top-loading

balance and dried in a gravity convection oven. Dried samples were sent to University

of Florida laboratories for further analysis.

Geochronology

Subsamples of Eastern and Big Redfish Lake sediment cores were dated using

210Pb, 137Cs, and 226Ra isotope signatures. These isotopes are common variables used

to date sediments of the late Holocene epoch, approximately 100 to 200 years before

present (BP), and provide an estimation of a waterbody’s sedimentation rate. Lead-210

is a naturally occurring radioactive element that forms as part of the radioactive decay of

Uranium-238 (Jeter 2000; de Souza et al., 2012). Uranium occurs at an “unchanging

concentration” over time and is present in all soils and sediments (Jeter 2000; de Souza

et al., 2012). Eventually, it decays into radium-226 which exhibits the same static

concentration (Jeter 2000; de Souza et al., 2012). Then, 226Ra is transformed into 210Pb

which maintain secular equilibrium (production rate is equal to decay rate). Generally,

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210Pb is formed from the radioactive decay of Radon-222 (Jeter 2000; de Souza et al.,

2012). It can either be deposited through natural atmospheric fallout (“unsupported

210Pb”) or produced by radioactive decay of 226Ra into 222Rn (“supported 210Pb”) in

sediments (de Souza et al., 2012). 210Pb dating is calculated by the excess of

“unsupported 210Pb” activities, subtract the “supported 210Pb” from 210Pb activities in

every sediment subsample (de Souza et al., 2012; O’Rielly et al., 2011). The Constant

Rate of Supply model (CRS) assumed the excess “unsupported 210Pb” is supplied at a

constant rate over time and was the method used when determining the age of the

sediments (de Souza et al., 2012). The CRS model calculates the sedimentation rates

of materials deposited over time through the sediment core (de Souza et al., 2012).

Subsamples from entire sediment core were prepared in pre-weighed ceramic

crucibles and a wet weight was recorded using an electronic top-loading balance.

Sediments were dried at 105° Celsius in a convection oven for 48 hours and dried

subsamples were ground with a mortar and pestle and re-weighed to determine dry bulk

density weight.

Sediment dry bulk density data and dried samples were shipped to the University

of Florida Institute of Paleoenvironmental Research (FLIPER) laboratory for analysis. At

FLIPER laboratory, the radiometric measurements (210Pb, 226Ra and 137Cs) were made

using low-background gamma counting with well-type intrinsic germanium detectors

(Schelske et al., 1994). Sediment ages were calculated using the constant rate of

supply (CRS) model (Appleby and Oldfield 1983; Oldfield and Appleby 1984) with age

errors propagated using first-order approximations and calculated according to Binford

(1990).

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Total Phosphorus

A total of 85 subsamples were analyzed for total phosphorus (TP) at the

University of Florida’s Institute of Fisheries and Aquatic Sciences Analytical Research

Laboratory (ARL). Subsamples from entire sediment cores were prepared for ARL

analysis at the Mattie Kelly Environmental Institute of Northwest Florida State College

Laboratory. Subsamples were dried in crucibles dried at 105° Celsius in a convection

oven in ceramic crucibles for 48 hours, followed by grinding with a mortar and pestle,

passage through a 2mm mesh sieve, and weighing to obtain dry weight. Samples were

then placed in sterile plastic Whirl-Paks and shipped to ARL for analysis.

The ARL follows the semi-automated colorimetry protocol of the United States

Environmental Protection Agency (EPA) Method 365.1, Revision 2.0: Determination of

Phosphorus by Semi-Automated Colorimetry (1992). Subsamples were placed into 250

mL high density polyethylene (HDPE) containers and preserved with sulfuric acid, then

gently boiled at approximately 100° Celsius to convert all the phosphorous in the

sample to the orthophosphate form. A portion, 50 mL, of the sample was measured into

a digestion vessel and ammonium molybdate or antimony potassium tartrate solution

added to each sample portion and boiled. This allows for the organophosphorus

compounds to digest and formmolybdenum blue, the intensity of which is proportional to

the amount of phosphorous in solution.

Geochemistry

Eastern and Big Redfish Lake surface sediment-water interface cores were

analyzed for bulk organic carbon (%C) and nitrogen (%N) percent contents and stable

isotopes signatures of δ13C and δ15N of sediment organic matter. The sediment core

subsamples were weighed in pre-weighed ceramic crucibles. Then, dried at 105°C in a

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convection oven in crucibles for 48 hours. Subsamples were then ground with a mortar

and pestle, passed through a 2 mm sieve and weighed again. Dry sediment bulk density

were calculated using these measurements and weighed to 100 to 250 milligrams,

packed in sterile plastic Whirl-Paks, and shipped to the University of Florida’s

Department of Geological Sciences Light Stable Isotope Mass Spectrometry Laboratory

for analysis.

Subsamples were loaded into tin capsules and placed in a 50-position automated

Zero Blank sample carousel on a Carlo Erba NA1500 CNHS elemental analyzer. After

flash combustion in a quartz column containing chromium oxide and silvered

cobaltous/cobaltic oxide at 1020°C in an oxygen-rich atmosphere, the sample gas was

transported in a He carrier stream and passes through a hot reduction column (650°C)

consisting of reduced elemental copper to remove oxygen. The effluent stream then

passes through a chemical (magnesium perchlorate) trap to remove water. The stream

then passes through a 0.7 meter GC column at 125°C that separates the nitrogen gas

(N2) and carbon dioxide (CO2) gases. Finally, the gases pass through a

thermal conductivity detector that measures the size of the pulses of N2 and CO2.

The sample gas next passed into a ConFlo II interface and into the inlet of a Thermo

Electron Delta V Advantage isotope ratio mass spectrometer running in continuous flow

mode where the sample gas was measured relative to laboratory reference N2 and CO2

gases. All carbon isotopic results were expressed in standard delta notation relative

to VPDB, and all nitrogen isotopic results were expressed in standard delta

notation relative to air.

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Figure 2-1. Eastern Lake and catchment area

This image demonstrates the variety of land use within the Eastern Lake catchment. Development dominates the southern region, while wetlands and upland forests comprise the northern regions of the catchment area.

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Figure 2-2. Big Redfish Lake and catchment area

Big Redfish Lake and its catchment area is presented in this aerial image demonstrating the variety of land use within it. Coastal land use in the southwest area is made up of predominantly residential development, while the northern portion consists of wetlands and upland forests.

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CHAPTER 3 RESULTS

Surface Water Chemistry

Nutrients

Eastern Lake

The 2016 Coastal Dune Lake Water Chemistry Summary Report produced by

CBA and MKEI of Northwest Florida State College reported that Eastern Lake has

observed statistically significant positive trends in TP, TN, and total chlorophyll with a

statistically significant negative trend in water transparency over a 19 year period,1997-

2016 (Figure 3-1) (CBA 2017). Long term trophic state variable trend analysis statistics

were calculated on an annual basis using monthly water quality data from three

monitoring stations within Eastern Lake for TP (µg/L), TN (µg/L), total chlorophyll (µg/L),

water transparency (m). The results show the inter-annual (monthly variability within the

year) and intra-annual variance (variability among years) (CBA 2017). Throughout the

19-year monitoring period, TP had a mean concentration of 12 µg/L, a maximum of 17.8

µg/L and a minimum of 9.14 µg/L (CBA 2017). TN concentration during this time frame

had a mean of 286 µg/L, a maximum of 399 µg/L and a minimum of 214 µg/L (CBA

2017). Total chlorophyll had a mean value of 3.55 µg/L, a maximum of 6.71 µg/L and a

minimum of 2.14 µg/L (CBA 2017). Secchi water transparency depth had a mean of

1.45 meters, a maximum of 1.97 meters and a minimum of 0.94 meters (CBA 2017).

The Kendall’s Tau coefficient, a statistical measure of rank between variables, was

applied to determine the long term trophic state trend analysis in TP, TN, total

chlorophyll and water transparency (CBA 2017). Statistical results display significant

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positive trends in nutrients (TP, TN) and total chlorophyll with a significant negative

trend in water transparency (CBA 2017).

Big Redfish Lake

The 2016 Coastal Dune Lake Water Chemistry Summary Report produced by

CBA and MKEI of Northwest Florida State College reported that Big Redfish Lake has

observed statistically significant positive trends in TP, TN, and total chlorophyll with a

statistically significant negative trend in water transparency. Long term trophic state

variable trend analysis statistics were calculated on an annual basis using monthly

water quality data from three monitoring stations within Big Redfish Lake TP (µg/L), TN

(µg/L), total chlorophyll (µg/L), water transparency (m) over an 18-year period, 1998

through 2016 (CBA 2017). The results show the inter-annual (monthly variability within

the year) and intra-annual variance (variability among years) (CBA 2017). Long term TP

(µg/L) concentrations had a mean of 13 µg/L, with a max of 22.6 µg/L and minimum of

4.67 µg/L based on sampling events throughout the 18-year monitoring period (CBA

2017). Long term summary statistics of TN (µg/L) concentrations measured a mean of

364 µg/L, a max of 657 µg/L and a minimum of 149 µg/L. Results of long term summary

statistics of total chlorophyll (µg/L) concentrations measured a mean of 5.39 µg/L, a

max of 10.5 µg/L and a minimum of 1.67 µg/L (CBA 2017). Long term summary

statistics of water transparency, measured with a Secchi disk in meters, had results of a

mean transparency of 0.98 (m), max transparency of 1.5 meters and a minimum of 0.68

meters (CBA 2017). The Kendall’s Tau coefficient analysis, a statistical measure of rank

between variables, was used to statistically analyze the data of long-term trophic state

trends of TP, TN, algal biomass (total chlorophyll) and water transparency within Big

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Redfish Lake (CBA 2017). Statistical analysis results (Figure 3-2) over an 18-year

period show positive trends in nutrients (TP, TN) and total chlorophyll with a negative

trend in water transparency (CBA 2017).

