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 CITY UNIVERSITY OF HONG KONG
香港城市大學

Vanadium in Coal Mining Area: Distribution,

Modes of Occurrence, and Environmental
Behavior
煤礦區中的釩：分布，賦存形態，和環境行
為

Submitted to
Department of Chemistry
化學系
in Partial Fulfillment of the Requirements
for the Degree of Doctor of Philosophy
哲學博士學位
awarded by City University of Hong Kong
for successful completion of the joint programme with
The University of Science and Technology of China

by

Liu Yua n
劉源

June 2018
二零一八年六月
 I

ABSTRACT

Vanadium in coals may have potential environmental and economic impacts.

However, comprehensive knowledge of the environmental geochemistry of V in coal

mining areas is lacking. In this study, > 2,900 reported Chinese coal samples were

collected from published papers to investigate V concentration in Chinese coal. 21

coal samples of different coal ranks were collected from nine provinces in China,

with the aim of studying the abundance, chemical speciation and combustion

behavior of V in coals by sequential extraction and combustion experiment. In the

Anhui coal mining area, sediment samples from the Huai River near the Huainan

coal district, as well as soil and fish samples from Huaibei coal mining area were

collected to study the concentration, distribution, chemical speciation, transformation

and environmental effect of V in coal mining areas. In addition, as a contrast, the soil

from the Yellow River Delta and aquatic organism samples from the Yellow River

Estuary and Laizhou Bay, impacted by petroleum production, were also collected to

study the geochemistry of V in petroleum-producing regions.

The major findings of the present research work were as follows: (1) With coal

reserves in individual provinces as the weighting factors, V in Chinese coals was

estimated to have an average abundance of 35.81 μg/g. The concentrations of V in

Chinese coals were categorized into depleted, normal, and slightly enriched based on

concentration coefficients. (2) Silicate-bound V had the highest fraction among six

operationally defined modes of occurrence of V extracted from coal samples. With

increasing of coal rank, organic matter-bound V exhibited declining trends. We

found that V and Cr were highly correlated in the coal samples, which might be

attributed to the fact that silicate-bound and organic-bound V and Cr are the leading

modes. (3) The Chinese V emission inventory in the last decade during coal
 II

combustion and the global V emission flux by different sectors were estimated.

Vanadium emissions by electric power plants are the largest contributor. The

relationship between the chemical speciation and combustion behavior of V, as well

as the relationship between volatilization ratios of V in coals and coal rank, was

revealed. (4) The sediment core in the Huai River has recorded V deposition

spanning 60 years. The concentrations and distribution of V in soils and fish from

Huaibei coal mining area were investigated to reveal the impact of coal gangue and

coal-fired plants on the V. The impact of oil exploitation on V in soils and aquatic

organisms was also studied. (5) The results of enrichment factor and

geo-accumulation index (Igeo) tests revealed that: some Huai River sediments were

considered to have minor or moderate contamination with V; no V pollution was

found in soils from the Yellow River Delta and Huaibei coal mining area; the mean

concentrations of V in fish in the Yellow River Estuary were found to be

significantly higher than the results of Huaibei coal mining area; through estimation

of daily intake of V via fish consumption, the V contamination level of fish samples

from both the Yellow River Delta and Huaibei coal mining area fell within an

acceptable range, indicating no potential hazard to human health.

Keywords: Coal; Vanadium; Environmental geochemistry; Coal mining area;

Petroleum-producing regions
 III

CITY UNIVERSITY OF HONG KONG

Qualifying Panel and Examination Panel

Surname: LIU

First Name: Yuan

Degree: Doctor of Philosophy

College/Department: Department of Chemistry

The Qualifying Panel of the above student is composed of:

Supervisor(s)
Prof LAM Kwan Sing Paul Department of Chemistry,
City University of Hong Kong

Prof. LIU Guijian School of Earth and Space Science

University of Science & Technology of China

Qualifying Panel Member(s)

Prof. LAM Hon Wah Michael Department of Chemistry,
City University of Hong Kong

This thesis has been examined and approved by the following examiners:

Prof LAM Kwan Sing Paul Department of Chemistry,

City University of Hong Kong

Dr. KO Chi Chiu Vincent Department of Chemistry,

City University of Hong Kong

Prof. LAM Hon Wah Michael Department of Chemistry,

City University of Hong Kong

Prof. YAO Suping School of Earth Sciences and Engineering

Nanjing University

Prof. LIU Weiguo Institute of Earth Environment

Chinese Academy of Sciences

Prof. GUI Herong School of Earth and Environment

Anhui University of Science and Technology
 IV

List of publications

1. Yuan Liu, Guijian Liu, Cuicui Qi, Siwei Chen, Ruoyu Sun: Chemical speciation

and combustion behavior of chromium (Cr) and vanadium (V) in coals. Fuel11/2016;

184:42-49. DOI:10.1016/j.fuel.2016.07.003.

2. Yuan Liu, Guijian Liu, Zijiao Yua n, Houqi Liu, Paul K.S. LAM: Heavy metals

(As, Hg and V) and stable isotope ratios (δ13C and δ15N) in fish from Yellow River

Estuary, Science of the Total Environment 02/2018; 613-614:462-471. DOI:

10.1016/j.scitotenv.2017.09.088.

3. Yuan Liu, Guijian Liu, Zijiao Yua n, Houqi Liu, Paul K.S. LAM: Presence of

arsenic, mercury and vanadium in aquatic organisms of Laizhou Bay and their

potential health risk. Marine Pollution Bulletin 12/2017; 125(1-2):334-340.

DOI:10.1016/j.marpolbul.2017.09.045.

4. Yuan Liu, Guijian Liu, Qinyuan Qu, Cuicui Qi, Ruoyu Sun, Houqi Liu:

Geochemistry of vanadium (V) in Chinese coals. Environmental Geochemistry and

Health10/2017; 39(5):1-20. DOI:10.1007/s10653-016-9877-2.

5. Yuan Liu, Guijian Liu, Jie Wang, Lei Wu: Spatio-temporal variability and

fractionation of vanadium (V) in sediments from coal concentrated area of Huai

River Basin, China. Journal of Geochemical Exploration 01/2017; 172:203-210.

DOI:10.1016/j.gexplo.2016.11.008.

6. Jiao Wang, Guijian Liu, Yuan Liu, Chuncai Zhou, Yaqin Wu, Qing Zhang:

Mobilization of substance around stackable fly ash and the environmental

characteristics of groundwater: with particular reference to five elements: B, Ba, Pb,

Sb and Zn. Fuel 06/2016; 174:126-132. DOI:10.1016/j.fuel.2016.01.092.

7. Biao Fu, Guijian Liu, Yuan Liu, Siwei Cheng, Cuicui Qi, Ruoyu Sun: Coal

quality characterization and its relationship with geological process of the early
 V

Permian Huainan coal deposits, southern north China. Journal of Geochemical

Exploration 07/2016; 166, 33-44. DOI: 10.1016/j.gexplo.2016.04.002.

8. Jiao Wang, Guijian Liu, Yuan Liu, Chuncai Zhou, Yaqin Wu: Photocatalytic

degradation of methyl orange by Fe2O3–Fe3O4 nanoparticles and

Fe2O3–Fe3O4–montmorillonite nanocomposites. Clean – Soil Air Water 08/2017;

45(9), 1600472. DOI: 10.1002/clen.201600472.

9. Siwei Cheng, Guijian Liu, Yuan Liu, Dun Wu: Cadmium in Chinese coals:

Abundance, distribution, occurrence, and environmental effects. Human and

Ecological Risk Assessment 03/2018. DOI: 10.1080/10807039.2018.1450136.

10. Lanlan Lu, Guijian Liu, Jie Wang, Yuan Liu: Accumulation and health risk

assessment of trace elements in Carassius auratus gibelio, from subsidence pools in

the Huainan coalfield in China. Environmental Monitoring and Assessment

08/2017; 189 (9), 479. DOI: 10.1007/s10661-017-6178-x.

11. 瞿沁嫄, 刘桂建, 孙梅, 齐翠翠, 刘源. 中国煤中微量元素锡(Sn)的研究进展

[J]. 地学前缘, 2016, 23(03), 68-73.

 VI

Acknowledgements

My five-year Ph.D. life is coming to an end, and at this moment my heart is a

little more relaxed with a more wonderful feeling. After these five years of study,

besides the professional knowledge and skills I have learned, I have also become

more optimistic and mature, and understand life more profoundly and better than

before. During these five years, I felt confusion, helplessness, loneliness, and

desperation. Nevertheless, I also felt warmth, surprise, and happiness. Looking back,

all the joys and sorrows of the past have now become a valuable asset in the journey

of my life, as an illusion of light and a guide to the future. Five years of Ph.D. life is

not ordinary at all, and it’s filled with various emotions and memories. I would like

to thank every people I have met during the Ph.D. who accompanied me through this

special period.

I want to thank my supervisors. Thank you, my supervisor at the University of

Science and Technology of China, Professor Guijian Liu. In addition to teaching us

professional knowledge, he also often taught us the truth of life, from which I

benefited a lot. He always encourages us to go forward bravely and does his utmost

to support the research we want to do and provide us with good conditions for

scientific research. Another supervisor from the City University of Hong Kong, Paul

Kwan Sing Lam, also gave me a lot of help. He gave us the mildness and love like a

friend or a father, and made me feel the warmth in Hong Kong, a strange city at the

beginning, but more like home to me now. He led us to participate in some academic

exchange activities to broaden my horizons, which was of great help to my research

and study.

I also want to thank many of my classmates and friends. Jie Wang, Zijiao Yuan

and Lanlan Lu provided some important samples to me; Houqi Liu, Mei Sun, Ting
 VII

Fang and Libin Wu provided a lot of help for my experimental testing work; Ruoyu

Sun gave me many suggestions about the thesis; Yunke Tian gave me great help in

modifying the grammar used in this thesis. In addition, I cherish Jiamei Zhang, Jiao

Wang, Qinyuan Qu, Jingjing Liu, Yu Kang, Xiaohui Sun, Quan Tang, Ruoyu Hu,

Yaqin Wu, Meng Ge, Wenhui Ren, Huaqin Xue, Chao Xu, Pengzhen He, Bin Wu,

Chuncai Zhou, Ruwei Wang, Zhi Cao Yan, Bingyu Chen, Dianshi Ding, Yong Wei,

Hao Sun, and Biao Fu's companionship. I would also like to thank Maggie, Thomas

and Yuefei Ruan of the Hong Kong Laboratory for their help in my experiments,

accompanied by Yanxia Li, Xin Li, Kai Zhang and Zhen Wu as well as Xiaofei Shen

in Suzhou Laboratory, Yinhua Cui, Xinrong Pan, and Jie Li. In addition, thanks go to

my Cantonese teachers Karen and Jacob, who are not only teachers but rather friends,

who left me with a lot of good memories.

Finally, I must thank my parents, who always give me company and support.

Their love is the source of motivation and the reason for all that I have achieved.

Thanks!
 VIII

List of figures

Fig. 1.1 The technical route of this study.................................................................... 7

Fig. 2.1 Location of the typical coal mining area and petroleum-producing region .. 8

Fig. 2.2 Study area with the designated sites (Y1, Y2, Y3, Y4 and Y5) for sample

collection in the Yellow River Estuary. ..................................................................... 11

Fig. 2.3 Study area with the designated sites (L1, L2 and L3) for sample collection in

Laizhou Bay. ............................................................................................................. 12

Fig. 2.4 Location map showing the sampling sites and sampling profiles ............... 15

Fig. 2.5 Sampling locations in the Huai River, China .............................................. 17

Fig. 2.6 Sampling locations in the Huaibei coal mine, China................................... 18

Fig. 2.7 The locations of 46 surface soil samples from the Yellow River Delta....... 19

Fig. 3.1 Spatial distribution of V in coals from different provinces of China .......... 40

Fig. 3.2 Mean V abundances in Chinese coals of different ages .............................. 42

Fig. 3.3 Vanadium abundances in coals of different ages and ranks ........................ 43

Fig. 3.4 Mean V abundances in coals of different ranks as well as in stone coal ..... 45

Fig. 4.1 Correlation analysis of Cr vs. Fe (A), V vs. Fe (B), Cr vs. Ad (C), V vs. Ad

(D), V vs. Cr (E) in studied coals. ............................................................................. 55

Fig. 4.2 Variations of water-leachable (a), ion-exchangeable (b), carbonate-bound (c),

silicate-bound (d) sulfide-bound (e) and organic-bound fractions (f) of Cr and V in

coal samples of different ranks. ................................................................................ 65

Fig. 5.1 Vanadium emission inventories for Chinese and global coal consumption

from 2004 to 2014 ..................................................................................................... 69

Fig. 5.2 Vanadium emission flux of different sectors by global coal consumption

from 1990 to 2035 ..................................................................................................... 70

Fig. 5.3 The volatilization ratio of Cr and V during simulated coal combustion
 IX

experiment. ................................................................................................................ 72

Fig. 6.1 Vanadium concentration-depth profile from sediment core D. ................... 79

Fig. 6.2 The water quality of the Huai River. ........................................................... 84

Fig. 6.3 The fraction of V variation along the depth in sediment core D. ................ 86

Fig. 7.1 Stable nitrogen (δ15N) and carbon isotope (δ13C) ratios of the fish species in

the Yellow River Estuary .......................................................................................... 96

Fig. 7.2 Vanadium concentrations in fish, shellfish, crab and shrimp. ................... 101

Fig. 7.3 Ratios of stable nitrogen (δ15N) and carbon (δ13C) isotopes in muscle tissues

of aquatic organisms in Laizhou Bay. ..................................................................... 102

 X

List of tables

Table 2.1 Basic information of studied coal samples ............................................... 14

Table 2.2 The amount of samples in the Huaibei coal mining area.......................... 19

Table 2.3 The detailed information of fish from the Yellow River Estuary.............. 21

Table 2.4 Sample details from Laizhou Bay. ............................................................ 23

Table 2.5 Summary of the main steps of the sequential extraction experiment. ...... 27

Table 2.6 Linear equations and regression coefficients of the calibration curves, as

well as LOD and LOQ of V. ...................................................................................... 29

Table 3.1 Abundances of V in coals from individual provinces of China ................ 37

Table 3.2 The abundances of V in worldwide coals and continental crust ............... 39

Table 3.3 The abundances of V in coals of different ages ........................................ 42

Table 3.4 The abundances of V in coals of different ranks ...................................... 45

Table 4.1 Proximate and ultimate analysis in the samples. ...................................... 53

Table 4.2 Al, Fe, V and Cr concentrations (μg/g) in samples (on a whole-coal basis)

................................................................................................................................... 56

Table 4.3 Fraction (%) of V ± 1SD (n=3) defined by sequential extraction

experiment in 11 selected samples. ........................................................................... 57

Table 4.4 Fraction (%) of Cr ± 1SD (n=3) defined by the sequential extraction

experiment in 11 selected samples. ........................................................................... 64

Table 5.1 Vanadium emission budgets (mt) during global coal consumption by

different sectors ......................................................................................................... 70

Table 5.2 Vanadium concentrations in feed coal, bottom ash and fly ash from some

power plants in China. .............................................................................................. 71

Table 6.1 Vanadium in coal gangue, soil and fish from Huaibei coal mining area .. 76

Table 6.2 Vanadium concentrations in coal gangues and surface sediments (mg kg-1,
 XI

dry weight). ............................................................................................................... 77

Table 6.3 The V concentration, enrichment factor (EF), geoaccumulation index (Igeo)

and dating year of sediment core D........................................................................... 82

Table 6.4 Fractionation (%) of V in surface sediments. ........................................... 85

Table 6.5 Enrichment factor (EF) and geoaccumulation index (Igeo) of V in surface

sediment. ................................................................................................................... 87

Table 7.1 Chemical properties of soils collected from the Yellow River Delta ....... 92

Table 7.2 The V concentration and geoaccumulation index (Igeo) of the soils from the

Yellow River Delta .................................................................................................... 93

Table 7.3 Concentrations of V and stable isotope ratios of δ15N and δ13C in 11 fish

species from the Yellow River Estuary. .................................................................... 95

Table 7.4 Vanadium concentrations (Mean ± SD) in some fish (μg g−1 ww) reported

in other regions.......................................................................................................... 95

Table 7.5 Estimated daily intake (EDI) and Target Hazard Quotient (THQ) of V from

composite fish samples ............................................................................................. 97

Table 7.6 Concentrations of V (μg g−1 ww) and stable isotope ratios in aquatic

organisms from Laizhou Bay. ................................................................................... 99

Table 7.7 Vanadium concentrations (Mean ± SD) in some aquatic organisms (μg g−1

ww) reported in other regions. .................................................................................. 99

Table 7.8 Estimated Daily Intake (EDI) and Target Hazard Quotient (THQ) of V

from the samples ..................................................................................................... 104

 XII

List of contents

ABSTRACT ····················································································· I

Qualifying Panel and Examination Panel ·············································· III

List of publications ···········································································IV

Acknowledgements···········································································VI

List of figures ··············································································· VIII

List of tables ···················································································· X

List of contents ·············································································· XII

Chapter 1 – Introduction ···································································· 1

1.1 Physiochemical properties of V ····················································· 1

1.2 The resources and usage of V ······················································· 2

1.3 Toxicity of V and its compounds ··················································· 2

1.4 Environmental fate of V ····························································· 3

1.5 Research progress of V in coal and coal mining areas ··························· 4

1.6 Overall objective ······································································ 6

1.7 Research strategy and technical route ·············································· 6

Chapter 2 – Samples and methodology ··················································· 8

2.1 Introduction of the research area···················································· 8

2.1.1 Huaibei Coal Mining Area ···················································· 8

2.1.2 Huai River in Huainan Coal Mining Area ·································· 9

2.1.3 Typical petroleum-producing region ······································· 10

2.2 Samples ··············································································· 13

2.2.1 Coal samples ··································································· 13

2.2.2 Coal gangue samples ························································· 15

2.2.3 Sediment core ································································· 15

 XIII

2.2.4 Soil samples ··································································· 17

2.2.5 Aquatic organism samples ··················································· 19

2.3 Methodology ········································································· 24

2.3.1 Proximate and ultimate analysis ············································ 24

2.3.2 Elemental analysis ···························································· 24

2.3.3 Leaching test ··································································· 25

2.3.4 Simulated combustion experiment ·········································· 26

2.3.5 Sequential chemical extraction procedure ································· 26

2.3.6 Stable isotope analysis ······················································· 27

2.3.7 Geochronology ································································ 28

2.3.8 Quality control ································································ 28

2.3.9 Statistical analysis····························································· 30

2.3.10 Data analysis ································································· 30

Chapter 3 – Abundance, distribution, and enrichment of V in Chinese coals ···· 33

3.1 Introduction··········································································· 33

3.2 Average V abundance in Chinese coals ··········································· 34

3.3 Distribution of V in Chinese coals················································· 39

3.3.1 Distribution of V in coals from different regions ························· 39

3.3.2 Vanadium abundance in coals of different ages ··························· 41

3.3.3 Vanadium abundance in coals of different ranks ·························· 44

3.4 The enrichment of V in Chinese coals ············································ 45

3.4.1 Highly-elevated V in Chinese coals ········································ 45

3.4.2 Enrichment mechanism of V in Chinese coals ···························· 46

3.5 Summary ·············································································· 50

Chapter 4 – Modes of Occurrence of V in coals ········································ 51

 XIV

4.1 Introduction··········································································· 51

4.2 Correlation of V with ash yield ···················································· 52

4.3 Correlation of V with major elements ············································· 54

4.4 Modes of occurrence of V in studied coal by sequential extraction ··········· 56

4.4.1 Inorganically associated V ··················································· 58

4.4.2 Association with organic matter ············································· 58

4.5 The factors influencing the occurrence of V in coals ··························· 59

4.5.1 Coal rank ······································································· 59

4.5.2 Coal-forming environment··················································· 61

4.6 Comparison of chemical speciation between V and Cr ························· 61

4.6.1 Correlation between V and Cr ··············································· 61

4.6.2 Correlation of the chemical speciation of V and Cr ······················ 62

4.7 Summary ·············································································· 65

Chapter 5 – The behavior of V during coal combustion ······························ 67

5.1 Introduction··········································································· 67

5.2 Emission inventory of V by coal consumption ·································· 68

5.2.1 The V emission flux by Chinese and global coal consumption ········· 68

5.2.2 The global V emission flux by different sectors ·························· 69

5.3 The combustion behavior of V in coal ············································ 70

5.3.1 The distribution of V among different coal combustion products ······ 70

5.3.2 Volatility of V during coal combustion ····································· 71

5.4 Comparison of the combustion behavior between V and Cr ··················· 72

5.5 Summary ·············································································· 73

Chapter 6 – Environmental geochemistry of V in coal mining areas ·············· 74

6.1 Introduction··········································································· 74
 XV

6.2 Vanadium concentration in coal gangue from Huaibei and Huainan coal

mining areas ·············································································· 75

6.3 Vanadium concentration in soils from Huaibei coal mining area ·············· 77

6.4 Vanadium in sediments in Huai River from Huainan coal mining area ······ 78

6.4.1 Sedimentation rate ···························································· 78

6.4.2 Vanadium concentrations in surface sediments ··························· 79

6.4.3 Temporal characteristics of V in sediments ································ 81

6.4.4 The fractionation of V in sediments ········································ 84

6.4.5 Enrichment factor and geo-accumulation index ·························· 87

6.5 Vanadium concentration in fish from the Huaibei coal mining area ·········· 88

6.6 Summary ·············································································· 88

Chapter 7 – Environmental geochemistry of V in petroleum-producing areas ·· 90

7.1 Introduction··········································································· 90

7.2 Vanadium concentration in soil from the Yellow River Delta·················· 92

7.3 Vanadium in fish from the Yellow River Estuary ································ 94

7.3.1 Concentrations of V in fish from the Yellow River Estuary ············· 94

7.3.2 Stable isotope values of fish from the Yellow River Estuary ············ 95

7.3.3 Estimated daily intake of V via fish consumption ························ 97

7.3.4 The relationship between V and geographical environment ············· 98

7.4 Vanadium in aquatic organisms from Laizhou Bay ····························· 98

7.4.1 Concentrations of V in aquatic organisms ································· 98

7.4.2 Stable isotope values of aquatic organisms from Laizhou Bay ······· 101

7.4.3 Estimated daily intake of V via aquatic organism consumption ······ 103

7.5 Summary ·············································································104

Chapter 8 – Major conclusions and innovations ····································· 106

 XVI

8.1 Major conclusions ··································································106

8.1.1 The environmental geochemistry of V in coals ························· 106

8.1.2 Contamination level and potential risk of V in coal mining areas ···· 107

8.1.3 Comparison of the environmental geochemistry of V between

petroleum-producing areas and coal mining areas ···························· 108

8.2 Innovations ··········································································109

Reference······················································································110
 1

Chapter 1 – Introduction

1.1 Physiochemical properties of V

Vanadium (V) is a silvery white metal with the atomic number 23 and the

atomic weight of 50.94. It belongs to the transitional metal group (5th A Group) of

the periodic table. Common valences of V are +5, +4, +3, and +2, among which, +5

is the most stable, followed by +4 (WHO 1988). A compound with pentavalent V

has oxidation properties, while low-valent V has reducibility properties. The lower

the V valence is, the stronger the reduction capability. Vanadium has a very high

melting point of about 1,919 ± 2 °C and is often referred to as a refractory metal

together with niobium, tantalum, tungsten, and molybdenum (Bunt et al. 2010). It

also has a boiling point of 3,000-3,400 °C. Vanadium is malleable, hard and

non-magnetic.

