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A low detection limit sulfide measurement method in marine environments

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A low detection limit sulfide measurement method in marine environments

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University of Southern California
Ocean Sciences Program
Master of Science

A Low Detection Limit Sulfide
Measurement Method in Marine
Environments

Yang Weber
Advisor: James W Moffett
August 2015

2

Table of Contents

Abstract……………………………………………………………………………...Page 3
Acknowledgement………………………………………………………...…………Page 4
Introduction……………………………………………………………...…………..Page 5
Experimental Procedure……………………………………………………………..Page 8
Results and Discussion…………………………………………………………..…Page 13
Conclusion.…………………………………………………………………………Page 21
Reference…………………………………………………………………………..Page 22

3

Abstract
Sulfide plays a significant role in sediment geochemistry through its role in
reactions including sulfate reduction and sulfide oxidation. However, , sulfide
concentration in the upper sediment layers is usually below the detection limit of most
commonly used methods. This limits our understanding about the sulfur cycle in the
upper sediment layers.

Monobromobimane (mBBr) is a common fluorescence reagent used for thiol
measurement. However, mBBr can also be used to measure sulfide. In the presented work,
the detection limit of the mBBr method is as low as 6.75nM and the linear range is from
0µM to 10 µM. The mBBr method has been used successfully to measure sulfide in
sediment pore water.

4

Acknowledgement
First of all, I want to thank my advisor Dr. Jim Moffett. Jim is the best advisor in my eyes.
He is so patient with me and guides me step and step through the research project. He always
goes on field trip with me and always makes sure I have enough resources to carry out the work.
Jim always thinks the best plan for me and cares about me greatly. His insight and vision also
helps me broaden my view. I have been so blessed by my advisor. In addition, I want to thank my
committee member Dr. Wiebke Ziebis. I have been so blessed to receive great help from Wiebke
for the Catalina work. Wiebke has been so generous to me lending supplies and instruments to me
all the time. Also, I appreciate the opportunities working with Wiebke and learned a lot from her.
Besides, I want to thank my committee member Dr. Doug Hammond. Doug has taught me the
two main courses, chemical and physical oceanography and Marine Geochemistry. I have had the
opportunity to build up systematic knowledge base through Doug’s challenging problem sets and
well-organized in-depth lectures. I also appreciate the encouragement and sincere useful advice
given by Doug.
I also want to thank my past lab-mate and dear friend Jagruti Vedamati. She is like a big
sister for me and cares about me greatly and passed down her HPLC skills to me. Then, I want to
thank Jane Dentinger and Bingran Cheng for their tremendous help to me with the fieldwork and
nutrients analysis. I also want to thank Phoebe Moffett for her help to me with sampling.
Furthermore, I want to thank Lynda Cutter for her help to me with HPLC and Mass Spec. I want
to thank the staff of Wrigley Institute for their help and support to me on Catalina. I also want to
thank my mom and dad for their great support to me along the years and their love and care to me.
Another special person I want to thank is my dear husband Jürgen. He is always so caring and
loving to me. He accompanied me all the time during my thesis writing either in person or over
skype and tried to make sure I can finish my master thesis.
Finally, I want to give my special thanks to my ever-present friend, helper, savior and
Lord, Jesus Christ. He always answered my prayers to solve the experimental challenges I have
met. He saved my wretched soul bonded in fear and darkness, and gave me a brand new life
purchased by his blood on the cross.

