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Preliminary Investigation of Yellow
Water in the Manasquan River
Prepared on behalf of Kean University and the Manasquan Water Treatment Facility
Submitted May 3rd, 2013
Project Director: Ryan J. Grantuskas
CR-ITEAM: Jennifer Closson, Courtney Deckenbach, Anthony Ingato, Michael Rizzo, Renato
Rodrigues
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Table of Contents
Executive Summary .......................................................................................................................4
Purpose & Intent............................................................................................................................5
Introduction....................................................................................................................................5
Literature Review .........................................................................................................................5
Statement of Work........................................................................................................................7
Study Area ....................................................................................................................................7
Research Design.........................................................................................................................10
Environmental Setting.................................................................................................................13
Geologic History........................................................................................................................13
Soil Quality ....................................................................................................................................14
Water Quality.............................................................................................................................24
Flora ...........................................................................................................................................26
Fauna & Microbial .....................................................................................................................29
Anthropogenic................................................................................................................................30
Air Quality .....................................................................................................................................32
Climatology& Meteorology...........................................................................................................36
Methodology .................................................................................................................................40
Field Work..................................................................................................................................40
Laboratory Investigation ............................................................................................................43
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Results& Analysis .......................................................................................................................47
Results ........................................................................................................................................47
River Behavior ...........................................................................................................................51
Conclusions & Discussions..........................................................................................................57
Recommendations ........................................................................................................................58
Remediation..................................................................................................................................58
Acknowledgements ......................................................................................................................59
References.....................................................................................................................................60
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I. Executive Summary
Occurrences of yellow water in the Manasquan River watershed were investigated. The
discoloration of the river is a seasonal phenomenon in which the coloration becomes more
pronounced in the summer. Nine sampling sites along the Manasquan River and its tributaries
were focused on for analytical and geographical investigation. This study focused on potential
biogeochemical processes and pathways to conceptualize a model to describe the natural system
causing the intense development of color in the river water. The team developed a conceptual
model that describes the behavior of the watershed and any influences on the system. These
processes were examined through chemical analysis, remote sensing data, and climatological
information. Chemical lab work was performed to test reactions that would produce a precipitate
of Fe2+. The team identified geological conditions as the major source of the discoloration.
Glauconitic river bed sediments have been identified through chemical and physical tests and
observations. Further investigation found atmospheric phenomena plays a direct role in the
response of the hydrosphere and lithosphere that cause the yellow water to become an issue.
Recommendations are given based on project findings with regard to how and where the
glauconitic materials are entering the system, and how they behave within. Remediation tactics
involving precipitating the Fe2+ and Fe3+ from the river can be employed to discontinue the
coloration. However, this is a natural process and glauconitic soils in the river bed cannot be
remediated.
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II. Purpose & Intent
The CR-ITEAM was “hired” by the Kean University research investigative unit on behalf
of the Manasquan Water Treatment Plant to determine the cause and source of the yellow water.
Prior research has identified that there are suspended particulates in the water that do not
dissolve and that the coloration of the river becomes more pronounced during the summer
season. The study area is the Manasquan River located in Monmouth County, NJ. The team’s
current study took place from March 1st through May 10th. The dates allowed a sampling of early
spring conditions.
To investigate the causes of the coloration with regard to seasonal variations, the team
decided to compare winter samples that were collected during the early spring season. of our
investigation to summer samples from the USGS that were previously investigated. The team
decided upon developing a conceptual model to portray the processes and influences on the
Manasquan River watershed. Two different hypotheses relating to biogeochemical impacts were
developed and tested throughout the course of the study. The hypotheses were developed based
III. Introduction
Literature Review
In the Manasquan River, it has been noted by previous studies that there is a coloration
issue within its system (Yee, 2011). According to the study, there is a seasonal change in
coloration for the river because as temperatures get warmer, the coloration gets is seen to be
yellow through insolation (Yee, 2011). The main distinguishing features of glauconitic
inclusions are their rounded shape, dark color and peculiar chemical composition. During the
firing – as also evidenced by a few preliminary experimental tests on glauconitic sediments – the
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pellets change in color (from green to red or black in thin section) because of the oxidation of
divalent iron and their texture becomes more homogeneous, up to the partial or complete
verification at moderately high temperatures (Basso, Capelli, Capella, Riccardi, 2008).
Greensand (also known as Glauconite) is used as a fertilizer for plantation in the state of
New Jersey and historically it has been deposited into the state millions of years ago. The
greensand deposits of central and southern New Jersey were locally quarried by 18th century
farmers for use as a fertilizer in order to keep their land fertile for use year after year
(Introduction to the mineral Glauconite). It was also recently found that these greensand soils
and fertilizers were spread out throughout the Manasquan River system (Rutgers University,
2011).
In a study done by the Manasquan Water Supply System and USGS, it was found that
there is an increase trend in turbidity and even some sections of the Manasquan River has been
unstable and erodible (USGS, 2011) . The Manasquan Water Supply also found that there is
twenty percent of iron inside the glauconite composition. Fe3+ is highly soluble whenever the
acidity gets lower and since the acidity along the Manasquan is ranging from 3.5-5 (as shown in
figure 2), there is highly soluble Fe3+ particles surrounding the river. When iron (Fe) is
combined with other chemicals (like phosphorous and sulfur), a different coloration will occur.
Glauconite might also experience a different type of the mineral if there are any physical or
chemical changes to it. Other factors, such as sedimentation rate, water temperature, water depth
and parent material can have an influence on the specific nature (type) of glauconite that forms
(Hower, 1961). Temperature had only minor influence on the synthesis of glauconite which
formed at both 3C and 20C. However, higher temperatures generally led to better and more rapid
crystallization (Harder, 1980) . This proves that during the summer months, glauconite is present
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more and leads to the yellow-coloration in the summer. The USGS conducted an investigation
over the summer in 2011 and their data proved that there was a distinct coloration noticed.
Statement of Work
To investigate the coloration of the water inside the Manasquan watershed, the chemical
and physical processes were compared for seasonal variation. Field studies were utilized to
observe physical properties in the environment. Spatial and temporal behaviors were assessed by
examining soil, air and water samples to identify the microclimate and its micro-scale features.
Following the field visits, the team used the samples from the sites to perform lab analyses to
determine changes in chemical and physical processes. The previous USGS research identified
the presence of iron and zinc in the river water. The team’s chemical analysis and experiments
identified that precipitation is the trigger of both chemical interactions (including Zn and Fe) and
physical processes. The conceptual model that was developed by the team for the Manasquan
River deals with the biological, geological and chemical processes that are involved within the
system. All these observed processes are consistent with the team’s conceptual model of the
Manasquan River system.
Study Area
The Manasquan River is a 42.65-kilometer long waterway in central New Jersey (USGS
2013). Located predominately in Monmouth County, beginning in Freehold, it extends to the
Atlantic Ocean and into Ocean County. The river is approximately 144.8 m across at its widest
part before it lets out into the Manasquan inlet.
The Manasquan River Watershed covers a total area of 82 square miles including 13
municipalities (See Figure #) (Manasquan Watershed Management Group 2000).
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The land use in the watershed varies as shown in Table 1 (Kratzer 2012).
Land Type Percentage
Water/Wetlands 38 %
Urban 31%
Forest 19%
Ag 10%
Barren 2%
Figure 1 The Manasquan River Watershed covers a
total area of 82 square miles including 13
municipalities
Table 1 Land usage
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Monmouth County began to see changes in terms of land use occurring in the 1980’s
within the watershed. These changes were significant alterations from agricultural farms and
wetlands to urbanized development. The increasing development runs the risk of soil
contamination and shocks to the system with these changes (Kratzer 2012).
Monmouth County has a 2012 population estimate of 629,384 people, (US Census). The
watershed supplies drinking water to over 250,000 residents. Drinking water is treated by the
Manasquan Water Supply System to send to public or private water distributors. A $75 million
dollar reservoir with a 4.7 billion gallon storage capacity was constructed. The reservoir is
supplied by the Manasquan River says Madsen et al. (2003) in the event that the quality or
quantity of water from the river was not up to par. The reservoir water can be used alone or in
conjunction with river water.
There are nine plotted sites along the river chosen by the Manasquan River Water Supply
System (table 2). There are two sites on the main stem of the river and the remaining seven are
located on tributaries.
Site # Description Coordinates
1 Manasquan River @
Georgia Road
40.211814, -74.295523
2 Manasquan River @
Wyckoff Mills
40.203149, -74.261312
3 Yellow Brook near
Farmingdale
40.202709, -74.202387
4 Manasquan River @ 40.185028, -74.18411
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Southard Ave. near
Farmingdale
5 Marsh Bog Brook @
Squankum
40.168282, -74.15853
6 Mingamahone Brook @
Squankum
40.16616, -74.149287
7 Debois Creek @
Adelphia
40.220562, -74.261422
8 Mill Run near
Squankum
N/A
9 Manasquan River @
Allenwood (WSA Plant)
40.084868, -74.065069
ResearchDesign
The study is designed to target answers to the question of the yellow water. This will
determine preliminary responses and reasons that explain the state of the river. It is expected that
there will be a connection with many characteristics and properties of the natural environment.
Therefore, based on environmental features within the watershed, a hypothesis was developed
based on the chemical and physical attributes of the area. The first hypothesis suggests that
chemical reactions occur to interact with warm water temperatures, zinc, and iron. This would
describe the stronger state of the summer condition. Part of the chemical-based hypothesis is
relative to the variation of water pH as it determines the solubility of glauconitic rock.Zinc-based
fertilizers also undergo a natural weathering process that exposes zinc particles to the
Table 2 Sites along Manasquan River
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environment. In combination with Fe(III) particles and heat, a chemical reaction occurs that
reducesFe(III) to Fe(II), giving the yellow-green coloration. High temperatures and higher
stream flows in the summer increases the dissolution rate of the glauconite resulting in a higher
pH and suspended particulates in water.
The second focus is on physical interactions such as weathering, runoff of fertilizers,
infiltration, and urban/anthropogenic development within the river system. It is hypothesized that
these components are occurring within the natural environment to contribute to the condition of
the river. Pre-existing evidence states that glauconitic rock outlines the riverbed in the upper
watershed. With the physical property of glauconite as soft and friable, exposure to physical
disruptions of soil and water will enhance erosion and dissolution of the material. Specifically,
these disruptions are: (1) erosion of exposed outcroppings of glauconite, (2) runoff of glauconitic
greensand fertilizers, and (3) relocation of farms and disruption of soil due to population-based
development.
Field observation, lab analysis, and comparative data analysis were used to identify
parameters that cause river coloration. Field locations are selected to compare the variability
between conditions of urban vs. rural, tributary vs. river, and upstream vs. downstream. River
water was sampled to identify the solution composition in correlation with the conceptual
models. The water samples are also compared to summer water samples that were previously
sampled. Soil samples were gathered to test for characteristics of glauconite and zinc. pH
sampling occurs on site to provide in-situ data of the river relative to stream flow and turbidity.
Experimentation to replicate situations that are hypothesized to contribute to the coloration will
be evidence to verify the occurrence. Concentrations will be altered in this experimentation to
simulate the Manasquan River environment.
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This design is created to give suggestions and recommendations to the solution of water
coloration. It is developed to assess various inputs and outputs by analyzing soil and water
conditions with its variations. These inputs and outputs are defined as processes that contribute
to the yellow state of the water. As these processes and sources become more prevalent, it will
justify preliminary findings that will work towards a comprehensive solution that would
eliminate the coloration completely. This design has certain limitations such as time. The client
has requested a preliminary finding to be established from March to May, which limits time
availability for sampling and lab analysis. Another limitation focuses on the sampling season. In
order to make connections to seasonal variation, a full year would be required to assess this
aspect. To compromise, USGS summer sampling data is used to make correlations to the early
spring/late winter samples. Ultimately this design targets the purpose of the study and creates a
conceptual model that infers different processes that make this phenomenon occur. The
conceptual model will explain how features of the environment are interacting based on their
current state. Observing the environment during a dry spell versus a precipitation event will
provide different modeling that suggests any activation processes. This will also define a stable
environment versus an active environment.
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III. Environmental Setting
Geologic History
The glauconitic soil layer of Manasquan-Freehold was formed during the Cenozoic era
from glacial and oceanic rises that pushed inland until elevation increased enough that land
collision could not stop (Tedrow 2002). Evidence of diagenesis can be found in the sandy
structures of the lands near the coastal plain study area. As deposited sediment from the ocean
began to undergo the transformation to rock, glauconite was formed in the reduction zones. The
glauconitic process began when phyllosilicates underwent bacterial digestion. This process
occurs when the phyllosilicates pass through the guts of organisms. As octahedral cations are
lost, the charge deficiency was balanced by the introduction of highly mobile marine cationssuch
as (magnesium, potassium and calcium). Since these elements are highly mobile, the structure
did not begin to fully form until ferrous iron began to bind to the digested phyllosilicates. As the
water levels receded, the material hit a drainage divide and isolated elevated hills that locked the
subsoil minerals into place. As changes have occurred over time in the watershed, the parent
material in the soil has been activated by changes in the water table. The importance of
understanding the history of the glauconite comes through prediction of its behaviors. As
glauconite ages, it continues to become more potassium rich, eventually breaking down in
structure. This breakdown over time could allow for an increased introduction of glauconitic
material to the water.
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Soil Quality
Glauconitic materials are being introduced to the watershed through physical processes
such as erosion, leeching and interaction with the river. This is the conceptual model of how this
system works.System processes and behaviors were observed by the team as they related to what
is in the system and how it got there, and its activation behaviors such as precipitation and
interaction with the glauconitic layer in the river. The team took observations and measurements
necessary to produce a conceptual model of the processes and systems relevant to the
introduction of glauconitic materials into the river.
To conceptualize the behaviors occurring in the river, the soil structure and composition
is important to identify. Soil composition in the study area is mainly sand, silt and clay (figure 2).
Figure 2 Soil Composition of New Jersey
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There are 12 classifications of soil types in Monmouth County (USDA 1989). Varying
soil types behave differently with the watershed. Specifically within Monmouth County,
glauconite erodes easily at lower pH and is a brittle mineral.
Varying elemental composition and pH values played an important role in identifying soil
elements contributing to biogeochemical interactions. The most prominent type of soil in
Monmouth County is the Freehold type series. This series comprises 22 percent of the soil type
in Monmouth County. The Freehold series consists of well drained soils. Precipitation will
infiltrate these soils and leech into the ground water table. Freehold series soil consists of 1 to 10
percent glauconite and less than 5 percent quartz. Relevant to the hypotheses of this study,
glauconitic behaviors were investigated to how the elements contained within are activated.
Since glauconitic soils are very erodible and soluble under lower pH, precipitation will cause the
activation of leeching of the glauconitic soils.