Vanadium can be combined with oxygen in the form of +2, +3, +4 and +5

valent states, forming four oxides: vanadium monoxide, vanadium oxide, vanadium

dioxide, and vanadium pentoxide. Vanadium pentoxide, which is the most

commercially significant compound of V, poses potential hazards during its

production, processing and usage (NTP 2002).

The pH and Eh conditions have a strong impact on the chemical speciation and

solubility of V species (Taylor and Van Staden 1994). In addition, at high

temperatures, metallic V easily interacts with oxygen and nitrogen. When metal V is

heated in the air, vanadium is oxidized to brown-black V trioxide, then dark blue V

tetroxide, and finally orange-colored vanadium pentoxide. Common vanadium salts

include: ammonium metavanadate, sodium metavanadate, vanadyl sulfate, V

 2

tetrachloride and V oxytrichloride.

Vanadium has a total of 31 kinds of isotopes, most of which are obtained

50 51
through artificial synthesis, except V and V which occur naturally with atomic

abundances of 0.25% and 99.75%, respectively (Huang et al. 2015).

1.2 The resources and usage of V

Vanadium resources are abundant in China. The basic V reserve in China is

estimated to be 9.10 million tons (China Statistical Yearbook 2014). Stone coal ores

and the vanadium–titanium magnetite ores are the two most important V sources (He

et al. 2007). The gross V reserve in Chinese stone coal accounts for > 87% of the

national reserve (Bin 2006). Environmentally friendly V (in the form of V2O5)

extraction methods for stone coal are under development (He et al. 2007; Wang et al.

2009; Zeng et al. 2009; Zhou et al. 2009).

Vanadium is a significant strategic resource. Vanadium can improve the strength

and toughness of steel as an alloying agent and is ubiquitously used in producing

ferrous and non-ferrous metals such as titanium alloy and other alloys for space

navigation or nuclear industry fields (Chandler 1998). Besides, the application of V

compounds in disease treatment is drawing more and more attention. Various V

compounds have been synthesized to offer better tolerance, more potent action,

better selectivity and less toxicity in cancer treatment (Evangelou 2002).

1.3 Toxicity of V and its compounds

However, V is also a toxic element. Rehder (1991) reported that high V

emissions from coal combustion could cause serious lung diseases in humans.

Workers chronically exposed to V-borne dust in factories can have slight to moderate
 3

eye irritation (Levy et al. 1984). The toxicity of V increases with the increase in its

valence state (-1 to +5) and solubility. According to the toxicology literature, the

main toxic inorganic V compounds include vanadium pentoxide (V2O5), sodium

metavanadate (NaVO3) and vanadyl sulfate (VOSO4) (Agency for Toxic Substances

and Disease Registry 1990). Regarding the human body, vanadate (V+5) is

considered to be more toxic than vanadyl (V+4) because vanadate reacts with a

number of enzymes and is a potent inhibitor of the Na+K+-ATPase of plasma

membranes (Patterson et al. 1986). Animal studies show that lung tumors were found

in mice of both genders after inhaling V2O5 (National Toxicology Program 2002),

suggesting that V2O5 is likely to be carcinogenic to humans (U.S. Environmental

Protection Agency 2005). Due to the fact that V2O5, VO2 and V2O3 can be released

during coal combustion (Frandsen et al. 1994), they may pose threats to human

health.

Vanadium is a trace element ranked as the 20th most abundant element in the

continental crust (Wedepohl 1995). Studies have demonstrated that V can be toxic to

plants, fish, invertebrates, wildlife and humans (Agency for Toxic Substances and

Disease Registry 1990). Excessive amounts of V2O5 in the human body can even

increase the possibility of cancer occurrence (U.S. Environmental Protection Agency

2005).

1.4 Environmental fate of V

Anthropogenic activities can cause important transformations in the

environment (Audry et al. 2004). The common possible anthropogenic sources of V

into soil, water and sediments include mining, metallurgy, metal-enriched slags,

manufacturing processes, coal burning power plants, urban runoff, air depositions of
 4

dust and aerosol, certain fertilizers, and so forth (Dean et al. 1972; Liu et al. 2017b;

Nriagu and Pacyna 1988; Pacyna et al. 1995). Among them, the combustion of

residual fuel oils and coal is the major source of anthropogenic V (Hope 2008).

Swaine and Goodarzi (1995) reported that V can be released into air, water and soil

along with coal gangue and coal combustion products. Concentration of sedimentary

V in the fuel combustion venues (i.e. areas close to oil refineries, petrochemical

plants, fuel powered facilities, and mining areas) is usually much higher than its

natural abundance (Nadal et al. 2004; Peltier and Lippmann 2010; Teng et al. 2003,

2009). Trace metals may accumulate to levels high enough to pose a hazard to

human health once they enter the food chain (Asante et al. 2010; Ip et al. 2005).

Tang et al. (2013b) found that the amount of V in the downwind residential soil

samples surrounding a coal-fired power plant (61.3 μg/g) is slightly higher than that

in upwind soil samples (44.98 μg/g). Vanadium in coal gangue poses low risks to the

ecosystem, based on its risk assessment code values calculated by Zhou et al. (2014).

1.5 Research progress of V in coal and coal mining areas

Some existing studies about V in coals mainly focused on the determination,

enrichment pathways and reclamation of V in coals and their by-products (Font et al.

2007; Maylotte et al. 1981). Besides, many researchers have studied the reasons for

enrichment and modes of occurrence of V in carbonaceous rock including petroleum,

oil shales and black shales. For example, Breit and Wanty (1991) reported that V-rich

carbonaceous rocks typically have high concentrations of organically bound sulfur

and are stratigraphically associated with phosphate-rich units. Black shales

concentrate V under an anoxic environment with high organic matter preservation

(Quinbyhunt and Wilde 1994). Vanadium enrichment in petroleum is partly

 5

attributed to V occurrence in highly stable porphyrin complexes (Lewan and

Maynard 1982). However, a specialized and systematic study regarding V in coals is

still lacking.

Thus, less attention is paid to the V in coals as compared to other trace toxic

elements such as mercury, arsenic, selenium, and lead (Fang et al. 2014; Kortenski

and Sotirov 2002; Tian et al. 2013). Vanadium is briefly mentioned in many studies

as one of the environmentally sensitive elements in coals that are important to human

health (Finkelman 1995; Liu et al. 2001; Querol et al. 2001; Zhang et al. 2002).

However, V in coals is considered to have potential economic value and conspicuous

environmental impacts (Seredin and Finkelman 2008; Swaine and Goodarzi 1995).

Gebearing coals and U-rich coals have already been well reported (Dai et al. 2012a,

2015c; Seredin et al. 2006). Similarly, V as an economically potential metal in coal

should be paid more attention.

As a key metal of concern associated with oil-related pollution, V was equally

paid attention to as compared to 13 priority pollutants under the US Environmental

Protection Agency’s Clean Water Act (Macdonald et al. 2016). Although the impact

of V from coal utilization is not paid as much attention as that from oil, V in coals is

still considered to have conspicuous environmental impacts (Liu et al. 2016; Seredin

and Finkelman 2008). Swaine and Goodarzi (1995) thought that V is one of the trace

elements in coal that are harmful to the environment. It is released into air, water and

soil along with coal gangue and coal combustion products, and then contaminates the

environment and threatens human health. Khan et al. (2011) found that V in

vegetable and grass tissues around a thermal power plant has the potential to impact

human health. Historical coal combustion caused V enrichment in the soil of the
 6

Liberty State Park, USA, which had been used for railroad transportation and coal

storage for over a century (Qian et al. 2014).

1.6 Overall objective

This study aimed to give a preliminary understanding of the environmental

geochemistry of V (concentrations, distribution, mode of occurrence, sources, and

health risk) in the coal, soil, sediment, and aquatic organisms from the Anhui coal

mining area, with the purpose of revealing the impact of V in the ecological

environment of this coal mining area due to the exploitation and utilization of coal.

Because anthropogenic sources of V mainly come from the combustion of coal and

oil, we also briefly studied the environmental geochemistry of V in oil-producing

areas in comparison to the environmental geochemical studies of V in coal mines.

1.7 Research strategy and technical route

In this study, coal was first studied using a variety of experimental and

analytical methods to reveal the concentration, enrichment mechanism, occurrence,

and combustion behavior of V in coals. Then, the coal mining areas were further

studied to understand the concentration, distribution, chemical speciation, transfer

behavior and ecological risk of V in their soil, sediment, and aquatic organisms. In

addition, a comparative study was conducted in the petroleum-producing areas; thus

a study of the environmental geochemical behavior of V in petroleum-producing

areas were also conducted. The specific technical route for this study is shown in Fig.

1.1.
 7

Literature review

Geological survey and sample collection

Sample processing

Geochemical Sequential
Coal property Depositional environment
analysis extraction

Detection

Environmental
Lithology Geochemistry Mineralogy Coal geology Coal petrology
chemistry

Synthetical analysis

Mode of Enrichment Volatilization Environmental Environmental

Abundance occurrence mechanism behavior of geochemistry of V geochemistry of V
of V in coal of V in coal of V in coal V in coal in coal mining area in petroleum producing area

Vanadium in coal mining area: distribution, modes of occurrence, and environmental behavior

Fig. 1.1 The technical route of this study

 8

Chapter 2 – Samples and methodology

2.1 Introduction of the research area

Anhui province is known as a typical region having rich coal resources, in

which Huaibei coal mining area and Huainan coal mining area were chosen as the

research area. In addition, a well-known petroleum-producing area was selected as

the comparative study area (Fig. 2.1).

Huai

Fig. 2.1 Location of the typical coal mining area and petroleum-producing region

2.1.1 Huaibei Coal Mining Area

Huaibei Coal Mining Area, which is located in the north of Anhui province,

was discovered half a century ago in 1958. There are many coal mines in Huaibei
 9

coal mining area: Renlou coal mine, Wugou coal mine, Baishan coal mine, Qidong

coal mine, Luling coal mine, Qinan coal mine and Zhuxianzhuang coal mine. Due to

the long-term exploitation and utilization of coals, a large amount of coal gangues

have accumulated and been distributed around each coal mine, thus having a

non-ignorable impact on the ecological environment of the mining area. Furthermore,

because of coal mining, many subsidence ponds have formed, some of which have

developed into fishponds.

2.1.2 Huai River in Huainan Coal Mining Area

The Huai River watershed (268,957 km2), located about mid-way between the

Yangtze River and Yellow River, is one of the major Chinese river systems. It is a

river with the largest number of tributaries in China. The Huai River flows broadly

from west to east, with a total length of about 1,000 kilometers. It originates from

Taibai Crest of Tongbai Mountain, flows through Henan Province, Anhui Province,

Shandong Province, Hubei Province and Jiangsu Province, and ends up entering into

the Yangtze River at Sanjiangying District, Jiangsu Province. The Huai River Basin

combines strong anthropogenic pressures (160 million of inhabitants, 23% of

national agricultural activities, important energy resources base) (Yan 2006). With

the rapid pace of industrialization and urbanization, increasing amounts of pollutants

are discharged into the Huai River, leading to more severe ecological problems

(Wang et al. 2015).

The Huai River Basin within Huainan City (HRBHC) is an industrial and

agricultural concentrated region, where coal mines, coal gangues, and coal-fired

power plants are densely distributed, and it has a relatively higher level of

industrialization and water pollution (Zhang et al. 2015a). At present, there are three
 10

main coal power plants in HRBHC, and the total installed capacity is around 10,000

Mw, which provides approximately an 82 billion kWh/y electricity output (Chen et

al. 2016b). The gangue production is about 20% of the raw coal production in

Huainan, and the annual coal gangue output was calculated to be 3 million tons in

HRBHC (Cai et al. 2008). Therefore, HRBHC, which lies in the middle reaches of

the Huai River Basin, with a length of ~50 kilometers, was selected as a case study

in this research.

2.1.3 Typical petroleum-producing region

The Yellow River Estuary is one of the most important petroleum production

bases in China. The GD (Gudong), HL (Hongliu), XT (Xintan) oil field as shown in

Fig. 2.2, belonging to Shengli oil field, are also located in the YRDNR and pose a

potential threat to the ecosystem due to oil well blowouts, leaks and spills from

underground tanks, pipelines and illegal disposal (Wang et al. 2011). In addition, the

Yellow River Delta Nature Reserve (YRDNR) is located in the Yellow River

Estuary, including three areas: core area, buffer area and experimental area (Fig.

2.2).
 11

Fig. 2.2 Study area with the designated sites (Y1, Y2, Y3, Y4 and Y5) for sample
collection in the Yellow River Estuary

Laizhou Bay is one of the three major bays of the Bohai Sea in North China and

covers about 4,600 km2. The investigated area is in the south of Yellow River Delta

Natural Reserve, covering approximately 50 km of shoreline of Laizhou Bay (Fig.

 12

2.3). There are several coastal rivers around the watershed of the study area, and

large amounts of riverine input (industrial wastewaters, domestic sewage, and

agricultural discharges) have caused high nutrient and contaminant concentrations in

Laizhou Bay (Yu et al. 2017; Zhuang and Gao 2013). Located in the Bohai

Economic Circle, the study area contains two industrial zones, DY (Dongying) Port

Industrial Zone and WF (Weifang) Port Industrial Zone (Xu et al. 2015). In addition,

it is also one of the typical petrochemical areas in China. Many branch oilfields (GD,

HL and XT), belonging to Shengli oil field, the second largest oil field in China, are

also located nearby.

Fig. 2.3 Study area with the designated sites (L1, L2 and L3) for sample collection in
Laizhou Bay
 13

2.2 Samples

2.2.1 Coal samples

Twenty-one coal samples from nine provinces in China (Liaoning, Hebei,

Shandong, Shanxi, Hubei, Chongqing, Yunnan, Guizhou and Sichuan) and one

sample of stone coal from Hubei were collected according to the Chinese National

Standard Method (GB/T 19222-2003). These samples include eight coal seam

channel samples (labeled as DZ16-6, NT6-3, NT6-8, TP18-2, TP18-3, TP18-10,

TP18-11 and TP18-13 in Table 2.1), 13 coal bench samples and one open-pit stone

coal (ES). The sampling sites and sampling profiles of channel samples are shown in

Fig. 2.4. The basic information (coal mine, coal seam, coal-forming period) of each

coal sample is listed in Table 2.1. Each sample of approximately 1 kg was collected.

All samples were stored in sealed polyethylene bags to avoid potential pollution and

weathering. Samples were then air-dried, crushed, pulverized and passed through

200 mesh sieve, and stored in brown bottles for further analysis.
 14

Table 2.1 Basic information of studied coal samples

coal
sampling site* sample ID coal mine Rank coal-forming period
seam
A TF Tiefa 1 Lignite Jurassic
B KL-7 Kailuan 7 high volatile bituminous coal Early Permian
C DT-11 Datong 11 lignite Jurassic
D HY-4 Hunyuan 4 boghead coal Carboniferous-Permian
HY-5 Hunyuan 5 boghead coal Carboniferous-Permian
E LA-3 Luan 3 medium volatile bituminous coal Permian
F DZ16-6 Daizhuang 16 high volatile bituminous coal Late Carboniferous
Open-
G ES Yutangba stone coal Permian
pit
ES-4 Tianba 4 medium volatile bituminous coal Permian
H NT6-3 Nantong 6 low volatile bituminous coal Late Permian
NT6-8 Nantong 6 low volatile bituminous coal Late Permian
I ZJ Zhijin 16 medium volatile bituminous coal Permian
J TP18-2 Taiping 18 low volatile bituminous coal Late Triassic
TP18-3 Taiping 18 semi-anthracite Late Triassic
TP18-10 Taiping 18 low volatile bituminous coal Late Triassic
TB18-11 Taiping 18 semi-anthracite Late Triassic
TP18-13 Taiping 18 low volatile bituminous coal Late Triassic
K MEG-M4 Maoergou M4 semi-anthracite Late Triassic
XJY-C5 Xujiayuan C5 anthracite Carboniferous
Changshe
CS-C5 C5 anthracite Carboniferous
ng
L XD-M8 Kelang M8 lignite Carboniferous
M QJ-C16 Gongqing C16 semi-anthracite Permian
*refer to Fig. 2.4 for sampling sites.
 15

Fig. 2.4 Location map showing the sampling sites and sampling profiles

2.2.2 Coal gangue samples

Abundant coal gangues have been piled up along the riverbank near sites A-D

along the Huai River, and three representative coal gangue samples (G1, G2, G3)

were collected (Fig. 2.5). Within 3 km of sites A-F, four coal-fired power plants (IDs:

TJ, PW, TJA, LH) are distributed. All samples were sealed in polyethylene bags

after collection.

In the Huaibei coal mining area, coal gangue samples were collected from four

coal mines (BS, ZXZ, WG and RL). Coal gangue samples were obtained at the top,

waist and bottom (0.5 m above the ground) of the coal mines, respectively. The

depth of one sample was about 20 cm. Each coal gangue sample (1 kg) was a

mixture of five subsamples.

2.2.3 Sediment core

′N,
Six surface sediment samples (i.e., the top 8 cm) from A (32°43.98

116°46.95′E), B (32°40.36′N, 116°53.27′E), C (32°40.22′N, 116°54.51′E), D

 16

(32°40.55′N, 116°55.78′E), E (32°40.88′N, 117°1.9′E) and F (32°41.58′N, 117°4.7′E)

were collected along the Huai River from upstream to downstream, and the distances

of the adjacent two sampling sites were 12, 2, 2, 9 and 5 km, respectively (Fig. 2.5).

A sediment core (50 cm) was retrieved using a gravity corer from site D. The

sediment core was sectioned into 2.0-cm intervals using a vertical extruder. All

samples were air dried at room temperature, then ground by agate mortar to pass

through a 120-mesh nylon sieve. Then, all specimens were stored at 4°C in

polyethylene containers for further analysis.

 17

Fig. 2.5 Sampling locations in the Huai River, China

2.2.4 Soil samples

In the Huaibei coal mining area, soil samples were collected from BS, ZXZ,

WG, and RL coal mines along two lines starting from the coal gangue location,
 18

directing northwest and northeast, respectively (Fig. 2.6). Due to certain terrain

limits, there were just four sampling sites in the ZXZ coal mine. Each mixed soil

sample was about 2.5kg.

Fig. 2.6 Sampling locations in the Huaibei coal mine, China

In August 2013, 46 soil samples (0 - 5cm) were collected from the Yellow

River Delta (Fig. 2.7). Five subsamples were collected at each sampling site, so as to

form the samples of each sample site after mixing. After the samples were brought

back to the laboratory, they were frozen and dried. The samples were thoroughly

pulverized and sifted, and a particle size < 0.15 mm was obtained. The obtained

samples were stored in the dryer at room temperature.

 19

Fig. 2.7 The locations of 46 surface soil samples from the Yellow River Delta

2.2.5 Aquatic organism samples

A total of 72 fish (Carassius carassius) samples were collected from subsidence

ponds near the ZXZ coal mine (18), WG coal mine (18), RL coal mine (18) and BS

coal mine (18) in the Huaibei coal mining area. Six fish were used to constitute a

composite specimen from a certain sampling site, and three composite specimens

were used for further analysis. Sample details of the fish are shown in Table 2.2.

