chapter 2 methodology 2.1 introduction

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CHAPTER 2 METHODOLOGY 2.1 Introduction To accomplish in this study, observation and description of Quaternary strta and sediment samples collection in the field and laboratory analysis on the samples were importance. The field methods include surveying, lithostratigraphic study, sample collection and fossil collection. The purposes of surveying is to measure the depths and position of sediment sections in the study area using topographic map and global positioning system instrument. The careful study of lithology and sedimentary structure allowed determining depositional environment. The sediment samples were analyzed for grain size distribution, mineral composition, lithostratigraphy and fossil were used to interpret the palaeoenvironment. Laboratory methods include grain size distribution analysis, grain shape analysis, total organic carbon analysis, heavy minerals and light minerals analysis, x- ray diffraction analysis and 14 C age dating determination. Grain size distribution studies include sieve analysis both dry sieve and wet sieve for sand up to gravel size and mud size were used pipette method. Grain shape analysis, especially sphericity and roundness were analyzed by binocular microscope. Total organic matter study was analyzed by loss on ignition (LOI) method and convert to total organic carbon values. Heavy minerals and light minerals were separated by gravity separation method and identified by optical properties using binocular and polarizing microscope. The mineralogy of the mud fractions were determined by x-ray diffraction method. The mineral determination under heavy mineral and light minerals analysis and x-ray diffraction analysis allowed interpreting the source rocks and the diagenetic processes. Fossils, wood fragments and leaf fragments, were determined for age dating by 14 C dating method, which lead to understand the age of sediment layers in the study area.

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Page 1: CHAPTER 2 METHODOLOGY 2.1 Introduction

CHAPTER 2

METHODOLOGY

2.1 Introduction

To accomplish in this study, observation and description of Quaternary strta

and sediment samples collection in the field and laboratory analysis on the samples

were importance. The field methods include surveying, lithostratigraphic study,

sample collection and fossil collection. The purposes of surveying is to measure the

depths and position of sediment sections in the study area using topographic map and

global positioning system instrument. The careful study of lithology and sedimentary

structure allowed determining depositional environment. The sediment samples were

analyzed for grain size distribution, mineral composition, lithostratigraphy and fossil

were used to interpret the palaeoenvironment.

Laboratory methods include grain size distribution analysis, grain shape

analysis, total organic carbon analysis, heavy minerals and light minerals analysis, x-

ray diffraction analysis and 14C age dating determination. Grain size distribution

studies include sieve analysis both dry sieve and wet sieve for sand up to gravel size

and mud size were used pipette method. Grain shape analysis, especially sphericity

and roundness were analyzed by binocular microscope. Total organic matter study

was analyzed by loss on ignition (LOI) method and convert to total organic carbon

values. Heavy minerals and light minerals were separated by gravity separation

method and identified by optical properties using binocular and polarizing

microscope. The mineralogy of the mud fractions were determined by x-ray

diffraction method. The mineral determination under heavy mineral and light

minerals analysis and x-ray diffraction analysis allowed interpreting the source rocks

and the diagenetic processes. Fossils, wood fragments and leaf fragments, were

determined for age dating by 14C dating method, which lead to understand the age of

sediment layers in the study area.

Page 2: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 16

2.2 Field surveying method

The sand pit in the study area has been surveyed by measuring its size,

dimension and elevation using global positioning system instrument, compass and

measuring tape. Data of nine locations of the border of sand pit are shown in table

2.1. The area of study area was calculated by dividing the study area into seven

triangles and calculating the area of each triangle from the angles and distances is

shown in Figure 2.1. Calculation based on Heron’s formula.

where

a, b and c is the distances of triangle

From the computation by using Heron’s formula, total area of the study area is

184,802.31 m2 (115.50 Rai).

2.3 Lithostratigraphy and sedimentary characteristics

2.3.1 Stratigraphy

A common system of stratification terminology was purposed by McKee and

Weir (1953). In this system, a lamina is a stratum less than 1 centimeter thick and a

bed has a thickness greater than 1 centimeter. Layers oblique to bedding surfaces are

cross-strata. Basic measurements are dip and strike direction of each structure for

interpreting palaeocurrent directions. The sediment features within each stratum are

its facies.

Page 3: CHAPTER 2 METHODOLOGY 2.1 Introduction

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Table 2.1 Station elevation and UTM coordinates.

Figure 2.1 The study area was reconstructed by UTM coordinate data.