5

1. Introduction
1.1 The importance of sulfide measurement in the sediment
Sulfide is a very important sulfur species in the sediment sulfur cycle, as a
reactant in the sulfide oxidation process as well as a product in the sulfate reduction
process, both of which are widely existent in marine sediments (Aller and Rude, 1988;
Bertics and Ziebis, 2010). Meanwhile, sulfide is also an important species linking the
sulfur cycle and nitrogen cycle in sediments. Sulfide is involved in two main pathways of
nitrate reduction including sulfide-driven denitrification and dissimilatory nitrate
reduction to ammonia (Shao, 2011;Roberts, 2014). It has also been shown that the
concentration of sulfide can affect which nitrate reduction pathway is more dominant
(Brunet, 1996). The measurement of sulfide in marine sediments can help increase the
understanding of microbial processes linked with sulfide in sediments.
Sulfide also plays an important role in metal speciation. On one hand, sulfide can
bind with metal ions to form metal-sulfide precipitates. On the other hand, metal oxides
such as Fe oxides and Mn oxides can oxidize sulfide (Thamdrup, 1994). The metal-
sulfide interactions can have a profound influence on the bioavailability of toxic metals in
sediments (Morse and Luther, 1999). Thus, it is crucial to understand the concentrations
of sulfide in sediments in order to have a more accurate estimate of the bioavailable metal
concentrations.
Finally, sulfide is inhibitory to multiple microbial processes in sediments. It has
been shown that the addition of sulfide can significantly decrease nitrification rates in
coastal sediments (Joye and Hollibaugh, 1995). Sulfide can also be inhibitory to nitrous
oxide reduction, the final step in denitrification (Manconi, 2006).
Considering the multiple roles of sulfide in biogeochemical cycles in sediments, it
is very important to have accurate sulfide profiles. However, due to the fact that sulfide is
very easily oxidized by oxygen; measuring sulfide at low concentrations has been very
challenging. This forms the basis for the motivation of this work: to develop a low
detection-limit sulfide measurement method to understand sulfide distribution more
completely in marine sediments.

6

1.2 Current methods of sulfide measurement in the sediments
There are multiple ways to measure sulfide in sediments. The most commonly
used way is the so-called Cline method, which was established in the 1960s and has been
widely used for sulfide measurement in sediments (Cline, 1969; Simpson, 2001;
Hernandez-Crespo, 2012). According to the Cline method, a blue compound (methylene
blue) is generated from the reaction between sulfide and the mixed diamine reagent (N,N-
dimethyl-p-phenylenediamine sulfate and ferric chloride in 50% hydrochloric acid). The
sulfide concentration can be derived from measuring methylene blue concentration by
using UV-Vis Spectrometer. The detection limit of the traditional Cline method is at the
micromolar level.
With the development of microelectrode techniques, an amperometric H
2
S
microelectrode has been developed for sulfide measurement in aquatic environments and
sediments (Jeroschewski, 1996; Kühl, 1998; Wilson and Vopel, 2012). After penetrating
the silicone membrane at the sensor tip, sulfide is oxidized by K
3
[Fe(CN)
6
] at the cathode,
generating K
4
[Fe(CN)
6
]. The current generated during K
4
[Fe(CN)
6
] generation is
proportional to the sulfide concentration in sediments (Jeroschewski, 1996). The H
2
S
microelectrode provides a fast way to obtain high-resolution sulfide data in sediments.
However, this method is still limited by its micromolar level detection limit.
Due to the high heterogeneity in sediments, the technique of diffusive gradients in
thin films (DGT) has been applied to sulfide measurement in sediments, which can
provide 2D sulfide distribution in sediments. Sulfide diffuses through thin films and
reacts with pale yellow AgI(s) forming black precipitate Ag
2
S (Teasdale, 1999). The
color change in the accumulating gel can be analyzed by computer-imaging densitometry
so that the sulfide concentration can be derived from the color change. The DGT
technique provides 2D sulfide distribution and it helps us to have a more accurate
understanding about sulfide distribution in sediments. Despite the superiority of this
method, DGT can not measure sulfide at nanomolar levels, which limits our
understanding about the complete sulfide distribution especially in upper sediment layers.

7

1.3 The mechanism of mBBr Method
Monobromobimane (mBBr) is a thiol-specific derivatization reagent, which can
react with thiols and generate a fluorescent compound. It has been used extensively to
measure thiols in marine environments with a low detection limit at nanomolar levels
(Ahner, 2002;Dupont, 2006; Pawlik-Skowronska, 2007). Our lab is well equipped for
thiol measurement and has used a robust thiol protocol for many years. The reaction
between mBBr and thiol (R-SH) is essentially a nucleophilic substitution reaction, in
which the bromide anion of the mBBr molecule leaves mBBr, generating an active mBBr
carbocation. With eight electrons in the outermost orbital of the sulfur atom, RS- is a very
active nucleophilic reagent, attacking the mBBr carbocation and generating mBBr-SR.
The mechanism of thiol and mBBr reaction offers the potential to measure sulfide by
adding the derivatization reagent mBBr, because sulfide can also be a very strong
nucleophilic reagent with eight electrons in the outermost orbital. This idea was
confirmed by the satisfactory linearity of a sulfide standard curve by using our thiol
measurement protocol. Furthermore, a literature search showed that the mBBr method
has been developed to measure sulfide in human blood at nanomolar levels (Wintner,
2010; Shen, 2011; Shen, 2012).
Shen(2011) indicated that sulfide can react with mBBr and generate fluorescent
sulfide dibimane as shown in the following reaction ( Fig 1.1). In the first step, HS
-