Table 2.2 The amount of samples in the Huaibei coal mining area
Coal gangue Soil Fish
ZXZ 3 4 3
RL 3 12 3
WG 3 12 3
BS 3 13 3

A total of 129 individual fish representing 11 species were collected from five

sites (Y1, Y2, Y3, Y4 and Y5) (every 10 to 15 km) in the Yellow River Estuary in

August 2014 (Fig. 2.2). The 11 species of fish are commonly consumed with

different feeding habits and living environments. Sample details (sampling sites,
 20

body length and weight, feeding habits, living environments and habitats) for the fish

are shown in Table 2.3. The samples were collected with a gill net by professional

fishermen, placed into a clean polythene bag, preserved on ice, transported to the

laboratory and then stored at −20 °C prior to processing.

A total of 327 samples from seven species of fish, three species of shellfish, one

species of crab and two species of shrimp were collected from three sites (L1, L2 and

L3) in Laizhou Bay (Fig. 2.3). Table 2.4 provides general information about the

aquatic organisms analyzed in this study. The samples were collected with a gill net

by professional fishermen, placed in clean polythene bags, preserved on ice, and then

stored in the laboratory at −20 °C for further processing.

 21

Table 2.3 The detailed information of fish from the Yellow River Estuary
Scientific Common Mean length Mean weight Feeding Living
Code Sites (Na) Nb Habitatc
name name (cm) (g) habitc environmentc
Carassius Crucian Cc 3 Freshwater Demersal
Y1(1), Y3(1), Y5(1) 23.8 ± 5.5 269.7 ± 146.1 Omnivore
carassius carp
Channa argus Snakehead Ca Y1(1) 1 37 404 Carnivore Freshwater Benthopelagic
Cyprinus carpio Carp Cyc Y1(1), Y3(1) 2 27.5 ± 0.50 298.5 ± 6.5 Omnivore Freshwater Benthopelagic
Hypophthalmic Silver carp Hm Y1(7), Y3(3) 2 19.9 ± 7.4 109.1 ± 96 Omnivore Freshwater Benthopelagic
hthys molitrix
Lateolabrax Weever Lj Y1(11,11)d,Y2(11),Y3(5), 5 19.6 ± 1.7 76.1 ± 19.4 Carnivore Marine & Reef-associated
japonicas Y4(1) freshwater
Liza Redeye Lh Y1(4,4,3)e, Y2(1), Y3(4), 11 27.6 ± 4.8 220.9 ± 118.9 Omnivore Marine & Pelagic-neritic
haematocheila mullet Y4(9,5,3)f, Y5(4,6,4)g freshwater

Megalobrama Wuchang Ma 2 Freshwater Benthopelagic

Y3(2), Y4(3) 17.1 ± 0.25 47.9 ± 6.9 Herbivore
amblycephala bream
Mugil cephalus Flathead Mc Y3(2) 1 49.5 1168 Omnivore Marine & Benthopelagic
linnaeus grey freshwater
mullet
Pelteobagrus Yellow Pf 3 Freshwater Demersal
Y2(10), Y3(3), Y4(1) 17.2 ± 0.6 42.3 ± 7.9 Omnivore
fulvidraco catfish
Silurus asotus Catfish Sa Y1(1,1)h, Y2(1), Y3(1) 4 51.4 ± 12.6 1052.8 ± 784.5 Carnivore Freshwater Demersal
Synechogobius javelin Sh Y2(2) 1 12.8 15 Carnivore Marine & Demersal
hasta goby freshwater
a
The number of fish that were used to constitute a composite sample in a certain sampling site.
b
The number of composite samples that were used in stable isotopes and heavy metals analysis.
c
Froese and Pauly (2017)
 22

d
Represents two composite samples of similar weight from Y1: one sample comprised 11 Lateolabrax japonicas of large size (63~137
g) and one sample was 11 Lateolabrax japonicas of small size (21~50 g).
e
Represents three composite samples of similar weight from Y1: one sample comprised four Liza haematocheila of large size
(353~368 g), one sample was four Liza haematocheila of medium size (191~240 g), and one sample was three Liza haematocheila of
small size (77~122 g).
f
Represents three composite samples of similar weight from Y4: one sample comprised nine Liza haematocheila of large size
(325~553 g), one sample was five Liza haematocheila of medium size (181~234 g), and one sample was three Liza haematocheila of
small size (101~161 g).
g
Represents three composite samples of similar weight from Y5: one sample comprised four Liza haematocheila of large size
(373~483 g), one sample was six Liza haematocheila of medium size (172~248 g), and one sample was four Liza haematocheila of small
size (132~145 g).
h
Represents two composite samples of similar weight from Y1: one sample comprised one Silurus asotus of large size (2357g) and
one sample was one Silurus asotus of small size (707 g).
 23

Table 2.4 Sample details from Laizhou Bay

Scientific name Common name Species Sites (n*) Mean length (cm) Mean weight (g)
Acanthogobius hasta - Fish L2 (40), L3 (26) 16.25 ± 1.75 31.6 ± 9.3
Acanthopagrus schlegelii Blackhead sea bream Fish L3 (2) 12.3 32.5
Busycon canaliculatum Conch Shellfish L1 (15), L2 (28) - 34.75 ± 6.45
Chelon haematocheilus Redeye mullet Fish L1 (2) 21.3 78
Lateolabrax japonicus Japanese sea bass Fish L1 (1), L2 (2), L3 (7) 18.8 ± 1.59 66.63 ± 10.45
Loligo beka Sasaki Cuttlefish Shellfish L1 (3), L2 (2) 13.05 ± 1.25 15.25 ± 0.25
Mugil cephalus Mullet Fish L2 (1) 46 982
Oratosquilla oratoria Mantis shrimp Shrimp L1 (44), L2 (16) 12 ± 2 21.1 ± 4.2
Penneropenaeus chinensis Chinese shrimp Shrimp
L2 (45) 11 7.6
Platycephalus indicus Bartail flathead Fish
L2 (1) 26 86
Pleuronectiformes Flatfish Fish
L1 (40), L2 (4) 16.7 ± 3.7 31.9 ± 20.1
heterosomata Portunid Crab
L1 (3), L2 (24) - 84.45 ± 56.55
Portunus trituberculatus
Scapharca subcrenata Ark shell Shellfish L1 (21) - 17
* Number of pooled samples for analysis.
 24

2.3 Methodology

2.3.1 Proximate and ultimate analysis

The proximate and ultimate analyses of studied samples were determined

according to ASTM standards: standard test methods for total sulfur in the analysis

sample of coal (ASTM 2007); standard test methods for instrumental determination

of carbon, hydrogen, and nitrogen in laboratory samples of coal (ASTM 2008);

standard test methods for moisture in the analysis sample of coal (ASTM 2011a);

standard test methods for volatile matter in the analysis sample of coal (ASTM

2011b); standard test methods for ash in the analysis sample of coal (ASTM 2011c).

2.3.2 Elemental analysis

For coal and coal ash, the powder samples of approximately 0.1 g were digested

with 8 mL of HNO3, 2 mL of H2O2, 3 mL of HF and 4 mL of HClO4 in teflon

digestion vessels. Then the samples were gradually heated on a hot plate from 100 to

210 °C for 12 h. After cooling down, the digested solutions were diluted to 25 mL

with 5% HNO3, and then the Al, Fe, Cr and V in the diluted solutions were

determined by inductively coupled plasma mass spectrometry (ICP-MS, Thermo

Fisher Scientific, X Series 2). The instrument was calibrated using multi-elemental

standard solutions containing known concentrations of Al, Fe, Cr and V. The

calibration curves for all these elements were linear (R2 > 0.995, n = 6) over the

concentration range of the studied samples.

For soil, sediment and coal gangue, all samples (0.10 g) were digested by 2 mL

of HNO3, 1 mL of HClO4, and 5 mL of HF, following Li et al. (2000). The samples

were heated on an electrothermal plate at a temperature of 90-190 °C for 16 h. After

cooling, the digested solution was diluted to 25 mL with 2% HNO3. The V and Al
 25

(as the normalized element to calculate the enrichment factor) in the solutions were

determined by an inductively coupled plasma-optical emission spectrometer

(ICP-OES, Perkin Elmer Optima, 2100DV) with the resonance lines at 396.153 nm

for Al and 292.464 nm for V.

For aquatic organism samples, the muscle (the epaxial muscle on the dorsal

surface without skin and backbone) from the fish samples was dissected and washed

with double-distilled water. Composite samples made of fish with a similar weight

for each species from each sampling site were chopped, homogenized and dried at

60 °C to a constant weight to calculate the water content. The dry weight was also

measured after freeze drying, and then the wet weight to dry weight quotients was

calculated. The powdered sample (0.25 g) was digested by a microwave system

−12H, China) with HNO 3. Vanadium was measured by an

(APL, MD8H

inductively-coupled plasma mass spectrometer (ICP-MS X Series II, Thermo

Scientific, Bremen, Germany), according to the method described by Cui et al. (2011)

and Asante et al. (2008).

2.3.3 Leaching test

To evaluate the potential mobility of V in coal gangues, the compliance

leaching test (EN, 12457-2, 2002) was applied in this study. Briefly, coal gangue

samples were leached by deionized water at a liquid to solid ratio of 10 L/kg and

with an agitation time of 24 h. Each sample was leached in duplicate. Vanadium

concentrations in leachates were determined by ICP-OES.

To investigate the toxicity and bioavailability of V in coal gangue and to assess

the potential environmental impacts, the leaching rate (Lr) of V was used to evaluate

the degree of V mobility in the coal gangue during leaching, which is defined as:
 26

Trace element concentration in the leachates

Lr= ×100%
Trace element concentration in the samples

2.3.4 Simulated combustion experiment

Coal combustion experiments were carried out in a temperature-controlled

quartz tube furnace fed by a constant O2 flow. Approximately 10 g of coal sample

aliquots were placed in the center of the furnace, and were step-heated to 950 °C

(~12 °C /min) and kept for 30 min. After the oven cooled down, the coal ash samples

were taken out from the furnace, digested and measured for elemental concentrations

as coal samples.

Volatilization ratio (Vr) was used to evaluate the degrees to which the trace

elements volatilize during the coal combustion, and is defined as:

  CA × Ad 
Vr = 1 −   ×100%
  Cc 

where CC and CA are the elemental concentrations in coal and its corresponding

combustion ash, respectively. Ad is the ash yield of coal.

2.3.5 Sequential chemical extraction procedure

For coal samples, the sequential chemical extraction procedure for V was based

on the previous methods for Se (Zhang et al. 2007) and Sb (Qi et al. 2008) in coals

developed in our laboratory. Eleven samples (HY-4, XD-M8, KL-7, DZ16-6,

TP18-10, NT6-3, NT6-8, MEG-M4, XJY-C5, CS-C5 and ES) were selected for the

SCE procedure. According to the procedure shown in Table 2.5, V is operationally

defined as water leachable, ion exchangeable, organic matter-bound,

carbonate-bound, silicate-bound, and sulfide-bound forms.

 27

Table 2.5 Summary of the main steps of the sequential extraction experiment
Chemical speciation The main steps
water leachable A sample of 5 g was treated with 20 mL of Milli-Q water at
25 °C for 24 h; suspension was then centrifuged at 3500
rpm for 20 min.
ion exchangeable Add 30 mL of NH4C2H3O2 to the residue, stirring for 24h,
centrifugate.
organic matter bound The residue was treated with 20 mL of CHCl3, stirring for
24 h, a float-sink separation was performed by
centrifugation. A float fraction (< 1.47g/cm3) of the sample
was dried at 40 ℃ and then digest.
carbonate bound Add 20 mL of HCl (0.5%) to the sink fraction (> 1.47g/cm3)
of residue from last step, centrifugate.
silicate bound Add 20 mL of CHBr3 to the residue from last step, stirring
and centrifugating. The float fraction (< 2.89g/cm3) was
digested.
sulfide bound The sink fraction (> 2.89g/cm3) from last step was digested.

The sequential extraction procedures of sediment samples were performed

following the modified BCR (Community Bureau of Reference of the European

Commission) sequential extraction method proposed by Rauret et al. (1999). Four

fractionation of V are operationally defined by the sequential extraction procedure:

“weak acid soluble” (exchangeable and carbonate bound, F1), “reducible”

(associated with Fe-Mn oxides, F2), “oxidizable” (associated with organic materials

and sulfides, F3) and “residual” (occurs in the crystalline structure, F4).

2.3.6 Stable isotope analysis

Analyses of δ15N and δ13C were carried out as described in Kaehler et al. (2000).

Each homogenized sample was dried at 60 °C for 24 h and treated with 2:1 of

chloroform: methanol solution to remove lipids. Stable isotope ratios of δ15N and

δ13C were measured with elementary analyzer-stable isotope ratio mass

spectrometers (EA-IRMS) (Flash EA 1112 HT- Delta V Advantages, Thermo).

Stable isotopic ratios of δ15N and δ13C were expressed as the deviation from
 28

standards in parts per thousand (‰) according to the following equation:

δ13C or δ15Nsample (‰) = [(Rsample/ Rstandard)-1]*1000

where R stands for the ratio 15N/14N or 13C/12C.

2.3.7 Geochronology
210
Pb dating was used to establish the chronology of sediment core D.
210 226
Radioactive measurements of Pb and Ra were conducted at Nanjing Normal

University, China. Knowledge gained from Guo et al. (2007) and Wu et al. (2006)
210
was used to inform our sediment dating approach. Pb activities were determined

using gamma emissions at 46.5 keV, and 226Ra by 295 keV and 352 keV gamma rays
214
emitted by the daughter isotope Pb after storage for three weeks in sealed

containers to allow radioactive equilibration. The relative error for this method was <

10%.

2.3.8 Quality control

For coal samples, procedural coal reference material ZMB1121 was processed

and analyzed in the same manner as the samples. The recoveries of ZMB1121 for Al,

Fe, Cr, V were 104.47%, 93.54%, 94.70% and 89.95%, respectively.

For soil, sediment and coal gangue samples, the accuracy of V and Al was

determined using the certified reference material GSS-5 (GBW07405) for soil,

GSD-9 (GBW07309) for sediment and ZBM1121 for coal gangue. The recovery of

GSD-9 for V was 98.32 ± 2.8 %. The recoveries of GSD-9 for V and Al were 106 ±

5.6 % and 90 ± 4.1 %, respectively. The recoveries of ZBM1121 for V and Al were

104 ± 6.4 % and 85 ± 5.2 %, respectively.

For aquatic organisms, certified reference material (Shale-GBW07107 from the

 29

Institute of Geophysical and Geochemical Exploration in China) was used for the V

quality control. Analytical blanks were similarly treated as samples. The results were

in good agreement with the certified values and the recoveries ranged from 86% to

92%. The limit of detection (LOD) and the limit of quantification (LOQ) of V were

expressed using equations of 3×SD/S and 10×SD/S, respectively, where SD means

the standard deviation of six repeated measurements of the blank sample and S

means the slope of the calibration curve for the corresponding metal. Calibration

curve equations for V are shown in Table 2.6. Vanadium in this study was converted

into wet weight using the respective moisture contents. Concentrations of V for fish

muscle in this study were expressed as both μg g−1 dry weight (dw) and μg g−1 wet

weight (ww).

Table 2.6 Linear equations and regression coefficients of the calibration curves, as
well as LOD and LOQ of V
Heavy metal Equation Regression LOD LOQ
coefficient (μg L ) (μg L−1)
−1

V Y = 0.00026X − 0.05341 0.9999 5.146 17.153

For the sequential extraction procedures of sediment samples, to guarantee the

reproducibility, each sample was treated in triplicate. The recovery of the sequential

chemical extraction (RSCE) was calculated by dividing the sum of elemental masses

in six binding forms by the total elemental mass in coal. The uncertainty of the

extraction methods was checked with a certified sediment standard GSD-9, with

recovery ranging between 102 and 110% (n=3). The standard deviations of replicate

extracted samples were all below 8.2%.

For stable isotope analysis, atmospheric air nitrogen (N2-atm) and Vienna Pee

Dee Belemnite (V-PDB) were used as the isotope standards for nitrogen and carbon,
 30

respectively. The analytical precision was ± 0.3‰ and ± 0.2‰ for δ15N and δ13C,

respectively, based on the analysis of the standards.

2.3.9 Statistical analysis

Statistical analysis was performed using the software SPSS 22.0 (SPSS Inc.,

Chicago, Illinois, USA) and Microsoft Excel 2007. Linear regression models were

used to reveal the relationships between variables. A p-value of less than 0.05 was

considered to indicate statistical significance. The Kolmogorov-Smirnov Normality

Test was used to test whether the samples we selected were representative of

Chinese coal deposits. For the aquatic organism samples, concentrations of heavy

metals were log transformed before all statistical analyses to meet the assumptions of

normality based on the Kolmogorov-Smirnov test. The Tukey–Kramer method,

along with one-factor ANOVA was applied to detect the differences of heavy metal

levels among species, sampling sites, feeding habits, living environments and

habitats. As the sample sizes of Channa argus (n=1), Mugil cephalus linnaeus (n=1),

and Synechogobius hasta (n=1) were small, their data were not included in the

further analysis for post-hoc testing.

2.3.10 Data analysis

2.3.10.1 Enrichment factor

The enrichment factor (EF) is an important index for evaluating the

anthropogenic influence on the environment. Geochemical normalization of the

heavy metal data to a conservative element (Al) is employed in order to identify

anomalous metal concentrations (Zhang et al. 2009). The EF is defined as: EF = [(Cn

/ CAl)sample] / [(Cn / CAl)reference], where (Cn / CAl)sample is the ratio of the concentration

of the element of concern Cn to that of CAl in the sediment sample, and (Cn / CAl)
 31

reference is the same ratio applied to the referenced background value of soil of China

(Yan et al. 1995; Pekey 2006).

2.3.10.2 Geoaccumulation index

Another commonly used criterion to evaluate the heavy metal pollution in

sediments is the geoaccumulation index (Igeo), which is an indicator of the metal

enrichment and has been applied to distinguish anthropogenic sourced metals from

natural origin metals (Müller 1979). The Igeo calculation for sediments can be

expressed as the following formula: Igeo = log2 (Cn / 1.5Bn), where Cn is the metal

concentration determined in the sediment (mg kg-1), Bn is the geochemical

background value (mg kg-1) (sediment background in the river system of China) and

1.5 is the correction factor for metal lithologic variations. The background value of

V is the same as that used in the aforementioned enrichment factor calculation. This

approach has been widely used to study the sources of V and its contamination of

riverine, estuarine and coastal environments (Adamu et al. 2015; Zhang et al. 2009).

2.3.10.3 Health risk assessment

The risk to human health that results from aquatic organism ingestion was

calculated using the daily trace element exposure:

EDI = (C×DC)/BW

THQ = EDI/RfD

where EDI (μg kg−1bw day−1) represents the estimated daily intake, C is the

mean trace element concentration in aquatic organisms (μg g−1 ww), DC is the daily

aquatic products consumption by the Chinese population (g day−1) (reported as 30.68

g day−1 in 2015 by the National Bureau of Statistics of China) (CSY, 2016), BW is

human body weight (70 kg), THQ is the target hazard quotient, and RfD is the oral
 32

reference dose (μg kg−1bw day−1) available for V (USEPA 2013). THQ values higher

than 1 indicate a potential human health risk (Hosseini et al. 2015).

 33

Chapter 3 – Abundance, distribution, and enrichment of V

in Chinese coals

3.1 Introduction

Vanadium is widely distributed on the Earth. As compared to V abundance in

the upper continental crust (97 μg/g) (Rudnick and Gao 2014), coals, in general, are

depleted of V, with an arithmetic average V for global coals of 25 μg/g (Ketris and

Yudovich 2009). Seredin and Finkelman (2008) reported that V is a rare metal in

coal. However, coals with high V concentrations have also been detected in many

coal basins, and coal is thus considered a potential industrial V source in the near

future. For example, several coal seams from local regions of coal basins in

southeastern China have V concentrations of above 500 μg/g (Dai et al. 2005a,

2008b, 2014a; Li et al. 2013b; Yang 2009; Zeng et al. 2005; Zhuang et al. 2000,

2007). As a low volatile element, V tends to be enriched in fly ash during coal

combustion (Dai et al. 2010b; Li et al 2012a; Liu et al. 2004; Tang et al. 2013a).

Thus, fly ash of coals with anomalously high V has the potential for economic V

recovery (Seredin and Finkelman 2008). Besides, V is significantly enriched in

low-calorific (< 10 MJ/kg) stone coals (carbonaceous shale), which are mainly

distributed in provinces in southern China (Duan et al. 2006; Moskalyk and

Alfantazi 2003; Zhang et al. 2011). Jiang et al. (1994) found V concentration as high

as 8000μg/g in stone coals from Anhui province, while the V concentrations in

global black shales and carbonaceous shales are only 205 ± 15 and 99 ± 23 μg/g,

respectively (Ketris and Yudovich 2009).

Vanadium was well documented to be present in coal samples as early as the

 34

middle of the 20th century in the USA (Cahill et al. 1976; Swaine 1976; Zubović et al.

