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

Research Design

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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So il 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

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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

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

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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

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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

Wat er 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

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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

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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.

F lora

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

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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

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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).

Faun a & 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.

Anthro pogenic

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 Qu ality

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.

Figure 11 Monitoring Networks of tri-state area

Figure 12Aerosal optical depth Jan 2012 to Aug 2012 Figure 13Aerosol optical depth Jan 2013 to March 2013

35

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

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 & Meteo rology

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

Table 5Climatologicalcontingency table March 2013

37

water, which keeps the soil dry. Therefore topsoil samples will contain elements that have not

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.

Table 6Climatological contingency table July 2012

38

Figure 7 shows the monthly precipitation averages in Freehold Boro. The highest average values

are noted in early spring and again in late summer.

Climatological:

FREEHOLD MARLBORO (283181)Monthly Totals/AveragesPrecipitation (inches)Years: 1981-2010

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec3.24 2.88 4.03 4.12 3.61 3.61 4.57 3.71 4.18 3.66 3.43 3.71

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec0

1

2

3

4

5

Monthly Precipitation Avg. 1991-2010 (in)

Months

Prec

ipita

tion

Graph 7(above) Monthly precipitation average, note maximas during early Spring and late Summer

FREEHOLD MARLBORO (283181)Monthly ExtremesHighest Daily Precipitation (inches)Years: 1981-2010 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec2.84 2.05 3.10 2.90 3.09 2.01 2.50 3.31 4.75 3.20 2.10 3.30

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec0

0.51

1.52

2.53

3.54

4.55

Monthly Precipitation Extremes 1991-2010 (in)

Months

Prec

ipita

tion

39

Graph 8 (above) Monthly precipitation extremes,

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

41

Ammonia Level

Nitrate Level 0.67

0.64

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

42

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

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.

43

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.

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.

44

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

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.

45

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

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

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

Graph 11Graphical Analysis

47

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.

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

1 XRD Peak analysis Sample from in River

48

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).

Glauconite

Figure 18 XRD in river sampe

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

Table 8Elements in the in river sample

Table 9 Elements in erosional layer sample

50

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.

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.

51

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

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.

52

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 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

Recom mendations

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.

Reme diation

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

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