Glauconite consists of iron in a reduced and oxidized state. 20 percent of the composition
of glauconite is iron (3 percent FeO and 17 percent Fe203). Glauconitic soils retain more
moisture than the surrounding feldspar quartz soils in the area. Glauconitic soils retain 14 percent
moisture at tension of 15atm and feldspar quartz retains only 8 percent (Tedrow 2002). The
moisture retaining qualities of glauconitic soil make it easier for other elements to react with iron
in the glauconitic soils. Glauconitic soils in New Jersey have an increased concentration of
oxidized iron (Fanning et al.).In the reduced state the glauconite appears green under polarized
light but appears yellow in the oxidized state. The slope of this soil layer underneath the surface
ranges from 0 to 25 percent. A cross section of this soil type performed near Wermock Road in
West Freehold revealed topsoil surface sand that was strongly acidic (Tedrow 2002). Glauconite
became common at a depth of 12 to 18 inches, and was the primary mineral observed in soil at a
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depth of 25 to 70 inches embedded in a sandy layer that is well drained. The entire layer was
observed at pH values of less than 3, ranging from very to extremely acidic. At a depth of 40
inches a layer consisting of iron (1 inch thick) was observed in the cross section (Tedrow 2002).
As changes in land use and water table depth have occurred, elements in the Freehold soil
type layer have become introduced to runoff water. Seasonal variations in the water table depth
pose a problem for agriculture. The water table depth rises from 28 to 25 feet as shown in graph
1. This rise in water table depth during the summer months could indicate a bottom up process
may be occurring. A bottom up process would indicate that the glauconite is being introduced
from underneath the surface and rising up. This process neglects the effect of precipitation which
does not have relevance to this study. A bottom up process was not fully investigated during this
study, as a top down process seemed to be more prominent (especially as occurring with
precipitation events and subsequent leeching out of subsurface).
Graph1Water table depth 2012-2013 as compared against average
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This causes the rooting structures of crop life to be non-adequately aerated. Also, the rise
in water table depth with regard to season plays a role in percolation and dissemination of water
runoff. The crop vegetation during the summer and harvest seasons aid in the extraction of
ground water. This added ground water closer to the surface allows precipitation to travel
through less soil before reaching the water depth level. The introduction of runoff to the
groundwater will allow mixing of chemical elements. As water level rises, unconsolidated
elements contained within the soil will rise closer to the surface. The increased availability of
these suspended particles in the water table being nearer the surface introduces higher
concentrations of these elements during the summer months.
In addition to seasonal variations, an investigation of the water table depth back to 1991
when USGS started tracking the water table depth near the Fort Dix Military Reserve shows a
rise of the water table towards the surface. In 1991 the water table depth was 28 feet, and
currently stands at near 25 feet below the surface. The glauconitic soil layer runs from 0 to 25
feet below the surface to just above the water table (Tedrow 2002). The water table depth has
had more extreme values closer to the surface then further down. Concurrent with the rise in the
water table, precipitation can penetrate the soil layer and interact with the glauconitic layer
underneath easier during the summer.
Sources for the water table rising over the past few decades include erosion of the soil
layers, urbanization and agricultural production. Erosion of the Freehold type soil layer has
occurred through the past few decades. Urban area comprises 40 percent of this soil type in
Monmouth County currently. Urbanization has removed the topsoil layer, thus exposing the
glauconite contained 1 foot below the surface layer. Through urbanization within the watershed,
the soil structure has been compromised. As the soil structure was compromised, the glauconitic
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layer became exposed to weathering. Agricultural production, which makes up 30 percent of the
Freehold soil layer, removes the top soil layer seasonally for crop production (Tedrow 2002).
During the summer months the increased vegetation due to agricultural production and natural
seasonal changes, affects the amount of water pulled from the soils. As the ground water table
begins to rise through the summer months, the vegetation will pull some of the ground water up
through its rooting system. This introduces new chemicals and behaviors into the system.
Ammonia hydroxide, a common by product of vegetation, increases in concentration during the
summer months as a result of the agricultural land use. Thus, the behaviors of the soil layer and
water table through space and time introduce iron, zinc and ammonia hydroxide into the system.
Management of soil is an ongoing issue in Monmouth County as it pertains to soil
quality. Glauconite bearing soils are commonly sought for the use of agricultural production. The
potassium in the soil is considered to be the main reason that crops thrive in this soil type.
However, the high acidity of the surface soil makes crop management a challenge. To solve this,
remediation efforts have been undertaken. Some of the soil management techniques suggested by
the USGS include removing the surface soil through moderate tilling and adding greensand
(glauconitic deposits). Since compaction of the surface soil layer is common in this soil type,
efforts were taken to keep the soil structure intact to maintain its runoff characteristics. Excessive
tilling of the soils breaks down the soil structure, thus reducing its infiltration. Plowing under the
surface layer helps to keep the soil structure intact by reducing compaction and introducing
organic matter into the surface layer. These remediation efforts have introduced increased
concentrations of heavy metal elements in glauconitic bearing soils near the surface.
Investigation of activation of glauconitic materials into the riverbed was investigated.
Weathering of glauconite plays a role in the introduction of glauconite to the river water (figures
19
3 and 4) (Velde 1980). In the topmost layer of glauconitic materials, there was little Fe, but in the
mid portions the material was iron rich. The process identified that as weathering occurred, the
glauconite became gradually destabilized, opposite its formation process (Velde 1980). As
glauconite becomes destabilized, the iron and potassium are the primary minerals removed from
the material. This destabilization will introduce more iron and potassium into the river since the
glauconitic layer was observed in the riverbed. Dissolution of glauconitic materials occurs faster
for glauconitic materials under acidic conditions then neutral or alkaline conditions (Bastero
2008).
A geo-hydro process was investigated to determine the behaviors of the glauconite in the
Manasquan River. The concave slope of the riverbed indicates erosion occurring over time. The
level of glauconitic material will also indicate what level the river will need to rise to in order to
interact with that layer. Glauconite was observed directly in the riverbed, lending to the theory
that interaction between the river water and glauconite were occurring.
Figure 3 Close-up image of glauconite mineral Figure 4 Suspected glauconite along riverbed
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Figure 5(left) The concavity of the riverbed in regards to location of glauconitic layer
Figure 6(right) The green murky appearance of the storm water run-off; this was traced to the river itself
Indirect introduction of glauconite can also occur through leeching of ground water. This
process will occur during precipitation events as the precipitation infiltrates through the
subsurface and interacts with glauconitic material 12-18 inches below the surface.
Soil compaction and reduced plant coverage account for reduced infiltration rates; this is
called the low condition. During the low condition, the necessary infiltration rate for glauconitic
materials to be introduced may not be present. It is not known exactly when low condition and
high condition exist for this system; however, since low condition is during soil compaction and
reduced plant coverage, it can be assumed that low condition is generally associated with winter
season. During the summer, when vegetation and flora are abundant, and soil temperatures rise,
this could be assumed to be the high condition. The infiltration rates during winter may not be
enough for precipitation to reach the glauconitic layer (figure 5).
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Physical characteristics and activation features can be investigated using the WSS (Web
Soil Survey). Drainage characteristics change during the summer and winter. During the warm
season when the soils began to loosen and infiltration values rise, most of the soils near the river
are moderately well drained or better (figure 7). Also during the summer months when
precipitation averages are higher, the liquid limit holding capacity of the soils in the watershed
become increasingly important. The liquid limit of the soils will indicate how much water the
soils can hold before they begin to pond or leech back towards the surface. This physical process
can aid in the transport of glauconitic materials to the surface during precipitation events. In
figure 8, note that most of the soils near the river have poor liquid limit and cannot hold much
water.
Graph 2 Infiltration rate as a function of low condition versus high
condition
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Figure 8 Liquid limit capacity revealing most of area has low liquid
capacity
Figure 7Soil drainage behaviors where bluer shades are excessively
well drained and red are poorly drained
The hydraulic conductivity of water changes as temperature changes. When temperature
increases, viscosity decreases and hydraulic conductivity is increased. This relationship is a
function of temperature, where if temperature of soil is known, conductivity can be calculated.
Graph 3 shows the relationship between viscosity and temperature.
Graph 3Viscosity versus temperature C
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The viscosity of water changes as much as 2 percent per degree Celsius. This leads to a
40 percent change in infiltration between the summer and winter months (Braga 2005). This
change in infiltration processes can be inferred to be related to the seasonal change in the
coloration of the river.
The soil temperature of a nearby site was examined (Cinnaminson, Burlington County).
This was the closest site with archived data from the NCDC, and it closely represents the
characteristics of the Monmouth county sites. As is seen in figure 7, the soil types are the
composition, therefore making it practical and meaningful to analyze soil data from the
Cinnaminson site. Graph4 shows three years average data at the Cinnaminson site for
meteorological winter soil temperatures. Most of the data fell within about 34 to 37 degrees,
directly elating to higher viscosity values. These temperatures may be low enough that the
viscosity values of the water are high enough that glauconitic material is not introduced to the
system.
Graph4 3 year average soil temperatures in degrees Fahrenheit for meteorological winter at Cinnaminson site
24
Atmospheric changes with respect to season, especially precipitation events and
temperature, tend to activate and introduce more glauconitic materials into the system. Greater
convective activity during the summer months yields greater amounts of precipitation than
events during the winter season. These high precipitation summer events have an easier time
infiltrating the less dense soils in the summer. Glauconite soils that are 12-18 inches below the
surface are introduced to the system when precipitation infiltrates to the groundwater table.
Hydrologic groupings are assigned for their response to precipitation events. Groups A and B are
well drained and moderately well drained, meaning infiltration values are very high.
Approximately 76.1 percent of the AOI being investigated by the WSS is classified as either well
drained or moderately well drained (figure 9).
Figure 9 Image of hydrologic classifications based on response to precipitation events, yellow and dark blue represent very low
infiltration
Water Quality
The watershed covers 13 municipalities and a population just over 500 thousand
residents. The river water is treated at the Manasquan Water Supply System to redistribute to
these residents as drinking water. Water quality information from testing done by the MWSS is
as follows (table 3). There is evidence of iron and zinc concentrations that have been detected in
25
the water being treated. These concentrations interact with glauconite materials present in river
water, which leads to the yellow coloration.
Table 3MWSS water quality report
26
As per the relationship between air and water quality, pollutants from smokestacks and
car/truck exhaust fall back to the ground as precipitation and these contaminates will eventually
end up in rivers and streams. Rainfall and snowmelt will travel over a variety of landscapes
picking up pollutants including soils, fertilizers, and pesticides from farmlands and residential
lawns. Pesticide application on agricultural land, sewage discharge from residential
developments, and increased runoff are additional factors influencing water pollution. Fragments
of tires, salt, shreds of brake lining and oil contaminate roads that get picked up by rainfall and
melted snow (Madsen et al. 2003). These contaminants have the chance of ending up in the river
waters through these precipitation/runoff transport mechanisms.
Flora
In the Manasquan River, there are soil types that influence the river directly. The main ones in
particular are listed in the table below:
Top ten soil types w/ characteristics
10. Kresson
Poorly drainable and features glauconitic soils. Also features a PH reading
between 3.6 and 5.5.
9. Pemberton
Features a PH reading between 3.6 and 5.0 and has marine sediments that feature
Glauconitic material. It also features iron and is used with drainage and
irrigation.
8. Collington
Well drained soil that also featured the Glauconite mineral. It is a well-drained
soil and also has some parts of Quartz inside the soil, which was one of the
27
minerals found. Glauconite was averaged out from 10-20%. Also it features a
PH Reading from 3.6-5.5.
7. Humaquepts
Organic-rich wetland soils that are arsenic in nature and Glauconitic soils have
contributed to the increase in arsenic inside this wetland soil (Barringer, Szarbo,
Holmes, 1997).
6. Evesboro Sand
Features Quartz material and excessive drainage. Also, features a PH Reading
from 4.6-5.5.
5. Adelphia
Features a PH around 3.6-5.5 and also deals with Glauconitic minerals and
deposits.
4.Colts Neck
Features 2-10% Glauconite (from marine sediments) and a PH reading of 4.5-6.5.
3.Marlton
Features a PH of 4.5-5.5 and also has Glauconitic soil (about 20% in volume).
Itisalsowelldrainable.
2. Manahawkin Muck
This features a water PH of 4.5-5.0 and is very poorly drained. It is also part of
the wetland feature.
1.Colemantown
This features 20% of Glauconite material and is also poorly drained. It is also
featured to be low or medium surface runoff index
Table 4Main top 10 soil types that influence the river directly
28
The interesting feature about these soil types features the Glauconitic soils that have
influenced the system. Some of these soil types also have a poorly or somewhat drained soil and
that allows for the Glauconite materials to seep up to the surface. With low PH’s as well, the
ground is susceptible to the chemical reactions involved with the Glauconite and even the quartz
material present in some of the sandy soils.
Allaire State Park is one of the many parts to the ecosystem that is influencing the river
due to its proximity to it. During the fall and spring months, there is a removal process, which
can include things like pollen and even leaves as it falls to the ground from groundwater, runoff
and seasonal variation. The groundwater and runoff can leech all the litter into the river and have
an impact inside the Manasquan system.
Fertilizers for growing crops have been on the increase and with any sort of rainwater or
runoff, it would allow for the minerals in the soil to leach up and go into the system. Soils that
contain Fe3+ have a very low solubility in water so that any dissolved particles that are in the
water won’t be easily dissolved. As a result of that, the calculated turbidity values will be higher
since the more particles there are that can’t be dissolved; the more sunlight will have an impact
on the system.
Glauconite (Greensand fertilizer) is used in the system as a source of potassium.
Potassium is the changes between iron redox states and drive numerous reactions involving
electron transfer that are important for plants. However, there is great variation in the availability
of iron in the soil, and starvation or excess can cause severe nutritional disorders, which
significantly affect the physiology of the plant. In response, signals are produced that modulate
the expression of genes involved in either the transport or storage of iron. Recent progress has
29
been made in delineating the cellular and molecular aspects of these processes, highlighting new
mechanisms in plant adaptive responses (Briat and Lobreaux, 1997).
Greensand (also known as Glauconite) is used as a fertilizer for plantation in the state of
New Jersey and historically it has been deposited into the state millions of years ago. The
greensand deposits of central and southern New Jersey were locally quarried by 18th century
farmers for use as a fertilizer in order to keep their land fertile for use year after year
(Introduction to the mineral Glauconite).
Fauna & Microbial
Monmouth County has a large variety of animal life, from snakes to raccoons to birds.
Some significant animals include the opossum, armadillo, and groundhogs, as these animals are
known for their borrowing. As these animals burrow through the ground, this can loosen the soil,
which allows vegetation to grow longer stronger roots. Also the loosening of the soil can make
the ground water infiltrate through easier and carry out more sediment to the river (Cited 2004-
2013).
Iron bacteria are found within the Manasquan River. While they pose no health risk, the
effect is seen on the system through the discoloration or staining appearance of the water,
especially during the summer months. The iron bacteria will not oxidize all the Fe2+ in the river,
however a greater amount of iron bacteria will oxidize a greater amount of Fe2+. The degree of
bacteria in the water will play a role in the coloration of the water as dependent on pH of water
and temperature of water. These iron bacteria can be found to colonize near pipes and effect the
rate of flow in the water. The slimy growth of the bacteria can interfere with the development of
animals and fish (Cullimore 1978). Microscopicimages of iron bacteria collected from water
30
samples were compared to reference images of known iron reducing bacteria. After analyzing
three different water samples (two from site #1 and one from site #7), the team was able to count
the amount of iron bacteria from 3 drops of water on a 1 square inch microscope slide. The team
discovered that the more green the water, the less amounts of iron bacteria there are present, and
the more yellow the water the more iron bacteria there is present. This would confirm the team’s
conceptual model that iron bacteria oxidizes Fe2+ with a green color to Fe3+, which has a
yellow color.