1961). Many researchers have measured V along with other elements in coal

(Finkelman et al. 1995; Querol et al. 1999; Song et al. 2007). As reported by Swaine

(1990), V in most of the global coals is in the range of 2–100 μg/g. Based on 7,924

US coal samples, the average V in US coals was calculated as 22 μg/g (0.1–5100

μg/g) by Finkelman (1993). Swain (1990) gave a mean V estimation of 25 μg/g in

Australian coals. Ketris and Yudovich (2009) also calculated a global mean V value

of 25 μg/g. It appears that the mean estimates of V in Chinese coals except Tang et al.

(2004) are all higher than coals from other countries. However, the abundance of V

in Chinese coals has not been specially researched so far.

3.2 Average V abundance in Chinese coals

To investigate V in Chinese coals comprehensively, this paper compiles data

from all available published literature (Table 3.1). In total, 2,940 data items of V

were collected, among which 1,079 samples from Huainan Coalfield and Huaibei

Coalfield in Anhui province and six from Jining Coalfield in Shandong province are

cited from our laboratory’s published work (Chen et al. 2011; Li et al. 2013a; Liu et

al. 1999, 2002; Sun et al. 2010a; Zheng et al. 2006, 2008). In the process, we first

figured out whether the data were based on a whole-coal basis or ash basis, and the

geochemical data we quoted here are all on a whole-coal basis to avoid spurious

statistical correlation (Geboy et al. 2013; Dai et al. 2015a). Then the sampling

location, as well as the coal forming periods, environment, coal rank, etc. were

recorded. Finally, the data were grouped by province, coal forming period, and coal

rank, for statistical analysis.

Besides the arithmetic mean of V in Chinese coal calculated, to correct for the
 35

uneven distribution of samples, we used the demonstrated coal reserves from

different regions (China Statistical Yearbook 2015) as the weighting factor to

calculate the weighted average V abundance in Chinese coal (Table 3.1). The

numbers of samples collected from different regions are usually not proportional to

coal reserves. For instance, the ratio of coal samples from Anhui, Hunan, Guangxi,

Guizhou, Yunnan, and Chongqing to the total samples of China is 54.86%, while the

corresponding coal reserves ratio is just 11.04%. Therefore, the weighted average,

rather than pure arithmetic average, can better represent the national average V

abundance in coals.

The weighted average V concentration in Chinese coals was calculated as 35.81

μg/g (n = 2940) in a range from 0.65 μg/g to 1405 μg/g. This value is lower than the

arithmetic average (46.81 μg/g) and median of V (45 ± 5.28 μg/g) (Table 3.1). The V

abundances in coals from China and other significant coal-producing countries, as

well as V abundances in shale and continental crust, are listed in Table 3.2. By

compiling 1,257 coal samples, Tang et al. (2004) gave an arithmetic average V of 25

μg/g, with most coal samples varying between 2 μg/g and 100 μg/g. A slightly

higher V concentration of ~35 μg/g is estimated by Ren et al. (2006) (n = 1266) and

Dai et al. (2012b) (n = 1324). Bai et al. (2007) obtained an average V concentration

as high as 51 μg/g from 1123 samples. Our newly updated V abundance is

comparable to that of Ren et al. (2006) and Dai et al. (2012b), but higher than that of

Tang et al. (2004) and lower than Bai et al. (2007).

The concentrations of V in 21 studied coal samples collected from nine

provinces in China ranged from 2.74 to 61.45 μg/g, with a mean value of 25.09 ±

17.06 μg/g, comparable to the global mean value of V in coals (25 μg/g) (Ketris and
 36

Yudovich, 2009) and lower than the calculated weighted average of 35.81 μg/g in

Chinese coals in this study. Notably, the concentrations of V in stone coal sample

(ES) are two orders of magnitude higher than coals, reaching 2997 μg/g.
 37

Table 3.1 Abundances of V in coals from individual provinces of China

Number Minimum Maximum Arithmetic Coal Reserve References
of samples (μg/g) (μg/g) Mean (μg/g) (*100 Mt)
Hebei 63 4.22 333.2 43.73 40.97 Tang et al. (2005), Tewalt et al. (2010), Zhuang et al. (1999)
Liu et al. (2001), Song et al. (2007), Sun et al. (2010b), Tewalt et al. (2010),
Shanxi 183 3.18 107 21.8 920.9 Wang et al. (2002a), Wang et al. (2011), Zhuang et al. (1998), Zhang et al.
(2004a)
Shandong 58 2.53 284 53.58 77.22 Jiang et al. (2011), Liu et al. (1999), Querol et al. (1999), Tewalt et al. (2010)
Jiangsu 10 23 46 30.05 10.71 Ren et al. (2006), Tewalt et al. (2010), Zhou et al. (2011)
Chen et al. (2011), Jiang et al. (1994), Li et al. (2013a), Liu et al. (2005), Sun
Anhui 1098 0.65 340 25.2 83.96 et al. (2007), Sun et al. (2010a), Tewalt et al. (2010), Zheng et al. (2006,
2008)
Zhejiang 2 34.5 70 52.25 0.43 Li et al. (1993), Ren et al. (2006)
Jiangxi 84 4 117 76.23 3.43 Querol et al. (2001), Tewalt et al. (2010), Zhuang et al. (2001)
Hunan 31 3.6 751 167.9 6.68 Li et al. (2013b), Tewalt et al. (2010), Wang et al. (1999)
Dai et al. (2013a, b), Shao et al. (2003), Tewalt et al. (2010), Zeng et al.
Guangxi 64 11 1405 161.7 2.27
(2005)
Cheng et al. (2013), Dai et al. (2003, 2005a, 2005b), Ding et al. (2005), Ni et
Guizhou 307 13 574 109.9 93.98 al. (1998), Tewalt et al. (2010), Yang (2006), Zeng et al. (1998), Zhang et al.
(2004b), Zhuang et al. (2000)
Shaanxi 76 4.9 223 63.4 95.48 Lu et al. (2003), Tewalt et al. (2010), Yang et al. (2008), Yang (2011a)
Inner Dai et al. (2008c, 2012a, b), Du et al. (2009), Tewalt et al. (2010), Zhuang et
169 1 267 29.21 490
Mongolia al. (2006), Zou et al. (2013)
Kong et al. (2001), Querol et al. (1997), Ren et al. (2004), Tewalt et al.
Liaoning 54 14.3 153 38.04 27.57
(2010)
Ningxia 12 1.35 28 11.53 38.04 Song et al. (2007), Tewalt et al. (2010)
Jilin 61 18.27 150.7 65.21 9.71 Tewalt et al. (2010), Wu et al. (2004)
Dai et al. (2006, 2008a, b, 2014a), Du et al. (2009), Tewalt et al. (2010),
Yunnan 58 11 621 170.3 59.47
Wang et al. (2012), Yang (2009)
 38

Table 3.1 Continued

Number Minimum Maximum Arithmetic Coal Reserve References
of samples (μg/g) (μg/g) Mean (μg/g) (*100 Mt)
Dai et al. (2007, 2010a), Tewalt et al. (2010), Wang et al. (2007), Zhu and
Chongqing 55 13 552 95.86 18.03
Li (2009), Zhuang et al. (2007), Zhuang et al. (2003)
Sichuan 47 16.9 195 76.01 54.1 Dai et al. (2014b), Tewalt et al. (2010), Wang (2009), Zhuang et al. (2012)
Li et al. (2012b), Tewalt et al. (2010), Wang and Zhang (2012), Yang and
XinJiang 363 1 147 15.21 158
Li (2007), Yang et al. (2011b), Zhou et al. (2010), Zhuang et al. (2013)
Hubei 34 24 301 84 3.19 Jiang et al. (1994), Tewalt et al. (2010), Zhuang et al. (2007)
Guangdong 3 13 37.6 13 0.23 Ren et al. (2006), Tewalt et al. (2010)
Fujian 6 19.1 54.8 30.8 4.22 Ren et al. (2006), Tewalt et al. (2010)
Beijing 2 11 11 11 3.75 Ren et al. (2006), Tewalt et al. (2010)
Gansu 8 13.8 34 26.75 32.86 Ren et al. (2006), Tewalt et al. (2010)
Heilongjiang 22 13 181 50.64 62.12 Ren et al. (2006), Tewalt et al. (2010)
Tibet 32 6.81 107.9 43.79 0.12 Fu et al. (2013)
Henan 37 7 148 65.51 86.49 Ren et al. (2006), Tewalt et al. (2010)
Qinghai 1 19.9 19.9 19.9 11.82 Tewalt et al. (2010)
China 2940 0.65 1405 46.81a 2396
35.81b
45±5.28c
a Arithmetic mean
b Reserve-weighted average
RWA=∑(AR×WR)/∑WR. RWA: reserve-weighted average; AR: arithmetic mean from different provinces; WR: coal reserve from
different provinces (China Statistical Yearbook 2015).
c Me ± δMe (Me, median; δMe= (Q3−Q1)/ 2 n , n is the number of samples, Q1 and Q2 are the first and third quartiles of frequency
distribution (Ketris and Yudovich 2009).
 39

Table 3.2 The abundances of V in worldwide coals and continental crust

Mean Minimum Maximum References
n
(μg/g) (μg/g) (μg/g)
China a 2940 35.81 0.65 1405 This study
China b 1266 35.05 0.1 1405 Ren et al. (2006)
China c 1257 25 2 100 Tang et al. (2004)
China d 1123 51.18 Nd Nd Bai et al. (2007)
China e 1324 35.1 Nd Nd Dai et al. (2012b)
Ketris and Yudovich
World Nd 25 Nd Nd
(2009)
Upper continental crust Nd 97 Nd Nd Rudnick and Gao (2014)
Ketris and Yudovich
black shales Nd 205±15 Nd Nd
(2009)
Ketris and Yudovich
carbonate shales Nd 99±23 Nd Nd
(2009)
Continental crust Nd 135 Nd Nd Tayor (1964)
US 7924 22 0.1 5100 Finkelman (1993)
Australia Nd 25 Nd Nd Swain (1990)
Nd-no data

3.3 Distribution of V in Chinese coals

3.3.1 Distribution of V in coals from different regions

Vanadium in coals varies significantly in different regions in China. To have a

standard and unified description of the abundance, Dai et al. (2015c) introduced an

evaluation method for toxic trace elements in coals. In this method, concentration

coefficients (CC) equal the ratio of element concentration in investigated coals vs.

world hard coals. The concentration of trace elements in coals are classified into six

groups based on CC values: depleted (0 < CC < 0.5), normal (0.5 < CC < 2), slightly

enriched (2 < CC <5), enriched 5 < CC < 10, significantly enriched 10 < CC < 100, and

unusually enriched (CC > 100).

In this study, we adopted this evaluation method. We defined CCW as the ratio of

V in investigated coals to V in world hard coals (28 μg/g) (Ketris and Yudovich 2009).

Based on the CCW values of V, Chinese coal samples were categorized into four
 40

groups (Fig. 3.1). Since our paper focuses on V in Chinese coals, we set the weighted

average (35.81 μg/g) from samples as the referenced Chinese coal V value, and

calculated the CCC (CCC: ratio of V in investigated coals vs. Chinese coals) (Fig. 3.1).

According to the CCC of V in Chinese coals, the provinces in China can be divided into

three groups: 0.0 < CCC < 0.5 (Ningxia, Xinjiang, Beijing), 0.5 < CCC < 2 (Hebei,

Shanxi, Shandong, Jiangsu, Anhui, Zhejiang, Shaanxi, Inner Mongolia, Fujian,

Liaoning, Jilin, Sichuan, Henan, Gansu, Guangdong, Heilongjiang, Qinghai and Tibet),

and 2 < CCC < 5 (Hunan, Guangxi, Guizhou, Jiangxi, Chongqing, Yunnan, and Hubei).

Vanadium is depleted in coals from Ningxia, Xinjiang, Beijing, and rich in coal from

Hunan, Guangxi, Guizhou, Jiangxi, Chongqing, Yunnan, and Hubei. Overall, coals in

southern China are richer in V than those in northern China.

(a) (b)
Fig. 3.1 Spatial distribution of V in coals from different provinces of China
(a) CCW: ratio of V in investigated coals vs. world hard coals
(b) CCC: ratio of V in investigated coals vs. Chinese coals
 41

3.3.2 Vanadium abundance in coals of different ages

In China, the major coal-forming periods were the Late Carboniferous and Early

Permian (C2–P1), Late Permian (P2), Early and Middle Jurassic (J1-2), Late Triassic (T3),

Early and Middle Jurassic (J1–2), Late Jurassic and Early Cretaceous (J3–K1), and

Paleogene and Neogene (E–N). Among them, C2–P1 and J1-2 were the periods with

more abundant coal reserves (Ren et al. 2006). The V concentration in coals varies with

different periods (Fig. 3.2, Table 3.3), with a descending order of arithmetic mean as P2

(115.59 μg/g) > E–N (80.38 μg/g) > T3 (60.78 μg/g) > C1-2 (31.65 μg/g) > C–P (27.93

μg/g) > J–K (26.17 μg/g) > J (17.71 μg/g), which can be contrasted with the spatial

distribution of V in coals (Fig. 3.3). The variation of V concentration in coals in

different period was caused by the difference in paleoenvironment, including

paleobotany, paleoclimate, paleogeography and geotectonics (Swaine and Goodarzi

1995; Tian et al. 2013).

 42

Fig. 3.2 Mean V abundances in Chinese coals of different ages

C: Carboniferous, C-P: Carboniferous-Permian, P2: Late Permian, T3: Late Triassic,
J1-2: Early and Middle Jurassic, J3-K1: Late Jurassic-Cretaceous, E-N: Cenozoic

Table 3.3 The abundances of V in coals of different ages

Coal-forming age n Mean
（µg/g）
Carboniferous (C1-2) 113 31.65
Carboniferous-Permian (C-P, P, P1) 1247 27.93

Late Permian (P2) 557 115.6

Late Triassic (T3) 95 60.78
Early-middle Jurassic (J1-2, J1, J2) 452 17.71
Late Jurassic and early Cretaceous (J3-K1) 49 26.17
Cenozoic (E-N) 31 80.38
 43

Fig. 3.3 Vanadium abundances in coals of different ages and ranks

I, Northeastern area; II, Northern area; III, Northwestern area; IV, Southern area; V,
Tibet-western Yunnan area (Dai et al. 2012b; Liu 2013)

Dai et al. (2012b) outlined five coal-distribution areas: the northern area

(dominated by C2–P1 coals), the southern area (P2, T3 and C1 coals), the northeastern

area (J3–K1 and E–N coals), the northwestern area (J1-2 coals) and the Tibet–western

Yunnan area (E–N and T3 coals). The V concentration in Late Permian coals is the

highest because those coals are mainly distributed in the coal basins of southwestern

China (Fig. 3.3), which are characterized by high concentrations of mineral and trace
 44

elements resulting from the marine transgression of abundant terrigenous detrital

matters during coal deposition (Dai et al. 2014a; Shao et al. 2003; Zhuang et al. 2012).

The Jurassic coals are mainly distributed in northern China, with the lowest V

concentration. Li et al. (2012b) reported that Jurassic coal has a low V concentration of

18.14 μg/g from the Junggar Coalfields in Xinjiang, which is attributed to the limited

detrital supply to the very stable shallow-lake sedimentary sequences during peat

accumulation.

3.3.3 Vanadium abundance in coals of different ranks

The ranks of coal include, from low organic matter maturity to high maturity,

lignite, bituminous, and anthracite. The coal rank is related to the coal-forming period

and geological setting of coal basins (Ren et al. 1999). Significant differences in V

concentration (arithmetic mean) are also observed in coals of different ranks (Fig. 3.4,

Table 3.4): lignite (54.58 μg/g, n = 34), bituminous coal (39.34 μg/g, n = 1,790) and

anthracite (58.29 μg/g, n = 99). However, there is no clear relationship pattern between

V concentration and coal rank (Fig. 3.4).

 45

Fig. 3.4 Mean V abundances in coals of different ranks as well as in stone coal

Table 3.4 The abundances of V in coals of different ranks

Coal rank N Arithmetic mean（µg/g）
Lignite 34 54.58
Bituminous 1790 39.34
Anthracites 99 58.29

3.4 The enrichment of V in Chinese coals

3.4.1 Highly-elevated V in Chinese coals

The degree of V enrichment in different coals varies with different factors. We

compiled the V concentration in Chinese coals under different environmental settings,

and compared their average values with the national V average of 35.81 μg/g to

calculate their CCC. Vanadium is found slightly enriched in Jiangxi, Hunan, Guangxi,

Guizhou, Yunnan, Chongqing and Hubei province, with CCC exceeding 2. However, it

is worth noting that in southwestern China, the distribution of V in coals is uneven. For

instance, in some coals from Xinde mine, Yunnan Province, the V concentration can be
 46

as high as 545.5 μg/g, with the CCC > 15, belonging to the “significantly-enriched”

class (Dai et al. 2015c).

3.4.2 Enrichment mechanism of V in Chinese coals

The enrichment of specific elements in coal deposits depends on various factors.

Ren et al. (1999) summarized five major genetic types of trace elements enrichment in

Chinese coals: source-rock-controlled, sedimentation-controlled,

hydrothermal-controlled, fault-controlled and groundwater-controlled. Recently, two

additional types, i.e. marine-controlled and volcanic ash-controlled, were added (Dai et

al. 2012b). In Chinese coals, V enrichment is influenced by sediment source,

sedimentary environment, hydrothermal fluids and some other factors as stated below.

3.4.2.1 Sediment source

Dai et al. (2012b) concluded that the background values of trace elements in

Chinese coals are dominated by sediment source regions. Vanadium concentration in

coals is closely related to the terrigenous materials from source regions, and the

resulting V enrichment degree includes depleted (CCC < 0.5), normal (0.5 < CCC < 2),

and slightly enriched (2 < CCC < 5).

The amounts of terrigenous materials, which can be affected by rate of basin

subsidence and the distance between the source region and coal basin, is a significant

factor for V concentration. Xiheishan and Wucaiwan are two coal-bearing units of

Zhundong Coalfield in the Junggar basin. Vanadium concentration is higher in

Xiheishan (23 μg/g) than Wucaiwan (5 μg/g) due to the higher subsidence rate of the

Xiheishan unit (Zhou et al. 2010). Cheng et al. (2013) reported that the mean V

concentrations in the east, south, and northwest of Bijie coal basin in Guizhou Province
 47

are 82.15 μg/g, 108.6 μg/g, and 152.1 μg/g, respectively. The high V concentration

in northwestern coals is probably attributed to its closed position to a basalts source

region (Cheng et al. 2013).

Apart from the amounts of sediment source, the lithology of sediment source is

another influencing factor. The concentrations of V in different kinds of rock vary in

the following descending order: basic rock (250 μg/g), clay (80–130 μg/g), felsic

rock (40 μg/g), ultrabasic rocks (40 μg/g), intermediate rock (30 μg/g), sandstone

(10–60 μg/g) and carbonate rocks (10–45 μg/g) (Kabata and Pendias 2001; Turekian

and Wedepohl 1961). The Kangdian Upland supplies most of the terrigenous

materials into coal basins in southwestern China, which are composed of Emeishan

basalts enriched in V (Wang et al. 2012). Many researchers attributed the V

enrichment in coals to the terrigenous materials derived from the Kangdian Oldland

(Ren et al. 2006; Zhang et al. 2002). Coals in Bijie of Guizhou and Chongqing

districts are closely related to the Emeishan basalt in the Kangdian Oldland, and the

V in coals of those two regions is 101.8 μg/g and 132 μg/g, respectively, classified

as slightly enriched (Cheng et al. 2013; Zhuang et al. 2003). In addition, Ren et al.

(2004) reported that the V concentration of 88 μg/g (slightly enriched) in the

Paleogene lignite of the Shenbei Coalfield, a small intracontinental basin (400 km2)

in Liaoning, is due to the weathered matters derived mainly from the olivine basalt.

Dai et al. (2014b) suggested that the normal V value of 70.82 μg/g in the

Huayingshan coal of Sichuan is derived from the dominant sediment-source regions

including Dabashan Uplift, Hannan Upland, and Leshan-Longnvsi Uplift composed

of carbonate, sandstone and mudstone (Dai et al. 2014b; Jiang et al. 2007; Zhang et

al. 2010). The normal V (27.91 μg/g) in Fushui high Fe-sulfide coals in Guangxi is

mainly caused by the epiclastic source from the Yunkai Upland, composed of felsic
 48

Permo-Carboniferous rocks depleted in V (Dai et al. 2013b).

3.4.2.2 Sedimentary environment

The degree of V concentration influenced by sediment environment is ranked

from slightly enriched to enriched. Many researchers have studied the high-organic

sulfur coals in southwestern China, formed in tidal flat environments of restricted

carbonate platforms, and these coals were found to have high V concentration. For

instance, V was found slightly enriched to enriched in coals from Heshan, with the

average value of V reported from 126 to 294 μg/g (Dai et al. 2013a; Shao et al. 2003;

Zeng et al. 2005). Li et al. (2013b) reported that V is rich in the high organic sulfur

coals in Chenxi, with the average value of 296.3 μg/g. This enrichment is correlated

to inertinite concentration, but positively correlated to the ratio of vitrinite/inertinite,

indicating that the reducing condition could promote V accumulation in coal basins

with a marine-influenced transitional environment. It has been suggested that algae

have a strong capacity to enrich V in the coals formed in tidal flat environments of

restricted carbonate platforms by creating a low Eh value, forming a strongly

reducing environment (Dai et al. 2012b). The mechanism for V enrichment in black

shales can also give some clues to investigate the reasons for V enrichment in some

coals. Quinbyhunt and Wilde (1994) reported that the wide variety of black shale

depositional environments from oxic to methanic leads to different V concentrations.