replaces Br
-
in the monobromobimane molecule forming mBBr-HS, which is further
hydrolyzed in an alkaline solution (pH=9.5) to become mBBr-S
2-
. In the second step,
mBBr-S
2-
can replace Br
-
in another monobromobimane molecule to form mBBr-S-mBBr,
or sulfide dibimane (SDB).
After mBBr derivatization, a C16-amide column is used to separate sulfide
dibimane from other mBBr derivatives, by using a gradient elution. Subsequently, sulfide
dibimane is excited at the wavelength of 395nm from the Xe lamp in a fluorescence
detector. As SDB comes back to the stable state from the excited state, it emits light with
the wavelength of 475 nm. The intensity of the emitted light at 475 nm (fluorescence) is
proportional to the concentration of SDB. Accordingly, SDB concentration can be
measured based on its fluorescence.

8

Fig 1.1 The mBBr derivatization of sulfide
2. Experimental Procedure
2.1 Standard Curve
Monobromobimane powder (25mg) of FluoroPure Grade was purchased from
Life Technologies. To make 50mM monobromobimane solution, 1.84 mL acetonitrile
(HPLC grade, EMD) was added to the bottle containing monobromobimane. The solution
needs to be stored at -20°C in the dark.
Shen (2011) suggested that the optimal pH for mBBr derivatization is 9.5,
adjusted by 100mM Tris-HCl buffer with 0.1mM DTPA (diethylenetriamine-pentaacetic
acid calcium trisodium salt hydrate). But, 100mM Boric Acid (99.5%, Sigma) buffered
with 10mM DTPA (97%, Fluka) was used in this work, according to the thiol protocol of
Dupont (2004). The buffer pH was changed from 9.0 suggested in the thiol protocol to
9.5, as suggested by Shen (2011). The preliminary experimental data also showed that
pH=9.5 was the optimal pH for sulfide and mBBr reaction.
A sulfide stock solution (10mM) was freshly prepared in a 250mL serum bottle
every time analyses were done. Sodium Sulfide nonahydrate (Na
2
S•9H
2
O, EMD, 0.1801
g) was dissolved in 101mL of 10mM DTPA solution, which had been deoxygenated by
vigorous bubbling with 99.999% nitrogen for at least one hour. The purpose of adding
DTPA was to complex metal ions in MilliQ-water and from serum bottles, so that sulfide
does not bind with metal ions. Unfortunately, as the balance is unable to fit in the
anaerobic hood, the sulfide stock solution was made in oxic environments.

9

Sulfide working solutions and sulfide standards were prepared in the anaerobic
hood, which is filled with nitrogen and hydrogen (Less than 1% hydrogen, below the
explosion point). First, 1 mL sulfide stock solution was injected into 101 mL of 10mM
deoxygenated DTPA solution, to make a primary sulfide working solution with the
concentration of 73.51 µM. The primary sulfide working solution was then diluted 100
times using de-oxygenated water to create the secondary sulfide working solution with a
final concentration of 727.80 nM.
At this point, 50 µL boric Acid/DTPA buffer (pH=9.5) and 5 µL mBBr (50mM)
were added into 2 ml amber vials with marking spot and bonded PTFE silicone slit septa.
It is very crucial to use amber vials to avoid the light, because mBBr is not stable under
light. Subsequently, a 500 µL mixture of varying amounts of sulfide working solutions
and deoxygenated MilliQ water were added into different vials to make standard
concentrations from 0 µM to 1 µM and 0 µM to 10 µM. Triplicates were prepared
respectively at each concentration. After being vortexed for 30 seconds, the amber vials
were put in darkness for the 15 min reaction time. The resulting product sulfide dibimane
(SDB) after mBBr derivatzation was purified and measured in the following HPLC
analysis step.
2.2 Quantitative Analysis by HPLC with Fluorescence detector
Reversed-phase liquid chromatography was used to separate SDB from other
interferences through a SUPELCO C16-amide column. (Length: 25cm; diameter: 2.1mm;
particle size: 5 µm) The Agilent HPLC system includes the following modules: degasser
(G1379B); Bin pump (G1312A); Auto Sampler (G1313A); Fluorescence Detector
(G1321A).
The aqueous mobile phase A was made of 1% acetonitrile (HPLC grade, EMD)
and 0.025% acetic acid (HPLC grade, EMD) in MilliQ water, while the non-polar mobile
phase B was made of 0.025% acetic acid in acetonitrile. The flow rate was set as 0.15
mL/min. The non-polar mobile phase B was 0% for the first 8 min after injection
(injection volume=100 µL), and then linearly increased to 30% in the next 60 min.
During the following 2 min, the acetonitrile percentage increased sharply from 30% to