Physicochemical Variables

Eastern Lake

Due to the coastal dune lake’s interactions with the Gulf of Mexico and its high

color status, its dissolved oxygen, pH and salinity long term summary statistics will be

described. As reported in the Coastal Dune Lake Water Chemistry Summary Report

(2017), Eastern Lake surface measurements (Table 3-1) of dissolved oxygen display a

range of dissolved oxygen from a minimum of 5.55 to a maximum of 7.79 mg/L with a

mean of 6.77 mg/L (CBA 2017). Eastern lake’s surface pH measurements vary between

a minimum of 7.12 and a maximum of 7.97 pH, with a mean of 7.53 pH (CBA 2017).

The surface salinity is measured in parts per thousand (ppt) have a minimum of 2.01

and a maximum of 18.5 ppt, with a mean of 8.23 ppt (CBA 2017). Eastern lake’s true

color (Platinum-Cobalt units) measurements range from a minimum of 45 to a maximum

of 173 Pt-Co units and mean of 96.9 Pt-CO Units (CBA 2017). Bottom measurements of

all variables except for TN, TP and total chlorophyll (~0.5 meters above bottom) are also

collected at each water quality monitoring station, however, only surface water

measurements are analyzed for the report Eastern Lake Long Term Summary Statistics

(CBA 2017)

Big Redfish Lake

Big Redfish lake’s long-term summary statistics (Table 3-2) of dissolved oxygen,

pH and salinity will be described because of its relativity to this research. As reported in

the Coastal Dune Lake Water Chemistry Summary Report (2017), Big Redfish Lake’s

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surface dissolved oxygen has minimum of 4.49 mg/L and maximum of 7.36 mg/L, with a

mean of 5.98 mg/L (CBA 2017). The surface water pH ranges from a minimum of 6.6 to

a maximum of 7.72 pH, with a mean of 7.2 pH (CBA 2017). Surface salinity (ppt)

measurements range from minimum of 0.66 to 16 ppt, with a mean of 5.14 ppt (CBA

2017). The true color (Platinum-Cobalt Units) range from a minimum of 43.3 to a

maximum of 326 Pt-Co Units, with a mean of 150 Pt-Co Units (CBA 2017). Bottom

measurements are recorded during field collections but are not analyzed or reported in

the annual Coastal Dune Lake Water Chemistry Summary Report.

Geochronology and Sedimentation Rates

Geochronology results provided reliable dating for sediment core samples from

both Eastern and Big Redfish Lake sediment-water interface cores. A combination of

210Pb, 137Cs and 226Ra isotopes were used to measure the isotopic activity levels and

provide high-resolution age-depth relationships (Kenney et al., 2016). These are

commonly applied paleolimnological methods which offer an approximate chronology to

the sediment core samples. The age of the sediment core subsamples were calculated

using the constant rate of supply (CRS) model (Appleby and Oldfield 1983; Oldfield and

Appleby 1984). The approximate measurements of sedimentation accumulation rates

(mg/cm2/yr) for the sediment core profiles were also determined through the CRS

model.

Eastern Lake

A successful total of 14 samples were measured for 210Pb, and 137Cs on Eastern

Lake (Figure 3-3). These results provided a sediment record of 151 years at a down

core depth of 28 cm. The date at 28 cm was approximately 1866 with a surface date of

close to 2017. Total 210Pb decreased down core until it reached supported levels at 28

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centimeters. 137Cs activity remained near-constant, with an area of slight activity at

approximately 14 cm. 226Ra displayed relatively constant activity with a slight increase at

roughly 18 cm. Eastern Lake sedimentation accumulation rates (Figure 3-4) display a

decreasing down core trend with one significant peak and a less significant peak within

core. The largest measurement of accretion was in the uppermost 2 cm, at 161

(mg/cm2/yr). Decreasing down core to 18.5 (mg/cm2/yr) at 2 cm until 8 cm where rates

increase to a small peak of 20 (mg/cm2/yr). A gradual decreasing trend continues down

core until 16 cm where a significant accumulation rate increases from 14 cm depth of

15.1 to 31.4 (mg/cm2/yr). A down core decrease continued to 24 cm where the lowest

accumulation rate occurrs at 9.5 (mg/cm2/yr). Sedimentation rates peaked again at 26

cm at 14.1 (mg/cm2/yr) then decreased to the last measurement at 28 cm to 13.0

(mg/cm2/yr). The average accumulation rate of the sediment core from Eastern Lake

was 27.15 (mg/cm2/yr).

Big Redfish Lake

A total of 11 samples were measured for 210Pb, and 137Cs from Big Redfish Lake.

The successful measurement of these isotopes provided a record of 122 years at a core

depth of 22 centimeters, 1889 through 2011 (Figure 3-5). 210Pb was constant for the

upper 6 cm, peaked at 8 cm and then decreased with depth. At 24 cm, it increased and

then decreased until 26 cm. 137Cs activity remained constant with little measured activity

near 8 cm. 226Ra activity was constant for the upper 20 cm, then decreased until 22 cm

where a small peak occurred at 26 cm. Big Redfish lake sedimentation accumulation

rates (Figure 3-6) decrease down-core with two peaks. The largest accumulation rate

occurred at the surface 2 cm depth with 22.1 (mg/cm2/yr), then decreased to 16.6

(mg/cm2/yr) at 4 cm depth, and continuing to decrease to 7.2 (mg/cm2/yr) at 10 cm. A

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peak in sedimentation occurred at 12 cm and increasing to 8.0 (mg/cm2/yr). A decrease

in accumulation continued for the next six centimeters (depth 14, 16, 18 cm) with no

change in rates between 16 and 18 cm, 4.5 (mg/cm2/yr). An increase to a peak of 5.4

(mg/cm2/yr) at 20 cm occurred and then a decrease occurred at the last depth

measurement of 22 cm to 4.0 (mg/cm2/yr). The average accumulation rate of the core

from Big Redfish Lake was 9.41 mg/cm/yr2.

Total Phosphorus

Eastern Lake

The Eastern Lake surface sediment-water interface core TP (Figure 3-7)

concentrations had a mean of 0.37 mg g-1 within the 75-cm sample depth. There was an

increasing trend in TP from the base of the core to the surface, modern day sediments.

A significant positive trend occurs between 32 cm and 30 cm, just outside of the Pb-210

date range of 1866.2. The TP concentration between 30 to 2 cm, had a pronounced

increase with a mean of 0.62 mg g-1. A decrease occurred between max depth 4 and 2

cm, correlating with Pb-210 dates of approximately 2011 and 2017. The mean of TP

concentrations between 32 cm and 75 cm depth, prior to the positive trend mentioned

above, was 0.21 mg g-1. The TP concentrations in this interval (32 to 75 cm) were

somewhat variable with four distinguished peaks near 38, 44, 56 and 70 cm. The range

of TP between 32 and 75 cm had a minimum of 0.13 mg g-1 and maximum of 0.37 mg g-

1. Kendall Tau significance analysis determined sediment core results exhibited a

significant positive increase up core in TP values, p-value< 0.05.

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Big Redfish Lake

Big Redfish Lake surface sediment-water interface core measured a TP mean of

0.31 mg g-1 within the 95 cm sediment depth (Figure 3-8). The TP concentrations

showed an increasing trend to the core surface, along with some variability within core.

A positive significant trend occurs towards the sediment surface. An increase is

observed at approximately 36 cm and continues into the uppermost portion of the

sediment. The mean TP concentration between 36 cm and the upper portion of the core

was 0.50 mg g-1. This portion of the core had a minimum concentration of 0.09 mg g-1

and a maximum concentration of 0.77 mg g-1. There was a steep decrease in TP

concentrations between 32 and 36 cm. The second lowest concentration of the whole

sediment core, 0.09 mg g-1, occurred at 36 cm. Between depths 38 and 95 cm, there

was more variability than in the Eastern lake core. The mean TP concentration between

38 and 95 cm was 0.21 mg g-1, with a minimum value of 0.08 mg g-1 occurring at 95 cm

and a maximum value of 0.45 mg g-1 at 92 cm. Within this section, there were five

significant peaks at 46, 58, 66, 78 and 92 cm. Kendall Tau significance analysis of

sediment core data determined a significant positive increase, p-value<0.05, in TP

values with depth.

Geochemistry

Eastern Lake

Eastern and Big Redfish Lake surface sediment-water interface cores were

analyzed for bulk organic carbon (%C) and nitrogen (%N), (C/N) weight percent (wt%)

contents and stable isotopes signatures of δ13C and δ15N of sediment organic matter.

The Eastern Lake core weight percent of carbon and nitrogen displayed an increasing

trend up core but varied with multiple peaks and troughs (Figure 3-9). The core %C

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mean was 3.24%, with a minimum of 1.08% and a maximum of 7.04%. The average

core %N was 0.25% with a minimum of 0.08% and a maximum of 0.60%. The ratio of

Eastern Lake presented a decreasing trend towards the sediment surface. The mean

C/N ratio of Eastern Lake sediment core was 13.21 (% weight).

The stable isotope measurements of δ13C and δ15N varied within and among

sediment cores of Eastern and Big Redfish Lake. Carbon isotope ratios (δ13C/ δ12C)

were presented as per mille (‰) deviations (δ13C) from Vienna Pee Dee Belemnite

(VPDB) (Lamb et al., 2006). Nitrogen stable isotope ratios (δ15/ δ14N) were presented as

per mille deviations (δ15N) from atmospheric air (vs. air). Eastern Lake sediment stable

isotope δ13C values display a variable trend with depth (Figure 3-10). The minimum

value was -26.39‰ and the maximum was 24.07‰ (per mil, vs VPDB), with a mean

δ13C value of -24.92‰, respectively. Sediment δ15N of the Eastern Lake core displayed

a slight increasing trend (Figure 3-11). The minimum δ15N value was 2.80‰ and the

maximum was 4.40‰ (per mil, vs AIR), respectively. The mean δ15N value of Eastern

Lake core was 3.67‰, respectively.