Black shale deposition under conditions of high organic preservation have an

average V concentration of 1500 μg/g, considerably higher than the average

130–150 μg/g reported for more oxic shale composites (Taylor and McLennan 1985).

Cheng et al. (2012) indicated that V ores in Early Paleozoic stone coal formed in

marine facies of shallow sea or oldland edge developed from Protista-like bacteria

and algae in the static ambient environment.

 49

3.4.2.3 Hydrothermal fluids

Hydrothermal fluids can significantly enhance the V concentration in coal.

However, their influences are only limited to some local coal seams. Different kinds

of hydrothermal fluids, such as low-temperature hydrothermal fluids, magmatic

fluids and submarine exhalation fluids depending on their sources and properties,

have been observed in coal basins. The Xinde coals in western Yunnan were

intruded by multi-stage hydrothermal fluids, resulting in the formation of vanadinite

and high enrichment of V in C2 coal (545 μg/g) (Dai et al. 2014a). Dai et al. (2015e)

found that upper portions of the coal seams from Yili Basin in proximity to the

oxidized host rocks were influenced by a U–Se–Mo–Re rich infiltrational fluids, and

they have high enrichment of V (745 μg/g) in addition to U. The effect of submarine

exhalation fluids is one of the major contributors to the enrichment of V in black

shales including stone coals (Wu et al. 1999). Dai et al. (2008b) observed significant

enrichment of V (567 μg/g) in M9 coal from the Yanshan Coalfield of southeastern

Yunnan, along with albite and dawsonite, which is presumed to be influenced by

submarine exhalation invasion accompanying seawater into the anoxic peat swamp.

However, not all hydrothermal fluids lead to the enrichment of V. For example,

Wulantuga (Inner Mongolia) and Lincang (Yunnan) Ge-rich coals are extensively

invaded by hydrothermal fluids, while their V concentrations are only 9.31 μg/g and

14.17μg/g, respectively (Dai et al. 2012a; Dai et al. 2015d). Comparable V levels

(7.14 μg/g) were also observed in non-hydrothermal fluid influenced low-Ge coals

from the Shengli Coalfield, suggesting that the effect of hydrothermal fluids on V

enrichment in coals is site-specific (Dai et al. 2015b).

3.4.2.4 Other factors

Syn-sedimentary volcanic ash, usually occurring as layers of tonstein or tuff in

 50

coal-bearing sequences, has been regarded as an important V source in coal basins

(Bohor and Triplehorn 1993). Premović et al. (1997) suggested that the abundant V

(> 1000 μg/g) in coal deposits of Western Kentucky, USA is probably sourced from

the fallouts of volcanic ash. In the Songzao Coalfield, China, Nos. 6-11 coal seams

without influences of volcanic ash have normal V levels of around 65 μg/g, whereas

the No.12 coal seam, deposited directly above mafic tuff beds (V = 490 μg/g), has a

mean V concentration as high as 121 μg/g (Dai et al. 2010a). Depending on the

origins of volcanic ash, V in deposited tonstein and tuff can vary significantly. Dai

et al. (2011) observed higher levels of V (400-600 μg/g) in mafic tonstein and tuff

compared to silicic and alkali counterparts (<50μg/g). Zhou et al. (2000) also

indicated that tonstein sourced from silicic magmas has V below 20 μg/g.

3.5 Summary

About 2,900 data items of V concentration in Chinese coals were collected by

reviewing published literature. The reserve-weighted V concentration in Chinese

coals was calculated as 35.81 μg/g, which can be a referenced baseline of V in

Chinese coals. In addition, the concentrations of V in 21 coal samples collected from

nine provinces in China ranged from 2.74 to 61.45 μg/g, with a mean value of 25.09

± 17.06 μg/g, which is lower than the calculated reserve-weighted V concentration

in Chinese coals. A significant variation of V is observed in different coal-producing

regions of China. Coals formed in southern China, such as coals from Yunnan,

Guizhou and Chongqing, are generally more enriched in V. The factors affecting V

concentration in coals can be sediment-source, sedimentary environment and

hydrothermal fluids. The degree of V enrichment influenced by sediment source and

sediment environment can be slightly enriched or enriched. Hydrothermal fluids can

result in significant enrichment of V, but this effect is limited to certain areas.

 51

Chapter 4 – Modes of Occurrence of V in coals

4.1Introduction

Trace elements in coal are generally associated with both organic matter and

mineral matter (Finkelman et al. 1990; Querol et al. 2001; Spears 2013). The modes

of occurrence are the primary factors in determining the fate of elements during

combustion, weathering, conversion, leaching, and cleaning of coal (Finkelman

1994). There are two methods for studying the occurrence of trace elements in coals:

direct and indirect methods (Ren et al. 2006). The direct method includes electron

microprobe, ion microscopy mass analyzer and an X-ray absorption fine structure

method (Dai et al. 2006; Maylotte et al. 1981). The indirect method includes

mathematical statistics, float and sink technique and sequential chemical extraction,

which can quantitatively study the modes of occurrence of trace elements.

Sequential chemical extraction is especially effective as a quantitative analysis

method (Tomschey et al. 1986).

Generally, V in coals can be associated with organic and mineral matter.

Regarding its mineral association, V mainly exists in aluminosilicate minerals.

Regarding its organic association, V is mainly combined with fulvic acid and

organic macromolecule fractions. Finkelman (1994) concluded that the confidence

levels for the modes of occurrence of V are extremely low in coals, with little

agreement between coals from different depositional settings.

Vanadium and Chromium (Cr) are both siderophile elements, mainly enriched

in basic and ultrabasic rocks (Turekian and Wedepohl 1961). Both V and Cr in coals

have been found to be highly correlated with clay minerals (Dai et al. 2005b, 2012d;

Hower et al. 2000; Querol et al. 2001; Zhou et al. 2010). Statistical analysis shows a
 52

high correlation between V and Cr in coal (Dai et al. 2005b, 2012d; Hower et al.

2000; Querol et al. 2001; Zhou et al. 2010). However, their binding forms are still a

matter of debate. Therefore, further studies on V and Cr forms in coals are needed.

In this study, by collecting coals of different ranks from several coal basins of China,

we used the SCE method to investigate the chemical speciation of V and Cr.

4.2 Correlation of V with ash yield

The results of proximate and ultimate analyses in 21 coal samples are listed in

Table 4.1. Ash yields of the samples ranged from 4.71% to 29.24%, with an average

value of 12.57%. According to the Chinese National Standard (GB/T,

15224.1-2010), the studied samples were classified as extremely low-ash coal to

medium-ash coal. The total sulfur concentrations ranged from 0.25% to 6.67%, with

an average value of 1.49%. According to the Chinese National Standard (GB/T,

15224.2-2010), the studied coals span from extremely low-sulfur coal to high-sulfur

coal. The volatile matter contents of the coal samples varied from 5.67% to 56.34%,

indicating different ranks of studied coal samples based on ASTM Standard

D388-12 (ASTM 2012) and various chemical compositions.

 53

Table 4.1 Proximate and ultimate analysis in the samples

Ad (wt%) Mad(wt%) Vdaf(wt%) Sd(wt%) Cdaf(wt%) Hdaf(wt%) Odaf(wt%) Ndaf(wt%)
TF 7.13 4.19 43.28 0.48 69.39 4.71 24.50 0.92
KL-7 21.49 0.45 30.54 0.48 65.61 3.57 29.35 0.99
DT-11 7.28 3.20 39.51 0.67 72.46 3.83 22.53 0.51
HY-4 11.72 7.64 43.09 0.85 57.8 4.2 36.48 0.67
HY-5 9.97 6.36 41.85 0.62 62.11 4.06 32.32 0.89
LA-3 16.67 1.33 22.42 0.35 73.12 3.27 21.52 1.74
DZ16-6 12.54 2.22 43.94 1.59 77.53 4.33 14.88 1.66
ES 76.85 2.40 18.15 0.35 15.93 0.63 82.91 0.18
ES-4 16.78 1.32 23.73 1.69 73.6 2.48 21.37 0.86
NT6-3 13.81 0.57 17.22 2.21 76.83 3.63 16.10 1.23
NT6-8 9.72 0.6 16.52 6.67 80.79 2.38 8.90 1.27
ZJ 10.65 2.14 24.03 2.17 76.64 2.55 17.89 0.75
TP18-2 23.78 0.85 23.61 0.42 69.01 3.26 26.01 1.30
TP18-3 7.74 0.84 9.00 0.69 86.84 4.66 6.18 1.63
TP8-10 5.36 0.57 18.92 0.46 84.34 4.71 8.89 1.61
TP18-11 5.90 0.95 10.13 0.40 88.73 4.24 4.97 1.67
TP18-13 13.76 0.97 14.75 0.66 80.74 4.16 12.84 1.59
MEG-M4 29.24 1.20 12.66 4.00 88.39 3.75 2.94 0.92
XJY 9.47 0.47 7.00 1.68 93.02 3.3 1.18 0.82
CS-C5 4.71 0.61 5.67 0.83 94.09 3.04 1.27 0.77
XD-M8 15.46 9.97 56.34 4.05 68.89 5.16 20.31 1.59
QJ-C16 10.85 0.69 22.64 0.25 89.9 4.77 3.40 1.68
Notes: A, ash yield; M, moisture; V, volatile matter; S, sulfur; C, carbon; H,
hydrogen; O, oxygen; N, nitrogen; ad, air-dry basis; d, dry basis; daf, dry and
ash-free basis.

The correlation coefficient of V with the ash yield is usually used to judge the

organic or inorganic affinity of V, while the correlation coefficients of V with major

elements like Al, Si and Fe are usually to identify the mineral affinities of V (Querol

et al. 1997; Kortenski and Sotirov 2002; Zhuang et al. 2003). The V and ash yields

were found to be highly correlated, indicating a highly strong association between V

and inorganic matter (Song et al. 2007; Sun et al. 2010a; Zhou et al. 2010).

As suggested by Swaine and Goodarzi (1995), a positive correlation between

specific trace element and ash yield in coals indicates the occurrence of trace

element mainly in mineral matter, while a negative correlation indicates its

occurrence mainly in the organic matter. In this study, high correlations of V vs. ash
 54

yield (r V-ash = 0.66) were found in the 21 studied coals, indicating that mineral

matter is probably the primary host of V. This is consistent with conclusions from

other studies (Song et al. 2007; Yan et al. 1999; Zhou et al. 2010). However,

insignificant correlations of V with ash yield have also been reported, suggesting

that the occurrence of V is largely variable (Dai et al. 2005b, 2012d; Kortenski and

Sotirov 2002).

4.3 Correlation of V with major elements

Aluminosilicate minerals were found to be the dominant carriers for V in many

coal samples, inferred from the high correlation coefficient of V with Al (Chen et al.

2011; Du et al. 2009; Querol et al. 1997, 2001; Zhou et al. 2010; Zhuang et al. 2000).

Dai et al. (2012a) and Fu et al. (2013) found that the Pearson’s correlation

coefficients between V in coals (both low-ash and high-ash coals) and ash yield are

all above 0.90, and those between V in coals and Al2O3 and SiO2 are higher than 0.7,

suggesting that V is closely associated with aluminosilicate minerals. Zhuang et al.

(2001) observed that V is closely related to kaolinite in the Late Permian coal from

Guizhou. Vanadium has even been detected in clay minerals of coal by a scanning

electron microscope equipped with energy dispersive X-ray spectrometer

(SEM-EDX) (Dai et al. 2006).

The results of Al, Fe, V and Cr concentrations in the studied coal samples are

shown in Table 4.2. The correlation coefficients of trace elements with major

elements (e.g., Al, Si, Fe and S) are commonly used to identify the mineral affinity

of trace elements. Many researchers have concluded that V is governed by

aluminosilicate (including clay minerals and feldspars) as deduced from the high

correlations of V with Al (Spears and Zheng 1999; Zhou et al. 2010; Zhuang et al.

2012; Zivotic et al. 2008). Spears and Booth (2002) reported that V is highly
 55

correlated with Al2O3, with correlation coefficients of more than 0.95 for both. For

our studied coals, however, the correlation coefficient was only 0.42 between V and

Al, indicating that the aluminosilicate affinity of V is not dominant.

As siderophile elements, V shows strong correlations with Fe in some coals

(Wagner and Hlatshwayo 2005). For our studied coals, the coefficient of V with Fe

was 0.55 (Fig. 4.1). Wang et al. (2008) found that if four high-pyrite coals are

excluded, the strong correlations of V with Fe disappear, suggesting that V may be

enriched in pyrite of coals. However, by examining the correlations of V with S in

our coals, we did not observe significant correlation (rV-S = 0.21) (Fig. 4.1),

indicating V may also be controlled by other Fe-bearing minerals.

70
180
(A) (B) rT = 0.55 (p<0.01)
1 60 rT = 0.92 (p<0.01) 60
14 0 rS = 0.96 (p<0.01) rB = 0.72 (p<0.05)
50
12 0 rS = 0.78 (p<0.01)
V (μg/g)
Cr (μg/g)

1 00 40

80 30
60
20
40 Anthracite Anthracite
Semi-anthracite Semi-anthracite
20 Bituminous coal 10 Bituminous coal
0 Lignite Lignite
Boghead coal 0 Boghead coal
-20
0 5 000 1 000 0 15 000 2 000 0 2 500 0 300 00 35 00 0 0 50 00 10 000 150 00 20 000 2 500 0 3 000 0 35 000
70
180
Fe (μg/g) Fe (μg/g)
1 60 (C) 60 (D)
1 40
50
12 0 rT = 0.64 (p<0.01)
Cr (μg/g)

rT = 0.66 (p<0.01)
V (μg/g)

100 40

80 30 rS = 0.89 (p<0.01)
60
Anthracite 20 Anthracite
40
Semi-anthracite Semi-anthracite
20 Bituminous coal 10 Bituminous coal
Lignite Lignite
0 Boghead coal 0 Boghead coal
-20
70 5 10 15 20 25 30 5 10 15 20 25 30
Ad (wt%) Ad (wt%)
60 (E)
rT = 0.56 (p<0.01)
50
rB = 0.88 (p<0.01)
V (μg/g)

40
rS = 0.77 (p<0.01)
30

20 Anthracite
Semi-anthracite
10 Bituminous coal
Lignite
0 Boghead coal

0 30 60 90 1 20 1 50 1 80
Cr (μg/g)
Fig. 4.1 Correlation analysis of Cr vs. Fe (A), V vs. Fe (B), Cr vs. Ad (C), V vs. Ad
(D), V vs. Cr (E) in studied coals. rT, the correlation coefficient in a total of 21 coal
samples; rB, the correlation coefficient in 10 bituminous coal samples; rS, the
correlation coefficient in selected 10 coal samples for the sequential extraction
experiment
 56

Table 4.2 Al, Fe, V and Cr concentrations (μg/g) in samples (on a whole-coal basis)
Number Al Fe Cr V
Boghead coal 2 range 16358.14-22316.94 3221.41-3965.69 15.91-29.00 19.90-26.46
average 19337.54 3593.55 22.45 23.18
Lignite 3 range 5943.23-13399.48 3864.64-7241.09 10.93-28.63 8.51-29.38
average 9787.73 5187.29 20.19 21.51
Bituminous 10 range 2499.02-31161.09 852.79-13039.36 1.65-51.86 3.75-61.45
coal average 13930.18 5981.18 22.66 28.30
Semi-anthracite 4 range 1616.53-21583.28 1562.27-34028.47 0.12-175.64 2.74-55.80
average 8163.35 10227.52 48.66 28.38
Anthracite 2 range 4421.49-4722.00 4417.19-8227.83 12.99-68.42 9.29-10.09
average 4571.75 6322.51 40.71 9.69
All coal 21 range 1616.53-31161.09 852.79-34028.47 0.12-175.64 2.74-61.45
samples average 11863.66 6481.71 28.96 25.09
Stone coal 1 19056.19 9026.39 1738.07 2997.07

4.4 Modes of occurrence of V in studied coal by sequential

extraction

The fractions of different forms of V in 11 selected samples are listed in Table

4.3. The sum of the V mass in the six fractions is in good agreement with each total

mass in coals, with recoveries of 85.24-109.09%. The fractions of different V forms

generally follow the order of silicate bound (46.09 ± 0.80%) > organic matter bound

(37.64 ± 0.67%) > sulfide bound (13.63 ± 0.87%) > carbonate bound (1.82 ±

0.08%) > ion exchangeable (1.95 ± 0.03%) > water leachable (1.62 ± 0.07%) (Table

4.3).
 57

Table 4.3 Fraction (%) of V ± 1SD (n=3) defined by sequential extraction experiment in 11 selected samples
water leachable ion exchangeable carbonate bound silicate bound sulfide bound organic matter bound RSCE
Boghead coal HY-4 1.24±0.14 1.80±0.08 2.38±0.23 43.98±2.35 Bdl 56.02±3.01 105.42±4.35
Lignite XD-M8 1.09±0.12 1.20±0.05 0.16±0.02 44.08±2.35 8.04±1.34 47.88±2.57 102.45±4.39
Bituminous coal Mean fraction 1.75±0.10 1.64±0.04 2.53±0.16 42.05±1.04 16.41±1.39 37.50±0.93
KL-7 1.48±0.17 1.50±0.07 1.19±0.11 55.92±2.98 Bdl 44.08±2.37 104.17±4.39
DZ16-6 3.81±0.43 2.82±0.13 1.04±0.10 35.89±1.91 22.47±3.74 40.71±2.19 106.74±4.93
TP18-10 1.47±0.17 1.34±0.06 2.33±0.22 36.11±1.93 14.35±2.39 48.59±2.61 104.19±4.54
NT6-3 0.88±0.10 1.16±0.05 0.35±0.03 28.09±1.50 23.99±3.99 30.78±1.65 85.24±6.80
NT6-8 1.10±0.13 1.40±0.06 7.75±0.74 54.25±2.89 21.22±3.53 23.35±1.26 109.09±4.86
Semi-anthracite MEG-M4 0.48±0.05 0.73±0.03 0.36±0.03 48.69±2.60 14.22±2.36 30.78±1.65 95.27±5.01
Anthracite Mean fraction 2.34±0.19 3.80±0.12 1.32±0.09 56.92±2.24 15.99±2.21 27.08±1.06
XJY-C5 2.63±0.30 4.07±0.19 1.38±0.13 73.57±3.92 6.11±1.02 20.32±1.09 108.07±4.50
CS-C5 2.06±0.23 3.54±0.16 1.26±0.12 40.28±2.15 25.88±4.30 33.85±1.82 106.86±5.17
Stone coal ES 0.12±0.01 0.32±0.01 2.57±0.24 40.89±2.18 1.86±0.31 47.31±2.54 93.07±4.86
All samples Mean fraction 1.62±0.07 1.95±0.03 1.82±0.08 46.09±0.80 13.63±0.87 37.64±0.67
bdl, below the detection limit.
 58

4.4.1 Inorganically associated V

Inorganically associated V included silicate-bound V (46.09 ± 0.80%),

sulfide-bound V (13.63 ± 0.87%), and carbonate-bound V (1.82 ± 0.08%),

accounting for about 60% of the total V in studied coals. Vanadium was found to

have an association with many minerals and heavy metals. High correlation between

V and Cr in coal was observed, with their correlation coefficients equal to 0.67 for

48 bench samples from the Adaohai Mine (Dai et al. 2012d). Wang et al. (2002b)

showed a positive correlation between V and REE (rare earth elements) in the

medium and high sulfur coals, indicating the possibility of the existence of

yttrium-vanadium ores and kusuite. Positive but weak correlation was also observed

for V vs. Fe (r = 0.31) in the Antaibao surface mine, indicating that part of V is

associated with iron-bearing minerals (Liu et al. 2001). Dai et al. (2012d) reported

that Sn, Te, Zn, Cd, V, As, Cr, Cu, Mo, Ni, and Re are weakly correlated with ash

yield in low volatile bituminous coals and are associated with unidentified trace

sulfide minerals by cluster analysis. Vanadinite is found in the coal seams from

Xinde Mine in western Yunnan, resulting from multi-stage hydrothermal fluids (Dai

et al. 2014a). Zhuang et al. (2003) suggested that V is governed by the occurrence of

phosphate minerals, as deduced from the cross-correlation in the study of the density

fractions obtained from the bulk coal in the Late Permian coals from Chongqing. By

using X-ray absorption spectroscopy, Maylotte et al. (1981) found that V is

coordinated to oxygen rather than nitrogen and sulfide environments in the coals

from the Kentucky No. 9 seam.

4.4.2 Association with organic matter

The V associated with organic matter accounts for 37.64 ± 0.67% of the total V

in studied coal. Many other researchers also proved the existence of organically
 59

associated V. Ren et al. (2004) reported that V in the Shenbei lignite samples is

highly organically associated. By sequential chemical extraction, V is found mainly

associated with fulvic acid and/or organic macromolecule fractions (Ren et al. 2004).