Anthropogenic
The highest point in Monmouth County is Crawford Hill at 119 m above sea level located
in Holmdel, NJ (Monmouth County 2013). Varying elevations between this and sea level are
present throughout the county and a general topographic overview of the area can be seen in
figure 10.
Figure 10 General topographic overview of Manasquan River area
31
The river generally flows from Northwest to southeast and finally into the Manasquan
Inlet. Stretching the river, there has been increased expansion. The development of residential
communities, industries, and commercial business began in the upper watershed in the 1980’s.
Half of the land in the upper watershed was used for growing crops and grazing animals
in 1995 (Madsen et al. 2003). Many large-scale housing developments in the area are
transforming the county from agricultural to suburban. Continued development in this area
threatens water quality (Madsen et al. 2003). This area of New Jersey is one of the most quickly
growing in the state. 34,000 residents moved into the area in the 1990’s, urban area in the
watershed grew by 17.6%, over 12,000 new housing units were built in the 1990’s, and
approximately 6.1% of the total land area in the watershed was developed between 1986 and
1995. Replacing just 5% of land in the watershed with paved surfaces results in a decline in
water quality. Increasing development brings amplified discharge from sewage treatment plants
and higher levels of runoff from roads, rooftops, and other man-made surfaces (Madsen et al.
2003). This runoff caused by development picks up a variety of pollutants, which end up in
rivers and streams over time. This influx of development leads to greater areas of impervious
surfaces and less water seeping into the ground. Less seeping leads to greater runoff values and
decreasing water habitat quality. Wetlands or forests can also be lost in the event of poor
development planning. These areas act as important habitats for wildlife and protectors of water
quality.
32
Air Quality
Monmouth University readily supplies air quality data through the NJ Department of
Environmental Protection. As seen in graph 5 below, data for the later half of March 2013 is
supplied. This graph readily shows that the air quality as monitored at Monmouth University
during the time of study was recorded average.
In conjunction with annual reports from Spirling (2013) in past years, Monmouth County
ranks as a typically unhealthy county in regards to overall air quality, during the time of study
however, average values for general air quality were reported. Increased sunlight and heating
will bring in higher values of overall air quality, thus resulting in expected higher values (graph
6) in the summer months (Lew 2013).
Graph 5Air quality of March 2013monitored from Monmouth University
33
Ozone is not directly put into the atmosphere. It forms on windless days when exhaust
from gasoline fumes mixes with sun and heat. Ozone alert days are when ozone levels rise to
unhealthy levels as set by the Environmental Protection Agency. Classification for alerts range
green-yellow-orange-red. Orange and red denominations indicate an Ozone Alert Day (Missouri
2013). The air quality in Monmouth County is ranked 11 out of 100 on a scale based on ozone
alert days and the number of pollutants in the air (Spirling 2013). Generally, the lower the
number is for an area, the worse the air quality (Spirling 2013).
Ozone is extremely soluble in water based on a couple factors. Colder temperatures of
water due to seasonal variations increase the solubility of ozone. Generally speaking the
troposphere is denser in the winter, leading to a higher pressurized “gas” pushing down on the
water, increasing the solubility. Expected dissolved ozone counts in water are expected to be
high in the winter, but because ozone is very reactive with itself and contaminants in the water,
high values often are not recorded.
Graph 6 Air quality of August 2012 monitored from Monmouth University
34
Two stations monitoring air quality are located in Monmouth County (figure 11),one
located in Freehold is inactive.
Freehold’s measuring station has data sets to 2011. The station measured Carbon
Monoxide for one hour using non-dispersive infrared instrumentation. Ozone is the only active
measured station located in West Long Branch at Monmouth University. Ozone is measured on a
neighborhood scale of 500m to 4km. Sample duration occurs for one hour using ultra violet
analysis and it records the highest concentration of ozone to the New Jersey Environmental
Protection Agency. For other parameters like Lead, Carbon Monoxide, PM 2.5, PM 10, and
NO2, measured at active stations, nearby New York City and Philadelphia areas are to be looked
at.
Parameters regarding Aerosol Optical Depth both Terra and Aqua Modis and Fine
Particulate Matter were plotted using the NOAA Giovanni (2013) website. Aerosol optical depth
Figure 11 Monitoring Networks of tri-state area
35
Figure 12Aerosal optical depth Jan 2012 to Aug 2012 Figure 13Aerosol optical depth Jan 2013 to March 2013
increases in the summertime; this could be due to sea breeze influence bringing in greater aerosol
counts as well as pollen and unstable humid air in the summer.
Pollutants present in air can be deposited back both on land and water bodies. Even at
great distances from the source, the quality of the air is an important contributor to declining
water quality. The pollutants found in water bodies can be traced to atmospheric sources. As
previously stated, both natural and anthropogenic processes lead to air pollution through
combustion of fossil fuels, release of chemical byproducts from industrial and agricultural
processes and forest fires. This airborne pollution falls back to the ground through precipitation.
These pollutants can reach water bodies in two ways; one way is deposition directly into a water
body and second is deposition on to land and transportation to water bodies through runoff. Air
quality is directly related to water quality as the pollutants in air can be found declining the
quality of water bodies (USEPA 2013).
36
Climatology& Meteorology
Climatological data determines the atmospheric influence on the lithosphere and
hydrosphere. Temperature and precipitation were the two primary climatological indicators that
were investigated. These were chosen due to the relevance to the team’s hypotheses on seasonal
variations. A geohydrologic process can be influenced by precipitation since it will cause
leeching of the material into groundwater. Temperature was investigated to determine the
correlation between temperature and the heating of the sub surface soils.
March Climatological Average
1981-2010
March 2013 Δ
4.03 inches 2.47 inches -2.40 inches
Freehold Marlboro NOAA Climatology data reported a -2.4 difference of a
climatological average of rainfall versus March 2013 as referenced in Table 1. This led to drier
than normal soil conditions, which prevents a surplus of surface runoff and enhances infiltration.
Infiltration will provide an input to the river from riverbanks at the bedrock level if not absorbed
by vegetation. Given the lacking of surplus, infiltration as a groundwater input will not be as
effective. The absorption of rainfall into the soils allows the vegetation to use the available
water, which keeps the soil dry. Therefore topsoil samples will contain elements that have not
Table 5Climatologicalcontingency table March 2013
37
runoff into the river. It can be inferred that fertilizers were not as directly affecting the water
quality based on this connection.
July Climatological Average
1981-2010
July 2012 Δ
4.57 inches 3.21 inches -1.36 inches
Climatological data for the summer samples are comparable to the winter samples,
reflecting a similar condition in regards to the runoff in both seasons. As seen in Table 2, July
typically has higher rainfall amounts than March. With the summer season at its peak during
July, the vegetation will be using the water at a higher rate than the winter. Vegetation will help
to pull more water out from underneath the surface during the summer months. This process does
not occur in winter, and could be part of the reason why more reactants are being introduced to
the system during the summer months.
Freehold receives the highest precipitation values from April through September. This
corresponds with the timeframe for the warmest river temperatures. At Freehold, the greatest
extreme values for precipitation were also in the late summer months (table 6). This puts
Freehold’s wet season during the late spring into late summer months. According to climatology,
the most runoff and precipitation is being introduced to the river system during the warm season.
Figure 7 shows the monthly precipitation averages in Freehold Boro. The highest average values
are noted in early spring and again in late summer.
Table 6Climatological contingency table July 2012
38
0
1
2
3
4
5
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Precipitation
Months
Monthly Precipitation Extremes 1991-2010
(in)
Climatological:
FREEHOLD MARLBORO (283181)
Monthly Totals/Averages
Precipitation (inches)
Years: 1981-2010
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
3.24 2.88 4.03 4.12 3.61 3.61 4.57 3.71 4.18 3.66 3.43 3.71
Graph 7(above) Monthly precipitation average, note maximas during early Spring and late Summer
FREEHOLD MARLBORO (283181)
Monthly Extremes
Highest Daily Precipitation (inches)
Years: 1981-2010
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
2.84 2.05 3.10 2.90 3.09 2.01 2.50 3.31 4.75 3.20 2.10 3.30
Graph 8 (above) Monthly precipitation extremes,
0
1
2
3
4
5
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Precipitation
Months
Monthly Precipitation Avg. 1991-2010 (in)
39
Monthly precipitation extremes show the time of year in which the most daily precipitation could
be expected to occur (figure 8).
Graph 9(left) Histogram of daily precipitation extreme occurrences in inches for summer
Graph 10 (right) Histogram of daily precipitation extreme occurrences in inches for winter
In the above figures, during the summer there is a greater occurrence of days with greater
than 2.25 inches of precipitation, while during the winter there are greater days less than 2.25
inches of precipitation. These histograms were created using climatic data from NOAA for
Freehold Boro. For the winter season, the graph represents November thru February while the
summer graph represents May thru August. These months were chosen to represent the seasons
as well capture transitional time frames as well. These extremes are likely related to convective
downpours in the summer.
40
IV. Methodology
Field Work
Site Number and Date Visit Metadata
Site 1 March 22nd, 2013 Water Temperature 4.3˚C
Stream-flow 0.50m/s
Site 2 March 22nd, 2013 Water Temperature 4.3˚C
Stream-flow 0.25m/s
Site 3 March 22nd, 2013 Water Temperature 4.4˚C
Stream-flow 0.55m/s
Site 5 March 15th, 2013 Air Temperature 7.8˚C
Water Temperature 6.5˚C
Turbidity 0.4m/s
Site 6 March 15th, 2013 Air Temperature 7.9˚C
Water Temperature 5.4˚C
Turbidity 0.7m/s
Stream-flow 3.6m/s
Site 7 March 1st, 2013 Air Temperature 7.6 ˚C
Water Temperature 7.2˚C
Stream-flow 0.16m/s
Turbidity 28 FTU
Depth 16 in
Ammonia Level
Nitrate Level 0.67
0.64
41
Dissolved Oxygen 9.6mg/L
Site 7 March 22nd, 2013 Water Temperature 4.3˚C
Stream-flow 0.15m/s
Turbidity 19 FTU
Site 9 March 1st, 2013 Air Temperature 7.6 ˚C
Water Temperature 6.9˚C
Sky Condition Mostly Cloudy
Stream-flow 0.10m/s
Turbidity 23 FTU
Depth 15 in
Ammonia Level 0.10
0.04
Phosphate Level 0
Nitrate Level 0.27
0.70
Dissolved Oxygen 9.8mg/L
Table 7 Metadata of site visits
Specific metadata (table 7) was chosen to collect and measure for the comparison of
USGS data. At each site, it was ideal to sample and measure downstream and travel upstream to
not interrupt and synthesize the river’s atmosphere. 100mL of water was collected near the river
bed using a syringe and transported into containers for zinc and iron testing. Testing for zinc
and iron verifies the oxidation of zinc in water that forms Fe2+. Collecting 100mL of water
gives enough samples to test for these reactions. An additional 10mL of water samples were
collected to test the turbidity using a LaMotte Smart2 Colorimeter to provide what sites have the
42
most suspended particles. The sites with the most suspended particles were visited multiple
times.
Using a shovel, top soil was collected nearby the riverbed. The soil was placed into a jar.
Top soil samples are essential to identify how zinc, iron, and glauconite react with precipitation
to distinguish an element variance between the two soils. The core soil sample was collected by
using a corerand placed into a jar. Core soil samples are significant to evaluate the elements
under the surface layer to deduce where the Fe2+ transpires. Two samples of both soils were
placed into separate jars and filled to the top of the jar. All jars were labeled with the site
number, date, and time.
After the samples were collected, the stream-flow, water temperature, and air temperature
were measured using an electronic instrument called the Xplorer GLX. By attaching the stream-
flow meter to the GLX, the meter was held perpendicular to the river motion to record stream-
flow. Using the stream-flow meter, the stream-flow and water temperature were measured. The
stream-flow was measured because there is a correlation with pH of the river water that portrays
higher stream-flow with lower pH and lower stream-flow with higher pH. With lower pH, the
river water tests to be more acidic which could potentially carry iron bacteria. Using an external
probe on the GLX, air temperature was able to be measured. Air and water temperatures were
measured to investigate microclimate changes from each site.
Surrounding observations were recorded to consider other influences on the Manasquan
River and correlate with other metadata. Pollen samples were collected at site 5 by using scotch
tape around two posts and left exposed for an hour then collected and brought back to the lab.
43
Pollen was collected to investigate the pollen counts and what concentrations of zinc and
iron were being contributed to the system. Other metadata such as water depth, dissolved
oxygen, phosphate, ammonia, and nitrate levels were tested to investigate the water quality,
however during the investigation it did not relate to the hypothesis and did not validate the
conceptual model the team developed.
Laboratory Investigation
Two samples, one from the water and one from the erosional layer, were placed in a
heating oven. The oven was set to 80 degrees Celsius and left for 48 hours in order to dry the two
samples. Once these samples were dried out, they were removed from the oven and turned into a
powdery substance by pestle and mortar method. This was necessary to do in order to prepare the
samples to be shipped out for elemental analysis. The samples were sent to Rutgers University
for that analysis. The goal of this analysis is to determine if the samples were glauconite, and
what the concentration of that glauconite was.
The team also had water samples that needed to be prepared to be shipped for IC-PMS
analysis. The goal of this analysis is to determine concentrations of iron, copper, and zinc within
the water samples. These concentrations and their associated spectrophotometer intensity signals
were compared against standardized samples to identify the availability of those elements for
reaction.
To prepare the samples for analysis, the team used a filtration apparatus with 4 micron
filtration paper to remove solid particulate matter. Water samples were poured into the filtration
apparatus attached to a vacuum underneath a fume hood to filter through. Once filtered, samples
were put into 15 ml plastic containers, and a drop of HCL (1M) was added to keep heavy metal
44
elements suspended. The containers were then sealed and labeled accordingly. After each sample
was filtered, concentrated HCL (4M) was used to acid wash the beakers to prevent
contamination.
To prove that a reaction occurs with the iron in the glauconite, an experiment was
designed to prove that a seasonal reaction was taking place. Since iron reacts with zinc and heat
to precipitate an iron Fe2+ product, the team decided to prove this reaction. In order to do this (x)
amount of iron sulfate and (x) amount of zinc sulfate powder was mixed together in a test tube.
The compound was then reacted with (sensible heat, UV, and IR).
Once the sample was determined to be glauconite (hopefully), the team designed the
following experimentation to see how the mineral behaves under certain circumstances that can
vary with season. Added 5 mL of 0.1 mol solution of FeSO4 (iron sulfate) test tube using pipette,
using a different clean pipette, 5 mL of 0.1 mol solution of Zinc Sulfate was added to the iron
sulfate in the test tube. With this mixture in the test tube, using a dropper, 3 drops of ammonium
hydroxide (NH2OH) were added until a green coloration was noticed. This was our 1 to 1 ratio.
Different concentrations of zinc and iron solutions in addition to distilled water were conducted.
All test tubes were transported to be in refrigeration and were covered so that no further reactions
occurred when the samples came in contact with air, and that no light reached the samples in
order to later test for spectrophotometer analysis concentration versus standard solution
concentrations. ORDER: ALWAYS iron, zinc, water, then 3 drops of ammonium.
A side experiment was performed. 5 grams of suspected glauconite sample placed in test
tube. 1.5 mL of DI to create aqueous solution. This glauconite aqueous solution was mixed with
45
2 mL of Zinc Sulfate and 10 drops of ammonium. The test tube was left in the refrigerator,
covered, for later observation.