Station Elevation

(meters above mean sea level)

Position

(UTM zone 47)

N E

A 3.20 1624595.00 659189.00

B 3.10 1624625.00 659489.00

C 2.90 1624690.00 659494.00

D 3.50 1624696.00 659655.00

E 1.60 1624943.00 659613.00

F 1.80 1624945.00 659556.00

G 4.30 1625056.00 659475.00

H 3.30 1625069.00 659252.00

I 1.80 1624809.00 659116.00

Page 4: CHAPTER 2 METHODOLOGY 2.1 Introduction

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2.3.2 Sedimentary facies analysis

The study of sedimentary facies is an important tool for recognizing

depositional processes, sedimentary environments and sedimentary evolution. Facies

types are described by employing a hierarchical scheme. The scheme used in this

study is the one suggested by Miall (1977). This scheme recognizes three major

grain-size classes, gravel, sand and fines, each of which may be further subdivided

according to texture and style of bedding and lamination.

One characteristic structure of sediments is cross-stratification. Two systems

are used for classifying and describing cross-stratification. The one purpose by

McKee and Weir (1953) is simple but it is less complete than the classification of

Allen (1963) that attempts to include all major factors that may be encountered.

These systems recognize three main types of stratification:

1. Simple cross-stratification are represented by non-deposition or a change in

character.

2. Planar cross-stratification consisting of sets whose lower bounding surfaces

are a plane surface of erosion.

3. Trough cross-stratification consisting of sets whose lower bounding surface

are a curved surface of erosion.

There are two kinds of cross-strata based on shape: lenticular-set and wedge

set. Cross-stratification is small scale if it is less than 30 centimeters in length,

medium scale if it is between 30 centimeters and 6 meters in length and large scale if

it is more than 6 meters in length. The stratification dip divides the cross strata into

high angle, 20 degrees or more and low angle, less than 20 degrees.

2.3.3 Sediments sampling

The locations of stratigraphic sections (section 1 to section 5) and fossils were

determined using global positioning and measuring tape (Figure 2.2). The elevation

of sediment profile was determined. Sample location, sediment strata and fossils

Page 5: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 19

Figure 2.2 Location of stratigraphic section (S1 to S5) in the sand pit of study area.

were photographed. The samples were collected, interval 30 centimeters each

sample, along vertical profile (Figure 2.3). One hundred and eighty-three samples

were collected and analyzed. Twenty-six samples were selected to determine by x-

ray diffraction method. Sixty-one fossil samples were collected from sediment layers.

2.4 Grain-size analysis

The purpose of measuring grain-size distribution is to classify sediments.

Various depositional environments tend to be characterized by distinct grain-size

distributions that can be used for statistical interpretations. Grain-size was based on

the Wentworth scale (Wentworth, 1922). The size classes used were boulders,

cobbles, gravel, sand, silt and clay (Figure 2.4). The frequency distribution of the

Page 6: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 20

Figure 2.3 Samples collection in the sand pit, Shows sediment and horizon layers.

Figure 2.4 Udden-Wentworth grain-size scale for siliciclastic sediment (Wentworth,

1922).

Page 7: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 21

weight or number of particles per size class tends to follow approximately a log

normal distribution when particles size are expressed metrically in millimeters.

Krumbein (1934) expressed particle size D as the negative logarithm to the base of 2

and called the result the �-scale. Particle sizes in �-unit were converted from particle

D size to units of millimeters by:

where D is the grain diameter in millimeters unit

2.4.1 Size analysis

One hundred and eighty-three samples from five stratigraphic sections at Ban

Beok sand pit were analyzed for their distribution of grain sizes. One hundred and

sixty-six mud fraction dominated samples were weighed estimation in 60 g and

transfer into glass that contain water. Seventeen sand fraction dominated samples

were transferred in metal pan and dried in oven at 40 �C. Drying time was just

overnight. Drying at high temperature causes in grain dispersion (Carver, 1971). Each

dry sample was divided into 150 g by riffle splitter. All samples were wet-sieved to

separate sand and gravel fractions from silt and clay fractions. Sand and gravel

fraction was analyzed and separated into each grade by dry-sieve method. Silt and

clay fraction was determined grain size based on gravity settlement by pipette

method.

2.4.1.1 Wet sieving method

All subsamples would normally be dealt during this procedure.

1. Set equipment used for wet sieve (Figure 2.5).

2. Transfer sample on the 63 �m sieve mesh.

3. Using the wash bottle containing pure water rinse the sample in sieve screen

until the water is clear as it runs into the cylinder.

Page 8: CHAPTER 2 METHODOLOGY 2.1 Introduction

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Figure 2.5 Arrangement of equipment for wet sieve method.

4. Washing the underside of sieve screen and funnel into the cylinder.

5. Transfer sample on the sieve mesh into the receiver.

6. Place the cylinder that contain fine fraction sample in the safety area.

2.4.1.2 Particle-size analysis of sand-grade material by sieving

Samples would normally be dealt with simultaneously during this procedure.

1. Transfer all the samples to the tray and allow it to air-dry.

2. If the sample contains a significant proportion of plant organic matter, this

should be removed before weigh sample.

3. Label and weigh sample to 0.01 g.

4. Remove silt and clay-grade from sand and gravel-grade for pipette analysis in

wet sieve technique into 1000 cm3 cylinder.