The organic affinity of V in coal is probably due to the enrichment of barkinite,

which can concentrate V during peat accumulation (Sun et al. 2007). Vitrinite is

probably the main V carrier, as revealed by its high correlation in Tangkou coals (r =

0.44) (Liu et al. 2002). Dai et al. (2013a) showed that V is inversely correlated with

ash yield in low-volatile bituminous coals where no V-bearing minerals are

identified, and suggested that V along with the hydrothermal solutions during peat

accumulation or at the early diagenetic stages was fixed in the coal matrix (Dai et al.

2013a). The negative correlation between ash yield and V is also detected in

Neogene lignite from the Sofia Basin, Bulgaria (Kortenski and Sotirov 2002) and

Paleogene lignite from the USA (Given and Miller 1987). For some metalliferous

coals, V is also suggested to be organically associated. For example, Liu et al.

(2015a) found that V in high-U coals is mainly distributed in organic fractions

(58.2%-68.3%), followed by the silicate fraction (22.5%-36.3%). Seredin et al.

(2006) observed double V peaks in moderate and heaviest fractions by gravity

separation of high-Ge coals, and proposed that V is dominated by both organic and

inorganic association.

4.5 The factors influencing the occurrence of V in coals

4.5.1 Coal rank

Among coals of different ranks, lignite XD-M8 has the highest proportion of

organic-bound V (47.88 ± 2.57%). Kortenski and Sotirov (2002) also found that V

in lignite tends to be associated with organic matter. Carbonate- and sulfide-bound

V is the highest in bituminous coals; the proportions of water leachable, ion

 60

exchangeable and silicate-bound V are the highest in anthracite. From the above

observation, the proportions of water leachable and ion exchangeable V increase and

organic-bound V decreases with increasing coal rank. Vanadium is primarily

associated with aluminosilicate minerals in the high rank of bituminous coals, which

is also observed by other researchers (Zhou et al. 2010; Zhuang et al. 2012). Song et

al. (2007) noted that organically associated V can be mobilized when its associated

functional groups are destroyed with increasing coal rank.

Ren et al. (2006) reported that V in lignite generally has an organic affinity,

while in bituminous coals and anthracites, it is associated with clays. Breit and

Wanty (1991) reported that V in carbonaceous rock is incorporated into silicate

minerals during metamorphism. It is also frequently reported that V in high-rank

coals (bituminous coal and anthracites) is mainly combined with inorganic matter

(Chen et al. 2011; Querol et al. 1997). The concentration of V greatly decreases

when the vitrinite reflectance exceeds 2.0%, and organically associated V can be

mobilized with the destroyed functional groups when coal vitrinite reflectance

increases (Song et al. 2007). Vanadium in lignite is indicated to have organic

affinity by many researchers (Given and Miller 1987; Kortenski and Sotirov 2002).

However, in the lignite samples in the Yili basin, V and ash yields were found to be

highly correlated, indicating that V is derived from minerals in coal (Yang et al.

2011b). Megalovasilis et al. (2013) reported that V has a clear inorganic affinity

during the combustion of lignite as V was found enriched in the bottom ash. In most

bituminous coal samples, V is mainly associated with aluminosilicate minerals

(Chen et al. 2011; Zhou et al. 2010; Zhuang et al. 2012), while in some other

samples, a more organic mode of occurrence of V is found (Dai et al. 2013a). For

anthracite from Baijigou mine in northern China, V has an inorganic affinity (Song
 61

et al. 2007).

4.5.2 Coal-forming environment

The coal-forming environment is also an important factor for the mode of

occurrence of V. Vanadium in most coals is mainly associated with aluminosilicate

minerals (Chen et al. 2011; Du et al. 2009; Querol et al. 1997, 2001; Zhou et al.

2010; Zhuang et al. 2000) due to the fact that V primarily exists in the clay minerals

inherited from detrital materials of the source region (Sun et al. 2010a). The special

coal-forming environment of restricted carbonate platform influenced by seawater

could affect the occurrence mode of V. High organic-sulfur coal is an example that

was formed in this environment. Here are some reports about the occurrences of V

in high organic-sulfur coal: Zhao et al. (2005) found that 90% of V exists in

inorganic phases and < 10% is associated with organic phases in high organosulfur

coal by using sequential chemical extraction, and V is found mainly associated with

aluminosilicate (34 %) and iron and manganese oxides (25%); Shao et al. (2003,

2006) thought that V is also associated with iron sulphides and calcium oxide in

coals with high organic sulfur; in the high organic-sulfur coals from Chenxi

Coalfield, V has a very weak relationship with ash yield and is inversely correlated

with organic sulfur, while the relationship between V and iron is pretty strong (Li et

al. 2013a); Liu et al. (2015a) found that high-elevated V in superhigh-organic-sulfur

coals mainly occurs in organic fractions, followed by silicate fractions.

4.6 Comparison of chemical speciation between V and Cr

4.6.1 Correlation between V and Cr

V and Cr concentrations in studied coals of different ranks are listed in Table

4.2. The correlation coefficient between V and Cr in 21 coal samples, 10 bituminous

coals, and 10 selected coals were 0.56, 0.88 and 0.77, respectively (Fig. 4.1),
 62

indicating both elements are likely to be associated with common mineral or organic

phases. Other researchers also observed high correlations between V and Cr in coals

collected elsewhere (Dai et al. 2005b, 2012d; Hower et al. 2000). For example, Dai

et al. (2012d) reported that the correlation coefficient is 0.67 between V and Cr for

48 bituminous coals from the Adaohai Mine. For Neogene lignite from the Sofia

Basin, both V and Cr co-vary with the ash yield, suggesting they have common

associations in coals (Kortenski and Sotirov 2002).

4.6.2 Correlation of the chemical speciation of V and Cr

The results of Cr fraction in 11 selected samples by the sequential extraction

experiment are shown in Table 4.4. Both V and Cr are positively correlated with ash

yield, suggesting their predominant inorganic affinity. This is in accordance with the

result from sequential extraction where silicate bound V and Cr account for about

40-50% of the total V and Cr in coals. The proportion of V in silicate (46.09 ±

0.80%) is slightly higher than that of Cr (39.12 ± 0.65%), which might explain the

higher correlation of V vs. ash yield than Cr vs. ash yield. Cr is highly correlated

with V, which is probably because silicate bound and organic bound are the leading

modes of occurrence for both Cr and V. With the increasing coal rank from lignite to

anthracite, V and Cr combined with organic matter decrease, whereas silicate-bound

V and Cr increase. Ren et al. (2004) reported that V and Cr in lignite samples from

the Shenbei Coalfield are primarily associated with fulvic acid and/or organic

macromolecule fractions by sequential chemical extraction. Yossifova et al. (2011)

suggested that V and Cr are organically associated in the Lower-Middle Miocene

lignite based on the correlation coefficients between both elements and ash yields.

Lignite samples from the Sofia Neogene Basin are also thought to be

organically-dominant for V and Cr, according to the correlations of V vs. ash yield
 63

(rV-ash yield = -0.37) and Cr vs. ash yield (rCr-ash yield = -0.27) (Kortenski and Sotirov

2002). Thus, in the low-rank coals, elements are likely to be mainly associated with

organically functional groups, and can be mobilized as coal rank increases, due to

the increased burial temperature and pressure (Spears and Zheng 1999). Additionally,

traces of minerals in coal may be expelled from the organic matter with increasing

rank (Ward 2002).

 64

Table 4.4 Fraction (%) of Cr ± 1SD (n=3) defined by the sequential extraction experiment in 11 selected samples
water leachable ion exchangeable carbonate bound silicate bound sulfide bound organic matter bound RSCE
Boghead coal HY-4 0.54±0.05 1.22±0.21 1.32±0.23 47.07±2.40 bdl 54.40±2.34 104.55±7.48
Lignite XD-M8 0.56±0.05 1.28±0.22 0.03±0.01 32.54±1.66 17.67±6.98 42.03±1.81 94.12±11.28
Bituminous Mean fraction 0.75±0.03 3.51±0.30 3.76±0.40 37.03±0.86 10.14±2.13 31.83±0.64
coal
KL-7 0.92±0.08 4.65±0.79 0.86±0.15 51.74±2.64 bdl 37.69±1.62 95.87±8.21
DZ16-6 0.98±0.08 3.47±0.59 2.34±0.41 31.48±1.61 10.26±4.05 27.37±1.18 75.90±12.29
TP18-10 Bdl bdl 5.30±0.92 36.11±1.84 8.28±3.35 48.58±2.09 98.27±8.57
NT6-3 0.81±0.07 4.55±0.77 0.54±0.09 33.16±1.69 12.20±4.82 24.97±1.08 76.24±13.03
NT6-8 1.06±0.09 4.90±0.83 9.76±1.69 32.66±1.67 19.96±7.88 20.52±0.88 88.86±13.25
Semi-anthracite MEG-M4 0.08±0.01 0.42±0.07 2.04±0.35 40.21±2.05 17.29±6.83 27.35±1.18 87.38±12.50
Anthracite Mean fraction 0.50±0.03 3.21±0.49 7.02±0.87 46.40±1.68 5.94±1.98 27.55±0.85
XJY-C5 0.77±0.06 5.77±0.98 7.82±1.36 50.45±2.57 2.05±0.81 23.88±1.03 90.75±8.84
CS-C5 0.22±0.02 0.65±0.11 6.21±1.08 42.35±2.16 9.84±3.88 31.21±1.35 90.48±9.80
Stone coal ES 0.11±0.01 0.17±0.03 0.83±0.14 32.49±1.66 3.34±1.32 57.34±2.47 94.28±8.40
All samples Mean fraction 0.55±0.02 2.46±0.18 3.37±0.27 39.12±0.65 9.17±1.50 35.94±0.48
bdl, below the detection limit
 65

With increasing coal rank, fractions of V and Cr share the same variation trends,

and the V fraction is generally higher than that of Cr (Fig. 4.2). However, there are

still noticeable exceptions in that the ion-exchangeable fraction of V is significantly

lower than Cr in bituminous coals KL-7, NT6-3 and NT6-8 and carbonate-bound V

is obviously lower than Cr in anthracite XJY-C5 and CS-C5.

7.5
(a) (b)
4.5 7 7.0
4 4.0 6.5
6 6.0
Cr 3.5 Cr 5.5
3
v 3.0 5 v 5.0
4.5
2.5 4 4.0

V
Cr (%)

Cr (%)
2.0 3.5
2 3 3.0

(%)

(%)
1.5 2.5
2 2.0
1 1.0 1.5
0.5 1 1.0
0.5
0 0.0 0 0.0

13 80 80
(c) (d)
12 12
11 70
10 10
Cr 9 Cr
8 8 60 60
v v
7
V

V
Cr (%)

Cr (%)

6 6 50
5
(%)

(%)
4 4 40 40
3
2 2
1 30
0 0
-1 20 20

40 40 70
(e) 35
60
(f) 65
60
30 55
Cr
v 25 50
Cr (%)

45
V

V
Cr (%)

20 20 40 40
(%)

(%)
15 35
Cr 30
10
v 25
5 20 20
0 0 15
10

Fig. 4.2 Variations of water-leachable (a), ion-exchangeable (b), carbonate-bound (c),

silicate-bound (d) sulfide-bound (e) and organic-bound fractions (f) of Cr and V in coal samples of
different ranks.

4.7 Summary

The chemical speciation of V was studied in coal samples of different chemical

characteristics collected from different regions of China. The sequential chemical

extraction experiments show that V is mainly associated with silicate matter

(40-50%), followed by organic matter (~30%) and sulfides (~10%). Other forms of

V are present at trace levels. The proportions of water leachable and ion

exchangeable V increase and organic-bound V decrease with increasing coal rank.

 66

Vanadium is primarily associated with aluminosilicate minerals in high-ranking

bituminous coals. We found that V and Cr are highly correlated in the coal samples,

which may be attributed to the fact that silicate-bound and organic-bound V and Cr

are the leading modes. With increasing coal rank, the decrease of organic-bound V

and Cr likely compensate for the increase of silicate-bound V and Cr.

 67

Chapter 5 –The behavior of V during coal combustion

5.1 Introduction

Coal is the major energy source in China, which accounts for ~70% of Chinese

total energy consumption up to now, and will continue to be > 50 % in 2020 (You

and Xu 2010). The large amounts of coal consumption in China might contribute

significantly to the V budget in the atmosphere. At present, the anthropogenic V

emission budget into the atmosphere is estimated to be ~86,000 mt/a, which has far

(3.1–5.7 times) outpaced the natural V emissions budget by wind-borne soil

particles, volcanoes, and sea-salt spray (Hope 2008; Nriagu 1989). The largest

contributor to atmospheric V emissions is the combustion of fossil fuels (84,000

mt/a), including petroleum (76,000 mt/a) and coal (8000 mt/a) (Hope 2008).

The study of the volatility of V is crucial for predicting its environmental

effects. Vanadium, with a very high melting point of 1,919 ± 2 °C and a high boiling

point of 3,000–3,400 °C, is generally considered to be a non-volatile or low-volatile

element during coal combustion (Bunt et al. 2010; Yan et al. 2001; Zhang et al.

2003). The variation of V concentration and volatility under different temperatures

during combustion has been studied. Pyrolysis experiments show that V in the chars

of coal increases with temperatures rising from 500 to 900 °C, where V is 144 μg/g

in raw coal and 180 μg/g in the chars under 900 °C (Chen et al. 2007). During coal

gangue combustion, the volatilization rate of V stays at a low level but increases

(from 2.0% to 3.0%) steadily with temperatures rising from 500 to 1200 °C (Zhou et

al. 2012). The fate of V in the thermal conversion of coal has also been deciphered.

Vanadium can form a homologous series of hydrated vanadyl sulfates under

standard oxidizing conditions. However, when the temperature rises to 640 K, this
 68

stable vanadyl sulfate begins to decompose into V2O5 (condensed state). The VO2

(gaseous state) will be formed when the temperature is above 1,640 K, and it is the

only stable form of V when the temperature is above 1,800 K. Vanadium is

transformed into V2O3 (condensed state) under standard reducing conditions

(Frandsen et al. 1994).

Unlike volatile elements such as Hg, As and Se, the environmental concerns of

V have generally been ignored during coal combustion in previous studies. Due to

the high correlation of V and Cr in coal, the combustion behaviors of Cr were also

studied to reveal their environmental mobility during coal combustion.

5.2 Emission inventory of V by coal consumption

5.2.1 The V emission flux by Chinese and global coal consumption

The level of V in the atmosphere is rising day by day due to anthropogenic

activities, mainly the burning of hydrocarbon fuel (Mejia et al. 2007). Vanadium

emissions are becoming a major environmental concern and need further in-depth

study (Imtiaz et al. 2015). Nriagu and Pirrone (1998) calculated a V emission factor

of 2.5 g/mt (mt: metric ton) of coal combustion, assuming a V removal efficiency of

75% by typical air pollution control devices in coal-fired utility boilers. Based on

analysis of the existing data for Chinese and global coal consumption from 2004 to

2014 (British Petroleum 2015a), the estimated emission flux of V caused by coal

combustion is calculated in Fig. 5.1. From the figure, it can be seen that from 2004

to 2014, V emissions caused by Chinese coal consumption increased year by year,

while for global coal consumption, V emission slightly reduced in 2009, and then

kept increasing afterward. The V emission flux in Chinese coal is 4,141 mt/a, and

the V emission flux in global coal is 8,787 mt/a over these ten years. The global

emission flux we calculated is in accordance with the report that atmospheric V

 69

emission from world coal is 8,000 mt/a (Hope 2008). The emission flux of V from

Chinese coals in 2004 was 2,813 mt, accounting for 38.60% of the global total flux

(7,286 mt); in 2014, the V emission flux in China was 4,906 mt, accounting for

50.55% of global flux (9,705 mt).

Fig. 5.1 Vanadium emission inventories for Chinese and global coal consumption
from 2004 to 2014

5.2.2 The global V emission flux by different sectors

According to the statistical results and future projection of coal combustion in

different sectors by the British Petroleum (BP) Statistical Review of World Energy

(2015b), we estimated V emission inventories from transport, power plants, industry

and other sectors during 1990-2035 (Table 5.1, Fig. 5.2). Based on this estimate, V

emissions by electric power plants will account for 63.43% of global emissions in

2035, followed by industrial V emissions of 33.45%.

 70

Table 5.1 Vanadium emission budgets (mt) during global coal consumption by
different sectors
Different sectors 1990 1995 2000 2005 2010 2013 2015 2020 2025 2030 2035
Transport 43.54 33.63 27.83 27.12 29.87 36.68 37.82 45.95 54.26 58.42 60.42
Power plant 2904 3237 3738 4620 5406 5913 5862 6653 6906 7046 7272
Industry 1930 1908 1828 2370 2915 3282 3312 3593 3677 3773 3834
Other Sectors 670.5 429.1 280.3 315.1 342.7 363.4 357.9 352.3 326.4 312 297.7
Total 5548 5607 5875 7333 8694 9595 9570 10644 10963 11190 11464

Fig. 5.2 Vanadium emission flux of different sectors by global coal consumption
from 1990 to 2035

5.3 The combustion behavior of V in coal

5.3.1 The distribution of V among different coal combustion products

During coal combustion, V is distributed among different coal combustion

products. It has been found that after coal combustion, V is mainly distributed in fly

and bottom ash, and has a tendency to be more enriched in fly ash (Table 5.2) (Dai

et al. 2010b; Li et al. 2012a; Liu et al. 2004; Tang et al. 2013a). Liu et al. (2004)

thought that the high concentration of V in fly ash is due to its small particle size

and large specific surface. Tang et al. (2013a) studied the V distribution between
 71

feed coal and combustion residues from two coal-fired power plants in Huainan,

China, and found that the average V concentration in feed coal was 78.47 μg/g

(74.3–86 μg/g), with 177.5 μg/g (120–209 μg/g) in bottom ash, and 252 μg/g (from

221 to 288 μg/g) in fly ash. By studying eight samples from two coal-fired power

plants in Xinjiang Province, Li et al. (2012a) also reported that the average V in fly

ash (160.7 μg/g) was higher than that in bottom ash (122 μg/g), and both were

higher than that in feed coal (24 μg/g). Similar results have also been reported in

other countries (Córdoba et al. 2012; Li and Sun 2016; Nielsen et al. 2002). Coals

with anomalously high concentrations of V have potential for economic by-product

recovery and V-bearing coals can present a source of V in the future (Seredin and

Finkelman 2008).

Table 5.2 Vanadium concentrations in feed coal, bottom ash and fly ash from some
power plants in China. FA/F, the ratio of fly ash to feed; BA/F, the ratio of bottom
ash to feed; FA/BA, the ratio of fly ash to bottom ash
Feed coal Bottom ash Fly ash FA/F BA/F FA/B References
(μg/g) (μg/g) (μg/g) A
78.47 177.5 252 2.26 3.21 1.42 (Tang et al. 2013a)
24 122 160.7 5.08 6.69 1.32 (Li et al. 2012a)
95.13 181 190.8 1.90 2.01 1.05 (Liu et al. 2004)
34.87 54.8 68.87 1.57 1.96 1.26 (Dai et al. 2010b)
35.09 82.89 84.81 2.36 2.42 1.02 (Wang et al.1996)

5.3.2 Volatility of V during coal combustion

The volatility of V during simulated coal combustion experiments under

950 °C is shown in Fig. 5.3. The mean volatilization ratio was 9.23% as V. Frandsen

et al. (1994) concluded that V2O5 is formed in the thermal conversion (~950 °C) of

coal under oxidizing conditions. For lignite (XD-M8), the volatilization ratio is

26.98% for V. The mean volatilization ratio for V decreases to 8.72% in bituminous

coals. The volatilization ratios of V in anthracite are only 1.61%.

 72

Boghead Lignite Bituminous coal Semi- Anthracite Stone

30.00
coal anthracite coal

25.00
The mean volatilization
Volatilization ratio (%)

ratio of Cr in different
20.00 coal ranks
The mean volatilization
ratio of V in different
coal ranks
15.00 Cr
V

10.00

5.00

0.00
HY-4 XD-M8 KL-7 DZ16-6 TP18-10 NT6-3 NT6-8 MEG-M4 XJY-C5 CS-C5 ES

Fig. 5.3 The volatilization ratio of Cr and V during simulated coal combustion
experiments

5.4 Comparison of the combustion behavior between V and Cr

Due to the similar chemical forms of V and Cr, they are expected to behave

similarly during coal combustion. Both V and Cr in coals belong to medium- to low

-volatile elements (Tang et al. 2013a; Zhao et al. 2013; Frandsen et al. 1994; Yan et

al. 2001). Zhao et al. (2013) found that organic Cr is more easily volatilized than

chromate-associated Cr. The predominant silicate bound form of V and Cr might be

responsible for their medium to low volatility. It can be concluded that the

volatilization ratio for both V and Cr decreases with increasing coal rank (Fig. 5.3).

In addition, the volatilization ratio of V is always lower than the volatilization ratio
 73

of Cr for the same rank of coal. As shown in extraction experiments, bituminous

coals have 37.03 ± 0.86% of silicate-bound Cr and 42.05 ± 1.04% of silicate-bound

V, while anthracite has even higher silicate-bound Cr (46.40 ± 1.68%) and V (56.92

± 2.24%). Silicate-bound elements are not easily volatilized, and the higher fraction

of silicate-bound V than Cr in coals is possibly responsible for the lower

volatilization ratio of V. Yan et al. (2001) suggested that Cr, V, Co and Mn can be

classified as elements of low volatility as long as the temperature is below 1400 K.