To investigate the hypothesis of a hydro-geologic process involving glauconite, two soil
samples were tested to determine their elemental composition and whether or not they were
glauconite. Two samples were taken to Rutgers Wright-Rierman Laboratory for X-Ray
diffraction analysis. The pulverized samples were placed into a metal container at zero height
(figure 14).
Figure 14 Sample Holder Figure 15Machine
Graph 11Graphical Analysis
46
The samples were placed into the Philips Panalytical X-Ray diffraction machine and set
for a 13 minute scan (figure 15).The device was calibrated and set to scan from 10-90 degrees at
4 seconds per revolution. As the x-rays diffracted from the various elements in the powder
sample, High-Score match was used to create the graphs of the signal intensity. Once the scan
was completed the signal intensities were compared against reference signal intensities to
determine matches (graph 11). By referencing the peak intensities from the sample versus the
known intensities, elemental compositions were matched. This was performed by looking at the
100% intensity signal from the reference signal and comparing against the sample signals. When
matching the reference signals to the sample signals, the 100% reference signal would tell the
analyst where the expected peak for that element would occur with 100% accuracy, therefore if
this peak did not match up with the 100% peak, a match would not be accepted. If the 100%
peak did matchup, it would be accepted and further analyzed for the other peak patterns.
The team used three different water samples collected from sites one and seven with
varying coloration. One sample was taken from the side of the road at site one, from storm runoff
(A), one was taken from in the river at site one (B), and the third was from in the river at site
seven (C). Sample A had the greenest color, while sample C had the most yellow color. Sample
B had more of a clear coloring. The team decided to look at these samples through a microscope
at levels of 40, 100, and 400 times magnification. The team used wet mounts to observe the
water samples with a one square inch area to analyze. Three drops of a water sample were placed
onto a microscope slide and covered with a one square inch clear covering to complete the wet
mount. Once under the microscope, the team used the 40x magnification to oversee the entire
slide and analyze if there were any microorganisms and/or particulate matter in the water.
47
The team discovered what seemed to be a microorganism in the water, and by using the
microscopes 100 and 400 times magnification, a better image was observed. Using microscopic
pictures (figure 16) to compare to our microscopic images (figure 17), the team believes that
there are iron bacteria in the water. Using the 40x magnification, a panoramic sweep was
conducted across the area to count the number of iron bacteria found in the one square inch area.
After observing sample A, the team found there to be 2 iron bacteria present, sample B had 11
iron bacteria and sample C had 23 present. The team was able to determine that with more iron
bacteria in the water, the coloration was more yellow. With less iron bacteria, the water has a
green coloration.
Figure 16 (left) Drawing of Microscopic Iron Bacteria
Figure 17 (right) CR-ITeam Microscopic Water Sample
V. Results& Analysis
X-Ray diffraction analysis of sample 1 in the river bed showed a composition of
glauconite, a siderite-like phase, namely (Ca,Mg,Fe)CO3, a zinc-containing biotite phase, quartz
and muscovite (figure 18). The second sample contained glauconite and quartz and a possible
cristobalite phase that would have accounted for the other quartz like peaks (figure 19).
48
1 XRD Peak analysis Sample from in River
Glauconite
Figure 18 XRD in river sampe
XRD
Figure 19 XRD Peak analysis of erosional layer sample
49
These results show that there is an abundance of iron rich materials in the soil, namely
glauconite. This was the suspected mineral in the soil that was leading to iron reactions in the
river. Also, further RIR analysis of the samples revealed zinc containing biotite phase that
accounted for the missing peaks in the XRD analysis. This is important because the presence of
zinc and iron together are leading to the chemical reaction that the team hypothesized. The
experimentation provides enough preliminary evidence that the physical process and chemical
process are both occurring within the system.
Table 8Elements in the in river sample
Table 9 Elements in erosional layer sample
50
Based on the teams conceptual hypothesis there should be higher levels of iron bacteria in
the water with the most yellow color since there would be more oxidized iron. Quantitative
analysis was conducted by counting the amount of iron bacteria within the one square inch
samples, and comparing the amounts based on the color of the samples. Site one storm runoff
sample, the greenest, had 2 iron bacteria. Site one in the river, mostly clear, had eleven iron
bacteria, and Site seven in the river, the most yellow, had 23 iron bacteria. Pictures were taken
for documentation of what was in the samples.
Samples of water from the winter indicated that the concentrations of iron and zinc were
less than the detectable range through the ICP-MS experiment. The ICP-MS experiment
(inductively coupled plasma mass spectrometry) experiment detects concentrations of heavy
metals by ionizing the sample and then separating and quantifying those ions. The testable limits
for iron and zinc are as follows. For iron <.5 ppm is the testable limit and zinc has a testable limit
of <.1 ppm. The only samples that tested over these limits were samples (insert). The remainder
of the samples had negligible amounts of iron and zinc in them. This proves that during the
winter this process is not occurring. However, the sample that was tested during the precipitation
event did have a level of (insert) of iron and (insert) of zinc. This shows that it is a physical
process driven by atmospheric influences. In the summer when the level of iron in the water
samples was higher, it was due to the iron running off from glauconite erosion and other iron rich
minerals. In summer the range of iron necessary for this process to occur would be (insert) and in
the winter the process will not occur unless these ranges are breached.
Based on the team’s conceptual model, there should be higher levels of iron bacteria in
the water with the most yellow coloration. Since Fe3+ is what creates the yellow coloration, the
oxidation from the iron bacteria would be the process occurring. Quantitative analysis was
51
conducted by counting the amount of iron bacteria within the one square inch samples from two
different sites, and comparing the amounts based on the color of the samples. Site one storm
runoff sample, the greenest, had 2 iron bacteria. Site one in the river, mostly clear, had eleven
iron bacteria, and Site seven in the river, the most yellow, had 23 iron bacteria. Pictures were
taken for documentation of what was in the samples.
River Behavior
To determine the river’s response to precipitation events in the investigation of a natural
geo-hydrologic process, tabulated history of discharge/gage height were compared against
precipitation events. For the days that the team visited the Manasquan sites, the gage height at
Squankum was observed (table 10).
March 1st March 15th March 22nd April 6th
2.9 feet 2.9 feet 2.93 2.77
Table 10 River gage height during initial site visits
The river gage height fell as the course of investigation went on. Drier conditions
prevailed for most of the study. The highest gage height during the Month of March occurred
March 19th at 2pm. In response to drier conditions, the river gage height failed to reach
theaverage values expected during the month of March.
To investigate the river gage height response to precipitation and infiltration processes,
precipitation data was looked at. On March 18th precipitation began at 8pm and accumulated to
.25 inches by midnight, with another .27 inches observed from midnight through noon on March
52
19th. A tenth of an inch of rain fell before a response was noted in the gage height. The gage
height began rising from 2.88 feet until a crest of 4.77 feet at 2pm March 19th (eight hours after
precipitation ceased).
In this event, half an inch of rain caused a 2 foot rise in gage height. The response time
was within two hours of the onset of precipitation .On April 10, 2013 precipitation began at 9:30
pm, with the first rise in gage height recorded at 11:30 pm. This was a response time of two
hours after the onset of precipitation (see figure ###).
Graph 12 Gage height March 2013
53
Graph 13 Gage height from April 5th 2013 to April 12 2013
The river’s response to precipitation events indicate what layer of soil will be affected by
the water level. With the observed glauconitic layer about 3-4 feet off the riverbed, it would take
an event similar to the one on April 10th 2013 to interact with the glauconitic layer.
Figure 20 Note the interaction of the river with the glauconitic layer observed April 10th 2013
54
The discharge values also correlate to the amount of water infiltrating into the river. This
can be traced back to the calculated viscosity and infiltration values. During this same timeframe,
pH values were also investigated.
Location pH Prior pH During pH After
Site 7 In River 6 4.5 4
Site 1 Storm Runoff 6 4.0 4.5
Site 1 in River 6 3.5 5
Table 11pH values measured before, during, and after April 10th precipitation event
While pH values expectedly dropped during the precipitation event as a result of
increased stream- flow and began to rose once the river had slowed, a correlation cannot be
drawn between pH and infiltration process. More investigation needs to be done here to gather a
larger sample size of pH values and whether or not the pH values play a role in the amount of
glauconitic material being introduced into the river, or whether it affects oxidation state once in
the river.
Two gage stations from the USGS were chosen along the river. The first site was the
Squankumsite; the gage height at this site was useful because the gage height and behavior is
very similar to the river height at site 1 (it is also geographically close). The behaviors are
assumed to be similar between the two sites. The Allenwood site was chosen because the gage
height is higher than at the Squankum site and provides behaviors for deeper river water. The
expectation that the team would observe coloration during higher gage height was verified
during the site visit. The coloration of storm water runoff was a cloudy green material leeching
55
out of the ground water. The specific conductance of the river also rose during the precipitation
event (graph 14).
Graph 14 Specific conductance
Specific conductance refers to the amount of water that can be transferred through a
surface. Since the specific conductance of the river water rose, the infiltration process was aided.
The river was observed to be reaching the glauconitic layer along the side of the riverbed (see
photo). The river water was observed to be “stripping” the material away from the side of the
river. Therefore, discharge values were investigated to look for a correlation between the amount
of water running over the surface and the stripping effect (graph 15).
56
Graph 15 Discharge at Squankum site from April 9 to April 16
To determine a threshold for where the discharge will start to strip away the glauconitic
material from the riverbed itself, more testing is necessary for before, during, and after
precipitation events.
As the river crested and began to lower, the coloration of the river started to dissipate.
The site visit on Sunday April 14th 2013 revealed nearly clear water again at site 1 and site 7.
Infiltration from storm water runoff appeared to have nearly stopped altogether. Therefore, no
further (or not enough) glauconitic material was being introduced to the river anymore.
Water samples taken during the course of the validation study will show the
concentrations of key elements within the river system. The conceptual river behavior model as
it relates to the physical processes dictate that the iron levels in the river should be less during
57
dry conditions and during the winter months as the physical processes of leeching and runoff are
occurring less frequently.
VI. Conclusions & Discussions
With the acceptance of the conceptual box model, previous hypotheses were validated.
Through experimentation and testing of soil and water samples, there was a presence of iron and
zinc supporting thoughts on the reaction that occurs in the river with the presence of these
elements. This reaction is in fact occurring in the river however due to time restrictions no
threshold could be measured. Thinking about the physical aspect of the conceptual model, the
most important process is a precipitation event jumpstarting the interaction of the river water and
glauconitic materials in the riverbed. Without any precipitation, there would be no mechanism to
trigger the process and there would be no apparent coloration. The presence of glauconite in the
riverbed on a macro-scale level provides the elements needed for the chemical reaction
aforementioned. On a micro-scale level, precipitation is required in order to trigger the process
leading to coloration.
While the group acknowledged there are measureable thresholds, due to time restrictions
these were not determined. There was additional instrumentation lacking, which would have
aided in measuring soil moisture and temperature to get threshold values for necessary levels of
moisture in the winter in order for the process to begin. It can be noted that this process differs
seasonally and there are variables on the micro and macro scales that affect the severity and
intensity of the coloration. This is an overall naturally occurring process with the currently
present glauconitic materials and an increase in coloration due to precipitation events.
58
Recommendations
Additional testing can be done in the future to further validate the hypotheses regarding
the weathering of glauconite from low pH levels. Long-term pH readings can be done to also
validate the relation between low pH levels and higher stream flow values. Long-term
precipitation studies can be done to determine threshold values of soil moisture and the amount
of precipitation needed to release glauconite from the soil. These threshold values will determine
the beginning of this process with regards to seasonal variations.
Remediation
To remediate the pronunciation of the yellow colored water, the team recommends that
the storm pipes that lead into the river be galvanized with plastic. This tactic is known to prevent
the colonization of iron bacteria in river water. Since iron bacteria oxidize the iron and have a
role in the appearance of yellow colored water, the removal of them should deter some of the
coloration. The team also recommends tactics to precipitate iron from the water. Through the
team’s investigation, when iron and zinc react, this chemical reaction is precipitated by
ammonia. Ammonia could be used to precipitate iron out of the water. However, this is all a
natural and non-toxic process. Remediation tactics may be too costly and cause more problems
in the long run than if it were left alone.
59
VII. Acknowledgements
The team acknowledges support for project activities as related to data collection and
analysis. In particular, we thank Dr. Codella (School of Environmental and Life Sciences) for his
contributions to the microscopic investigation into iron bacteria detection. Dr. Emge (Wright-
Riedmann Lab, Rutgers University) performed the XRD analysis on the soil samples the team
collected. Norberto Mapoy (School of Environmental and Life Sciences) prepared specific molar
chemical solutions for the team’s lab investigations into chemical processes in the water. Dr.
William Eaton (School of Environmental and Life Sciences) set up the team’s iron and zinc
reaction experiment. Stan (School of Environmental and Life Sciences) provided logistical
services regarding the technical report and presentation and data access. Dr. Juyoung Ha (School
of Environmental and Life Sciences) provided the team with peer review literature and
experimental design as well as data access. The team would also like to thank Kean University
and specifically the School of Environmental and Life Sciences.
60
VIII. References
Basso, E., Capelli, C., Riccardi, M. and Cabella R. (2008): A particular temper: mineralogical and petrographic characterisation
of ceramic fabrics with glauconitic inclusions. Archeo Sciences 93-97
Browne, F., and J.-P. Do, 2009: Manasquan River Non-Point Source Identification Project.Fanning, D. S., et al. "Oxidation state
of iron in glauconite from oxidized and reduced zones ofsoil-geologic columns." Clays and Clay Minerals 37.1 (1989):
59-64.
D. R. Cullimore, AnnetteE. McCann, cited 1978, The Identification, Cultivation and Controle of Iron Bacteria in Ground Water,
[http://www.dbi.sk.ca/Books/PDFs/Water-Paper.PDF]
F.X. Browne Inc., cited 2013: Manasquan River Non-Point Source Identification
Project.[http://www.raritanbasin.org/Projects/manasquan/090420%20Manasquan%20Presentation%20fxb%20version.p
df]
Ha, J., and N. Yee, 2010: Characterization of Nanoparticles in Manasquan River Water.
Harder, H. (1980): Synthesis of Glauconite at surface temperatures. Clays and Clay Materials 28, 217-222
Health Department Kansas City, Missouri, cited 2013: Ozone Alert!
Days.[http://ww4.kcmo.org/health/factsheets/OzoneAlert.pdf]
Isabella O, Krcˇ J, Zeman M. Modulated surface textures for enhanced light trappingin thin-film silicon solar cells. Applied
Physics Letters [serial online]. September 6, 2010;97(10):101106. Available from: Academic Search Premier, Ipswich,
MA. Accessed April18, 2013.
Kirk Moore, cited 2013: Shore ranks 15th on list of worst air quality in
America.[http://www.app.com/article/20110921/NJNEWS/309210077/Shore-ranks-15th-listworst-air-quality-
America?nclick_check=1]
Lew, cited 2013: Natural and Anthropogenic Sources of Pollution.
[http://apollo.lsc.vsc.edu/classes/met130/notes/chapter18/smog_var_season.html]
61
Manasquan Water Supply System, cited 2013: 2013 Water Quality Report.
[http://www.njwsa.org/Mwssccr.pdf]
My Topo, cited 2013: USGS Topographic Maps.