5. Place the sample after step 4 in the oven until samples are dry.

6. Assemble a set of sieve at half phi-unit intervals from 0.063 millimeters to 4

millimeters. Check that each sieve is clean (Figure 2.6).

Page 9: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 23

Figure 2.6 Arrangement of equipment for dry sieve method.

7. Stack the sieve in order from coarsest down to finest, place the receiver at the

bottom of stack.

8. Pour the dried sample onto the top of stack and the lid on the sieve stack and

clamp the stack firmly into the sieve shaker.

9. Sieve for 15 minutes.

10. Remove sieve stack from the shaker.

11. Take the coarsest sieve on sieve stack onto the paper and remove the sample

that retained on sieve into the container.

12. Label and weigh sample in container to 0.01 g.

13. Repeat the procedures in step 11 and 12 for each successively finer sieve in

the stack.

14. Materials that have passed into receiver should be weighed and added to the

remainder of silt and clay-fraction obtained in step 4 for pipette analysis.

Page 10: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 24

2.4.1.3 Particle-size analysis of silt and clay-grade material by pipette

analysis

The pipette analysis is based on the principle that particles will settle in a fluid

at a rate dependent upon their size, shape and density and upon the density and

viscosity of the fluid (Gale and Hoare, 1991). To simplify this relationship, it is

normally assumed that the particles involved are spheres with a density equal to that

of quartz (2650 kg m-3). Particle size as determined by sedimentation analysis is

expressed in terms of hydraulic-equivalent diameter. This method is not practicable

to determine the hydraulic-equivalent diameter of coarse particles.

The terminal settling velocity of small sphere in a fluid is given by Stokes’

Law.

where � terminal settling velocity (m s-1)

� � � particle density (kg m-3)

� � � fluid density (kg m-3)�

� � g acceleration due to gravity (m s-2)

� � D� spherical particle diameter (m)�

� � �� fluid dynamic viscosity (kg m-1 s-1)

If the sample of particles is dispersed evenly throughout a fluid, the velocity of

particle settling will be determined from Stokes’ Law. Assuming the fluid within

which settling take place to be pure water of known temperature, it is possible to

calculate the depth and time of sampling necessary to sample only particles finer than

a given size (Tables 2.2 and 2.3).

Page 11: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 25

Table 2.2 Depth of pipette insertion and time of withdrawal for 25�C (from Folk,

1974).

Depth (cm) Phi unit Diameter (mm) Time of withdrawal

20 4.0 0.063 20 sec

20 4.5 0.044 1 min, 45 sec

Remix suspension

10 5.0 0.031 1 min, 45 sec

10 5.5 0.022 3 min, 28 sec

10 6.0 0.016 6 min, 58 sec

10 7.0 0.008 28 min

10 8.0 0.004 1 hr, 50 min

10 9.0 0.002 7 hr, 30 min

5 10.0 0.001 15 hr

Table 2.3 Method of sampling various size fractions by varying the depth of pipette

insertion. Depth given for a range of temperatures (from Folk, 1974 and

Lewis, 1984).

Temp

(�C)

Total

suspension

4.5� 5.0� 5.5� 6.0� 7.0� 8.0� 9.0� 10.0�

20 sec 2 min 4 min 8 min 15 min 30 min 2 hr 8 hr 32 hr

18 20 19.8 19.7 19.8 19.6 9.8 9.8 9.8 9.8

19 20 20.2 20.1 20.2 20.0 10.0 10.0 10.0 10.0

20 20 20.7 20.6 20.7 20.6 10.3 10.3 10.3 10.3

21 20 21.3 21.1 21.3 21.1 10.5 10.5 10.5 10.5

22 20 21.8 21.6 21.8 21.6 10.8 10.8 10.8 10.8

23 20 22.3 22.1 22.3 22.1 11.1 11.1 11.1 11.1

24 20 22.8 22.7 22.8 22.6 11.3 11.3 11.3 11.3

25 20 23.3 23.2 23.3 23.2 11.6 11.6 11.6 11.6

26 20 23.9 23.8 24.0 23.7 11.9 11.9 11.9 11.9

27 20 24.5 24.3 24.5 24.2 12.1 12.1 12.1 12.1

Page 12: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 26

Stokes’ Law is only applicable to particles less than �60 �m in diameter

(Allen, 1983). The lower limit of measurement by pipette analysis is �2 �m because

effects of Brownian motion and convection (Allen, 1983).

In their natural state, fine particles tend to form aggregates or to flocculate into

chains and clusters. In laboratory, particles must be disaggregated and in which

individual particles are maintained in the suspension. Dispersion is usually achieved

by making up the suspension in a dilute solution of a compound, which builds up the

ionic charge on clay particles.