Big Redfish Lake

Big Redfish Lake’s core weight percent carbon and nitrogen measurements also

exhibited a decreasing trend up the sediment profile (Figure 3-12). The core %C had a

mean of 5.27% with a minimum of 0.73% and a maximum of 12.61%. Big Redfish Lake

had a mean %N of 0.36%, a minimum of 0.04% and a maximum of 0.79%. The average

C/N ratio of Big Redfish Lake sediment core was 14.95 (% weight).

Big Redfish Lake sediment core stable isotope values displayed more variation

than Eastern Lake with a mid-depth decrease for both δ13C and δ15N. The mean δ13C

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value for the Big Redfish Lake core was -25.95‰ (per mil, vs VPDB), with a minimum

value of -26.39‰ and a maximum value of -24.75‰, respectively (Figure 3-13). The

mean of δ15N was 2.90‰ (per mil, vs AIR), with a minimum of 1.96‰ and a maximum of

3.82‰, respectively (Figure 3-14). Stable isotope δ13C displayed a negative, decreasing

trend through the Big Redfish Lake core and a slight increasing trend of stable isotope

δ15N.

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Table 3-1. Eastern Lake long term summary statistics (CBA 2017)

Mean Max Min Median Std Error

TP (µg/L) 12 17.8 9.14 11.7 0.56

TN (µg/L) 286 399 214 288 10.8

CHL (µg/L) 3.55 6.71 2.14 3.48 0.3

Secchi Depth (m) 1.45 1.97 0.94 1.5 0.07

Temperature (C) 22.5 25.4 17.5 23 0.45

Dissolved Oxygen (mg/L) 6.77 7.79 5.55 6.76 0.17

pH 7.53 7.97 7.12 7.5 0.05

Salinity (ppt) 8.23 18.5 2.01 8.47 1.41

Turbidity (NTU) 2.48 8.97 0.7 2.6 0.55

Color (Pt-Co Units) 96.9 173 45 95.5 19.1

Specific Conductance (µS/cm) 3230 3950 2610 3190 201

Surface water chemistry was collected on Eastern Lake since 1998, this data was statistically analyzed to determine long term analysis of surface water variables.

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Table 3-2. Big Redfish Lake long term summary statistics (CBA 2017).

Surface water chemistry data was collected on Big Redfish Lake since 1999, this data was statistically analyzed to determine long term analysis of surface water chemistry variables.

Mean Max Min Median Std Error

TP (µg/L) 13 22.6 4.67 13.5 0.95

TN (µg/L) 364 657 149 448 32.6

CHL (µg/L) 5.39 10.5 1.67 5.97 0.55

Secchi Depth (m) 0.98 1.5 0.68 0.91 0.06

Temperature (°C) 23.9 30.5 21.6 23.4 0.52

Dissolved Oxygen (mg/L) 5.98 7.36 4.49 5.88 0.23

pH 7.2 7.72 6.6 7.22 0.07

Salinity (ppt) 5.14 16 0.66 8.32 1.31

Turbidity (NTU) 2.27 8.86 0.74 1.97 0.6

Color (Pt-Co Units) 150 326 43.3 156 47.5

Specific Conductance (µS/cm) 1520 4550 360 1840 694

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Figure 3-1. Eastern Lake long term trends analysis (CBA 2017) Eastern Lake water chemistry summaries indicate statistically significant positive trends in total phosphorus, total nitrogen and total chlorophyll, while water transparency exhibited a significant negative trend. The inter-annual (monthly variability) within 2016 is indicated by colored circles and intra-annual variance (variability among years) is indicated by black triangles.

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Figure 3-2. Big Redfish Lake long term trend analysis (CBA 2017)

Big Redfish Lake water chemistry summaries indicate statistically significant positive trends in total phosphorus, total nitrogen and total chlorophyll, while water transparency exhibited a significant negative trend. The inter-annual (monthly variability) within 2016 is indicated by colored circles and intra-annual variance (variability among years) is indicated by black triangles.

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Figure 3-3. Eastern Lake Lead-210 geochronology

Eastern Lake geochronological analysis provided 210Pb activity dating that resulted in a 151 year period of record.

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Figure 3-4. Eastern Lake sedimentation rate

Eastern Lake sedimentation rate displayed relatively unchanged depositional rates until 16 cm (1959) where a peak of 31 mg/cm2/yr occurred and then again at depth 2 cm (2017) where an increase of 161 mg/cm2/yr occured.

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Figure 3-5. Big Redfish Lake geochronology

Big Redfish Lake geochronological analysis of 210Pb activity resulted in a 127 year period of record.

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Figure 3-6. Big Redfish Lake sedimentation rate

Big Redfish Lake sedimentation rate displayed low depositional rates until 6 to cm (1997) where a peak of 16 mg/cm2/yr occurred. Sedimentation rates increased up core reaching a maximum of 22 mg/cm2/yr at 2 cm depth (2012).

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Figure 3-7. Eastern Lake sediment total phosphorus

Eastern Lake sediment total phosphorus concentrations (mg g-1) exhibited a significant increase toward the sediment surface, p<0.05.

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Figure 3-8. Big Redfish Lake sediment total phosphorus

Big Redfish Lake sediment total phosphorus concentrations mg g-1 exhibited a significant increase toward the sediment surface, p<0.05.

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Figure 3-9. Eastern Lake C/N ratio

Eastern Lake sediment organic matter C/N (wt%) ratios demonstrated a significant decrease with surface sediment core depths, p<0.05.

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Figure 3-10. Eastern Lake 13C

Eastern Lake sediment δ13C indicated organic matter sources are dominated by

terrestrial and aquatic C3 plants.

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Figure 3-11. Eastern Lake δ15N

Eastern Lake sediment geochemical proxy δ15N exhibited a significant decrease

towards sediment core surface, p<0.05.

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Figure 3-12. Big Redfish Lake C/N ratio

Big Redfish Lake sediment organic matter C/N (wt%) ratios exhibited a significant decrease towards sediment core surface, p<0.05.

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Figure 3-13. Big Redfish Lake δ13C

Big Redfish Lake sediment geochemical proxy δ13C demonstrated a significant

decrease towards sediment core surface, p<0.05.

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Figure 3-14. Big Redfish Lake δ15N

Big Redfish Lake sediment geochemical proxy δ15N exhibited an increase towards

sediment core surface.

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CHAPTER 4 DISCUSSION

Geochronology using 210Pb of sediment organic matter provided a reference

period of 151 years for Eastern Lake and 122 years for Big Redfish Lake. Results

indicated parallel changes throughout both Eastern and Big Redfish Lake sediment

cores. Lakes demonstrated significant increases in sediment TP from approximately 30

cm to the sediment core surface demonstrating that these lakes began to experience

changes caused by nutrients prior to the oldest 210Pb date of 1866. Throughout both

sediment cores, sediment C/N ratios exhibited a decrease towards sediment core

surface indicating that these waterbodies have historically become more influenced by

autochthonous-produced organic matter rather than allochthonous. Stable isotopes δ13C

and δ15N assisted in estimating the origin of organic matter sources, however terrestrial

and aquatic C3 plants demonstrated overlapping δ13C values. However, marine organic

matter origins can be distinguished from terrestrial sources by elevated δ13C and δ15N

values. These inferences assisted in the determination of seawater influences on lake

hydrology. Studies conducted on characteristic Florida lakes associated increases in

both stable isotope δ13C and δ15N values during periods of elevated primary productivity

(Brenner et al., 1999; Gu et al., 1996). Eastern Lake demonstrated a decrease in δ13C

and a significant increase in δ15N values toward surface sediments, while Big Redfish

Lake exhibited a significant decrease in δ13C values and an increase in δ15N values.

Inferred lake productivity through sediment TP and δ13C trends did not show strong

correlations in either Big Redfish or Eastern Lake. The absence of correlation between

TP and δ13C values indicates that primary productivity may not be the dominant source

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of organic matter to the lake systems or that bacteria has a coupled or dominant

influence on carbon cycling within the waterbody (Teranes and Bernasconi 2005).

Stable isotope values were also used to infer periods of marine or freshwater

dominance in the lakes. Although the research results from this study investigated

historical and modern trends within the lake study sites, the complexity of each coastal

dune lake’s ecosystems is evident and should involve comprehensive research

investigation.

Surface Water Chemistry

Surface water quality data Kendall-Tau analyses presented statistically

significant increases in nutrient concentrations and total chlorophyll for both coastal

dune lakes. Increasing trends in nutrient concentrations (TN and TP) and total

chlorophyll over a period of time indicates that a waterbody may be undergoing

eutrophication, experiencing an increase in nutrients and biological productivity moving

toward a higher trophic state. Collectively, these water quality variables provide insight

and understanding to the conditions of lake study sites over the last 20 years.

A waterbodies’ trophic state is evaluated using nutrients (TN and TP), chlorophyll

(algal response to nutrients) and Secchi disk clarity measurements to either calculate a

cumulative score, known as a trophic state index, or individual variable assessment

(Hoyer and Canfield 2008). Waterbodies with low nutrient concentrations and low

biological productivity are referred to as oligotrophic, and waterbodies with moderate

concentrations of nutrients and mid-biological activity are mesotrophic, while high

nutrient concentrations and biological activity are considered eutrophic conditions and

excessive nutrients and biological productivity are hypereutrophic conditions

(LAKEWATCH 2000). The trophic state variables had a strong correlation to amounts of

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algae, aquatic vegetation and wildlife that a waterbody can sustain (Hoyer and Canfield

2008). The Forsberg and Ryding (1980) trophic state classification (Table 4-1) provides

a range of values for each variable to assess trophic states based on individual

measurements of TN, TP, chlorophyll and Secchi depth. However, due to coastal dune

lake high true color value, use of Secchi depth measurements is not encouraged as

dark tannic waters can cause shallow Secchi depth measurements and would

deceptively indicate a eutrophic state (Hoyer and Canfield 2008).