[http://mapserver.mytopo.com/homepage/index.cfm?lat=40.155538&lon=74.1497164&scale=250000&zoom=50&type
=1&icon=0&searchscope=dom&CFID=18128527&CFTOKEN=86797360&scriptfile=http://mapserver.mytopo.com/h
omepage/index.cfm&latlontype=DMS]
New Jersey Department of Environmental Protection, cited 2013: Station Report.
[http://www.njaqinow.net/Default.ltr.aspx]
New Jersey’s Monmouth County, cited 2013: Office of Economic Development.
[http://www.visitmonmouth.com/page.aspx?ID=1538]
NASA, cited 2013: Aerosol Optical Thickness Intercomparison.
[http://gdata1.sci.gsfc.nasa.gov/daac]
Noel W Solomons, ManuelRuz, ZINC AND IRON INTERACTION:CONCEPTSAND PERSPECTIVES IN THE
DEVELOPING WORLD, Nutrition Research, Volume 17, Issue1, January 1997, Pages 177-185, ISSN 0271-5317,
10.1016/S0271-5317(96)00243-6.[http://www.sciencedirect.com/science/article/pii/S0271531796002436]
OzoneSolutions, cited 2013: Ozone Solubility.
[http://www.ozonesolutions.com/info/ozone-solubility]
Professional Wildlife Removal ,Cited 2004-2013,
[http://www.wildlife-removal.com/city/NJ-Monmouth-County.htm]
Rutgers Cooperative Extension; Greensand and Greensand Soils of New Jersey:A Review; J.C.F. Tedrow; 2002
S. Fernandez-Bastero, C. Gil-Lozano, M. J. I. Briones, andL. Gago-Duport, cited 2008, Kinetic and structuralconstraints during
glauconite dissolution: implications for mineral disposalof CO2
[http://minmag.geoscienceworld.org/content/72/1/27.short]
Skeen, J. (1925): Greensand as a source of potassiumfor Green Plants. American Journal of Botany 12, 607
62
Sperling, cited 2013: Health in Monmouth County, New Jersey.
[http://www.bestplaces.net/health/county/new_jersey/Monmouth]
Todd Kratzer, May 2012: Manasquan Watershed Source Water Protection Program,
[http://www.raritanbasin.org/Presentations/NJ%20WEA%202012%20Conference%20TK%20NJWSA.pdf]
Travis Madsen, Douglas O’Malley, Dena Mottola, April2003:Rivers in Danger: TheImpact ofDevelopment on Water Quality in
New Jersey, 44 pages.
United States Environmental Protection Agency, cited 2013: Interactive AirData Map.
[http://www.epa.gov/airdata/ad_maps.html]
US Census Bureau, cited 2013: State and County Quickfacts.
[http://quickfacts.census.gov/qfd/states/34000.html]
US Census Bureau, cited 2013: State and County Quickfacts.
[http://quickfacts.census.gov/qfd/states/34/34025.html]
USGS, cited 2013: The National Map Viewer.
[http://viewer.nationalmap.gov/viewer/]
Velde, C., Meunier, A. (1980): Weathering of Glauconites: Reversal of the Glauconitization Process in a Soil Profile in Western
France. Clay Minerals 16, 231-245
Yee, N., and P. Strom, 2010: UV/Visible SpectroscopicAnalysis of Manasquan River Water.

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Preliminary Investigation of Yellow Water in the Manasquan River

  • 1. Preliminary Investigation of Yellow Water in the Manasquan River Prepared on behalf of Kean University and the Manasquan Water Treatment Facility Submitted May 3rd, 2013 Project Director: Ryan J. Grantuskas CR-ITEAM: Jennifer Closson, Courtney Deckenbach, Anthony Ingato, Michael Rizzo, Renato Rodrigues
  • 2. 2 Table of Contents Executive Summary .......................................................................................................................4 Purpose & Intent............................................................................................................................5 Introduction....................................................................................................................................5 Literature Review .........................................................................................................................5 Statement of Work........................................................................................................................7 Study Area ....................................................................................................................................7 Research Design.........................................................................................................................10 Environmental Setting.................................................................................................................13 Geologic History........................................................................................................................13 Soil Quality ....................................................................................................................................14 Water Quality.............................................................................................................................24 Flora ...........................................................................................................................................26 Fauna & Microbial .....................................................................................................................29 Anthropogenic................................................................................................................................30 Air Quality .....................................................................................................................................32 Climatology& Meteorology...........................................................................................................36 Methodology .................................................................................................................................40 Field Work..................................................................................................................................40 Laboratory Investigation ............................................................................................................43
  • 3. 3 Results& Analysis .......................................................................................................................47 Results ........................................................................................................................................47 River Behavior ...........................................................................................................................51 Conclusions & Discussions..........................................................................................................57 Recommendations ........................................................................................................................58 Remediation..................................................................................................................................58 Acknowledgements ......................................................................................................................59 References.....................................................................................................................................60
  • 4. 4 I. Executive Summary Occurrences of yellow water in the Manasquan River watershed were investigated. The discoloration of the river is a seasonal phenomenon in which the coloration becomes more pronounced in the summer. Nine sampling sites along the Manasquan River and its tributaries were focused on for analytical and geographical investigation. This study focused on potential biogeochemical processes and pathways to conceptualize a model to describe the natural system causing the intense development of color in the river water. The team developed a conceptual model that describes the behavior of the watershed and any influences on the system. These processes were examined through chemical analysis, remote sensing data, and climatological information. Chemical lab work was performed to test reactions that would produce a precipitate of Fe2+. The team identified geological conditions as the major source of the discoloration. Glauconitic river bed sediments have been identified through chemical and physical tests and observations. Further investigation found atmospheric phenomena plays a direct role in the response of the hydrosphere and lithosphere that cause the yellow water to become an issue. Recommendations are given based on project findings with regard to how and where the glauconitic materials are entering the system, and how they behave within. Remediation tactics involving precipitating the Fe2+ and Fe3+ from the river can be employed to discontinue the coloration. However, this is a natural process and glauconitic soils in the river bed cannot be remediated.
  • 5. 5 II. Purpose & Intent The CR-ITEAM was “hired” by the Kean University research investigative unit on behalf of the Manasquan Water Treatment Plant to determine the cause and source of the yellow water. Prior research has identified that there are suspended particulates in the water that do not dissolve and that the coloration of the river becomes more pronounced during the summer season. The study area is the Manasquan River located in Monmouth County, NJ. The team’s current study took place from March 1st through May 10th. The dates allowed a sampling of early spring conditions. To investigate the causes of the coloration with regard to seasonal variations, the team decided to compare winter samples that were collected during the early spring season. of our investigation to summer samples from the USGS that were previously investigated. The team decided upon developing a conceptual model to portray the processes and influences on the Manasquan River watershed. Two different hypotheses relating to biogeochemical impacts were developed and tested throughout the course of the study. The hypotheses were developed based III. Introduction Literature Review In the Manasquan River, it has been noted by previous studies that there is a coloration issue within its system (Yee, 2011). According to the study, there is a seasonal change in coloration for the river because as temperatures get warmer, the coloration gets is seen to be yellow through insolation (Yee, 2011). The main distinguishing features of glauconitic inclusions are their rounded shape, dark color and peculiar chemical composition. During the firing – as also evidenced by a few preliminary experimental tests on glauconitic sediments – the
  • 6. 6 pellets change in color (from green to red or black in thin section) because of the oxidation of divalent iron and their texture becomes more homogeneous, up to the partial or complete verification at moderately high temperatures (Basso, Capelli, Capella, Riccardi, 2008). Greensand (also known as Glauconite) is used as a fertilizer for plantation in the state of New Jersey and historically it has been deposited into the state millions of years ago. The greensand deposits of central and southern New Jersey were locally quarried by 18th century farmers for use as a fertilizer in order to keep their land fertile for use year after year (Introduction to the mineral Glauconite). It was also recently found that these greensand soils and fertilizers were spread out throughout the Manasquan River system (Rutgers University, 2011). In a study done by the Manasquan Water Supply System and USGS, it was found that there is an increase trend in turbidity and even some sections of the Manasquan River has been unstable and erodible (USGS, 2011) . The Manasquan Water Supply also found that there is twenty percent of iron inside the glauconite composition. Fe3+ is highly soluble whenever the acidity gets lower and since the acidity along the Manasquan is ranging from 3.5-5 (as shown in figure 2), there is highly soluble Fe3+ particles surrounding the river. When iron (Fe) is combined with other chemicals (like phosphorous and sulfur), a different coloration will occur. Glauconite might also experience a different type of the mineral if there are any physical or chemical changes to it. Other factors, such as sedimentation rate, water temperature, water depth and parent material can have an influence on the specific nature (type) of glauconite that forms (Hower, 1961). Temperature had only minor influence on the synthesis of glauconite which formed at both 3C and 20C. However, higher temperatures generally led to better and more rapid crystallization (Harder, 1980) . This proves that during the summer months, glauconite is present
  • 7. 7 more and leads to the yellow-coloration in the summer. The USGS conducted an investigation over the summer in 2011 and their data proved that there was a distinct coloration noticed. Statement of Work To investigate the coloration of the water inside the Manasquan watershed, the chemical and physical processes were compared for seasonal variation. Field studies were utilized to observe physical properties in the environment. Spatial and temporal behaviors were assessed by examining soil, air and water samples to identify the microclimate and its micro-scale features. Following the field visits, the team used the samples from the sites to perform lab analyses to determine changes in chemical and physical processes. The previous USGS research identified the presence of iron and zinc in the river water. The team’s chemical analysis and experiments identified that precipitation is the trigger of both chemical interactions (including Zn and Fe) and physical processes. The conceptual model that was developed by the team for the Manasquan River deals with the biological, geological and chemical processes that are involved within the system. All these observed processes are consistent with the team’s conceptual model of the Manasquan River system. Study Area The Manasquan River is a 42.65-kilometer long waterway in central New Jersey (USGS 2013). Located predominately in Monmouth County, beginning in Freehold, it extends to the Atlantic Ocean and into Ocean County. The river is approximately 144.8 m across at its widest part before it lets out into the Manasquan inlet. The Manasquan River Watershed covers a total area of 82 square miles including 13 municipalities (See Figure #) (Manasquan Watershed Management Group 2000).
  • 8. 8 The land use in the watershed varies as shown in Table 1 (Kratzer 2012). Land Type Percentage Water/Wetlands 38 % Urban 31% Forest 19% Ag 10% Barren 2% Figure 1 The Manasquan River Watershed covers a total area of 82 square miles including 13 municipalities Table 1 Land usage
  • 9. 9 Monmouth County began to see changes in terms of land use occurring in the 1980’s within the watershed. These changes were significant alterations from agricultural farms and wetlands to urbanized development. The increasing development runs the risk of soil contamination and shocks to the system with these changes (Kratzer 2012). Monmouth County has a 2012 population estimate of 629,384 people, (US Census). The watershed supplies drinking water to over 250,000 residents. Drinking water is treated by the Manasquan Water Supply System to send to public or private water distributors. A $75 million dollar reservoir with a 4.7 billion gallon storage capacity was constructed. The reservoir is supplied by the Manasquan River says Madsen et al. (2003) in the event that the quality or quantity of water from the river was not up to par. The reservoir water can be used alone or in conjunction with river water. There are nine plotted sites along the river chosen by the Manasquan River Water Supply System (table 2). There are two sites on the main stem of the river and the remaining seven are located on tributaries. Site # Description Coordinates 1 Manasquan River @ Georgia Road 40.211814, -74.295523 2 Manasquan River @ Wyckoff Mills 40.203149, -74.261312 3 Yellow Brook near Farmingdale 40.202709, -74.202387 4 Manasquan River @ 40.185028, -74.18411
  • 10. 10 Southard Ave. near Farmingdale 5 Marsh Bog Brook @ Squankum 40.168282, -74.15853 6 Mingamahone Brook @ Squankum 40.16616, -74.149287 7 Debois Creek @ Adelphia 40.220562, -74.261422 8 Mill Run near Squankum N/A 9 Manasquan River @ Allenwood (WSA Plant) 40.084868, -74.065069 ResearchDesign The study is designed to target answers to the question of the yellow water. This will determine preliminary responses and reasons that explain the state of the river. It is expected that there will be a connection with many characteristics and properties of the natural environment. Therefore, based on environmental features within the watershed, a hypothesis was developed based on the chemical and physical attributes of the area. The first hypothesis suggests that chemical reactions occur to interact with warm water temperatures, zinc, and iron. This would describe the stronger state of the summer condition. Part of the chemical-based hypothesis is relative to the variation of water pH as it determines the solubility of glauconitic rock.Zinc-based fertilizers also undergo a natural weathering process that exposes zinc particles to the Table 2 Sites along Manasquan River
  • 11. 11 environment. In combination with Fe(III) particles and heat, a chemical reaction occurs that reducesFe(III) to Fe(II), giving the yellow-green coloration. High temperatures and higher stream flows in the summer increases the dissolution rate of the glauconite resulting in a higher pH and suspended particulates in water. The second focus is on physical interactions such as weathering, runoff of fertilizers, infiltration, and urban/anthropogenic development within the river system. It is hypothesized that these components are occurring within the natural environment to contribute to the condition of the river. Pre-existing evidence states that glauconitic rock outlines the riverbed in the upper watershed. With the physical property of glauconite as soft and friable, exposure to physical disruptions of soil and water will enhance erosion and dissolution of the material. Specifically, these disruptions are: (1) erosion of exposed outcroppings of glauconite, (2) runoff of glauconitic greensand fertilizers, and (3) relocation of farms and disruption of soil due to population-based development. Field observation, lab analysis, and comparative data analysis were used to identify parameters that cause river coloration. Field locations are selected to compare the variability between conditions of urban vs. rural, tributary vs. river, and upstream vs. downstream. River water was sampled to identify the solution composition in correlation with the conceptual models. The water samples are also compared to summer water samples that were previously sampled. Soil samples were gathered to test for characteristics of glauconite and zinc. pH sampling occurs on site to provide in-situ data of the river relative to stream flow and turbidity. Experimentation to replicate situations that are hypothesized to contribute to the coloration will be evidence to verify the occurrence. Concentrations will be altered in this experimentation to simulate the Manasquan River environment.
  • 12. 12 This design is created to give suggestions and recommendations to the solution of water coloration. It is developed to assess various inputs and outputs by analyzing soil and water conditions with its variations. These inputs and outputs are defined as processes that contribute to the yellow state of the water. As these processes and sources become more prevalent, it will justify preliminary findings that will work towards a comprehensive solution that would eliminate the coloration completely. This design has certain limitations such as time. The client has requested a preliminary finding to be established from March to May, which limits time availability for sampling and lab analysis. Another limitation focuses on the sampling season. In order to make connections to seasonal variation, a full year would be required to assess this aspect. To compromise, USGS summer sampling data is used to make correlations to the early spring/late winter samples. Ultimately this design targets the purpose of the study and creates a conceptual model that infers different processes that make this phenomenon occur. The conceptual model will explain how features of the environment are interacting based on their current state. Observing the environment during a dry spell versus a precipitation event will provide different modeling that suggests any activation processes. This will also define a stable environment versus an active environment.