10

60%. Then the acetonitrile percentage decreased to 0% over the next 10 min, and stayed
at the baseline 0% during the final 20 min. The fluorescence detector parameters were set
as: excitation wavelength =395 nm, emission wavelength =475 nm.
The area of the peak eluting at 59.7 min was proportional to the injected sulfide
concentration, and it was absent in the blank. To further confirm that sulfide dibimane
eluted out from the column at 59.7 min. LC-MS was used to test the structure of the
eluent at 59.7 min.
2.3 Structure confirmation by LC-ESI-MS
Liquid Chromatography-Electrospray- Mass Spectrometer is a very powerful
analytical instrument for quantitative and qualitative work. The targeted compound can
be purified by liquid chromatography before being analyzed by a mass spectrometer.
There are two types of scans performed in LC-MS: MS full Scan and MSn scan. The MS
full scan is used to measure the mass to charge ratio of molecules. The MSn scan is used
to measure the mass to charge ratio of the fragments after bombarding the chosen
molecules or fragments. In the MS2 scan, the chosen molecule is bombarded by a certain
amount of energy, generating a series of fragments. The MS3 scan is applied to further
break down the chosen fragments generated in MS2 scan. Theoretically, the compound
can be continuously bombarded till enough structure information has been obtained.
Though it is very challenging to decipher the structure of an unknown chemical
solely from a Mass Spectrometer without Nuclear Magnetic Resonance Spectroscopy, a
Mass Spectrometer can provide enough evidence to test whether the structure of the
eluent is the same as the suspected chemical. Thus, LC-MS can suffice to test whether
the 59.7 min eluent is the product of sulfide and mBBr reaction, sulfide dibimane.
The Mass Spectrometer (ThermoSceintific, LXQ) was operated in a positive ion
electrospray ionization mode with the following conditions: 1) Sheath gas was 30 units,
2) Auxiliary gas was 11 units, 3) Sweep gas was 12 units, 4) Maximum inject time was
400 ms, 5) Isolation width was 1.0, 6) Capillary temperature was 260 °C, 7) Spray
voltage was 4.95 kV, 8) The ion gauge pressure was 9.1Χ10
-4
Torr.

11

2.4 Catalina Sediment Porewater sampling
The sampling was carried out at low tide at the muddy area of Catalina Harbor on
Catalina Island, when the muddy sediment was exposed to the air. (33°25.23′N,
118°19.42′W) (Fig 2.1; 2.2) Two 15 cm cores were taken by using push cores (inner
diameters=5 cm, length =30 cm). Catalina Harbor seawater was added into the push cores
on top of the sediment samples. The overlying water of the two cores was oxygenated by
bubbling with air until they were processed. The first core was processed within one day
after sampling, while the second core was processed five days after sampling. The cores
were sliced into different layers at 1 cm intervals. Pore water was extracted by using a
KC pore-water pressing bench (KC Denmark). The KC pore-water pressing bench
consists of five 50 cm
3
black Delrin cylinders. The bottom part has a small hole (ø 1mm)
that serves as the pore water outlet, and holds a support screen for a filter (ø 47 mm). We
used 8 µm Nuclepore membrane filters. The top part has a hose connector to apply a gas
over-pressure. We used nitrogen gas. Sediment is filled into the cups (volume: ~ 50 cm
3
)
and covered by a latex membrane (dental dam). The top and bottom parts are fitted with
O-rings that seal the compression chamber, which is held together by a screw clamp. By
applying an overpressure of 0.4 bar, compressing the sediment, pore water is forced from
the sediment matrixand is collected in 5mL vacutainers (BD) underneath the compression
chambers. Afterwards, 500 µL pore water was filtered through 0.45 µm syringe filters
(VWR) and injected into 2mL centrifuge vials that contained 5 µL mBBr reagent
(50mM) and 50 µL Boric Acid/DTPA buffer. After reacting in the dark for 15 min, the
samples were frozen until HPLC analysis.