Eastern and Big Redfish Lake study sites are classified as predominantly

oligotrophic with nutrient poor conditions (Hoyer and Canfield 2008). As such, they are

considered unimpaired by cultural eutrophication in Florida (Hoyer and Canfield 2008).

An examination of surface water data reveals that Eastern Lake nutrients and

chlorophyll values fall within range of an oligotrophic waterbody, however the long-term

range of TP and chlorophyll cross into mesotrophic lake conditions (Table 4-2) (CBA

2017). Eastern Lake appears to be shifting towards a more biologically productive

waterbody based on the significant positive increases in nutrients and total chlorophyll.

Notable physicochemical variables analyzed in the Coastal Dune Lake Water

Chemistry Summary Report (2017) were dissolved oxygen, pH, salinity and

temperature. Both study lakes displayed a wide range of values between the surface

and bottom measurements. These variables were influenced by physical, chemical and

biological interactions of coastal dune lakes and should be examined as additional

indices of hydrologic conditions and external influences. The differences recorded

between the surface and bottom measurements depict the variability in lake conditions

and reflects external influences on the lake hydrology (Table 4-3).

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Eastern Lake exhibited a range of surface and bottom measurements of

dissolved oxygen, as its surface range indicated a generally well oxygenated system.

This would be expected in a surface water because oxygen is more easily mixed into

the water column through aeration, diffusion and photosynthetic activities. Bottom

dissolved oxygen measurements exhibited a wider range with low values near hypoxic

conditions.

Dissolved oxygen concentrations can be suggestive of algal and nutrient cycling,

as well as stratification within a waterbody. Dissolved oxygen is utilized throughout the

water column by organismal functions for energy or nutrients. Organisms engaging in

photosynthesis influence dissolved oxygen concentrations which fluctuate with the time

of day, along with aeration and mixing (Wetzel 2001; Boehrer and Schultze 2008).

Generally, dissolved oxygen values are lower in benthic layers due to upper layer

consumption by organisms and slow diffusion of oxygen from the surface. Lower

dissolved oxygen concentrations are influenced by a variety of physical and biological

functions. A strong influence on dissolved oxygen concentrations of the benthic layers is

the presence of saline water formed by a connection to seawater. During times of

intermittent outlet connections, salinity variations can change the amount of oxygen that

is able to diffuse to the bottom lake layers. Temperature can also impact the solubility of

oxygen in water, and oxygen and temperature are inversely related and can be strongly

influenced by seasonality and by changes in climate conditions (Wetzel 2001). Both

variables, salinity and temperature, can create stratification of lake waters and

potentially anoxic conditions which may trigger sediment nutrient release (Dittrich et al.,

2013). Furthermore, bacterial decomposition utilizes dissolved oxygen, lowering

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concentrations that are already limited and not easily replenished (Boehrer and

Schultze 2008).

It can be theorized that coastal dune lake study sites, Eastern and Big Redfish

Lake, are also influenced by these variables. Eastern Lake exhibited standard mean

surface dissolved oxygen concentrations but displayed with highly variable bottom

measurements. Benthic measurements displayed a range of measurements from

hypoxic to well oxygenated, but overall had a mean concentration slightly lower than

surface measurements. Due to Eastern Lake’s morphological and physicochemical

features it is susceptible stratification and lower benthic dissolved oxygen

concentrations. In addition, intermittent connections to seawater could play a critical role

in accentuating stratification within the lake water column, especially during closed

conditions. Long term trends of increasing nutrients and total chlorophyll may also

influence water column and benthic dissolved oxygen, however, studies to investigate

these occurrences have not been conducted.

Big Redfish Lake also displayed well oxygenated conditions of dissolved oxygen

concentrations and a wider range of bottom dissolved oxygen. Surface dissolved

oxygen means displayed slightly lower ranges of concentrations compared to Eastern

Lake. Surface dissolved oxygen levels are likely correlated with aeration, diffusion and

photosynthetic activities. Big Redfish Lake displayed bottom dissolved oxygen levels

ranging from anoxic to well oxygenated benthic conditions. Due to the nature of the

coastal dune lakes and their intermittent connection to seawater, the variation between

surface and bottom dissolved oxygen measurements are hypothetically correlated with

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lake outlet connections, freshwater inputs, periods of low circulation, nutrient inputs and

primary productivity within the lake.

Perissinotto et al., (2010) attributes low dissolved oxygen levels in South African

Temporarily Open or Closed Estuaries (TOCEs) to the absence of tidal influence and

strong freshwater inflows. Without strong influences on circulation water, column

stratification becomes more distinct in the TOCE systems (Perissinotto et al., et al.,

2010). Deteriorating dissolved oxygen levels in benthic waters of estuarine lagoons is

believed to be controlled by a combination of rainfall, solar insulation, wind stress and

tidal mixing (Gale et al., 2006). The coastal dune lakes exhibit a range of dissolve

oxygen levels, particularly in the bottom layers of the lake, and at times, dissolved

oxygen levels are anoxic on the lake bottom. There are likely many factors that

influence this phenomenon, such as seasonal lake temperatures, climate, and

intermittent saltwater connections. Current literature on the coastal dune lakes has not

examined lake stratification events or if they are associated with seasonal changes.

Stratification within coastal dune lake waterbodies is probable to occur after an outlet

connection occurs and seawater settles at the bottom of the lake creating a chemocline.

A lake could become further stratified if the outlet connection becomes disconnected

again and mixing decreases.

The pH measurements from the coastal dune lakes are informative to lake

system functions, physicochemical interactions and the subsequent influence on water

column conditions. Freshwater typically has a pH of 6-8 and measurements can reflect

photosynthetic and respirative activities of microorganisms and algae, determine the

solubility of nutrients and heavy metals, and influence the distribution of aquatic

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organisms in addition to other waterbody characteristics (Suwanee River Water

Management District 2018). Changes in pH can impact the solubility of nutrients and

one of the main drivers of phosphorus release is pH change in the water column and

sediments (Dittrich et al., 2013).

The coastal dune lakes are characterized by their dark, tea colored waters which

are a product of watershed inputs of dissolved organic matter. This dissolved organic

matter can have an influence on the water pH, typically lowering water pH (Hoyer and

Canfield 2008). An average lake pH is 6-8 but is ultimately dependent on the local

geology and inputs from surrounding lands. When freshwater inputs are low, coastal

dune lake water is clearer, whereas increased freshwater inputs cause dissolved

organic matter to increase (Hoyer and Canfield 2008). In addition, marine waters may

have an influence on water pH. Generally, estuary systems have pH averages near 7.0

to 7.5 in sections closer to freshwater inputs and a pH range of 8.0 to 8.6 near areas

with higher salinity influences (EPA 2006).

Similar variability in surface water pH was observed in lake study sites. Eastern

Lake surface pH had a mean of pH of 7.53 with little variability, however, benthic pH

measurements exhibited a wider range and a mean of 7.5. Big Redfish Lake

demonstrated alkaline pH water conditions in surface measurements and variable

bottom pH. Benthic pH levels have a wider range of variability but exhibited a mean

close to traditional fresh waterbodies. The pH variability in both lake study sites

indicates that other physical and biological factors may influence water column pH.

The salinity of the coastal dune lakes of Northwest Florida is directly driven by

the outlet connection frequency and duration which is based on a lake’s morphometry,

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watershed and hydrology (Hoyer and Canfield 2008). Storm surges that push saltwater

from the Gulf of Mexico can influence geochemical signatures in these lakes and impact

lake salinity (Das et al., 2013; Lambert et al., 2008). Limited literature exists of the

hydrologic exchanges between the intertidal zone of the Gulf of Mexico, lake water and

groundwater of the coastal dune lakes impact salinity. Other studies in Florida have

discussed this zone as an area of exchange between seawater and fresh groundwater

or aquifer sources (Hoyer and Canfield 2008; Heiss and Michael 2014). Salt spray from

the Gulf of Mexico can also potentially influence the salinity of the lakes as it effects

vegetation and soils further inland. Strong storms were identified to have large

influences on the coastal lake’s hydrology during seawater overwash events (Liu and

Fearn 1993; Liu and Fearn 2000; Lambert et al., 2008; Das et al., 2013). According to

water chemistry results, a vertical halocline of the coastal dune lakes water column is

commonly measured in lakes with outlet connections. The variable range of surface and

bottom salinity measurements exhibit the dynamic nature of the coastal dune lakes and

can resemble the salinity characteristics of estuaries influencing lake hydrology.

Eastern Lake exhibited a wide range of surface and bottom salinity

measurements, typically with lower surface and higher benthic salinities. Its surface

salinity exhibited a wide range of measurements from 2.0 to 18.5 ppt and bottom

measurements were 1.21 to 33.13 ppt (CBA 2017). Such a range demonstrates the

variability and influence of both freshwater and saltwater inputs which are ultimately

driven by a lake’s morphometry. Eastern Lake has a slightly higher surface and bottom

salinity compared to Big Redfish Lake. This may indicate that Eastern Lake salinity is

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correlated with more frequent or longer outlet opening events, however lake outlet data

is limited.

Big Redfish Lake also exhibited variable surface and bottom salinities, but

exhibited slightly lower measurements than Eastern Lake. Big Redfish Lake has a mean

surface salinity range of 0.66 to 16 ppt and a bottom range of 0.17 to 33.04 ppt (CBA

2017). The range of bottom salinities are, at their max, near measurements of the Gulf

of Mexico. Its slightly lower mean salinity could potentially indicate it receives more

freshwater inputs, less frequent or shorter outlet connections to seawater, and may be

more influenced by watershed hydrology.