  • 13. 13 III. Environmental Setting Geologic History The glauconitic soil layer of Manasquan-Freehold was formed during the Cenozoic era from glacial and oceanic rises that pushed inland until elevation increased enough that land collision could not stop (Tedrow 2002). Evidence of diagenesis can be found in the sandy structures of the lands near the coastal plain study area. As deposited sediment from the ocean began to undergo the transformation to rock, glauconite was formed in the reduction zones. The glauconitic process began when phyllosilicates underwent bacterial digestion. This process occurs when the phyllosilicates pass through the guts of organisms. As octahedral cations are lost, the charge deficiency was balanced by the introduction of highly mobile marine cationssuch as (magnesium, potassium and calcium). Since these elements are highly mobile, the structure did not begin to fully form until ferrous iron began to bind to the digested phyllosilicates. As the water levels receded, the material hit a drainage divide and isolated elevated hills that locked the subsoil minerals into place. As changes have occurred over time in the watershed, the parent material in the soil has been activated by changes in the water table. The importance of understanding the history of the glauconite comes through prediction of its behaviors. As glauconite ages, it continues to become more potassium rich, eventually breaking down in structure. This breakdown over time could allow for an increased introduction of glauconitic material to the water.
  • 14. 14 Soil Quality Glauconitic materials are being introduced to the watershed through physical processes such as erosion, leeching and interaction with the river. This is the conceptual model of how this system works.System processes and behaviors were observed by the team as they related to what is in the system and how it got there, and its activation behaviors such as precipitation and interaction with the glauconitic layer in the river. The team took observations and measurements necessary to produce a conceptual model of the processes and systems relevant to the introduction of glauconitic materials into the river. To conceptualize the behaviors occurring in the river, the soil structure and composition is important to identify. Soil composition in the study area is mainly sand, silt and clay (figure 2). Figure 2 Soil Composition of New Jersey
  • 15. 15 There are 12 classifications of soil types in Monmouth County (USDA 1989). Varying soil types behave differently with the watershed. Specifically within Monmouth County, glauconite erodes easily at lower pH and is a brittle mineral. Varying elemental composition and pH values played an important role in identifying soil elements contributing to biogeochemical interactions. The most prominent type of soil in Monmouth County is the Freehold type series. This series comprises 22 percent of the soil type in Monmouth County. The Freehold series consists of well drained soils. Precipitation will infiltrate these soils and leech into the ground water table. Freehold series soil consists of 1 to 10 percent glauconite and less than 5 percent quartz. Relevant to the hypotheses of this study, glauconitic behaviors were investigated to how the elements contained within are activated. Since glauconitic soils are very erodible and soluble under lower pH, precipitation will cause the activation of leeching of the glauconitic soils. Glauconite consists of iron in a reduced and oxidized state. 20 percent of the composition of glauconite is iron (3 percent FeO and 17 percent Fe203). Glauconitic soils retain more moisture than the surrounding feldspar quartz soils in the area. Glauconitic soils retain 14 percent moisture at tension of 15atm and feldspar quartz retains only 8 percent (Tedrow 2002). The moisture retaining qualities of glauconitic soil make it easier for other elements to react with iron in the glauconitic soils. Glauconitic soils in New Jersey have an increased concentration of oxidized iron (Fanning et al.).In the reduced state the glauconite appears green under polarized light but appears yellow in the oxidized state. The slope of this soil layer underneath the surface ranges from 0 to 25 percent. A cross section of this soil type performed near Wermock Road in West Freehold revealed topsoil surface sand that was strongly acidic (Tedrow 2002). Glauconite became common at a depth of 12 to 18 inches, and was the primary mineral observed in soil at a
  • 16. 16 depth of 25 to 70 inches embedded in a sandy layer that is well drained. The entire layer was observed at pH values of less than 3, ranging from very to extremely acidic. At a depth of 40 inches a layer consisting of iron (1 inch thick) was observed in the cross section (Tedrow 2002). As changes in land use and water table depth have occurred, elements in the Freehold soil type layer have become introduced to runoff water. Seasonal variations in the water table depth pose a problem for agriculture. The water table depth rises from 28 to 25 feet as shown in graph 1. This rise in water table depth during the summer months could indicate a bottom up process may be occurring. A bottom up process would indicate that the glauconite is being introduced from underneath the surface and rising up. This process neglects the effect of precipitation which does not have relevance to this study. A bottom up process was not fully investigated during this study, as a top down process seemed to be more prominent (especially as occurring with precipitation events and subsequent leeching out of subsurface). Graph1Water table depth 2012-2013 as compared against average
  • 17. 17 This causes the rooting structures of crop life to be non-adequately aerated. Also, the rise in water table depth with regard to season plays a role in percolation and dissemination of water runoff. The crop vegetation during the summer and harvest seasons aid in the extraction of ground water. This added ground water closer to the surface allows precipitation to travel through less soil before reaching the water depth level. The introduction of runoff to the groundwater will allow mixing of chemical elements. As water level rises, unconsolidated elements contained within the soil will rise closer to the surface. The increased availability of these suspended particles in the water table being nearer the surface introduces higher concentrations of these elements during the summer months. In addition to seasonal variations, an investigation of the water table depth back to 1991 when USGS started tracking the water table depth near the Fort Dix Military Reserve shows a rise of the water table towards the surface. In 1991 the water table depth was 28 feet, and currently stands at near 25 feet below the surface. The glauconitic soil layer runs from 0 to 25 feet below the surface to just above the water table (Tedrow 2002). The water table depth has had more extreme values closer to the surface then further down. Concurrent with the rise in the water table, precipitation can penetrate the soil layer and interact with the glauconitic layer underneath easier during the summer. Sources for the water table rising over the past few decades include erosion of the soil layers, urbanization and agricultural production. Erosion of the Freehold type soil layer has occurred through the past few decades. Urban area comprises 40 percent of this soil type in Monmouth County currently. Urbanization has removed the topsoil layer, thus exposing the glauconite contained 1 foot below the surface layer. Through urbanization within the watershed, the soil structure has been compromised. As the soil structure was compromised, the glauconitic
  • 18. 18 layer became exposed to weathering. Agricultural production, which makes up 30 percent of the Freehold soil layer, removes the top soil layer seasonally for crop production (Tedrow 2002). During the summer months the increased vegetation due to agricultural production and natural seasonal changes, affects the amount of water pulled from the soils. As the ground water table begins to rise through the summer months, the vegetation will pull some of the ground water up through its rooting system. This introduces new chemicals and behaviors into the system. Ammonia hydroxide, a common by product of vegetation, increases in concentration during the summer months as a result of the agricultural land use. Thus, the behaviors of the soil layer and water table through space and time introduce iron, zinc and ammonia hydroxide into the system. Management of soil is an ongoing issue in Monmouth County as it pertains to soil quality. Glauconite bearing soils are commonly sought for the use of agricultural production. The potassium in the soil is considered to be the main reason that crops thrive in this soil type. However, the high acidity of the surface soil makes crop management a challenge. To solve this, remediation efforts have been undertaken. Some of the soil management techniques suggested by the USGS include removing the surface soil through moderate tilling and adding greensand (glauconitic deposits). Since compaction of the surface soil layer is common in this soil type, efforts were taken to keep the soil structure intact to maintain its runoff characteristics. Excessive tilling of the soils breaks down the soil structure, thus reducing its infiltration. Plowing under the surface layer helps to keep the soil structure intact by reducing compaction and introducing organic matter into the surface layer. These remediation efforts have introduced increased concentrations of heavy metal elements in glauconitic bearing soils near the surface. Investigation of activation of glauconitic materials into the riverbed was investigated. Weathering of glauconite plays a role in the introduction of glauconite to the river water (figures
  • 19. 19 3 and 4) (Velde 1980). In the topmost layer of glauconitic materials, there was little Fe, but in the mid portions the material was iron rich. The process identified that as weathering occurred, the glauconite became gradually destabilized, opposite its formation process (Velde 1980). As glauconite becomes destabilized, the iron and potassium are the primary minerals removed from the material. This destabilization will introduce more iron and potassium into the river since the glauconitic layer was observed in the riverbed. Dissolution of glauconitic materials occurs faster for glauconitic materials under acidic conditions then neutral or alkaline conditions (Bastero 2008). A geo-hydro process was investigated to determine the behaviors of the glauconite in the Manasquan River. The concave slope of the riverbed indicates erosion occurring over time. The level of glauconitic material will also indicate what level the river will need to rise to in order to interact with that layer. Glauconite was observed directly in the riverbed, lending to the theory that interaction between the river water and glauconite were occurring. Figure 3 Close-up image of glauconite mineral Figure 4 Suspected glauconite along riverbed
  • 20. 20 Figure 5(left) The concavity of the riverbed in regards to location of glauconitic layer Figure 6(right) The green murky appearance of the storm water run-off; this was traced to the river itself Indirect introduction of glauconite can also occur through leeching of ground water. This process will occur during precipitation events as the precipitation infiltrates through the subsurface and interacts with glauconitic material 12-18 inches below the surface. Soil compaction and reduced plant coverage account for reduced infiltration rates; this is called the low condition. During the low condition, the necessary infiltration rate for glauconitic materials to be introduced may not be present. It is not known exactly when low condition and high condition exist for this system; however, since low condition is during soil compaction and reduced plant coverage, it can be assumed that low condition is generally associated with winter season. During the summer, when vegetation and flora are abundant, and soil temperatures rise, this could be assumed to be the high condition. The infiltration rates during winter may not be enough for precipitation to reach the glauconitic layer (figure 5).
  • 21. 21 Physical characteristics and activation features can be investigated using the WSS (Web Soil Survey). Drainage characteristics change during the summer and winter. During the warm season when the soils began to loosen and infiltration values rise, most of the soils near the river are moderately well drained or better (figure 7). Also during the summer months when precipitation averages are higher, the liquid limit holding capacity of the soils in the watershed become increasingly important. The liquid limit of the soils will indicate how much water the soils can hold before they begin to pond or leech back towards the surface. This physical process can aid in the transport of glauconitic materials to the surface during precipitation events. In figure 8, note that most of the soils near the river have poor liquid limit and cannot hold much water. Graph 2 Infiltration rate as a function of low condition versus high condition
  • 22. 22 Figure 8 Liquid limit capacity revealing most of area has low liquid capacity Figure 7Soil drainage behaviors where bluer shades are excessively well drained and red are poorly drained The hydraulic conductivity of water changes as temperature changes. When temperature increases, viscosity decreases and hydraulic conductivity is increased. This relationship is a function of temperature, where if temperature of soil is known, conductivity can be calculated. Graph 3 shows the relationship between viscosity and temperature. Graph 3Viscosity versus temperature C
  • 23. 23 The viscosity of water changes as much as 2 percent per degree Celsius. This leads to a 40 percent change in infiltration between the summer and winter months (Braga 2005). This change in infiltration processes can be inferred to be related to the seasonal change in the coloration of the river. The soil temperature of a nearby site was examined (Cinnaminson, Burlington County). This was the closest site with archived data from the NCDC, and it closely represents the characteristics of the Monmouth county sites. As is seen in figure 7, the soil types are the composition, therefore making it practical and meaningful to analyze soil data from the Cinnaminson site. Graph4 shows three years average data at the Cinnaminson site for meteorological winter soil temperatures. Most of the data fell within about 34 to 37 degrees, directly elating to higher viscosity values. These temperatures may be low enough that the viscosity values of the water are high enough that glauconitic material is not introduced to the system. Graph4 3 year average soil temperatures in degrees Fahrenheit for meteorological winter at Cinnaminson site
  • 24. 24 Atmospheric changes with respect to season, especially precipitation events and temperature, tend to activate and introduce more glauconitic materials into the system. Greater convective activity during the summer months yields greater amounts of precipitation than events during the winter season. These high precipitation summer events have an easier time infiltrating the less dense soils in the summer. Glauconite soils that are 12-18 inches below the surface are introduced to the system when precipitation infiltrates to the groundwater table. Hydrologic groupings are assigned for their response to precipitation events. Groups A and B are well drained and moderately well drained, meaning infiltration values are very high. Approximately 76.1 percent of the AOI being investigated by the WSS is classified as either well drained or moderately well drained (figure 9). Figure 9 Image of hydrologic classifications based on response to precipitation events, yellow and dark blue represent very low infiltration Water Quality The watershed covers 13 municipalities and a population just over 500 thousand residents. The river water is treated at the Manasquan Water Supply System to redistribute to these residents as drinking water. Water quality information from testing done by the MWSS is as follows (table 3). There is evidence of iron and zinc concentrations that have been detected in
  • 25. 25 the water being treated. These concentrations interact with glauconite materials present in river water, which leads to the yellow coloration. Table 3MWSS water quality report
  • 26. 26 As per the relationship between air and water quality, pollutants from smokestacks and car/truck exhaust fall back to the ground as precipitation and these contaminates will eventually end up in rivers and streams. Rainfall and snowmelt will travel over a variety of landscapes picking up pollutants including soils, fertilizers, and pesticides from farmlands and residential lawns. Pesticide application on agricultural land, sewage discharge from residential developments, and increased runoff are additional factors influencing water pollution. Fragments of tires, salt, shreds of brake lining and oil contaminate roads that get picked up by rainfall and melted snow (Madsen et al. 2003). These contaminants have the chance of ending up in the river waters through these precipitation/runoff transport mechanisms. Flora In the Manasquan River, there are soil types that influence the river directly. The main ones in particular are listed in the table below: Top ten soil types w/ characteristics 10. Kresson Poorly drainable and features glauconitic soils. Also features a PH reading between 3.6 and 5.5. 9. Pemberton Features a PH reading between 3.6 and 5.0 and has marine sediments that feature Glauconitic material. It also features iron and is used with drainage and irrigation. 8. Collington Well drained soil that also featured the Glauconite mineral. It is a well-drained soil and also has some parts of Quartz inside the soil, which was one of the
  • 27. 27 minerals found. Glauconite was averaged out from 10-20%. Also it features a PH Reading from 3.6-5.5. 7. Humaquepts Organic-rich wetland soils that are arsenic in nature and Glauconitic soils have contributed to the increase in arsenic inside this wetland soil (Barringer, Szarbo, Holmes, 1997). 6. Evesboro Sand Features Quartz material and excessive drainage. Also, features a PH Reading from 4.6-5.5. 5. Adelphia Features a PH around 3.6-5.5 and also deals with Glauconitic minerals and deposits. 4.Colts Neck Features 2-10% Glauconite (from marine sediments) and a PH reading of 4.5-6.5. 3.Marlton Features a PH of 4.5-5.5 and also has Glauconitic soil (about 20% in volume). Itisalsowelldrainable. 2. Manahawkin Muck This features a water PH of 4.5-5.0 and is very poorly drained. It is also part of the wetland feature. 1.Colemantown This features 20% of Glauconite material and is also poorly drained. It is also featured to be low or medium surface runoff index Table 4Main top 10 soil types that influence the river directly
  • 28. 28 The interesting feature about these soil types features the Glauconitic soils that have influenced the system. Some of these soil types also have a poorly or somewhat drained soil and that allows for the Glauconite materials to seep up to the surface. With low PH’s as well, the ground is susceptible to the chemical reactions involved with the Glauconite and even the quartz material present in some of the sandy soils. Allaire State Park is one of the many parts to the ecosystem that is influencing the river due to its proximity to it. During the fall and spring months, there is a removal process, which can include things like pollen and even leaves as it falls to the ground from groundwater, runoff and seasonal variation. The groundwater and runoff can leech all the litter into the river and have an impact inside the Manasquan system. Fertilizers for growing crops have been on the increase and with any sort of rainwater or runoff, it would allow for the minerals in the soil to leach up and go into the system. Soils that contain Fe3+ have a very low solubility in water so that any dissolved particles that are in the water won’t be easily dissolved. As a result of that, the calculated turbidity values will be higher since the more particles there are that can’t be dissolved; the more sunlight will have an impact on the system. Glauconite (Greensand fertilizer) is used in the system as a source of potassium. Potassium is the changes between iron redox states and drive numerous reactions involving electron transfer that are important for plants. However, there is great variation in the availability of iron in the soil, and starvation or excess can cause severe nutritional disorders, which significantly affect the physiology of the plant. In response, signals are produced that modulate the expression of genes involved in either the transport or storage of iron. Recent progress has
  • 29. 29 been made in delineating the cellular and molecular aspects of these processes, highlighting new mechanisms in plant adaptive responses (Briat and Lobreaux, 1997). Greensand (also known as Glauconite) is used as a fertilizer for plantation in the state of New Jersey and historically it has been deposited into the state millions of years ago. The greensand deposits of central and southern New Jersey were locally quarried by 18th century farmers for use as a fertilizer in order to keep their land fertile for use year after year (Introduction to the mineral Glauconite). Fauna & Microbial Monmouth County has a large variety of animal life, from snakes to raccoons to birds. Some significant animals include the opossum, armadillo, and groundhogs, as these animals are known for their borrowing. As these animals burrow through the ground, this can loosen the soil, which allows vegetation to grow longer stronger roots. Also the loosening of the soil can make the ground water infiltrate through easier and carry out more sediment to the river (Cited 2004- 2013). Iron bacteria are found within the Manasquan River. While they pose no health risk, the effect is seen on the system through the discoloration or staining appearance of the water, especially during the summer months. The iron bacteria will not oxidize all the Fe2+ in the river, however a greater amount of iron bacteria will oxidize a greater amount of Fe2+. The degree of bacteria in the water will play a role in the coloration of the water as dependent on pH of water and temperature of water. These iron bacteria can be found to colonize near pipes and effect the rate of flow in the water. The slimy growth of the bacteria can interfere with the development of animals and fish (Cullimore 1978). Microscopicimages of iron bacteria collected from water
  • 30. 30 samples were compared to reference images of known iron reducing bacteria. After analyzing three different water samples (two from site #1 and one from site #7), the team was able to count the amount of iron bacteria from 3 drops of water on a 1 square inch microscope slide. The team discovered that the more green the water, the less amounts of iron bacteria there are present, and the more yellow the water the more iron bacteria there is present. This would confirm the team’s conceptual model that iron bacteria oxidizes Fe2+ with a green color to Fe3+, which has a yellow color. Anthropogenic The highest point in Monmouth County is Crawford Hill at 119 m above sea level located in Holmdel, NJ (Monmouth County 2013). Varying elevations between this and sea level are present throughout the county and a general topographic overview of the area can be seen in figure 10. Figure 10 General topographic overview of Manasquan River area
  • 31. 31 The river generally flows from Northwest to southeast and finally into the Manasquan Inlet. Stretching the river, there has been increased expansion. The development of residential communities, industries, and commercial business began in the upper watershed in the 1980’s. Half of the land in the upper watershed was used for growing crops and grazing animals in 1995 (Madsen et al. 2003). Many large-scale housing developments in the area are transforming the county from agricultural to suburban. Continued development in this area threatens water quality (Madsen et al. 2003). This area of New Jersey is one of the most quickly growing in the state. 34,000 residents moved into the area in the 1990’s, urban area in the watershed grew by 17.6%, over 12,000 new housing units were built in the 1990’s, and approximately 6.1% of the total land area in the watershed was developed between 1986 and 1995. Replacing just 5% of land in the watershed with paved surfaces results in a decline in water quality. Increasing development brings amplified discharge from sewage treatment plants and higher levels of runoff from roads, rooftops, and other man-made surfaces (Madsen et al. 2003). This runoff caused by development picks up a variety of pollutants, which end up in rivers and streams over time. This influx of development leads to greater areas of impervious surfaces and less water seeping into the ground. Less seeping leads to greater runoff values and decreasing water habitat quality. Wetlands or forests can also be lost in the event of poor development planning. These areas act as important habitats for wildlife and protectors of water quality.