In this study, a 0.5% w:v solution of sodium hexametaphosphate ((NaPO3)6) is

used to disperse materials in suspension. This dispersant is recommended (Gale and

Hoare, 1991). Any reader requiring further information on flocculation and

dispersants is referred to Galehouse (1971) and the references therein. The following

steps should be performed for each subsample to be analyzed. Note that several

subsamples would normally be dealt with simultaneously during this procedure.

1. Weigh and label beakers to 0.0001 g.

2. Set up equipment for pipette analysis (Figure 2.7).

3. Add pure water in fine fraction sample cylinder to 1000 cm3.

4. Add sodium hexametaphosphate ((NaPO3)6) in fine fraction sample cylinder to

0.5% w:v solution.

5. Place cylinder of sample on non-vibrate table, away from direct sunlight and

other sources of heat.

6. Record the temperature of suspension.

7. Stir the contents in cylinder vigorously with the plunger-stirrer.

8. Remove stirrer from cylinder. When the stirrer emerges from suspension, start

the stop-clock.

9. In 20 seconds after stirring, insert the marked 20 cm3 pipette, to which is

attached the pipette filler, so that the tip is at a depth of 200 mm in suspension

and the pipette is centrally and vertically located in cylinder and draw up 20

cm3 of suspension into the pipette.

Page 13: CHAPTER 2 METHODOLOGY 2.1 Introduction

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Figure 2.7 Illustration of the pipette method of grain size analysis for fine fractions.

10. Withdrawn the pipette from cylinder and deliver the contents of the pipette

into the labelled beaker.

11. The next pipette sample should be taken following the same basic procedure.

Sampling time and depth of draw up suspension are given in Tables 2.2 and

2.3.

12. After the second sample has been taken, the suspension should be restired and

further samples taken following the procedure outlined in step 8 and 9.

Page 14: CHAPTER 2 METHODOLOGY 2.1 Introduction

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13. After final sample has been taken, placed all beaker and its contents in the

oven for removed water and moisture from the sample.

14. Weigh dried-sample and beaker to 0.0001 g.

15. Calculate pure-weigh samples in each beaker.

2.4.2 Sedimentary nomenclature

Folk (1954) considered the textural and mineral compositions related to grain-

size and introduced two triangular diagrams. The first diagram provides a

nomenclature based on the major textural groups, using gravel, sand, silt and clay

(Figure 2.8). The second triangle is used to define ten sedimentary rock types and is

based on the mineralogy of the clay, silt and sand fractions (Figure 2.9 and Table 2.4).

2.4.3 Graphic parameters

Apart from sieving as a means for general sediment classification, ratio of

various particle distribution parameters can be used to distinguish between sediments

of different origins, transportation modes and duration or distance of transportation.

Particle-size distributions are commonly characterized by four distribution

parameters: mean; standard deviation or sorting; skewness and kurtosis. The 50

percent diameter on a cumulative frequency curve defines the median. In this study,

the distribution parameters were cumulated according to Folk and Ward (1957).

Mean size: The central tendency of grain-size distribution is of prime

importance in classification. It immediately provides an average size to which

Wentworth’s nomenclature can be applied. However, Folk and Ward (1957)

considered that this was not sufficiently accurate for bimodal and strongly skewed

distributions. Thus, they introduced:

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Figure 2.8 The fifteen major textural groups as defined by the relative percentages of

gravel (grain size coarser than 2 mm), sand (grain size between 0.0625 to 2

mm) and mud (grain size finer than 0.0625 mm) (after Folk, 1954).

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Figure 2.9 The ten major textural groups as defined by the relative percentages of

sand (grain size between 0.0625 to 2 mm), silt (grain size between 0.0039

to 0.0625 mm) and clay (grain size finer than 0.0039 mm) (after Folk,

1954).

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Table 2.4 Twenty-two textural groups comparing unconsolidated and consolidated

sediments (after Folk, 1954).

Class Unconsolidated Consolidated

G Gravel Conglomerate

mG Muddy gravel Muddy conglomerate

msG Muddy sandy gravel Muddy sandy conglomerate

sG Sandy gravel Sandy conglomerate

gM Gravelly mud Conglomeratic mudstone

gmS Gravelly muddy sand Conglomeratic muddy sandstone

gS Gravelly sand Conglomeratic sandstone

(g)M Slightly gravelly mud Slightly conglomeratic mudstone

(g)sM Slightly gravelly sandy mud Slightly conglomeratic sandy mudstone

(g)mS Slightly gravelly muddy sand Slightly conglomeratic muddy sandstone

(g)S Slightly gravelly sand Slightly conglomeratic sandstone

M Mud Mudstone

sM Sandy mud Sandy mudstone

mS Muddy sand Muddy sandstone

S Sand Sandstone

cS Clayey sand Clayey sandstone

zS Silty sand Silty sandstone

sC Sandy clay Sandy claystone

sM Sandy mud Sandy mudstone

sZ Sandy silt Sandy siltstone

C Clay Claystone

Z Silt Siltstone

Standard deviation: Standard deviation is a measure of the spread about the

mean or width of a distribution. Distribution is the range of particle sizes within

which a preset percentage of all data are contained. It is generally used to describe

Page 18: CHAPTER 2 METHODOLOGY 2.1 Introduction

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the sorting of sediment. Folk and Ward (1957) introduced the inclusive graphic

standard deviation as follows:

In addition, Folk (1954) assigned terminology to the Inman (1952) standard

deviations, as in Table 2.5. The same terminology is used for the inclusive graphic

standard deviation (Folk and Ward, 1957).