Surface temperatures of the coastal dune lakes are likely influenced by

morphometric characteristics, fresh and saltwater inflows and climate. The size, shape

and volume of a waterbody influences circulation and vertical mixing within the water

column. Physical forces, such as wind or inflows, impact the temperature of a

waterbody. The coastal dune lakes are considered shallow lakes with an average

maximum depth of 2 meters. A lake’s depth is can have a role in its water temperature

and thermogradients which can develop into chemoclines. Shallow lakes heat up faster

in spring and summer months (Wetzel 2001). Colored waters, like that of the coastal

dune lakes, alter the light entering a waterbody by increasing the vertical light

attenuation and absorbing heat radiation (Wetzel 2001). Cooler ground and surface

water inflows can influence lake water temperatures and correlate with changes in

climate conditions. Air temperature can also have an influence on water temperatures.

Eastern Lake exhibited a mean surface water temperature that was lower than

bottom measurements. It had a mean surface temperature of 22.5°C and bottom mean

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of 23.9°C with the benthic temperatures exhibiting more variability (CBA 2017). Warmer

bottom temperatures may be influenced by seawater presence and lake depth, and

deeper saltwater layers could be more inclined to warm from solar radiation and reflect

higher mean benthic water temperatures. Warmer water temperatures are inversely

correlated with dissolved oxygen concentrations and could lead to additional lake

stratification.

Big Redfish Lake demonstrates a similar pattern of slightly warmer bottom

temperatures compared to its surface. Overall it exhibited a larger range of both surface

and bottom temperatures, with higher maximum values 9.5 to 33.7°C (CBA 2017). Big

Redfish Lake has an average depth of 1.58 meters, approximately 0.5 meters more

shallow than Eastern Lake. The slightly more shallow water depth may correlate with its

slightly warmer average surface and bottom temperatures.

Saltwater can influence water temperatures and subsequent circulation. As water

densities change between fresh and saltwater mixing, the denser saltwater settles to the

bottom. The heat capacity of saltwater is lower than freshwater and can heat up faster.

Estuarine lagoons can be described as waterbodies that routinely receive seawater

from an external source, known as ectogenic meromixis, in which more dense saltwater

sinks below the less dense freshwater (Wetzel 2001). Estuarine lakes often exhibit

heliothermic characteristics where a layer of dense saltwater becomes thermally

stratified from the less dense layer and may become heated influencing the

development of a chemocline (Wetzel 2001). The lake study sites may also

demonstrate these conditions by exhibiting slightly warmer mean bottom temperatures

due to heliothermic properties.

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Changes in water temperature stimulate a range of biological, physical and

chemical functioning within an aquatic system. Light intensity affects photosynthesis

and growth rates of algal communities which have a positive correlation to water

temperatures (Wetzel 2001). Increased growth and respiration of microorganisms can

cause higher oxygen consumption and could eventually lead to oxygen depletion in the

bottom layer of the lakes. Increased water temperatures can also impact the solubility of

compounds and bound elements (Wu et al., 2014). Temperature is one of the top three

contributing factors to phosphorus release from sediments (Wu et al., 2014), and these

changes could also cause a shift in microorganism communities within these layers and

at the sediment-water interface (Zu et al., 2014).

Coastal dune lake water chemistry summaries demonstrate that the coastal dune

lakes surface and bottom physicochemical variable measurements can be highly

variable and susceptible to seasonal climate influences causing lake stratification. The

variations in coastal dune lake waters are likely influenced by lake morphology and its

dynamic interactions with external environments. Outlet connections to saltwater,

freshwater inputs, dissolved oxygen, pH, nutrients and morphometric features of each

lake can all have an influence on the degree of stratification that occurs within the lakes.

Almost all the coastal dune lakes in Northwest Florida have highly colored tannic

waters that drain from the watershed into surface and groundwaters which feed into the

lakes as the true color of a lake is influenced by the dissolved organic matter in its

waters. Lakes with true color values of 51-100 (Pt-Co Units) are considered highly

colored waterbodies (LAKEWATCH 2004). Most coastal dune lakes, including Eastern

and Big Redfish Lake, exhibit highly colored true color values (Hoyer and Canfield

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2008). Eastern Lake has a mean true color of 96.9 Pt-Co Units and range of 45 to 173

Pt-Co Units (CBA 2017). Big Redfish Lake exhibits a wider range of true color values

from 43.3 to 326 Pt-Co Units and an elevated mean of 150 Pt-Co Units (CBA 2017). As

previously demonstrated in physicochemical variable ranges, Big Redfish Lake is

potentially influenced more by its watershed hydrology. This is also depicted through its

higher mean and range of true color values. True color is associated with climate

conditions, mainly precipitation and drought, which can affect the amount of runoff that

seeps into a waterbody or lack of inflow to transport dissolved organic matter

(LAKEWATCH 2004).

Water Column Nitrogen to Phosphorus Ratios

As freshwater lakes, the coastal dune lakes are presumed to be phosphorus

limited, however variations in water column nitrogen and phosphorus ratios indicate that

the study lakes may shift between nutrient limiting states or are nutrient co-limited.

Variations between nutrient limitations have been observed in other lakes and estuaries,

however the estuarine features of the coastal dune lakes may be have a key role in

nutrient limitations and co-limitations of the lakes.

According to the Florida LAKEWATCH Nutrient Circular (2001), phosphorus and

nitrogen are the most common limiting nutrients in Florida waterbodies due to the

regional geology. Determining the limiting nutrient to a lake is often analyzed by

reviewing the TN/TP ratios and the relationship of TP to TN/TP, increasing TP typically

causes a decrease in TN/TP (Downing et al., 1992). The TN/TP ratio can often be

correlated to the trophic state of a waterbody (Downing et al., 1992). Most literature

discuss phosphorus (P) as the limiting nutrient in freshwater lakes and nitrogen (N) as

the limiting nutrient in coastal marine waterbodies (Taylor et al., 1995). Discrepancies to

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this standard can be observed in marine environments that receive large seasonal

inflows of freshwater and exhibit shifts between P- and N-limitations, as well as marine

waterbodies with restricted or low freshwater inputs and long residence time that can

become P-limited (Taylor et al., 1995). These types of conditions may also be reflected

in the coastal dune lakes that have intermittent outlet connections. Lakes can display

more variability than marine environments in total nitrogen and total phosphorus levels,

with some of the lowest and highest concentrations of TN and TP (Guildford and Hecky

2000). These examples of contrasting nutrient limitations and co-limitation were

discovered to be similar among key types of ecosystems and have been observed

nearly many studies (Ptacnik et al., 2010). Thus, indicating that many systems exhibit

these conditions and therefore it would not be unlikely to see these trends in the coastal

dune lakes.

Florida lakes show three general ranges of TN/TP (μg/L) ratios which can provide

some insight into which nutrient has the most significant role (LAKEWATCH 2000). A

TN/TP ratio that falls in the range less than 10, indicates that phosphorus may not be

the only factor affect productivity in a lake and nitrogen limitation may have a large role

as limiting nutrient (LAKEWATCH 2000; Guildford and Hecky 2000). Lakes that have a

TN/TP range between 10 and 17 can be interpreted as having nutrient limitation by

either nitrogen or phosphorus or potentially co-limitation of these nutrients

(LAKEWATCH 2000). Lakes that exhibit a TN/TP range greater than 17 would be

expected to be phosphorus limited (LAKEWATCH 20000; Guildford and Hecky 2000).

There may be some caveats to these nutrient generalizations, a potential exists for

nitrogen to be the limiting factor when the TP value is greater than 100 μg/L due to its

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overabundance (LAKEWATCH 2000). In addition, lakes with TN/TP values less than 10

may still be phosphorus limited when TP values are less than 50 μg/L (LAKEWATCH

2000). Downing et al., (1992) associated a lake’s TN/TP ratio with its trophic status:

oligotrophic lakes ranged from 21 to 240, mesotrophic lakes ranged 17 to 96, eutrophic

lakes ranged 4 to 71, and hypereutrophic lakes have a range of 0.5 to 9.

Over a 19 year period of surface water samples, Eastern Lake demonstrated a

typical phosphorus limitation. Its average TN/TP value was 26 μg/L, but displayed a

range of 7 to 75 (μg/L) (CBA 2017). Generally, Eastern Lake would place into a

category of an oligotrophic phosphorus limited system. However, its range of TN/TP

values also indicate that it potentially experiences intermittent nitrogen limitations

(TN/TP < 9) or co-nutrient limitation and may classify as a mesotrophic stat according to

Downing et al., (1999).

Big Redfish Lake demonstrated an average phosphorus limitation, but also

exhibited a range of TN/TP ratio values that indicate it may also fall into nitrogen or co-

nutrient limitation. It has a mean TN/TP value of 31 μg/L and exhibits a range of 8 to

133 (μg/L) indicating a potentially mesotrophic (17 to 96) to eutrophic system (4 to 71).

The variable nature of the coastal dune lakes makes it challenging to determine a

single limiting nutrient, but it seem evident that they can change between nutrient

limitations and may be impacted by factors other than just nutrients and productivity.

Supplementary information is necessary to make a comprehensive assessment of the

nutrient dynamics of the coastal dune lakes. The dominant sources of new nutrients to

lakes are terrestrial runoff and atmospheric input (Guildford and Hecky 2000). As

coastal development continues to increase along the Florida Panhandle corridor,

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development along the shorelines and within the watersheds of the coastal dune lakes

may change the dynamics of nutrient limitations within the coastal dune lakes.