Yi et al. (2008) calculated that approximately 10% of V and 20% of Cr are

volatilized into flue gases during coal combustion, which is in line with our

observation that 9.23% of V and 13.52% of Cr were volatilized during simulated

coal combustion.

5.5 Summary

As a low-volatile element, V tends to be enriched in ash, especially in fly ash

during combustion. Significant volatilization of V only occurs under temperatures

above 1800 K with the main volatilization species VO2. An estimation of V emission

flux has been made in this study, and the result suggests that in the period 1990-2035,

V emission by electric power plants will share the largest part (63.43%), and keep

increasing.

The simulated coal combustion experiment at 950 °C showed that 9.23% of V

is volatilized. The volatilization ratio for V decreases with increasing coal rank. We

speculate that the lower volatility of V than Cr might be related to the higher

fraction of silicate-bound V than Cr in coal.

 74

Chapter 6 – Environmental geochemistry of V in coal

mining areas

6.1 Introduction

Coal is the major energy source in China, and over 4.5 billion tons of coal

gangue have accumulated around nationwide coal fields (You and Xu 2010; Zhou et

al. 2014). Therefore, it is important to study the impacts of V on the surrounding

environment (soil, water, sediment) from coal utilization. Some researchers have

found that coal utilization has some impact on the surrounding environment in coal

mining area. Tang et al. (2013b) found that, for V in the residential soil samples

collected from Huainan coal mining area, the concentration of the downwind

directions of the coal power plant (61 mg kg-1) was higher than that of the upwind

soil samples (45 mg kg-1). Vanadium in coal gangue from the Huainan coalfield

shows some risk to the ecosystem, based on its risk assessment code values

calculated by Zhou et al. (2014).

Metals, including V, can settle and become incorporated in bottom sediments

(Chakraborty et al. 2011, 2014; Chakraborty and Babu 2015). Thus, historical

records of the anthropogenic emissions into the fluvial environment can be revealed

by river sediments (Audry et al. 2004; Swarzenski et al. 2008). Sediments play an

important role in the pollution pattern of river systems (Casas et al. 2003).

Time-series records of contaminants in sediments have been successfully applied to

assessing pollution from a variety of sources and to determining pathways of

deposition (Macdonald et al. 2016).

Compared to the total level, the bioavailability of target elements in sediment

can be measured by ex-situ chemical methods, such as sequential extraction and

 75

single-step extraction, and thus reveals a more accurate behavior of trace elements

(Chakraborty et al. 2016; Filgueiras et al. 2004; Liu et al. 2015b; Wang et al. 2016a).

Sequential extraction is considered to be an effective method to study the

fractionation of trace elements in sediments and has been widely used (Chakraborty

and Babu 2015; Gowd et al. 2010; Rauret et al. 1999; Rosado et al. 2016).

Vanadium is generally of little importance in environmental legislation and

knowledge of the environmental behavior of V, especially in areas concentrated with

coal, is still limited. The aim of this study was to improve knowledge of the

spatio-temporal characteristics of V in soils, sediments, and fish collected from coal

mining areas to assess the degree of contamination and deduce the possible sources,

which may reveal the environmental impacts of V from coal-related industries.

6.2 Vanadium concentration in coal gangue from Huaibei and

Huainan coal mining areas

The results of V concentration in coal gangue from Huaibei coal mining area

are shown in Table 6.1. The concentration of V in coal gangue from Huaibei coal

mining area was far lower than the soil background of V in China (82 μg/g) (Wei et

al. 1991), but higher than the average concentration of V in global coal (25 μg/g)

(Ketris and Yudovich 2009). The descending order of V concentration in coal

gangue of the four coal mines was: RL (78.06 μg/g) > WG (73.09 μg/g) > BS (59.97

μg/g) > ZXZ (56.41 μg/g).

 76

Table 6.1 Vanadium in coal gangue, soil and fish from Huaibei coal mining area
V (μg/g)
Coal gangue Soil Fish
ZXZ Mean 56.41 78.95 0.44
Range 44.07~72.33 76.15~81.48 0.24~0.64
RL Mean 78.06 79.42 0.43
Range 66.88~91.87 69.02~94.09 0.27~0.60
WG Mean 73.09 71.37 0.40
Range 59.66~88.29 55.43~80.90 0.04~0.76
BS Mean 59.97 89.81 0.47
Range 55.73~65.09 63.31~149.01 0.00~1.14

The results of V concentration in coal gangue near Huai River from Huainan

coal mining area are shown in Table 6.2. The mean V concentrations in coal gangue

of G1, G2 and G3 were 130 mg kg-1, 95 mg kg-1 and 112 mg kg-1, respectively. The

concentration of V in coal gangue from Huainan coal mining area was higher than

from Huaibei coal mining area as well as the soil background of V in China (Wei et

al. 1991).

Leaching and weathering of coal gangue is a possible pathway for V to enter

the surrounding watershed (Zhou et al. 2014). Vanadium concentrations in the

leachates of coal gangue G1, G2 and G3 were 0.74 mg kg-1, 0.30 mg kg-1 and 0.59

mg kg-1, respectively, and the corresponding leaching rates were 0.57%, 0.31% and

0.53%. It appears that the leached V concentration in coal gangues is too low to

significantly affect V in sediments. Moreover, the enrichment degrees of V in

corresponding sediments were not consistent with the leached V from the coal

gangues.
 77

Table 6.2 Vanadium concentrations in coal gangues and surface sediments (mg kg-1,
dry weight)
V
Samples V
Mean ± SD
A 87 ± 2.6 soil BK in Chinaa 82
b
B 75 ± 3.9 sediment BK in the river system of China 80
C 65 ± 2.8 average value for global shalec 130
D 93 ± 1.4 upper continental crustd 97
e
E 78 ± 1.9 average value for global coal 25
F 100 ± 1.8 average value for fly ash in Huainan coal 252
plantsf
G1 130 ± 2.8
G2 95 ± 3.0
G3 112 ± 0.88
a Soil background values in China (Wei et al. 1991)
b Sediment background values in the river system of China (Yan et al. 1995)
c Average value for global shale (Forstner et al. 1993)
d Upper continental crust (Rudnick and Gao 2014)
e Average value for global coal (Ketris and Yudovich 2009)
f Average value for coal ash in Huainan coal plants (Tang et al. 2013a)

6.3 Vanadium concentration in soils from Huaibei coal mining area

The average concentration of V in surface soil samples near the coal gangue in

Huaibei area was 80.87 μg/g, lower than the soil background of V in China (Wei et

al. 1991) and the average V concentration of the upper crustal level (Rudnick and

Gao 2014). The order of V concentration in the soil of the four coal mines was: BS

(89.81 μg/g) > RL (79.42 μg/g) > ZXZ (78.95 μg/g) > WG (71.37 μg/g) (Table 6.1),

which is in accordance with the order of the age of the coal mines. The rank of the

age of coal mines is: BS (41 years) > ZXZ (36 years) > RL (21 years) > WG (10

years). No relationship was found between the V concentrations in soil near each

coal mine and the available reserves of the coal mine. The rank of available reserves

of the coal mines is: RL > ZXZ > WG > BS. The highest V concentration of all soil

samples was observed at sampling site B2-5 in BS coal mining area, with the value

reaching 149.01 μg/g. In addition, the sampling sites with V concentration greater

than 100 μg/g were B2-6 and B1-5 in BS coal mining area. The cumulative index
 78

method was conducted to assess the risk of V in the soil, and the result of

geoaccumulation index shows that only soil sample B2-5 presented possible V

pollution, while coal gangue was found to have no effect on the concentration of V

in the soil.

6.4 Vanadium in sediments in Huai River from Huainan coal mining

area

6.4.1 Sedimentation rate

The 50-cm sediment core from Huai River spanned the period ranging from
210
1955 to 2014 according to the results of Pb dating (Fig. 6.1), and the estimated

linear sedimentation rate was 0.83 cm yr.-1. The dating results were also reported in

our earlier study (Wang et al. 2016b). A similar sedimentation rate of 0.8 cm yr.-1 by

Wu et al. (2015), and 0.5 cm yr.-1 by Liu et al. (2015b) were reported for the

sediment cores collected from the Yellow River Delta, China. Sedimentation rates as

high as 1.5 cm yr.-1 have been reported for the Pearl River Delta by Gan et al. (2002).

The difference in sedimentation rate between different fluvial systems might relate

to the hydrological structure and regional supply of sediments.

 79

Fig. 6.1 Vanadium concentration-depth profile from sediment core D

6.4.2 Vanadium concentrations in surface sediments

The concentrations for V in surface sediment samples (dry weight basis) are

listed in Table 6.2. Vanadium concentration varied from 65 to 100 mg kg-1 in the

surface sediments, with a regional average of 83 ± 12 mg kg-1, which is comparable

to Chinese soil (82 mg kg-1) and Chinese river systems (80 mg kg-1) (Wei et al. 1991;

Yan et al. 1995). The regional average is also comparable to the V concentration in

fluvo-aquic soils (83 mg kg-1) which dominates the study area (Teng et al. 2011), but

lower than the average values for global shale (130 mg kg-1) and the upper

continental crust (97 mg kg-1) (Fostner et al. 1993; Rudnick and Gao 2014). The

source rocks in the studied watershed include limestone, sandstone, igneous rock,
 80

and sandy mudstone, with their mean V concentrations reported as 105 mg kg-1, 11

mg kg-1, 24 mg kg-1, and 82 mg kg-1, respectively (Chen et al. 2013, 2016a). Wang

et al. (2013) reported that V in the sediments of Huai River (Anhui Section) ranged

from 40 to 129 mg kg-1, with a mean concentration of 78 ± 25 mg kg-1, which is

similar to the value reported in this study. In the adjacent river systems, for

sediments sampled from the Yellow River and the Yangtze River, their V

concentrations were 58 ± 5 mg kg-1 and 104 ± 14 mg kg-1, respectively (Lim et al.

2006).

The mean V concentrations in the surface sediments of individual sampling

sites were as follows: F (100 mg kg-1) > D (93 mg kg-1) > A (87 mg kg-1) > E (78 mg

kg-1) > B (75 mg kg-1) > C (65 mg kg-1), exhibiting no obvious spatial gradient.

Vanadium presented the largest concentration in site F in the downstream of the

study area, which might relate to the nearby (0.4 km) LH coal power plant. Emission

of V attached to the coal combustion fly ash is the primary anthropogenic pathway

(Goodarzi 2006). Tang et al. (2013a) reported that V in the fly ash from LH coal

power plant could reach 288 mg kg-1. Khan et al. (2011) also found that thermal

power plants have a potential impact on human health, and the V concentrations in

vegetable and grass tissues around a thermal power plant ranged from 3 mg kg-1 to

14 mg kg-1. However, the distances from power plants might not be the only reason

for V enrichment in sediments. For sites B, C and D, their distances from PW coal

power plant are quite similar, i.e. 2, 2 and 3 km, respectively. However, an obvious

elevation of V was observed in the sediment of site D, indicating no significant

correlation between V concentrations and their distances from nearby power plants.

Therefore, other factors, such as the combusted coals, the capacity of the power

plant and wind direction might also be responsible for the spatial heterogeneity of V
 81

in sediments.

6.4.3 Temporal characteristics of V in sediments

The V concentrations in sediments covering the 1955-2014 period are listed in

Table 6.3 and depicted in Fig. 6.1. Between 1955 and 2000, V concentrations in

sediment core exhibited a stepwise and broad increasing trend, and reached a peak

value of 131 mg kg-1 in around 2000. The ascending trend might be due to the

accelerated coal mining activities and the combustion of coal for electricity

generation since the establishment of the People’s Republic of China in 1949, as

well as the Policy of Reform and Opening-up from 1979, after which LH and PW

power plant were both established in the 1980s (Song et al. 2010). The obvious

increase in V around 1994-1995 (129 mg kg-1) has a good correspondence with a

contamination event of 1994 reported by Zuo et al. (2015). In 1994, many fish and

shrimps died in the studied watershed, and some residents suffered from nausea,

emesis and diarrhea, which were caused by water pollution (Zuo et al. 2015).
 82

Table 6.3 The V concentration, enrichment factor (EF), geoaccumulation index (Igeo)
and dating year of sediment core D
Depth V (mg kg-1)
Year EF Igeo
(cm) Mean ± SD
0 2014 93 ± 1.6 1.1 -0.37
2 2007 100 ± 2.2 1.2 -0.26
4 93 ± 1.8 1.3 -0.36
6 106 ± 2.5 1.3 -0.18
8 2002 106 ± 1.5 1.3 -0.18
10 106 ± 1.4 1.0 -0.18
12 131 ± 3.3 1.4 0.13
14 1998 109 ± 4.7 1.1 -0.14
16 122 ± 1.7 1.1 0.023
18 122 ± 1.7 1.2 0.021
20 1995 122 ± 1.3 1.2 0.022
22 129 ± 1.5 1.4 0.10
24 115 ± 2.3 1.2 -0.059
26 1994 114 ± 3.6 1.3 -0.079
28 111 ± 3.6 1.1 -0.12
30 114 ± 4.3 1.4 -0.069
32 1985 102 ± 1.7 1.3 -0.24
34 97 ± 1.3 1.1 -0.30
36 105 ± 1.0 1.3 -0.19
38 1968 108 ± 1.1 1.1 -0.16
40 110 ± 3.5 1.1 -0.13
42 102 ± 2.5 1.2 -0.23
44 1961 108 ± 1.4 1.4 -0.15
46 109 ± 1.1 1.4 -0.14
48 97 ± 2.8 1.3 -0.31
50 1955 91 ± 4.5 1.1 -0.40

From 1995 to 1998, the V concentrations maintained a stable level of about 120

mg kg-1. A peak of V occurred around the year 2000, which may relate to the water

pollution and flood events that took place in the Huai River in 1999 (Zuo et al. 2015;

Zhang et al. 2015b). Following this peak, V in sediment core exhibited a stable

declining trend from 131 to 93 mg kg-1, suggesting a significant change of V input

sources into the Huai River Basin. In the recent decade, the local government has

enacted stricter environmental protection policies and regulations. The provisional

regulation for proctoring water pollution in the Huai River, as the first critical

project for pollution control in China, was issued in 1995 by the State Council of the
 83

People's Republic of China. Afterward, highly polluting factories were shut down,

and sewage treatment facilities were improved. The local government also

reinforced the regulations on power plant proctoring and coal gangue storage in the

Huai River Basin. The State Economic and Trade Commission reformulated the

regulation of the comprehensive utilization of coal gangue in 1998. Three Five-year

Plans for pollution prevention in relation to the Huai River were put into force in

1996-2010 and the water quality was notably improved (Zhai et al. 2014).

The water quality of the Huai River from 1991 to 2014 is compiled in Fig. 6.2.

The data were collected from the Environmental Bulletin of China (1991-2014)

reported by the Ministry of Environmental Protection of the People’s Republic of

China. Three types of water standards have been issued for evaluating water quality

of China (State Environmental Protection Administration 1998, 1999, 2002).

Vanadium variation in sediments is in good correspondence with the water quality

of the Huai River. The water was of drastically low quality in 1991-1994 and

1998-1999, and correspondingly, two peaks of V concentrations occurred in

1994-1995 and 1998-2002. From 2002 to 2014, the water quality of the Huai River

was improved significantly, while the declining trend of V concentration dominated

this period.
 84

Fig. 6.2 The water quality of the Huai River (from 1991 to 2014, the data for 1997
are missing). Water environmental quality is divided into six classes, i.e., Classes Ⅰ
-Ⅴ, and Class Ⅴ+. The classes of Water quality of 1991-1999, 2000-2001, and
2002-2014 are divided according to the State Environmental Protection
Administration (SEPA) (1998), SEPA, (1999) and SEPA, (2002), respectively. Ⅰ-
Ⅲ include class Ⅰto class Ⅲ. Class Ⅰrefers to the water in the source and
national natural reserve. Class Ⅱ refers to the water in the first-grade protection
zone of centralized drinking water source, rare aquatic habitats, spawning ground
and little fish feeding grounds, etc. Class Ⅲ refers to the water in the second-grade
protection zone of centralized drinking water source, fish and shrimp overwintering
ground, migration route, aquaculture area and swimming area, etc. Ⅳ-Ⅴ include
class Ⅳ and class Ⅴ. Class Ⅳ refers to the industrial water and recreational
water, etc. Class Ⅴ refers to agricultural water and landscape water. Ⅴ+ refers to
water inferior to Class Ⅴ.

6.4.4 The fractionation of V in sediments

The chemical forms of heavy metals in the sediments can strongly influence

their behavior, such as mobility, bioavailability, toxicity and chemical interactions

(Dang et al. 2002). The different fractions (%) of V in the surface sediments are

shown in Table 6.4. The recovery rates of V by sequential extraction procedure

varied from 85% to 100%, indicating excellent reproducibility and closure of mass

balance. In general, the highest fraction of V was observed in the residual form, with

an average value of 84 ± 2.6%, suggesting low mobility and bioavailability of V.

The weak acid soluble fraction of V (i.e. exchangeable and carbonate bound) in all

the surface sediments was found in the range of 0.14-0.45%. The highest percentage
 85

of weak acid soluble V (0.45 ± 0.22%) was present in the sediments collected at

sampling site C, which was surrounded by coal gangues G2 and G3. The reducible

fraction of V in surface sediments accounts for 8.2 ± 2.4%, while approximately 8%

of the total V was found in oxidizable fraction. The extraction experiment suggests

that V is mainly associated with inert Fe-Mn oxides complexes, organic materials

and sulfides. Only 16% of V was found to be associated with non-residual fractions

(exchangeable, carbonate, reducible and oxidizable). The non-residual V is thought

to be derived from the anthropogenic sources, whereas the residual fraction is from

the lithogenic source (Syaizwan et al. 2010). Teng et al. (2009) also found that most

V occurs in insoluble residue (83%-93%). Cappuyns and Swennen (2014) pointed

out that V generally displays a very limited actual and potential mobility in

sediments.

Table 6.4 Fractionation (%) of V in surface sediments.

F1 F2 F3 F4 Recovery
Mean ± SD Mean ± SD Mean ± SD Mean ± SD Mean ± SD
A 0.26 ± 0.053 9.7 ± 5.8 7.7 ± 0.62 82 ± 8.4 93 ± 6.8
B 0.14 ± 0.051 8.7 ± 4.1 9.1 ± 2.0 82 ± 8.1 85 ± 4.6
C 0.45 ± 0.22 6.2 ± 1.8 9.1 ± 3.1 84 ± 8.4 88 ± 7.0
D 0.16 ± 0.04 9.0 ± 1.1 6.7 ± 0.81 84 ± 7.5 85 ± 8.8
E 0.26 ± 0.10 4.3 ± 2.2 6.1 ± 2.0 89 ± 6.5 100 ± 8.1
F 0.26 ± 0.021 12 ± 1.9 6.4 ± 7.4 82 ± 2.9 88 ± 4.7
All samples 0.25 ± 0.10 8.2 ± 2.4 7.5 ± 1.2 84 ± 2.6 90 ± 5.3
F1, F2, F3, and F4 are fraction 1 (weak acid soluble), fraction 2(reducible), fraction
3(oxidizable), and fraction 4 (residual), respectively.

The fractions of V in sediment core D varied with the sedimentary years (Fig.

6.1). The sediment of 20 cm (ca. 1995) is characterized by the highest residual form

of V. The redox state of the sediment core can be reflected by the reducible fraction

(F2) and the oxidizable fraction (F3) of V (Fig. 6.3). The sediments from 50 to 20

cm corresponding to the period from 1955 to 1995, and larger depth generally leads

to the higher fraction of reducible fraction and oxidizable fraction. From 1995 to
 86

2002, the fractions of reducible and oxidizable V exhibited an increasing trend,

while from 2002 to 2014, their fractions started to decline. Sediment with the least

reducible and oxidizable V was deposited in 1995, while the highest was in 1955,

with the same variation trend of their fraction in sediments. The highest V

concentrations in sediments appeared in around 1994-2000. However, sediments

corresponding to this period were mostly in residue form, with less reducible and

oxidizable V, which may be attributed to the frequent floods carrying out the mobile

forms of V in sediments. There were actually frequent pollution incidents of the

Huai River in 1994, 1999, 2001 and 2004, suggesting that sudden water pollution

events are prone to occur when flood water is discharged from the sluices (Zuo et al.

2015; Zhang et al. 2015b).

Fig. 6.3 The fraction of V variation along the depth in sediment core D (F1, weak
acid soluble fraction; F2, reducible fraction; F3, oxidizable fraction; F4, residual
fraction)
 87

6.4.5 Enrichment factor and geo-accumulation index

The V enrichment factors in the surface sediments in this study, ranging from

0.56 to 1.1 (Table 6.5), show that sediments from C, E and F were not V enriched,

and sediments from A, B and D were only slightly V enriched. The EF values of V

in the sampling sites follow this order: D (1.1) > A (1.06) > B (1.03) > C (0.92) > F

(0.62) > E (0.56). In sediment core D, all the EFs were larger than 1, indicating

sediment core collected from D may have been slightly polluted (Table 6.3).