12

Fig 2.1 Catalina Harbor Location

Fig 2.2 Muddy area of Catalina Harbor
3. Results and Discussion
3.1 HPLC Separation
The mBBr derivative of sulfide eluted out from the C16-amide column at 59. 7
min. There are no interference peaks near 59.7 min. (Fig 3.1)

13

Fig 3.1 HPLC graph
3.2 Sulfide Standard Curves
The sulfide standard curve ranging from 0 µM to 1 µM had a very good linearity
(R
2
=0.99984). The simulated linear equation between sulfide concentration in the unit of
nM and peak area is C(Na
2
S)=0.4542×Peak Area+1.4988. (Fig 3.2) The standard
deviation of peak areas of triplicates ranges from 1% to 3%. The detection limit of this
mBBr method is three times the standard deviation of the low concentration measurement,
namely 6.75 nM.
Retention
time

Fluorescence
Intensity

14

Fig 3.2 Standard Curve 1 0-1µM
The sulfide standard curve ranging from 0 µM to 10 µM had even better linearity
(R
2
=0.99992). The simulated linear equation between sulfide concentration in the unit of
nM and peak area is C(Na
2
S)=0.4042×Peak Area+31.616 (Fig 3.3). The standard
deviation of peak areas of triplicates varies from 1% to 4%.

Fig 3.3 Standard Curve 2 0-10µM
It is shown that the mBBr method bears a very good linearity in the concentration
range from 0 µM to 10 µM and it can measure sulfide concentration at nanomolar levels.

15

3.3 SDB confirmation
The full MS spectrum of the eluent at 59.7 min showed the presence of the sulfide
dibimane molecular [M+H]
+
at m/z 415.37 (Fig 3.4), in good agreement with the
molecular weight of sulfide dibimane molecular [M] at 414.48. (Fig 3.5) The peak of m/z
432.37 might be [M+NH
4
]
+
. As with other peaks of m/z 460.34, 572.32 and 828.96 etc,
they might be caused by contaminants in the solvents. In the HPLC graph, another
significant peak was noticed at 49.86 minute, which was supposedly to be the reagent
peak. A series of small peaks were also observed, which might be the side products from
mBBr derivatization.

Fig 3.4 Mass Spec Full Scan

16

Fig 3.5 The structure of Sulfide Dibimane (C
20
H
22
N
4
O
4
S MW=414.48)
The MS2 spectrum of the parent ion 415.37 showed the dominant fragment after
bombardment is at m/z 193.07 (Fig 3.6), which can be explained by the following
equation. (Fig 3.7)

Fig 3.6 MS2 Scan

17

→ 2 + 𝑆
Fig 3.7 MS2 reaction mechanism
C
20
H
22
N
4
O
4
S (MW=414.48)→2C
10
H
12
N
2
O
2
(MW=192.21)+S

The fragment at m/z 193.07 was further bombarded in the MS3 scan, and
generated a predominant fragment at m/z 165.07 (Fig 3.8). The loss of 28 Da (193.07-
165.07=28) can be explained by the loss of two methyl groups (2CH3- 2H=2(15-1)=28)
(Fig 3.9)

Fig 3.8 MS3 Scan

18

→ + 2𝐶𝐻3−
Fig 3.9 MS3 reaction mechanism
C
10
H
12
N
2
O
2
(MW=192.21) → C
8
H
8
N
2
O
2
(MW=164.16)+ 2CH
3

With further bombardment in MS4, the remaining two methyl-groups on the
fragment m/z 165.07 were lost and generated the dominant fragment is at m/z 137. 10.
(Fig 3.10, 3.11)

Fig 3.10 MS4 Scan

19

→ 2 +2𝐶𝐻3−
Fig 3.11 MS4 Reaction Mechanism
C
8
H
8
N
2
O
2
(MW=164.16) → C
6
H
4
N
2
O2 (MW=136.11)+ 2CH3