  • 32. 32 Air Quality Monmouth University readily supplies air quality data through the NJ Department of Environmental Protection. As seen in graph 5 below, data for the later half of March 2013 is supplied. This graph readily shows that the air quality as monitored at Monmouth University during the time of study was recorded average. In conjunction with annual reports from Spirling (2013) in past years, Monmouth County ranks as a typically unhealthy county in regards to overall air quality, during the time of study however, average values for general air quality were reported. Increased sunlight and heating will bring in higher values of overall air quality, thus resulting in expected higher values (graph 6) in the summer months (Lew 2013). Graph 5Air quality of March 2013monitored from Monmouth University
  • 33. 33 Ozone is not directly put into the atmosphere. It forms on windless days when exhaust from gasoline fumes mixes with sun and heat. Ozone alert days are when ozone levels rise to unhealthy levels as set by the Environmental Protection Agency. Classification for alerts range green-yellow-orange-red. Orange and red denominations indicate an Ozone Alert Day (Missouri 2013). The air quality in Monmouth County is ranked 11 out of 100 on a scale based on ozone alert days and the number of pollutants in the air (Spirling 2013). Generally, the lower the number is for an area, the worse the air quality (Spirling 2013). Ozone is extremely soluble in water based on a couple factors. Colder temperatures of water due to seasonal variations increase the solubility of ozone. Generally speaking the troposphere is denser in the winter, leading to a higher pressurized “gas” pushing down on the water, increasing the solubility. Expected dissolved ozone counts in water are expected to be high in the winter, but because ozone is very reactive with itself and contaminants in the water, high values often are not recorded. Graph 6 Air quality of August 2012 monitored from Monmouth University
  • 34. 34 Two stations monitoring air quality are located in Monmouth County (figure 11),one located in Freehold is inactive. Freehold’s measuring station has data sets to 2011. The station measured Carbon Monoxide for one hour using non-dispersive infrared instrumentation. Ozone is the only active measured station located in West Long Branch at Monmouth University. Ozone is measured on a neighborhood scale of 500m to 4km. Sample duration occurs for one hour using ultra violet analysis and it records the highest concentration of ozone to the New Jersey Environmental Protection Agency. For other parameters like Lead, Carbon Monoxide, PM 2.5, PM 10, and NO2, measured at active stations, nearby New York City and Philadelphia areas are to be looked at. Parameters regarding Aerosol Optical Depth both Terra and Aqua Modis and Fine Particulate Matter were plotted using the NOAA Giovanni (2013) website. Aerosol optical depth Figure 11 Monitoring Networks of tri-state area
  • 35. 35 Figure 12Aerosal optical depth Jan 2012 to Aug 2012 Figure 13Aerosol optical depth Jan 2013 to March 2013 increases in the summertime; this could be due to sea breeze influence bringing in greater aerosol counts as well as pollen and unstable humid air in the summer. Pollutants present in air can be deposited back both on land and water bodies. Even at great distances from the source, the quality of the air is an important contributor to declining water quality. The pollutants found in water bodies can be traced to atmospheric sources. As previously stated, both natural and anthropogenic processes lead to air pollution through combustion of fossil fuels, release of chemical byproducts from industrial and agricultural processes and forest fires. This airborne pollution falls back to the ground through precipitation. These pollutants can reach water bodies in two ways; one way is deposition directly into a water body and second is deposition on to land and transportation to water bodies through runoff. Air quality is directly related to water quality as the pollutants in air can be found declining the quality of water bodies (USEPA 2013).
  • 36. 36 Climatology& Meteorology Climatological data determines the atmospheric influence on the lithosphere and hydrosphere. Temperature and precipitation were the two primary climatological indicators that were investigated. These were chosen due to the relevance to the team’s hypotheses on seasonal variations. A geohydrologic process can be influenced by precipitation since it will cause leeching of the material into groundwater. Temperature was investigated to determine the correlation between temperature and the heating of the sub surface soils. March Climatological Average 1981-2010 March 2013 Δ 4.03 inches 2.47 inches -2.40 inches Freehold Marlboro NOAA Climatology data reported a -2.4 difference of a climatological average of rainfall versus March 2013 as referenced in Table 1. This led to drier than normal soil conditions, which prevents a surplus of surface runoff and enhances infiltration. Infiltration will provide an input to the river from riverbanks at the bedrock level if not absorbed by vegetation. Given the lacking of surplus, infiltration as a groundwater input will not be as effective. The absorption of rainfall into the soils allows the vegetation to use the available water, which keeps the soil dry. Therefore topsoil samples will contain elements that have not Table 5Climatologicalcontingency table March 2013
  • 37. 37 runoff into the river. It can be inferred that fertilizers were not as directly affecting the water quality based on this connection. July Climatological Average 1981-2010 July 2012 Δ 4.57 inches 3.21 inches -1.36 inches Climatological data for the summer samples are comparable to the winter samples, reflecting a similar condition in regards to the runoff in both seasons. As seen in Table 2, July typically has higher rainfall amounts than March. With the summer season at its peak during July, the vegetation will be using the water at a higher rate than the winter. Vegetation will help to pull more water out from underneath the surface during the summer months. This process does not occur in winter, and could be part of the reason why more reactants are being introduced to the system during the summer months. Freehold receives the highest precipitation values from April through September. This corresponds with the timeframe for the warmest river temperatures. At Freehold, the greatest extreme values for precipitation were also in the late summer months (table 6). This puts Freehold’s wet season during the late spring into late summer months. According to climatology, the most runoff and precipitation is being introduced to the river system during the warm season. Figure 7 shows the monthly precipitation averages in Freehold Boro. The highest average values are noted in early spring and again in late summer. Table 6Climatological contingency table July 2012
  • 38. 38 0 1 2 3 4 5 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Precipitation Months Monthly Precipitation Extremes 1991-2010 (in) Climatological: FREEHOLD MARLBORO (283181) Monthly Totals/Averages Precipitation (inches) Years: 1981-2010 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 3.24 2.88 4.03 4.12 3.61 3.61 4.57 3.71 4.18 3.66 3.43 3.71 Graph 7(above) Monthly precipitation average, note maximas during early Spring and late Summer FREEHOLD MARLBORO (283181) Monthly Extremes Highest Daily Precipitation (inches) Years: 1981-2010 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 2.84 2.05 3.10 2.90 3.09 2.01 2.50 3.31 4.75 3.20 2.10 3.30 Graph 8 (above) Monthly precipitation extremes, 0 1 2 3 4 5 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Precipitation Months Monthly Precipitation Avg. 1991-2010 (in)
  • 39. 39 Monthly precipitation extremes show the time of year in which the most daily precipitation could be expected to occur (figure 8). Graph 9(left) Histogram of daily precipitation extreme occurrences in inches for summer Graph 10 (right) Histogram of daily precipitation extreme occurrences in inches for winter In the above figures, during the summer there is a greater occurrence of days with greater than 2.25 inches of precipitation, while during the winter there are greater days less than 2.25 inches of precipitation. These histograms were created using climatic data from NOAA for Freehold Boro. For the winter season, the graph represents November thru February while the summer graph represents May thru August. These months were chosen to represent the seasons as well capture transitional time frames as well. These extremes are likely related to convective downpours in the summer.
  • 40. 40 IV. Methodology Field Work Site Number and Date Visit Metadata Site 1 March 22nd, 2013 Water Temperature 4.3˚C Stream-flow 0.50m/s Site 2 March 22nd, 2013 Water Temperature 4.3˚C Stream-flow 0.25m/s Site 3 March 22nd, 2013 Water Temperature 4.4˚C Stream-flow 0.55m/s Site 5 March 15th, 2013 Air Temperature 7.8˚C Water Temperature 6.5˚C Turbidity 0.4m/s Site 6 March 15th, 2013 Air Temperature 7.9˚C Water Temperature 5.4˚C Turbidity 0.7m/s Stream-flow 3.6m/s Site 7 March 1st, 2013 Air Temperature 7.6 ˚C Water Temperature 7.2˚C Stream-flow 0.16m/s Turbidity 28 FTU Depth 16 in Ammonia Level Nitrate Level 0.67 0.64
  • 41. 41 Dissolved Oxygen 9.6mg/L Site 7 March 22nd, 2013 Water Temperature 4.3˚C Stream-flow 0.15m/s Turbidity 19 FTU Site 9 March 1st, 2013 Air Temperature 7.6 ˚C Water Temperature 6.9˚C Sky Condition Mostly Cloudy Stream-flow 0.10m/s Turbidity 23 FTU Depth 15 in Ammonia Level 0.10 0.04 Phosphate Level 0 Nitrate Level 0.27 0.70 Dissolved Oxygen 9.8mg/L Table 7 Metadata of site visits Specific metadata (table 7) was chosen to collect and measure for the comparison of USGS data. At each site, it was ideal to sample and measure downstream and travel upstream to not interrupt and synthesize the river’s atmosphere. 100mL of water was collected near the river bed using a syringe and transported into containers for zinc and iron testing. Testing for zinc and iron verifies the oxidation of zinc in water that forms Fe2+. Collecting 100mL of water gives enough samples to test for these reactions. An additional 10mL of water samples were collected to test the turbidity using a LaMotte Smart2 Colorimeter to provide what sites have the
  • 42. 42 most suspended particles. The sites with the most suspended particles were visited multiple times. Using a shovel, top soil was collected nearby the riverbed. The soil was placed into a jar. Top soil samples are essential to identify how zinc, iron, and glauconite react with precipitation to distinguish an element variance between the two soils. The core soil sample was collected by using a corerand placed into a jar. Core soil samples are significant to evaluate the elements under the surface layer to deduce where the Fe2+ transpires. Two samples of both soils were placed into separate jars and filled to the top of the jar. All jars were labeled with the site number, date, and time. After the samples were collected, the stream-flow, water temperature, and air temperature were measured using an electronic instrument called the Xplorer GLX. By attaching the stream- flow meter to the GLX, the meter was held perpendicular to the river motion to record stream- flow. Using the stream-flow meter, the stream-flow and water temperature were measured. The stream-flow was measured because there is a correlation with pH of the river water that portrays higher stream-flow with lower pH and lower stream-flow with higher pH. With lower pH, the river water tests to be more acidic which could potentially carry iron bacteria. Using an external probe on the GLX, air temperature was able to be measured. Air and water temperatures were measured to investigate microclimate changes from each site. Surrounding observations were recorded to consider other influences on the Manasquan River and correlate with other metadata. Pollen samples were collected at site 5 by using scotch tape around two posts and left exposed for an hour then collected and brought back to the lab.