Skewness: Skewness is the measure of the symmetry of the distribution and is

quantified as zero in phi units for a symmetrical distribution. If the distribution is

skewed towards smaller phi values, this being coarser size, the phi mean is

numerically less than the median causing negative skewness and for a distribution

skewed toward the finer size, the skewness is positive (Figure 2.10 and Table 2.6). In

1957, Folk and Ward introduced an inclusive graphic skewness:

In cases where the sizes of the limiting percentiles are not available, these

formulae cannot be used.

Kurtosis: Kurtosis is a measure of peakness or the ratio of the average spread

in the tails to the standard deviation of the distribution (Table 2.7). Folk and Ward

(1957) introduced an inclusive graphic kurtosis:

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Table 2.5 Folk and Ward (1957) classification of standard deviation values (after

Bunte and Abt, 2001).

Sorting Coefficient Characterization > 4 Extremely poor 2-4 Very poor 1-2 Poor

0.71-1 Moderate 0.50-0.71 Moderately well 0.35-0.50 Well

< 0.35 Very well

Table 2.6 Folk and Ward (1957) classification of skewness values (after Bunte and

Abt, 2001).

Table 2.7 Folk and Ward (1957) classification of kurtosis values (after Bunte and Abt,

2001).

Value Classification Explanation -0.3 to -1 Very negatively skewed Very skewed towards the fine side

-0.1 to -0.3 Negatively skewed Skewed towards the fine side -0.1 to 0.1 Nearly symmetrical Nearly symmetrical 0.1 to 0.3 Positively skewed Skewed towards the coarse side 0.3 to 1 Very positively skewed Very skewed towards the coarse side

Value Classification Explanation < 0.67 Very platykurtic Very flat frequency distribution

0.67-0.90 Platykurtic Flat 0.90-1.11 Mesokurtic Not especially peaked, normal 1.11-1.50 Leptokurtic Highly peaked

> 1.50 Very leptokurtic Very highly peaked

Page 20: CHAPTER 2 METHODOLOGY 2.1 Introduction

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Figure 2.10 The shape of symmetrical, positively and negatively skewed frequency

distributions curve (after Bunte and Abt, 2001).

2.4.4 Particle-size frequency and cumulative frequency distribution

The result of a laboratory particle size distribution analysis is a record of

particle weight or particle numbers retained on each sieve. The weight per size class

is then entered into a sheet table for all subsequent computations.

1. Compute the percentage weight for each size class.

2. Plotted as a percentage frequency distribution histogram.

3. The percentage of particle weight or number of particles retained on each

sieve is converted into the percentage of particle weight or number passing the

next larger sieve opening size.

4. The particle size classes and the percent finer by weight are plotted together to

make a cumulative particle size distribution curve, also called the sieve curve

or the gradation curve.

2.4.5 Percentiles and their computation

Two sediment mixtures of different particle size are usually distinguished by

comparing several of the percentile values of the two distributions or the parameters

derived from the percentiles. A percentile is a sediment size indicated by the

Page 21: CHAPTER 2 METHODOLOGY 2.1 Introduction

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cumulative distribution curve for a particular percent finer value. For example, the

sediment size for which 80 percent of the sediment sample is finer is the 80th

percentile. The notation is D80, where D represents particles size in millimeters and

the subscript 80 denotes 80 percent. D50 is the median point of distribution that

divides the distribution into two equal parts. The particle size for which 25 percent of

the distribution is finer is the 25th percentile, or D25. D25 and D75 are called quartiles.

Theoretically, any percentile value can be used for comparison, but, customarily the

particle size of D50, D25 and D75, D16 and D84 and D5 and D95 are used. In a normal

distribution, one standard deviation from the median encompasses all data between

D16 and D84 and is the point on a distribution curve at which the change of curvature

occurs. D5 and D95 characterize the distribution tails. Data between D5 and D95

comprise almost two standard deviations on either side of D50, or the median. These

seven percentiles may be compared as individual values or can be used to compute

distribution parameters, such as mean, standard deviation and skewness.

2.5 Roundness and sphericity

Particle forms are characterized by shape and angularity. Shape refers to the

ratio of the three axial lengths. Angularity refers to angular edges as opposed to

rounded surfaces. Particle form effect the area exposed to flow forces, drag forces,

lift forces and therefore, particle entrainment, transport and deposition.