Based on the results of full scan and MSn Scan, the conclusion can be drawn that
the eluent at 59.7 min is indeed sulfide dibamine, the product of sulfide and mBBr.
3.3 Sulfide profiles
The sulfide concentrations of the first core, which was processed within one day
after sampling, varied from 1.75 µM to 6.70 µM. With a general trend of increasing
concentration with depth, two maximum peaks of sulfide concentrations were observed at
3 cm and 6 cm respectively.
The second core was processed five days after the sampling, incubated in the dark
and the oxygenated overlying water was kept oxygenated by bubbling with air pump.
Due to the effect of sulfide oxidation, the sulfide concentrations of the second core were
consistently lower than that of the first core. The maximum peak at 3 cm disappeared in
the second core, while the maximum peak at 6 cm remained. The sulfide concentrations
of the second core varied from 250nM to 4.95 µM.

20

Fig 3.12The sulfide profiles in Catalina Harbor Porewater
In a general trend, the sulfide concentrations increased with the depth, with
decreasing oxygen concentration and the increasing activity of sulfate reduction.
However, from depth 6-8cm, the sulfide concentrations were decreased, which can be
caused by the presence of Fe (II) generated from Fe reduction or by non-local irrigation
effects. A similar process may cause the low concentrations between the two local
maxima in the first core.
The data of sulfide profiles in previous multiple trips were not presented here. In
previous work, pore water was extracted by Rhizons (0.45 µm). But, air contamination is
a potential problem in the Rhizons filtering technique. In the later research, it showed that
KC porewater processing bench provided more accurate sulfide data, excluding the air
contamination involved in pore water extraction.

21

4. Conclusion
The fluorescence sulfide measurement method showed a low detection limit at 6.
75 nM, and the linear range was from 0 to 10 µM. This method has been successfully
applied for sulfide measurement in marine sediments environments. Despite the low
detection limit, the mBBr method is unable to provide 2D sulfide distribution in the
marine sediments. Considering the high heterogeneity in the marine sediments, it is very
worthwhile to combine the mBBr method with DGT technique for the future research.
The salinity effect on sulfide measurement needs further investigation. The
standard curves in this work were done in MilliQ-water. Besides salinity effect, the
reaction time needs to be further explored as well. The reaction time used in this work
was the same from the thiol protocol but it has not been well explored for sulfide
measurement yet.

22

References
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Bertics, V. J., and W. Ziebis. "Bioturbation and the Role of Microniches for Sulfate
Reduction in Coastal Marine Sediments." . Environmental Microbiology 12, no.
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Brunet, R. C., and L. J. GarciaGil. "Sulfide-Induced Dissimilatory Nitrate Reduction to
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Hernandez-Crespo, C., M. Martin, M. Ferris, and M. Onate. "Measurement of Acid
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Abstract (if available)

Abstract Sulfide plays a significant role in sediment geochemistry through its role in reactions including sulfate reduction and sulfide oxidation. However, sulfide concentration in the upper sediment layers is usually below the detection limit of most commonly used methods. This limits our understanding about the sulfur cycle in the upper sediment layers. ❧ Monobromobimane (mBBr) is a common fluorescence reagent used for thiol measurement. However, mBBr can also be used to measure sulfide. In the presented work, the detection limit of the mBBr method is as low as 6.75nM and the linear range is from 0μM to 10 μM. The mBBr method has been used successfully to measure sulfide in sediment pore water.

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Asset Metadata

Creator Weber, Yang (author)

Core Title A low detection limit sulfide measurement method in marine environments

School College of Letters, Arts and Sciences

Degree Master of Science

Degree Program Ocean Sciences

Publication Date 08/04/2015

Defense Date 08/11/2015

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag marine environments,mBBr method,OAI-PMH Harvest,sulfide

Format application/pdf (imt)

Language English

Contributor Electronically uploaded by the author (provenance)

Advisor Moffett, James W. (committee chair), Hammond, Douglas E. (committee member), Ziebis, Wiebke (committee member)

Creator Email hantten1989@gmail.com,yanghan@usc.edu

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c3-625129

Unique identifier UC11305530

Identifier etd-WeberYang-3799.pdf (filename),usctheses-c3-625129 (legacy record id)

Legacy Identifier etd-WeberYang-3799.pdf

Dmrecord 625129

Document Type Thesis

Format application/pdf (imt)

Rights Weber, Yang

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the a...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus MC 2810, 3434 South Grand Avenue, 2nd Floor, Los Angeles, California 90089-2810, USA