  • 43. 43 Pollen was collected to investigate the pollen counts and what concentrations of zinc and iron were being contributed to the system. Other metadata such as water depth, dissolved oxygen, phosphate, ammonia, and nitrate levels were tested to investigate the water quality, however during the investigation it did not relate to the hypothesis and did not validate the conceptual model the team developed. Laboratory Investigation Two samples, one from the water and one from the erosional layer, were placed in a heating oven. The oven was set to 80 degrees Celsius and left for 48 hours in order to dry the two samples. Once these samples were dried out, they were removed from the oven and turned into a powdery substance by pestle and mortar method. This was necessary to do in order to prepare the samples to be shipped out for elemental analysis. The samples were sent to Rutgers University for that analysis. The goal of this analysis is to determine if the samples were glauconite, and what the concentration of that glauconite was. The team also had water samples that needed to be prepared to be shipped for IC-PMS analysis. The goal of this analysis is to determine concentrations of iron, copper, and zinc within the water samples. These concentrations and their associated spectrophotometer intensity signals were compared against standardized samples to identify the availability of those elements for reaction. To prepare the samples for analysis, the team used a filtration apparatus with 4 micron filtration paper to remove solid particulate matter. Water samples were poured into the filtration apparatus attached to a vacuum underneath a fume hood to filter through. Once filtered, samples were put into 15 ml plastic containers, and a drop of HCL (1M) was added to keep heavy metal
  • 44. 44 elements suspended. The containers were then sealed and labeled accordingly. After each sample was filtered, concentrated HCL (4M) was used to acid wash the beakers to prevent contamination. To prove that a reaction occurs with the iron in the glauconite, an experiment was designed to prove that a seasonal reaction was taking place. Since iron reacts with zinc and heat to precipitate an iron Fe2+ product, the team decided to prove this reaction. In order to do this (x) amount of iron sulfate and (x) amount of zinc sulfate powder was mixed together in a test tube. The compound was then reacted with (sensible heat, UV, and IR). Once the sample was determined to be glauconite (hopefully), the team designed the following experimentation to see how the mineral behaves under certain circumstances that can vary with season. Added 5 mL of 0.1 mol solution of FeSO4 (iron sulfate) test tube using pipette, using a different clean pipette, 5 mL of 0.1 mol solution of Zinc Sulfate was added to the iron sulfate in the test tube. With this mixture in the test tube, using a dropper, 3 drops of ammonium hydroxide (NH2OH) were added until a green coloration was noticed. This was our 1 to 1 ratio. Different concentrations of zinc and iron solutions in addition to distilled water were conducted. All test tubes were transported to be in refrigeration and were covered so that no further reactions occurred when the samples came in contact with air, and that no light reached the samples in order to later test for spectrophotometer analysis concentration versus standard solution concentrations. ORDER: ALWAYS iron, zinc, water, then 3 drops of ammonium. A side experiment was performed. 5 grams of suspected glauconite sample placed in test tube. 1.5 mL of DI to create aqueous solution. This glauconite aqueous solution was mixed with
  • 45. 45 2 mL of Zinc Sulfate and 10 drops of ammonium. The test tube was left in the refrigerator, covered, for later observation. To investigate the hypothesis of a hydro-geologic process involving glauconite, two soil samples were tested to determine their elemental composition and whether or not they were glauconite. Two samples were taken to Rutgers Wright-Rierman Laboratory for X-Ray diffraction analysis. The pulverized samples were placed into a metal container at zero height (figure 14). Figure 14 Sample Holder Figure 15Machine Graph 11Graphical Analysis
  • 46. 46 The samples were placed into the Philips Panalytical X-Ray diffraction machine and set for a 13 minute scan (figure 15).The device was calibrated and set to scan from 10-90 degrees at 4 seconds per revolution. As the x-rays diffracted from the various elements in the powder sample, High-Score match was used to create the graphs of the signal intensity. Once the scan was completed the signal intensities were compared against reference signal intensities to determine matches (graph 11). By referencing the peak intensities from the sample versus the known intensities, elemental compositions were matched. This was performed by looking at the 100% intensity signal from the reference signal and comparing against the sample signals. When matching the reference signals to the sample signals, the 100% reference signal would tell the analyst where the expected peak for that element would occur with 100% accuracy, therefore if this peak did not match up with the 100% peak, a match would not be accepted. If the 100% peak did matchup, it would be accepted and further analyzed for the other peak patterns. The team used three different water samples collected from sites one and seven with varying coloration. One sample was taken from the side of the road at site one, from storm runoff (A), one was taken from in the river at site one (B), and the third was from in the river at site seven (C). Sample A had the greenest color, while sample C had the most yellow color. Sample B had more of a clear coloring. The team decided to look at these samples through a microscope at levels of 40, 100, and 400 times magnification. The team used wet mounts to observe the water samples with a one square inch area to analyze. Three drops of a water sample were placed onto a microscope slide and covered with a one square inch clear covering to complete the wet mount. Once under the microscope, the team used the 40x magnification to oversee the entire slide and analyze if there were any microorganisms and/or particulate matter in the water.
  • 47. 47 The team discovered what seemed to be a microorganism in the water, and by using the microscopes 100 and 400 times magnification, a better image was observed. Using microscopic pictures (figure 16) to compare to our microscopic images (figure 17), the team believes that there are iron bacteria in the water. Using the 40x magnification, a panoramic sweep was conducted across the area to count the number of iron bacteria found in the one square inch area. After observing sample A, the team found there to be 2 iron bacteria present, sample B had 11 iron bacteria and sample C had 23 present. The team was able to determine that with more iron bacteria in the water, the coloration was more yellow. With less iron bacteria, the water has a green coloration. Figure 16 (left) Drawing of Microscopic Iron Bacteria Figure 17 (right) CR-ITeam Microscopic Water Sample V. Results& Analysis X-Ray diffraction analysis of sample 1 in the river bed showed a composition of glauconite, a siderite-like phase, namely (Ca,Mg,Fe)CO3, a zinc-containing biotite phase, quartz and muscovite (figure 18). The second sample contained glauconite and quartz and a possible cristobalite phase that would have accounted for the other quartz like peaks (figure 19).
  • 48. 48 1 XRD Peak analysis Sample from in River Glauconite Figure 18 XRD in river sampe XRD Figure 19 XRD Peak analysis of erosional layer sample
  • 49. 49 These results show that there is an abundance of iron rich materials in the soil, namely glauconite. This was the suspected mineral in the soil that was leading to iron reactions in the river. Also, further RIR analysis of the samples revealed zinc containing biotite phase that accounted for the missing peaks in the XRD analysis. This is important because the presence of zinc and iron together are leading to the chemical reaction that the team hypothesized. The experimentation provides enough preliminary evidence that the physical process and chemical process are both occurring within the system. Table 8Elements in the in river sample Table 9 Elements in erosional layer sample
  • 50. 50 Based on the teams conceptual hypothesis there should be higher levels of iron bacteria in the water with the most yellow color since there would be more oxidized iron. Quantitative analysis was conducted by counting the amount of iron bacteria within the one square inch samples, and comparing the amounts based on the color of the samples. Site one storm runoff sample, the greenest, had 2 iron bacteria. Site one in the river, mostly clear, had eleven iron bacteria, and Site seven in the river, the most yellow, had 23 iron bacteria. Pictures were taken for documentation of what was in the samples. Samples of water from the winter indicated that the concentrations of iron and zinc were less than the detectable range through the ICP-MS experiment. The ICP-MS experiment (inductively coupled plasma mass spectrometry) experiment detects concentrations of heavy metals by ionizing the sample and then separating and quantifying those ions. The testable limits for iron and zinc are as follows. For iron <.5 ppm is the testable limit and zinc has a testable limit of <.1 ppm. The only samples that tested over these limits were samples (insert). The remainder of the samples had negligible amounts of iron and zinc in them. This proves that during the winter this process is not occurring. However, the sample that was tested during the precipitation event did have a level of (insert) of iron and (insert) of zinc. This shows that it is a physical process driven by atmospheric influences. In the summer when the level of iron in the water samples was higher, it was due to the iron running off from glauconite erosion and other iron rich minerals. In summer the range of iron necessary for this process to occur would be (insert) and in the winter the process will not occur unless these ranges are breached. Based on the team’s conceptual model, there should be higher levels of iron bacteria in the water with the most yellow coloration. Since Fe3+ is what creates the yellow coloration, the oxidation from the iron bacteria would be the process occurring. Quantitative analysis was
  • 51. 51 conducted by counting the amount of iron bacteria within the one square inch samples from two different sites, and comparing the amounts based on the color of the samples. Site one storm runoff sample, the greenest, had 2 iron bacteria. Site one in the river, mostly clear, had eleven iron bacteria, and Site seven in the river, the most yellow, had 23 iron bacteria. Pictures were taken for documentation of what was in the samples. River Behavior To determine the river’s response to precipitation events in the investigation of a natural geo-hydrologic process, tabulated history of discharge/gage height were compared against precipitation events. For the days that the team visited the Manasquan sites, the gage height at Squankum was observed (table 10). March 1st March 15th March 22nd April 6th 2.9 feet 2.9 feet 2.93 2.77 Table 10 River gage height during initial site visits The river gage height fell as the course of investigation went on. Drier conditions prevailed for most of the study. The highest gage height during the Month of March occurred March 19th at 2pm. In response to drier conditions, the river gage height failed to reach theaverage values expected during the month of March. To investigate the river gage height response to precipitation and infiltration processes, precipitation data was looked at. On March 18th precipitation began at 8pm and accumulated to .25 inches by midnight, with another .27 inches observed from midnight through noon on March
  • 52. 52 19th. A tenth of an inch of rain fell before a response was noted in the gage height. The gage height began rising from 2.88 feet until a crest of 4.77 feet at 2pm March 19th (eight hours after precipitation ceased). In this event, half an inch of rain caused a 2 foot rise in gage height. The response time was within two hours of the onset of precipitation .On April 10, 2013 precipitation began at 9:30 pm, with the first rise in gage height recorded at 11:30 pm. This was a response time of two hours after the onset of precipitation (see figure ###). Graph 12 Gage height March 2013
  • 53. 53 Graph 13 Gage height from April 5th 2013 to April 12 2013 The river’s response to precipitation events indicate what layer of soil will be affected by the water level. With the observed glauconitic layer about 3-4 feet off the riverbed, it would take an event similar to the one on April 10th 2013 to interact with the glauconitic layer. Figure 20 Note the interaction of the river with the glauconitic layer observed April 10th 2013
  • 54. 54 The discharge values also correlate to the amount of water infiltrating into the river. This can be traced back to the calculated viscosity and infiltration values. During this same timeframe, pH values were also investigated. Location pH Prior pH During pH After Site 7 In River 6 4.5 4 Site 1 Storm Runoff 6 4.0 4.5 Site 1 in River 6 3.5 5 Table 11pH values measured before, during, and after April 10th precipitation event While pH values expectedly dropped during the precipitation event as a result of increased stream- flow and began to rose once the river had slowed, a correlation cannot be drawn between pH and infiltration process. More investigation needs to be done here to gather a larger sample size of pH values and whether or not the pH values play a role in the amount of glauconitic material being introduced into the river, or whether it affects oxidation state once in the river. Two gage stations from the USGS were chosen along the river. The first site was the Squankumsite; the gage height at this site was useful because the gage height and behavior is very similar to the river height at site 1 (it is also geographically close). The behaviors are assumed to be similar between the two sites. The Allenwood site was chosen because the gage height is higher than at the Squankum site and provides behaviors for deeper river water. The expectation that the team would observe coloration during higher gage height was verified during the site visit. The coloration of storm water runoff was a cloudy green material leeching
  • 55. 55 out of the ground water. The specific conductance of the river also rose during the precipitation event (graph 14). Graph 14 Specific conductance Specific conductance refers to the amount of water that can be transferred through a surface. Since the specific conductance of the river water rose, the infiltration process was aided. The river was observed to be reaching the glauconitic layer along the side of the riverbed (see photo). The river water was observed to be “stripping” the material away from the side of the river. Therefore, discharge values were investigated to look for a correlation between the amount of water running over the surface and the stripping effect (graph 15).
  • 56. 56 Graph 15 Discharge at Squankum site from April 9 to April 16 To determine a threshold for where the discharge will start to strip away the glauconitic material from the riverbed itself, more testing is necessary for before, during, and after precipitation events. As the river crested and began to lower, the coloration of the river started to dissipate. The site visit on Sunday April 14th 2013 revealed nearly clear water again at site 1 and site 7. Infiltration from storm water runoff appeared to have nearly stopped altogether. Therefore, no further (or not enough) glauconitic material was being introduced to the river anymore. Water samples taken during the course of the validation study will show the concentrations of key elements within the river system. The conceptual river behavior model as it relates to the physical processes dictate that the iron levels in the river should be less during
  • 57. 57 dry conditions and during the winter months as the physical processes of leeching and runoff are occurring less frequently. VI. Conclusions & Discussions With the acceptance of the conceptual box model, previous hypotheses were validated. Through experimentation and testing of soil and water samples, there was a presence of iron and zinc supporting thoughts on the reaction that occurs in the river with the presence of these elements. This reaction is in fact occurring in the river however due to time restrictions no threshold could be measured. Thinking about the physical aspect of the conceptual model, the most important process is a precipitation event jumpstarting the interaction of the river water and glauconitic materials in the riverbed. Without any precipitation, there would be no mechanism to trigger the process and there would be no apparent coloration. The presence of glauconite in the riverbed on a macro-scale level provides the elements needed for the chemical reaction aforementioned. On a micro-scale level, precipitation is required in order to trigger the process leading to coloration. While the group acknowledged there are measureable thresholds, due to time restrictions these were not determined. There was additional instrumentation lacking, which would have aided in measuring soil moisture and temperature to get threshold values for necessary levels of moisture in the winter in order for the process to begin. It can be noted that this process differs seasonally and there are variables on the micro and macro scales that affect the severity and intensity of the coloration. This is an overall naturally occurring process with the currently present glauconitic materials and an increase in coloration due to precipitation events.
  • 58. 58 Recommendations Additional testing can be done in the future to further validate the hypotheses regarding the weathering of glauconite from low pH levels. Long-term pH readings can be done to also validate the relation between low pH levels and higher stream flow values. Long-term precipitation studies can be done to determine threshold values of soil moisture and the amount of precipitation needed to release glauconite from the soil. These threshold values will determine the beginning of this process with regards to seasonal variations. Remediation To remediate the pronunciation of the yellow colored water, the team recommends that the storm pipes that lead into the river be galvanized with plastic. This tactic is known to prevent the colonization of iron bacteria in river water. Since iron bacteria oxidize the iron and have a role in the appearance of yellow colored water, the removal of them should deter some of the coloration. The team also recommends tactics to precipitate iron from the water. Through the team’s investigation, when iron and zinc react, this chemical reaction is precipitated by ammonia. Ammonia could be used to precipitate iron out of the water. However, this is all a natural and non-toxic process. Remediation tactics may be too costly and cause more problems in the long run than if it were left alone.
  • 59. 59 VII. Acknowledgements The team acknowledges support for project activities as related to data collection and analysis. In particular, we thank Dr. Codella (School of Environmental and Life Sciences) for his contributions to the microscopic investigation into iron bacteria detection. Dr. Emge (Wright- Riedmann Lab, Rutgers University) performed the XRD analysis on the soil samples the team collected. Norberto Mapoy (School of Environmental and Life Sciences) prepared specific molar chemical solutions for the team’s lab investigations into chemical processes in the water. Dr. William Eaton (School of Environmental and Life Sciences) set up the team’s iron and zinc reaction experiment. Stan (School of Environmental and Life Sciences) provided logistical services regarding the technical report and presentation and data access. Dr. Juyoung Ha (School of Environmental and Life Sciences) provided the team with peer review literature and experimental design as well as data access. The team would also like to thank Kean University and specifically the School of Environmental and Life Sciences.
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