The mode value of each sample was analyzed for roundness and sphericity.

The sand size particle is the major of the mode. Thus, the roundness and sphericity

were analyzed based on Powers (1953) to estimate grain roundness and sphericity

(Figure 2.11).

Page 22: CHAPTER 2 METHODOLOGY 2.1 Introduction

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Figure 2.11 Illustration of roundness and sphericity of sediments grains based on

comparisons with grains of calculated roundness (after Powers, 1953).

2.6 Total organic carbon analysis

Organic matter in soils and sediments is widely distributed over the earth’s

surface occurring in almost all terrestrial and aquatic environments (Schnitzer, 1978).

Soils and sediments contain a large variety of organic materials ranging from simple

sugars and carbohydrates to the more complex proteins, fats, waxes, and organic

acids. Important characteristics of the organic matter include their ability to form

water-soluble and water insoluble complexes with metal ions and hydrous oxides;

interact with clay minerals and bind particles together; sorb and desorb both naturally-

occurring and anthropogenically-introduced organic compounds; absorb and release

plant nutrients; and hold water in the soil environment (Schnitzer, 1978). As a result

of these characteristics, the determination of total organic carbon is an essential part

of any site characterization since its presence or absence can markedly influence how

chemicals will react in the soil or sediment.

In soils and sediments, there are three basic forms of carbon that may be

present. They are elemental C, inorganic C, and organic C. The quality of organic

Page 23: CHAPTER 2 METHODOLOGY 2.1 Introduction

� 37

matter in sediments is critical to the partitioning and bioavailability of sediment-

associated contaminants (Schumacher, 2002).

The basic principle for the quantitation of total organic carbon relies on the

destruction of organic matter present in the soil or sediment. The destruction of the

organic matter can be performed chemically or via heat at elevated temperatures. All

carbon forms in the sample are converted to CO2, which is then measured directly or

indirectly and converted to total organic carbon or total carbon content, based on the

presence of inorganic carbonates. These methods can either be quantitative or semi-

quantitative depending on the process used to destroy the organic matter and the

means used for detecting/quantifying the carbon present.

The loss on ignition (LOI) method is semi-quantitative technique based upon

the indiscriminant removal of all organic matter followed by gravimetric

determination of sample weight loss. The determination of organic matter involves

the heated destruction of all organic matter in the soil or sediment. A known weight

of sample is placed in a ceramic crucible (or similar vessel), which is then heated to

between 350�C and 440�C overnight (Blume et al., 1990; Nelson and Sommers,

1996; ASTM, 2000). The sample is then cooled in a desiccator and weighed.

Organic matter content is calculated as the difference between the initial and final

sample weights divided by the initial sample weight times 100%. All weights should

be corrected for moisture/water content prior to organic matter content calculation.

LOI method temperatures should be maintained below 440�C to avoid the

destruction of any inorganic carbonates that may be present in the sample. One

concern with this technique is that some clay minerals will lose structural water or

hydroxyl groups at the temperatures used to combust the samples. The structural

water loss will increase the total sample weight loss leading to an overestimation in

organic matter content. One possible means to avoid this concern is through the pre-

treatment of the sample via removal of the mineral matter using HCl and HF acids

(Rather, 1917). However, the use of HCI may dissolve part of the organic matter

leading to an underestimation of the organic matter content and the potential use of a

correction factor.

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� 38

Since these methods determine the organic matter content in the soil or

sediment, it is necessary to convert the organic matter content to total organic carbon

content. Traditionally, for soils, a conversion factor of 1.724 has been used to convert

organic matter to organic carbon based on the assumption that organic matter contains

58% organic C (i.e., g organic matter/l.724 = g organic C) (Nelson and Sommers,

1996). However, there is no universal conversion factor as the factor varies from soil

to soil, from soil horizon to soil horizon within the same soil, and will vary depending

upon the type of organic matter present in the sample. Conversion factors range from

1.724 to as high as 2.5 (Nelson and Sommers, 1996; Soil Survey Laboratory Methods

Manual, 1992). Broadbent (1953) recommended the use of 1.9 and 2.5 to convert

organic matter to total organic carbon for surface and subsurface soils, respectively.

The following steps should be performed for each subsample of matrix to be

analyzed. Note that several subsamples would normally be dealt with simultaneously

during this procedure.

1. Clean and dry crucible.

2. Weigh the labeled crucible to 0.0001 g. Since a label written on the crucible in

ink will not survive ignition, the crucible should be permanently and uniquely

marked by inscribing or etching a number or symbol on its side.

3. Weight �1 g of the clean sample into crucible and dry the crucible and its

content in the oven at 90 �C for 24 h.