Geochronology

Eastern and Big Redfish Lake sediment cores functioned properly as 210Pb,

137Cs, and 226Ra isotopic dating mediums and provided roughly 150-year periods for

both lake cores. Collectively, these radioactive isotopes are known as Lead-210 (210Pb)

dating methods but are often used together to obtain maximum chronological data

(Jeter 2000). The 137Cs dating methodology is based on its atmospheric fallout from

nuclear weapons testing events (Jeter 2000). Initial 137Cs measurements mark the date

of 1954 or after (Jeter 2000). Isotope 210Pb enters the environment through the fallout

and decay of 222Rn, referred to as unsupported 210Pb, as well as from natural 226Ra in

sediments known as supported 210Pb (Jeter 2000; de Souza et al., 2012). It may also

enter the environment through anthropogenic wastes enriched with radionuclide (de

Souza et al., 2012). Whichever pathway occurs, it mixes and accumulates or interacts

with sediments of a waterbody.

The 210Pb dating method is based on the measurement of unsupported 210Pb

activities (de Souza et al., 2012). The Constant Rate of Supply model (CRS) assumes a

constant unsupported flux of 210Pb to the waterbody sediments and allows for the

sediment supply to vary (de Souza et al., 2012). The oldest date from the Eastern Lake

sediment core determined through the 210Pb dating was 1866 at a depth of 30 cm, 151

years before present, with the most current date of 2017 at 2 cm. The 137Cs peaked at

depth 14 and 16cm indicating a time frame close to 1954 (nuclear weapons testing

events).

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The Big Redfish Lake sediment core dating determined 1890 to be the oldest

collected date at 22 cm. The most recent date 2012 was observed at 2 cm. The 137Cs

record was blurred more, however indicated a minor increase at 8 cm being associated

with the 1954 weapons testing time frame. The CRS model also provides the

sedimentation rates from core sediments analyses and can be indicative of external and

internal variations within waterbody. Both, Eastern and Big Redfish Lake sediment core

data displayed increasing up core trends in sedimentation rates. In addition to

chronological reconstructions, Bennett and Buck (2016) argue that the pattern of

sediment rates and accumulation can be used to interpret environmental change.

Eastern Lake’s mean sedimentation rate is 27 mg/cm2/yr. At depth 2 cm, a large

increase of 161 mg/cm2/yr occurs at a date of 2017. The other sedimentation rates

resemble stable increases in deposition. This large increase in sedimentation rates at

the surface sediment could indicate increasing sediment input from either

autochthonous or allochthonous sources (Bennett and Buck 2016). Eastern Lake’s

sediment C/N ratio results confirm a transition from allochthonous to autochthonous

throughout the core. However, C/N ratios increase around 2 cm and TP decreases at

this depth potentially indicating an increase in terrestrial input. If this peak value was

excluded the mean sedimentation rate it would be 16.9 mg/cm2/yr. However, Eastern

Lake would still exhibit an increasing rate of sedimentation which also indicates that

environmental changes are occurring, but cannot be determined through these

variables.

Big Redfish Lake exhibited a lower mean sedimentation rate of 9.4 mg/cm2/yr. A

notable increase from 8.7 to 15.7 mg/cm2/yr was observed at depth 6 cm at the 210Pb

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date of 1997. An environment with constant sedimentation will typically display

decreasing rate of sediment deposition (Bennett and Buck 2016). Sediment rates that

exhibit increasing accumulation rates, like Big Redfish Lake, indicate environmental

changes are occurring (Bennett and Buck 2016; Sommerfield 2006). However,

accumulation rates cannot provide data on frequency, duration or origin of sediments

and may also be influenced by other factors such as compaction and biological mixing

(Sommerfield 2006).

Sediment Total Phosphorus

Surface water data displayed significant increases in total phosphorus (TP)

concentrations in Eastern and Big Redfish Lake. This information was confirmed

through an R-software Kendall Correlation Rank analysis of sediment TP concentrations

from both study sites, Eastern Lake p-value <0.05 and Big Redfish Lake p-value <0.05.

Eastern Lake displayed relatively steady TP variations up core until 34 cm, then

exhibited a dramatic increase from 32 cm to 30 cm and steeply increased to the surface

(2 cm). Depth 34 is just outside of the geochronological dating depth, however depth 28

cm represents a date of approximately 1886. Big Redfish Lake displayed variable TP

values, but also experienced a steep increase at 36 cm. It continued to increase with

some variable positive trends until 2 cm where is drops slightly. The oldest available

lead-210 dating for Big Redfish Lake is depth 22 cm, representing approximately 1889 -

shortly after this dramatic increase in TP.

It is challenging to speculate what caused both lake cores to exhibit TP increases

near the same depth in the late 1800s. Historical records note this region of Florida

being used for timber and turpentine plantations. Various studies verify a strong

correlation between chlorophyll, representing algal biomass, and TP (Canfield 1983;

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Brenner et a 1999; Ptacnik et al., 2010; LAKEWATCH 2000). This association forms TP

into one of the main limiting nutrients in freshwater systems because of its effect on

biological activity and is often used as the trophic state variables (LAKEWATCH 2000;

Carey and Rydin 2011). Increases in surface water TP were correlated with significant

increases in surface water chlorophyll, indicating that both lakes could be moving

towards a eutrophic system. Internal and external TP inputs impact phytoplankton

growth which influence various other physical, chemical and biological aspects of the

aquatic environment. Phosphorus entering a waterbody via watershed drainage is

closely associated with particulates with iron, aluminum, calcium and humic substances

or can exist in dissolved inorganic forms of orthophosphates. (Wilson et al., 2008).

Sediments also play an important role in the source of nutrients to waterbodies

(Hou et al., 2013). Various processes allow for phosphorous to be released from

sediments into the water volume, some of the common interactions being dissolution

and desorption of bound phosphorus, dissolution of P in sediment pore water, and

mineralization of organic matter (Hou et al., 2013). Wu et al., (2014) state that P release

from sediments is one of the most important factors in the aquatic phosphorus cycle.

Remobilization of sediment P causes water column P concentration to increase (Carey

and Rydin 2011). This can occur when bottom anoxia exists, and P is released from

sediments (Wilson et al., 2008). Many of the coastal dune lakes do experience seasonal

anoxia due to water and climate temperatures, dissolved oxygen concentration and

bottom salinity. The potential exists that their sediments are releasing P back into the

water column. Sediments also act as sinks for phosphorus, removing it from the water

column through precipitation and storing it in sediments. Increasing trends in TP in

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Eastern and Big Redfish Lakes could indicate signs of increased nutrient loading to the

lakes and could lead to increased phytoplankton growth.

Organic Matter

Sediment organic matter C/N ratios are often analyzed in paleolimnological

studies to determine the dominant source of organic matter to a waterbody (Brenner et

al., 1999; Meyers and Teranes 2001; Lamb et al., 2006). The coastal dune lake study

sites, Eastern and Redfish Lake, display a decreasing trend of C/N ratios towards

sediment surface which suggest that both lakes are transitioning from dominantly

allochthonous, externally transported organic material, to autochthonous, internal in suit

origins, organic matter sources. These findings may potentially be correlated to changes

in the lake watersheds or development encroachment. Additionally, anthropogenic

nonpoint source pollution inputs may affect algal productivity altering its organic matter

sources from traditionally terrestrial to autochthonous. However, since these trends are

not significantly negative it is difficult to conclude a specific cause of change and is

more likely a cumulative impact from a variety of sources.

Determining the dominant source of organic matter to a waterbody can provide

an understanding to what the internal and external influences exist and how they may

affect the physical, chemical and biological qualities of a waterbody. Organic matter

consists mainly of carbon-based compounds and contains approximately 50% of carbon

(Meyers and Teranes 2001). It originates from a combination of organism components,

both living and dead, that are made up of an assortment of lipids, carbohydrates, and

proteins along with other portions produced from organisms and geochemical reactions

in and around a lake (Meyers and Teranes 2001).

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Organic matter is a source of nutrients, energy and storage of compounds for

both terrestrial and aquatic environments for both microorganisms and plants. As

organic matter moves through a landscape and into aquatic system it is altered with

only a small fraction surviving degradation (Lamb et al., 2006; Meyers 1994). Any

remaining portion of organic matter successfully escaped remineralization and is

incorporated into a waterbody’s sediments (Meyers 1994). Despite continued

diagenesis of sediment organic matter, geochemical markers are capable of being

preserved and utilized to identify organic matter sources (Meyers 1994). In particular,

sediment C/N ratio and stable isotope ratio of δ13C/ δ12C and δ15N/ δ14N have been

proven to be critical in identifying these sources (Meyers 1994; Meyers and Teranes

2001; Lamb et al., 2006; Gu et al., 1996; Brenner et al., 1999; Brenner et al., 2006).

The biogeochemical components of organic matter can be used to distinguish

between its origin of source, dominantly terrestrial and/or aquatic. Terrestrial vegetation

has greater refractory components and less labile portions, while aquatic contain more

labile fractions and less refractory leaving distinct differences in their organic matter

signatures (Khan et al., 2015; Meyers and Teranes 2001). Approximately 90% of

terrestrial vegetation are C3 photosynthetic plants and have high C/N (wt %) ratio

greater than 14, due to their high carbon and low nitrogen fractions (Khan et al., 2015;

Meyers and Teranes 2001). The coastal dune lakes are potentially largely influenced by

C3 terrestrial vegetation since many have watersheds that are partially preserved in

state parks or forest lands. Aquatic plants are also C3 plants, including macrophytes and

microscopic algae, and are composed of greater nitrogen, labile, fractions (Lamb et al.,

2006; Meyers and Teranes 2001; Meyers 1994; Khan et al., 2015). Due to a higher

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nitrogen content, C/N ratios decrease to between 5 and 7 or less than 12 (Lamb et al.,

2006; Meyers and Teranes 2001; Meyers 1994). C4 pathway plants, such as emergent

vegetation like S. alterniflora and J. roemerianus, are regularly observed along coastal

dune lake shorelines offering an additional source of organic matter input. C4 plants are

well adapted to saline intertidal areas and will increase C/N ratios to influenced

waterbodies and their sediments. C4 plants contain more carbon components and

create a larger C/N ratio of greater than 35 (wt %) (Lamb et al., 2006; Meyers 1994).