4. Remove the crucible from the oven, place it immediately in the desiccator, put

the lid on the desiccator and allow the crucible and its contents to cool to room

temperature. When they are cool, remove the crucible and its contents to

weigh immediately to 0.0001 g. The crucible and its contents should be

exposed to the air for as short a time as possible to minimize increases in mass

as the sample equilibrates with laboratory humidity.

5. Allow the furnace to reach a temperature of 440 �C. Using the tongs, place the

crucible and its contents in the furnace for 24 hour.

6. Using the tongs, remove crucible and its contents fro the furnace and place

them immediately in desiccator to cool to room temperature.

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7. When the crucible and its contents have cooled to room temperature, remove

them from desiccator and weigh immediately to 0.0001 g.

8. Calculate percentage of mass lost on ignition in the ground subsample.

9. Convert percentage of mass lost on ignition to percentage of total organic

carbon.

2.7 Minerals composition analysis

2.7.1 Minerals composition of coarse fraction

Concentration of heavy minerals and light minerals are performed by means of

high-density liquids. There is a considerable difference in densities between the

framework constituents and heavy accessory minerals of sediment. Upon immersion

of a sample in a liquid of an intermediate density ‘sink’ and ‘float’ fraction are

produced. There are called heavy and light fractions respectively (Mange and

Maurer, 1992). The ways of technique used will also have an effect on the quality of

the results obtained. Rittenhouse and Bertholf (1942) compare the effectiveness of

gravity settling and centrifuge separation. They observed that the weight percentage

of heavy mineral concentrate obtained by the two methods differ significantly, but the

number of the individual heavy minerals are the same in both methods. Recently,

Schnitzer (1983) presented results of his laboratory experiment. He found high

fluctuations in heavy mineral percentage from samples simultaneously, using

different liquids or different techniques. Variations also occurred when different

settling times or differ densities of bromoform were used. However, Schnitzer’s work

underline the importance of considering the possible influence of separation technique

on heavy mineral data. High density (highly toxic) liquids normally used for

separation are:

Density at 20 �C

Bromoform (tribromoethane) 2.89

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Tetrabromoethane (acetylene tetrabromide) 2.96

Methylene iodide (di-iodomethane) 3.32

Clerici’s solution 4.24

Washing liquids suitable for removing the heavy liquids from the grain are:

carbon tetrachloride, benzene, alcohol (ethyl alcohol or methylated spirite) and

acetone. Because of their low toxicity, alcohol and acetone are frequently used.

In geological laboratories two basic technique are employed for standard

heavy liquid fractionation: (a) gravity settling or funnel separation, and (b) centrifuge

separation. The latter is the best for separation both of very fine (<63 �m) and of

sand-size sediments. This technique was already advocated in the mid-1920s, but

workers consistently encountered difficultly in achieving complete and

uncontaminated recovery of the two separates from the centrifuge tube.

In this study, gravity settling separation technique and bromoform

(tribromoethane) solution are used for separate heavy fractions out of light fractions

in sediment samples. Samples would normally be dealt during this procedure.

1. Requirment particle size after sieving that 1 � below mode.

2. Set equipment used for separation by gravity settling (Figure 2.12).

3. The heavy liquid (bromoform) is filled in the separating funnel.

4. Dry and weighed sample is added to the liquid.

5. Stir to ensure that the grains are wetted.

6. Waiting for grains sink (after 6-8 hours separating time).

7. Open the pinch clip slowly.

8. After heavy fraction is poured onto the filter paper in the lower funnel, close

pinch clip immediately.

9. Heavy fraction and light fraction are washed with acetone and set aside to dry.

10. Weigh dried heavy and light fraction sediments and label.

11. Heavy fraction to be mounted on the microscope slide.

12. Slide mount of heavy fraction will be determined in optical analysis.

13. Light fraction to be determined by binocular microscope.

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Figure 2.12 Arrangement of equipments for heavy mineral separation by gravity

settling.

2.7.2 Minerals composition of fine fraction

X-ray diffraction method is the most widely used method for identification of

clay minerals and their crystalline characteristics. X-ray diffractogram was generated

using a Bruker x-ray diffractometer, model D8 Advance, at Department of Geological

Sciences, Faculty of Science, Chiang Mai University.

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X-ray diffraction analysis was carried out by a CuK� generated at 18

kilowatts, 40 kilovolts and 30 milliamperes. For fine fraction clay, 2-theta start at 2�,

stop at 70�, steps 0.04�. Semi-quantitative estimation was determined. The highest

intensity of d-spacing refraction obtained from each mineral was selected to represent

the proportion of the mineral in the sample. The estimation was based on the

composition of the half peak area calculated from the height of the peak multiplied by

the half width at the midpoint of the peak height. This method of calculating the half

peak areas overcomes problems associated with inclined base lines and overlapping

peaks. The calculated half peak areas of all minerals in a sample were summed and

recalculated to 100 percent (Figure 2.13). Each mineral was calculated and the results

presented as a percentage value that could be either an underestimate or an

overestimate of the true proportion present. Thus, the most effective comparisons can

be made only between samples containing similar constituents.

Twenty-six representative samples from 5 stratigraphic sections in study area

were determined to mineral composition. These samples were selected from

interesting sediment layers. The minerals determined by this method indicate some

aspects of depositional environment.

2.8 Carbon-14 dating

Age of sedimentary deposit is importance for stratigraphic correlation with

another area. Geochemical isotope analyses are carried out to determine carbon

element. It constraints on the age of sediment are provided by 14C dating. This

method is based on the amount of 14C that has been absorbed by plants though

photosynthesis and also by absorbtion though roots. The values of 14C in individual

living organisms are uniform. When organisms die, 14C starts to decay radioactively a

stable rate. Then, its activity in dead plant tissues may be employed in order to

calculate the times, which has elapsed since they died. It is also assumed that the

sample which is to be dated has not been contaminated by modern 14C and that the

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Figure 2.13 The calculated half peak area of every mineral found in a sample, was

summed and recalculated to 100 percent (after Ratanasthien, 1975).

observed activity is unaffected by any radioactive impurities in it (Attendorn and

Bowen, 1997).

The rate of decay of an unstable nuclide is proportional to the number of

atoms (N) remaining at any time (t). Translating the rate into mathematic language

results in below equation.

where = Rate of change of the number of present atoms. The minus sign

is required because the rate decreases as a function of time.

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= Decay constant, specific of each element.

= Number of atoms.

The rate of decay of an unstable nuclide is measured by means of ionization

chambers (Faul, 1954; Smales and Wager, 1960). The operation of radiation

detectors reveals the presence of background radiation caused by natural and

anthropogenic environmental radioactivity. The rate of decay is measured in units of

becquerels and curies.

When radionuclide decays in a close system, a number of stable radiogenic

daughters (D*) that accumulate in a unit weight of rock or mineral. Over a long

period of time, the number of daughter atoms approaches the number of parent atoms

present initially. The interpretation of dating depends on certain assumptions about

the geological history (Faure and Mensing, 2005) as follows.

1. The rock or mineral sample being dated has not gained or lost parent or

daughter atoms except by decay of the parent to the stable daughter.

2. The decay constant of the parent nuclide is in dependent of time and is not

affected by the physical condition to which the nuclide may have been

subjected and its value is known accurately.

3. An appropriate value of Do is used in the calculation based on either

knowledge of the chemical properties of the daughter element or its isotope

composition in the terrestrial reservoir from which the rock or mineral

originated.

4. The measured value of D and N are accurate and representative of rock or

minerals being dated.

The concentration of the parent and daughter elements to be dated can be

determined by several methods. The choice depends on concentration of the element,

the amount of sample, lower limit of detection and availability of the required

instrumentation. Isotope dilution is generally agreed to be the supreme analytical

method for very accurate concentration determinations. A half-life for the

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radioisotope of 5730±40a was gave by Godwin (1962) and indeed restated in 1982. A

previous and less accurate value of 5568±30a is still in use today.

De Vries (1958) demonstrated that the radiocarbon content of the atmosphere

varies in a systematic manner in the past, and also that the 14C activity around AD

1700 and 1500 was as much as 2% more than in the 19th-century. Another effect was

note by Suess (1995). He found that the activity of 20th-century wood is about 2%

lower than that of wood from the 19th-century and attributed this to the introduction of

dead CO2 into the atmosphere through the combustion of fossil fuel. This effect has

been exceeded since 1945 because the explosion of thermonuclear devices and

operating of nuclear reactors. They are artificial produce radiocarbon.

Carbon-14 age dating were generated using CAIS 0.5 MeV accelerator mass

spectrometer, at Center for Applied Isotope Studies, The University of Georgia,

United State of America. Sample would normally be dealt during this procedure.

1. The charcoal was given a standard chemical treatment similar the pretreatment

for cellulose described in Hedges et al. (1989) Archaeometry 31(2) 99-114.

2. The material was washed in ultrapure water.

3. Boiled in a sequence of mineral acids and bases (1M HCl/ 1 M NaOH/ 1M

HCl) to remove contaminating carbonate salts and humic acids.

4. The cleaned and treated material was then combusted at 900°C in evacuated

and sealed ampoules in the presence of CuO.

5. The resulting carbon dioxide was cryogenically purified from the other

reaction products and catalytically converted to graphite using the method of

Vogel et al. (1984).

6. Graphite 14C/13C ratios were measured using the CAIS 0.5 MeV accelerator

mass spectrometer.

7. The sample ratios were compared to the ratio measured from the Oxalic Acid I

(NBS SRM 4990).

8. The sample 13C/12C ratios were measured separately using a stable isotope

ratio mass spectrometer and expressed as �13C with respect to PDB, with an

error of less than 0.1%.