Variations in the C/N ratio can provide inferences to changes in organic matter sources.

However, post depositional and significant fractions of inorganic nitrogen can limit the

utility of C/N ratios in a marine setting (Hu et al., 2006).

C/N ratios are more effective when they are analyzed with concurrent stable

isotope (δ13C and δ15N) concentrations. The addition of these two stable isotopes in a

sediment analysis provide a more detailed indication of the organic matter contributions

from contrasting sources (Figure 4-1) (Lamb et al., 2006). The photosynthetic pathways

of plants produce distinct ranges between terrestrial and aquatic plants and even

between fresh and marine contributions (Lamb et al., 2006).

The range of δ13C in terrestrial plants is typically lower (more negative) than

aquatic C3 plants, approximately ranging from -32‰ to -21‰ (Lamb et al., 2006). These

ranges can overlap with aquatic C3 plants as well. Typically, freshwater C3 algae have

δ13C values from -30‰ to -26‰, a smaller range compared to terrestrial plants, while

marine algae have higher (less negative) δ13C values of -23‰ to -16‰ (Lamb et al.,

2006; Khan et al., 2015; Sampaio et al., 2010). C4 dominant vegetation can drive δ13C

values higher (less negative) having approximate values of less than or equal to -16‰

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(Lamb et al., 2006). Stable nitrogen isotope δ15N assist in identifying source specific

signatures of organic matter when analyzed with δ13C but is not as reliable as δ13C

values alone (Hu et al., 2006; Brenner et al., 2006). In terrestrial environments, C3

plants have a lower approximate δ15N range than algal values of organic matter; the

terrestrial range is approximately -5 to +18‰ with a mean of 3‰ (Hu et al., 2006) or

0.5‰ (Meyers 2003), while algae have higher range of δ15N values, 4 to 9‰ (Sampaio

et al., 2010; Meyers 2003).

These values can change due to physical, chemical and biological influences.

Das et al., (2013) investigated sand dune systems in the surrounding coastal dune lake

watersheds and found that dune organic matter inputs influenced a decrease in C/N and

stable isotope measurements. Bacteria also have the potential to influence these

variables but are typically minute and have a minimal effect on the sediment organic

matter (Lamb et al., 2006). Das et al., (2013) found that terrestrial plants including some

C4 plants around the coastal dune lakes have a range of δ13C values from -30.8 to

-13.5‰ and a δ15N range of -9.1 to 1.6‰. Submerged vegetation displayed δ13C values

of -25.6 to -23.2 ‰, with δ15N values of 4.4 to 8.7‰; while emergent plants displayed a

range of δ13C from -28.2 to -14.3 and δ15N values of 2.5 to 8.9 (Das et al., 2013).

Determining that the coastal dune lakes in their study, Eastern and Western Lake, were

influenced by predominantly C3 plants (Das et al., 2013).

In the present study, Eastern Lake displayed a mean C/N ratio of 13 (wt %) and a

range of 11 to 15 (wt %), indicating that aquatic C3 plants dominated organic matter

sources dominated. However, stable isotope analyses indicate that both terrestrial and

freshwater algae dominated the organic matter input. Eastern Lake (Figure 4-2)

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displayed a mean δ13C of -25‰ and a range of -26‰ to -24‰ with δ15N values of 2.8 to

4.4‰ and mean 3.7‰. These results demonstrate that these coastal dune lakes are

influenced by mainly terrestrial and freshwater C3 plants, with potentially some marine

organic matter sources.

Big Redfish Lake displayed similar variations in stable isotopes and a slightly

higher range of C/N values than Eastern Lake. Its C/N ratio mean was 15 (wt %) with a

range of 12 to 18 (wt %), indicating a stronger terrestrial dominance (Figure 4-3). Its

δ15N values were lower with a mean of 3.01 (wt %) and a range of 1.96 to 3.82‰,

indicating more terrestrial sources. Its δ13C values were more negative, with mean of -

26‰ and range of -28 to -25‰, than Eastern Lake’s measurements, also indicative of

more terrestrial dominance. Mackie et al., (2005) correlated high C/N ratios (14 to 26)

and ẟ13C values between -27 to -25‰ as freshwater aquatic and terrestrial organic

matter dominance (Mackie et al., 2005). This indicates that Big Redfish Lake may be

more influenced by its watershed and terrestrial organic matter inputs. Both lakes

display a decreasing C/N ratio trend that can be attributed to a change in organic matter

sources from terrestrial to aquatic (Das et al., 2013).

As exemplified by the literature and previous data, the coastal dune lakes are

influenced by all of the mentioned organic matter sources (terrestrial, freshwater and

marine algae, and C4 dominant vegetation) due to their dynamic nature and close

proximity to coastal interactions. This includes the influence of intermittent connections

to the Gulf, groundwater, and terrestrial vegetation along with saltwater and freshwater

marsh vegetation. Temporal variations in geochemical signatures of coastal dune lake

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sediments are believed to represent and correlate with climatic and lake hydrologic

variations (Das et al., 2013).

Paleoproductivity

In addition to organic matter sources and origins, geochemical signatures

indicate paleoproductivity of a waterbody. Stable isotope δ13C values are associated

with nutrient concentrations in a lake and correlate to nutrient increases (Brenner et al.,

1999). Increases in the heavier carbon isotope δ13C (versus δ12C) indicate the shift from

algae preference of δ12C due to its depletion during periods of increased productivity.

The depletion of δ12C forces C3 aquatic plants to rely on δ13C for carbon fixation

(Brenner et al., 1999). In addition, when water carbon dioxide levels are low, C3 aquatic

vegetation may rely more on bicarbonate as a carbon source which is enriched with

δ13C (Brenner et al., 1999).

Under eutrophic lake conditions, long periods of anoxia may occur causing

methanogenic bacteria to become active producing isotopically heavy carbon dioxide,

subsequently enriching produced organic matter with δ13C (Brenner et al., 1999). Gu et

al., (1996) provided results to support the use of δ13C as an indication of

paleoproductivity. Their study showed a positive correlation between δ13C and water

column chlorophyll-a in 83 Florida lakes (Gu et al., 1996). In addition, their study

showed that δ15N can be correlated to sediment TP and used to infer past productivity in

a lake (Gu et al., 1996).

According to Talbot and Laerdal (2000), increasing 15N values in an East African

Lake were a result of intense utilization of its DIN reservoir due to increases in lake

productivity caused by released nutrients from the flooded land surface. Interpretations

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using δ5N as an indicator alone can be limited by nitrification and nitrogen-fixing

bacteria, it was determined to not be as successful as δ13C (Gu et al., 1996).

Sediment δ13C can be influenced by physical, chemical and biological processes

within the lake as well as from its watershed (Brenner et al., 1999). Both study sites

demonstrate variations of increasing and decreasing δ13C values. These periods of

increases can potentially be correlated to periods of marine inundation where a greater

input of nutrient occurs and algal productivity peaks.

Paleosalinity

Stable isotopes, δ13C and δ15N, have previously been utilized to reconstruct

marine and freshwater inundation (Das et al., 2013; Lamb et al., 2006; Lambert et al.,

2008). This information can provide interesting insight into coastal formations such as

the coastal dune lakes. In fact, two separate studies have utilized some coastal dune

lakes of Northwest Florida sediment cores to reconstruct paleotempestology records in

the Gulf of Mexico coastal region (Das et al., 2013; Liu and Fearn 2000). These studies

determined that concurrent increases in both δ13C and δ15N indicate a marine dominant

state, likely caused by seawater inundation from major storm events, whereas a

decrease indicates freshwater dominance (Das et al., 2013; Liu and Fearn 2000; Lamb

et al., 2006; Lambert et al., 2008).

Organic matter of marine origins is generally more enriched with stable isotopes

δ13C and δ15N, than that of freshwater or terrestrial origins (Lambert et al., 2008; Das et

al., 2013). The Gulf of Mexico has more elevated nutrient concentrations and dissolved

inorganic carbon than coastal lake waters (Das et al., 2013; Lambert et al., 2008).

Coastal dune lake TN levels off at 300 µg/L, while the Gulf of Mexico averages 1600

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µg/L with higher levels near 6000 µg/L (Das et al., 2013). The geochemical signatures

that remain in the lake sediment are believed to represent strong storm events, in

addition to hurricanes, that caused seawater to enter the lakes (Lambert et al., 2008).

In the Lambert et al., (2008) model, coastal lakes have two states: isolated and

flooded. In isolated state, the lake is not connected to seawater and is characterized by

a dominant organic matter source of terrestrial input, indicated by low nutrients and

stable isotopes (Lambert et al., 2008). A flooded state is when the lake is subject to

seawater flooding produced by strong winds which force seawater into the lake causing

marine-like conditions with concurrent increases in stable isotope values (Lambert et al.,

2008). Marine water inundation would provide labile nitrogen components leading to

increased algal productivity and causing sediments to be further enriched with heavy

isotopes (Das et al., 2013). These increases or decreases in stable isotopes interpreted

with concurrent decreasing or no significant change of C/N ratios supports the Lambert

et al., (2008) model.

The study sites of the present research displayed variations that align with the

Lambert et al., (2008) model and Das et al., (2013) determinations. Eastern Lake

exhibited many variations in the stable isotope measurements with an increasing up

core trend of δ13C values and decreasing trend in δ15N measurements and C/N ratios.

Big Redfish Lake displayed less intermittent variations in stable isotopes and appears to

exhibit longer temporal ranges of increasing or decreasing isotope trends with an overall

decreasing C/N ratio. Extended increasing trends occur from 95 to 70 cm, 55 to 35 cm

with a slight decrease in both isotopes at 45 cm. These increasing events seem to cover

depth ranges of 15 to 20 cm, potentially over decades. Eastern Lake does display

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concurrent increases in isotopes with decreasing C/N ratios which are over smaller

depth intervals compared to Big Redfish Lake.

Perhaps these temporal variations are indicative of outlet openings of traditional

occurrences and not only associated with strong storms. These “traditional” openings

would be driven by climatic influences and not just strong storm events, and more

associated with dry or wet conditions over longer periods of time along with each lakes

morphometry. Since peaks and troughs of the data tend to cover multiple depth

intervals, this could represent decades of changes not induced by single storm events.

Oscillations in climate driven by events such as El Nino and La Nina variations could

potentially have a strong influence on the wet or dry periods of this region and may have

a strong influence on outlet opening events also influencing organic matter sources,

nutrient inputs and aquatic productivity (Elliott and Whitfield 2011).

This research project provides stimulating information to the past and present

functioning of the coastal dune lake study sites and has created a foundation for other

research endeavors to build and expand upon. However, additional research is

necessary to create a comprehensive library on these unique coastal features.

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Table 4-1. Trophic state classification (Forsberg and Ryding 1980).

Trophic State Total nitrogen (μg/L)

Total phosphorus (μg/L)

Chlorophyll (μg/L)

Secchi (m)

Oligotrophic <400 < 15 <3 >4.0

Mesotrophic 400-600 15-25 3-7 2.5-4.0 Eutrophic 600-1500 26-100 7-40 1.0-2.5 Hypereutrophic >1500 >100 >40 <1.0

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Table 4-2. Eastern and Big Redfish Lake mean long term trophic variables (CBA 2017).

Lake Total Nitrogen (μg/L)

Total Phosphorus (μg/L)

Chlorophyll (μg/L)

Secchi (m)

Big Redfish Lake 364 13 5.39 0.98 Eastern Lake 286 12 3.55 1.45

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Table 4-3. Surface and bottom physicochemical variables between Eastern and Big Redfish Lake

Variables Eastern Lake Big Redfish Lake

Dissolved Oxygen (mg/L) surface 6.77 7.79 5.55 5.98 7.36 4.49 bottom 6.33 9.5 2.4 3.91 10.12 0.13 pH Surface 7.53 7.97 7.12 7.2 7.72 6.6 Bottom 7.50 11.83 4.30 7.21 9.88 5.07 Salinity (ppt) Surface 8.23 18.5 2.0 5.14 16 0.66 Bottom 16.11 33.13 1.21 14.36 33.04 0.17 Temperature (C) Surface 22.5 25.4 17.5 23.9 30.5 21.6 Bottom 23.89 32.94 10.72 24.20 33.72 9.5

This table demonstrates water column stratification that can occur within Eastern and Big Redfish Lake’s surface and bottom measurements of water chemistry variables.

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Figure 4-1. Organic matter origins relationships between δ13C and C/N ratio (Lamb et

al., 2006).

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Figure 4-2. Eastern Lake sediment δ13C and C/N ratio relationship.

Eastern Lake δ13C and C/N ratio ranges demonstrate a lake system that is

predominantly influenced by C3 terrestrial plants, but also influenced by C3 freshwater aquatic plants and marine organic matter sources.

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Figure 4-3. Big Redfish Lake δ13C and C/N ratio relationship.

Big Redfish Lake δ13C and C/N ratio ranges demonstrate a lake system predominantly

influenced by C3 terrestrial plants, but also by C3 freshwater aquatic plants and marine organic matter sources.

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CHAPTER 5 CONCLUSION

Through sediment core analyses, coastal dune lake environments have been

reconstructed to infer what changes they have undergone and if these changes are

significant. In addition, knowledge of what previous conditions were provided insight to

what the future conditions of these lakes may hold, as well as indicate cycles or

variations that have occurred or may occur in the future. The study site coastal dune

lakes exhibit similar trends in organic matter sources over the last 150-year period. Both

lakes displayed decreases in C/N ratios due to increases in %C and %N. This trend

indicates organic matter sources may be transitioning from mainly terrestrial sources to

aquatic organic matter sources. Higher nitrogen in C3 aquatic plants caused the C/N

ratio to decrease as its N value increased. Big Redfish Lake exhibited slightly higher

C/N ratios than Eastern Lake leading us to believe that it was more influenced by

terrestrial vegetation inputs from its watershed. Further investigations into the origins of

organic matter using stable isotopes δ13C and δ15N allowed for a more detailed

perspective of the initial results from C/N ratio organic matter sources. Eastern Lake

displayed mean stable isotope ranges within the dominant range of terrestrial and

freshwater C3 plants organic matter sources. Big Redfish Lake displayed geochemical

signatures more closely aligned with terrestrial and freshwater algae dominance. The

sediment geochemical signatures are guidelines to the influences of terrestrial and

aquatic organic matter and show variation within the sediment core for all variables. It

seems likely that the coastal dune lakes would have some marine algae organic matter

sources at times, however it would be variable, and be expected to correlate with outlet

openings or strong storm events, demonstrating the complexity of these coastal

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systems and their interactions with both marine and freshwater and terrestrial

influences.

The paleolimnological methods utilized in this study provided information on

nutrients, organic matter sources, productivity and paleosalinity conditions of two

coastal dune lakes in Northwest Florida. These lakes are unique coastal features that

are dynamic and ever changing coastal environments that are significant on a global

and regional scale as subsets of coastal estuary-lagoon like formations. Gaining an

understanding of how environmental factors influence their natural conditions is

imperative to their future health and protection, as well as understanding such

anomalies.

Bolstering knowledge on the coastal dune lakes through reconstructing past

environmental conditions has proven to be an effective tool to gaining insight to

changes in environmental conditions and deducing potential causes. The present study

has helped to describe water chemistry, organic matter sources and origins, and the

hydrology of two coastal dune lakes found. Results provided background information on

historical changes within these systems, but due to limited published literature, there

remains a limited understanding on how these lakes function and interact with their

environment.

Both lakes exhibited surface water sample data indicating statistically significant

changes in nutrients, chlorophyll, and Secchi depth over the last two decades indicating

eutrophication. These variables are traditionally used to determine what trophic state a

lake exists in and if changes to its trophic state indicate a severe imbalance likely

caused from external sources. The surface water sample data indicates that both lakes

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have high levels of nutrients (TN and TP) and increased levels of algal biomass

correlated to amplified available sustenance, as well as decreased water clarity. Surface

water data has only been collected for roughly 20 years and in the scale of

environmental change this is only a fraction of the lakes existence. Furthermore,

determining if these changes may be due to environmental changes with only this

dataset is subjective and limits the scale of changes incorporated into an examination of

coastal dune lake variations. Nonetheless, any consistent data is important to long term

assessments of these lakes and has led us to the paleolimnology methodology we used

in this research.

Geochemical sediment signatures have also been used to illustrate

paleoproductivity trends within a waterbody. Correlations between δ13C and algal

biomass have been used in previous studies to demonstrate inclinations in

paleoproductivity. In some cases, δ15N was used as an indicator of productivity, but can

have many limitations. Using δ13C as an indicator for the two coastal dune lake study

sites past changes in aquatic productivity were inferred. Stable isotope measurements

did not correlate with sediment TP trends and indicate that primary productivity may not

be the dominant source of organic matter to these lake systems. Furthermore,

geochemical signatures are influenced by a variety of physical, chemical and biological

factors that can alter its sediment concentration.

Paleotempestology work from previous studies on the coastal dune lakes

indicated that variations in geochemical signatures could be used to determine storm

over wash events and subsequent marine inundation. These results were used to

estimate storm events but were discovered to be useful tools to evaluate marine and

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freshwater dominance within the coastal dune lakes. Utilizing the standards they

provide, this research projects coastal dune lake study sites were analyzed to show

variations between marine and freshwater conditions. Eastern Lake displayed shorter,

but more frequent occurrences of marine intrusions and Big Redfish Lake appears to

exhibit longer and less periods of marine dominance. These insights into coastal dune

lake hydrology and interactions with seawater are important aspects to understand and

enhance future research endeavors on them.

This research project provided stimulating information to the past and present

functioning of the coastal dune lake study sites and created a foundation of background

conditions of both study lakes for other research endeavors to build and expand upon.

Establishing historical trends in TP provides insight to nutrient conditions and can be a

platform for investigating other aspects of the lake community, such as diatom-inferred

TP values. Understanding primary producer communities within the coastal dune lakes

could help our understanding of how these lakes respond to nutrient inputs. In addition,

knowledge of the coastal dune lake outlet influences can help to fill data gaps that exist,

such as physicochemical variability and impacts on microbial communities within the

lake waters and sediments. Understanding outlet dynamics can also help in our

understanding on the influence of land use changes within their watershed and how it

may impact organic matter sources to the lakes.

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BIOGRAPHICAL SKETCH

Brandy Foley was born in Little Rock, Arkansas. After graduating from Cotter

High School in Cotter, Arkansas Brandy attended the University of West Florida in

Pensacola, Florida. She received a Bachelor of Science with a major in environmental

studies and a specialization in environmental policy in December 2009. In 2011, she

was employed as an AmeriCorps at the Northwest Florida State College in partnership

with the Choctawhatchee Basin Alliance (CBA) in Santa Rosa Beach, Florida. A year

later she was employed as a CBA program assistant and later became CBA’s

Monitoring Coordinator. In January 2016, she completed the Soil and Water Science

Department Wetland and Water Resource Management graduate certificate at the

University of Florida in Gainesville, Florida. In May 2018, she graduated with a Master

of Science in environmental science at the University of Florida.