Table 6.5 Enrichment factor (EF) and geoaccumulation index (Igeo) of V in

surface sediment (Birth 2003; Forstner et al. 1993)
Grade standards for Grade standards for Igeo
EF
EF Enrichment Igeo Sediment
Samples Value Value Class
of V status of V quality
no Practically
A 1.06 <1 -0.46 <0 0
enrichment uncontaminated
Uncontaminated
Minor
B 1.03 1-3 -0.68 0-1 1 to moderately
enrichment
contaminated
Moderately Moderately
C 0.92 3-5 -0.90 1-2 2
enrichment contaminated
Moderately Moderately to
D 1.1 5-10 severe -0.29 2-3 3 strongly
enrichment contaminated
Severe Strongly
E 0.56 10-25 -0.61 3-4 4
enrichment contaminated
Strongly to very
Very severe
F 0.62 25-50 -0.34 4-5 5 strongly
enrichment
contaminated
Extremely
Very strongly
Mean 0.88 >50 severe -0.55 >5 6
contaminated
enrichment

The results of geoaccumulation index show a practically uncontaminated status

of V in sediment (Table 6.5). The Igeo values of V are in the order D (-0.29) > F

(-0.34) >A (-0.46) > E (-0.61) > B (-0.68) > C (-0.90). For the profile of sediment

core D (Table 6.3), Igeo values were positive at the depth of 12, 16, 18, 20, 22 cm,

implying that sediments corresponding to the period 1994-2000 were

 88

uncontaminated or moderately contaminated.

6.5 Vanadium concentration in fish from the Huaibei coal mining

area

The concentration of Carassius carassius in the subsidence pond near four coal

mines from the Huaibei coal mining area was about 0.4 μg/g dw, which is similar to

the concentration of V (0.6 μg/g dw) in the fish from East China Sea (Asante et al.

2008). The order of V concentration in Carassius carassius from the four coal mines

is: BS (0.47 μg/g dw) > ZXZ (0.44 μg/g dw) > RL (0.43 μg/g dw) > WG (0.40 μg/g

dw) (Table 6.1), which is in accordance with the age order of the four coal mines.

The concentration of V in Carassius carassius may relate to the coal mining history.

The calculated daily intakes for V were lower than the corresponding oral

reference dose (RfD) (9 μg kg−1bw day−1) (USEPA 2013). The Target Hazard

Quotient (THQ) of V from all fish samples were below 1, implying that

consumption of the analyzed fish from Huaibei subsidence ponds posed no health

risk to consumers.

6.6 Summary

The concentration of V in coal gangue in the Huainan coal mine is higher than

that in the Huaibei coal mine. The leaching rate of V in coal gangue was about

0.05%. The average concentration of V in the soil around coal gangue in Huaibei

Coal Mine was lower than the soil background of V in China. This showed the weak

effect of coal gangue on the concentration of V in the soil. However, the order of V

concentration in the soil and fish of four coal mines was in accordance with the

order of the age of the corresponding coal mine, which might indicate a possible

correlation between the concentration of V in soil and fish from the Huaibei coal
 89

mining area and the history of coal mining.

Sampling of sediments from the Huai River Basin allows for the initial

evaluation of V release trends during the period of 1955-2014. The average

sedimentation rate was approximately 0.8 cm yr.-1. Coal gangue piled up along the

river bank and the rapid construction of power plants may have increased the

background levels of V in sediments. The vertical profiles of V indicate a good

correspondence to the recent economic development of China. The decrease of V

since 2000 reflects the local strict regulations. The highest proportion of V in

sediments was present in the residual fraction, and the lowest was observed in the

weak acid soluble fraction. Based on the values of VEF, sediments collected from A,

B and D were slightly contaminated. The results of geoaccumulation index showed

that some samples of sediment core were moderately contaminated with V.

 90

Chapter 7 – Environmental geochemistry of V in

petroleum-producing areas

7.1 Introduction

The Yellow River Delta, Yellow River estuary, and Laizhou Bay are

representative petroleum-producing areas in China. The Yellow River Estuary is an

important fishery area in the world, which provides spawning grounds for many

organisms in the Bohai Sea and the Yellow Sea. The Yellow River Delta Nature

Reserve (YRDNR) was established in 1992 as a national nature reserve to protect

the new wetlands at the mouth of the Yellow River, as well as rare and endangered

birds (Wang et al. 2011). However, the second largest oilfield in China (Shengli

Oilfield) and some chemical enterprises are located nearby, which threaten the

ecosystem of the Yellow River Delta and Yellow River Estuary (Xu et al. 2011,

2015). Thus, great concern has arisen over environmental contamination in this

region due to its unique environmental conditions, ecological sensitivity and

environmental significance (Liu et al. 2016a; Xie et al. 2014; Yuan et al. 2016).

Laizhou Bay, a typical estuary-bay ecosystem of the Bohai Sea, is an important

coastal zone for aquaculture in China (Zhang et al. 2017; Zhuang and Gao 2013).

However, the marine ecosystem of this semi-closed shallow bay is fragile. Rapid

urbanization and industrialization in the Laizhou Bay area have led to excessive

water contamination in the last few decades (Xu et al. 2015; Yuan et al. 2016).

Hence, serious concern over environmental contamination in this coastal region has

arisen.

Human activities have intensely raised heavy metal emissions into the

ecosystem (Asante et al. 2008; Nriagu and Pacyna 1988; Squadrone et al. 2016),
 91

especially the estuarine-coastal ecosystems (Delgado et al. 2010; Spencer et al.

2003), where an important sink takes place for heavy metals from rivers, runoff, and

land-based point sources. Thus, the aquatic organisms in estuaries might be exposed

to high levels of heavy metals. Once heavy metals propagate through the food web,

they may ultimately accumulate to dangerous levels and pose a potential risk to

human health (Ofukany et al. 2014). Vanadium is the second-most abundant

transition metal in the oceans (Winter and Moore 2009), and is highly related to

petrochemical product contamination which is serious in estuarine-coastal

ecosystems (Dsikowitzky et al. 2013; Villares et al. 2007). Fish with V

contamination can be a significant dietary contribution of V (Sepe et al. 2003) and

high doses of V can lead to neurologic, hematologic, renal and hepatic toxicity (NTP

2002).

Elevated V concentration in water and sediment in the Yellow River Estuary

have been found (Lin et al. 2016; Song et al. 2013; Wang et al. 2017). Heavy metals

(Cu, Pb, Zn, and Cr) have been studied in tissues of fish from the upper stream

(Wang et al. 2010) and middle reaches (Lü et al. 2010) of the Yellow River.

Relevant studies on the ecosystem in Laizhou Bay, including sediments (Xu et al.

2015; Yu et al. 2017; Zhang et al. 2017) and certain aquatic organisms (Liu et al.

2017a; Wu et al. 2014), have recently been carried out. However, there is no

comprehensive research about V contamination in soil and aquatic organism from

the Yellow River Delta, Yellow River Estuary or Laizhou Bay.

In this study, the concentrations of V in soil collected from the Yellow River

Delta, fish collected from the Yellow River Estuary, and aquatic organism (shellfish,

crab, and shrimp) collected from Laizhou Bay were investigated. The V

accumulations in aquatic organisms among all collected species were compared.

 92

This study also assessed the health risk of consuming aquatic organisms based on

daily intake calculation.

7.2 Vanadium concentration in soil from the Yellow River Delta

The results show that the mean pH in soils from the Yellow River Delta was

8.37, ranging from 7.22 to 9.35. The soil was alkaline. The mean value of total

organic carbon was 0.061%, with the range from 0.019% to 0.572% (Table 7.1).

Table 7.1 Chemical properties of soils collected from the Yellow River Delta

Sample pH TOC Sample pH TOC Sample pH TOC

(%) (%) (%)
S1 8.54 0.066 S17 8.32 0.036 S33 8.40 0.050
S2 7.22 0.036 S18 8.39 0.030 S34 9.05 0.040
S3 8.55 0.059 S19 7.86 0.057 S35 8.17 0.078
S4 8.67 0.028 S20 8.51 0.019 S36 8.20 0.052
S5 8.36 0.085 S21 9.23 0.041 S37 9.06 0.040
S6 7.67 0.046 S22 9.33 0.034 S38 8.73 0.054
S7 8.58 0.047 S23 9.35 0.041 S39 7.76 0.043
S8 8.41 0.031 S24 7.87 0.572 S40 8.52 0.192
S9 8.33 0.057 S25 7.77 0.038 S41 8.12 0.062
S10 9.22 0.019 S26 8.34 0.046 S42 8.22 0.026
S11 8.15 0.036 S27 8.11 0.077 S43 8.81 0.035
S12 8.22 0.042 S28 8.30 0.063 S44 8.42 0.048
S13 8.01 0.082 S29 8.31 0.031 S45 8.52 0.028
S14 8.25 0.090 S30 7.82 0.026 S46 8.67 0.048
S15 7.98 0.050 S31 8.36 0.065 Mean 8.37 0.061
S16 8.29 0.023 S32 8.07 0.051

The average concentration of V in soil samples in the Yellow River Delta was

85.12 μg/g, slightly higher than the V concentration of Chinese soil background

(Wei et al. 1991), but lower than the average concentration of the upper crust

(Rudnick and Gao 2014). The study found that sampling site S45 was very close to

the FYH oilfield, and the V concentration of this sampling site was the highest

among all the sampling sites, reaching 120.41μg/g. The sampling sites with V

concentration higher than 100 μg/g were S28 (114.93 μg/g), S36 (101.98 μg/g), S39

(100.65 μg/g), S40 (104.39 μg/g), and S42 (100.39 μg/g). Correspondingly,
 93

sampling site S28 was near XW oilfield, and S36, S39, S40, and S42 were near the

GD oil field. Therefore, the exploitation of oil and the burning of fossil fuels may

lead to the aggravation of V pollution.

The geoaccumulation index method was used to evaluate the risk of V in the

soil, and the results show that there was no V pollution in all soil samples from the

Yellow River Delta (Table 7.2).

Table 7.2 The V concentration and geoaccumulation index (Igeo) of the soils from
the Yellow River Delta
V Igeo V Igeo V Igeo
(μg/g) (μg/g) (μg/g)
S1 69.70 -0.82 S17 71.85 -0.78 S33 82.38 -0.58
S2 79.16 -0.64 S18 76.36 -0.69 S34 81.26 -0.60
S3 76.63 -0.68 S19 84.56 -0.54 S35 97.27 -0.34
S4 72.95 -0.75 S20 77.07 -0.67 S36 101.98 -0.27
S5 74.64 -0.72 S21 83.58 -0.56 S37 89.24 -0.46
S6 84.70 -0.54 S22 74.14 -0.73 S38 95.01 -0.37
S7 78.51 -0.65 S23 61.41 -1.00 S39 100.65 -0.29
S8 87.34 -0.49 S24 80.47 -0.61 S40 104.39 -0.24
S9 91.68 -0.42 S25 78.51 -0.65 S41 80.39 -0.61
S10 75.23 -0.71 S26 99.47 -0.31 S42 100.39 -0.29
S11 86.73 -0.50 S27 83.10 -0.57 S43 92.02 -0.42
S12 76.84 -0.68 S28 114.93 -0.10 S44 78.27 -0.65
S13 81.39 -0.60 S29 83.00 -0.57 S45 120.41 -0.03
S14 81.26 -0.60 S30 77.37 -0.67 S46 82.71 -0.57
S15 76.87 -0.68 S31 97.73 -0.33 Mean 85.12 -0.54
S16 89.98 -0.45 S32 81.79 -0.59
 94

7.3 Vanadium in fish from the Yellow River Estuary

7.3.1 Concentrations of V in fish from the Yellow River Estuary

A comparison between the data of this study and available data from previous

studies about other locations is presented in Table 7.4. The mean concentrations of

V in samples in this study were significantly higher than the results of previous

studies presented in Table 7.3 (Asante et al. 2008; Ip et al. 2005).

The mean concentrations of V for each fish species from the Yellow River

Estuary are detailed in Table 7.3. Vanadium significantly differed among species (P

= 0.025). Vanadium tended to accumulate more (P < 0.05) in Silurus asotus

compared to Lateolabrax japonicas and Pelteobagrus fulvidraco. The highest mean

concentration of V was observed in Silurus asotus (20.1 ± 4.8 μg g−1 dw), and the

lowest was found in Synechogobius hasta (3.0 μg g−1 dw). The mean concentration

of V in Carassius auratus was 8.5 ± 0.94 μg g−1 dw.

 95

Table 7.3 Concentrations of V and stable isotope ratios of δ15N and δ13C in 11 fish
species from the Yellow River Estuary
V
Scientific name δ15N (‰) δ13C (‰)
(μg g dw) (μg g−1 ww)
−1

Carassius auratus AM ± SD 8.5 ± 0.94 2.3 ± 0.14 11.4 ± 1.9 −17.9 ± 3.1
Range 7.8 ~ 9.9 2.2 ~ 2.5 8.8 ~ 13.3 −22.1 ~ −14.9
Channa argus AM 7.3 2.1 8.6 −27.6
Cyprinus carpio AM ± SD 10.6 ± 6.7 3.1 ± 2 12.8 ± 1.7 −18.3 ± 1.3
Range 3.9 ~ 17.3 1.1 ~ 5.1 11.1 ~ 14.6 −19.7 ~ −17
Hypophthalmichthys molitrix AM ± SD 15.9 ± 3.2 4.3 ± 0.92 9.6 ± 0.01 −22.0 ± 0.07
Range 12.8 ~ 19.1 3.4 ~ 5.2 9.5 ~ 9.6 −22.1 ~ −22
Lateolabrax japonicus AM ± SD 5.4 ± 3 1.3 ± 0.71 12.9 ± 0.62 −18.9 ± 0.57
Range 2.8 ~ 10 0.67 ~ 2.2 12.2 ~ 13.8 −19.3 ~ −17.8
Liza haematocheila AM ± SD 8.5 ± 3.3 2.8 ± 1 10.2 ± 0.74 −16.8 ± 1.2
Range 2.3 ~ 13.8 0.79 ~ 4.2 8.6 ~ 11 −18.6 ~ −14.9
Megalobrama amblycephala AM ± SD 6.4 ± 0.45 1.7 ± 0.1 11.3 ± 2.3 −22.8 ± 0.05
Range 5.9 ~ 6.8 1.6 ~ 1.8 9.0 ~ 13.5 −22.9 ~ −22.8
Mugil cephalus linnaeus AM 11.8 3.7 9.0 −16.2
Pelteobagrus fulvidraco AM ± SD 6.0 ± 3.5 1.6 ± 0.87 12.1 ± 1.6 −18.8 ± 1.5
Range 2.6 ~ 10.9 0.64 ~ 2.7 10.0 ~ 13.7 −20.9 ~ −17.5
Silurus asotus AM ± SD 20.1 ± 4.8 7.8 ± 2.2 10.0 ± 3.9 −17.4 ± 2.2
Range 12.4 ~ 25.5 4.5 ~ 10.6 5.1 ~ 14 −20.7 ~ −14.5
Synechogobius hasta AM 3.0 0.87 12.1 −19.3
AM, arithmetic mean; SD, standard deviation.

Table 7.4 Vanadium concentrations (Mean ± SD) in some fish (μg g−1 ww) reported
in other regions
Commodity n V Ref.
Yellow River Estuary, China - 3.0 ± 2.2 This study
Pearl River Estuary, South China 35 0.62 ± 0.45 (Ip et al. 2005)
the East China Seaa 42 0.15 ± 0.33 (Asante et al. 2008)
a
Calculated as 1/4 of dry weight.

7.3.2 Stable isotope values of fish from the Yellow River Estuary

Changes in ratios of stable isotopes of carbon (δ13C) and nitrogen (δ15N) are

frequently used in ecotoxicological investigations to relate contaminant levels to

trophic position (δ15N) or foraging location (δ13C) (Bond 2010; Bucci et al. 2007;

Das et al. 2003). The enrichment of δ15N occurs incrementally across trophic levels

with a constant rate (3-4‰) (Hobson et al. 1996), whereas δ13C enrichment is less

obvious (i.e., approx.1‰) amongst different trophic levels (Hobson and Welch
 96

1992).

Values of δ15N in fish from the study area ranged from 5.1‰ to 14.6‰,

indicating a wide range of trophic positions (Fig. 7.1). There were no significant

differences in stable isotope δ15N values among fish species (P = 0.302), sampling

sites (P = 0.869), feeding habits (P = 0.743), living environments (P = 0.932) or

habitats (P = 0.129). The highest and lowest δ15N were observed in Lateolabrax

japonicas and Channa argus, respectively, among all studied fish species (Table

7.3).

15

14
Cyc
Lj
13
Sh Pf
12
δ15N (‰)

Ma Cc
11
Sa Lh
10 Hm

9 Mc
Ca

5
-28 -26 -24 -22 -20 -18 -16 -14
δ13C (‰)
Fig. 7.1 Stable nitrogen (δ N) and carbon isotope (δ13C) ratios of the fish species in
15

the Yellow River Estuary (letters indicate species names following Table 2.3)

The δ13C values (from −27.6‰ to−14.5‰) demonstrated a wide range of

energy sources (Fig. 7.1). Channa argus was the most δ13C-depleted (−27.6‰)

compared to other species, and the highest δ13C values were observed in Mugil

cephalus Linnaeus (Table 7.3). Univariate analyses showed that δ13C significantly

varied with species (P = 0.000), feeding habits (P = 0.027), living environment (P =

0.02) and habitat (P = 0.003). The δ13C of Liza haematocheila was significantly

higher (P < 0.05) than that of Hypophthalmichthys molitrix and Megalobrama

 97

amblycephala, and the δ13C of Megalobrama amblycephala was significantly lower

than that of Silurus asotus (P = 0.031). Fish with different feeding habits showed

different δ13C signatures: the herbivore fish (Megalobrama amblycephala) had δ13C

ranging from −22.9‰ to −22.8‰, significantly lower (P = 0.032) than that of

omnivorous fish (Carassius carassius, Liza haematocheila, Cyprinus carpio,

Hypophthalmichthys molitrix, Mugil cephalus linnaeus and Pelteobagrus fulvidraco)

with δ13C ranging from −22.1‰ to −14.9‰. The δ13C of freshwater fish was

significantly lower (P = 0.020) than that of fish that can live in both fresh and

marine water. The δ13C of benthopelagic fish was significantly lower (P < 0.05) than

for both demersal fish and pelagic-neritic fish.

Non-significant correlation between V and δ15N (r2 = 0.045, P = 0.116 for both

tests) was observed, while V was observed to be positively correlated with fish

weight and length (r2 = 0.232 and r2 = 0.281, respectively, P < 0.01 for both tests).

7.3.3 Estimated daily intake of V via fish consumption

A preliminary estimation was made regarding the dietary exposure to V

through fish consumption for the Chinese population with an average weight of 70

kg (USFDA, 1993). The results are shown in Table 7.5. The target hazard quotient

(THQ) values of V were all lower than 1.0, suggesting no health risk from

consuming the analyzed fish with respect to V intake.

Table 7.5 Estimated daily intake (EDI) and Target Hazard Quotient (THQ) of V
from composite fish samples
Trace Estimated daily intake Oral reference dose Target Hazard Quotient
elements (EDI) (RfD) (THQ)
(μg kg−1bw day−1) (μg kg−1bw day−1)
V 1.31 9a 0.15
(0.28 ~ 4.64) (0.03 ~ 0.52)
a
USEPA (2013)
 98

7.3.4 The relationship between V and geographical environment

The species we analyzed are diverse and abundant and thus might reflect the

local background level. The mean concentrations of V in the samples in this study

were significantly higher than the results of previous studies presented (Asante et al.

2008; Ip et al. 2005), which is likely to be associated with oil spill or oil refineries

using V-rich fuel oil (Minelli et al. 2000; Sepe et al. 2003; Villares et al. 2007),

caused by the petroleum exploitation industry around the Yellow River Estuary.

7.4 Vanadium in aquatic organisms from Laizhou Bay

7.4.1 Concentrations of V in aquatic organisms

Average concentrations of V in each species of aquatic organisms from

Laizhou Bay were shown in Table 7.6. The mean concentrations of V in Laizhou

Bay aquatic organisms were 3.24 ± 1.58 μg g−1 ww. Vanadium concentration in

aquatic organisms was significantly higher than found in the previous studies

(Asante et al. 2008; Ikemoto et al. 2008; Ip et al. 2005) (Table 7.7). The highest V

concentrations in aquatic organisms were observed as 6.10 ± 0.11 μg g−1 ww, in

Busycon canaliculatum.
 99

Table 7.6 Concentrations of V (μg g−1 ww) and stable isotope ratios in aquatic
organisms from Laizhou Bay
Scientific name V δ15N (‰) δ13C (‰)
Fish
Acanthogobius hasta AM ± SD 3.17 ± 1.58 12.78 ± 1.06 −17.73 ± 1.08
Range 1.58 ~ 4.75 11.71 ~ 13.84 −18.82 ~ −16.65
Acanthopagrus schlegelii AM 3.77 14.09 −17.84
Chelon haematocheilus AM 3.30 9.65 −16.73
Lateolabrax japonicus AM ± SD 1.95 ± 0.20 14.52 ± 1.00 −18.05 ± 0.28
Range 1.69 ~ 2.16 13.27 ~ 15.71 −18.33 ~ −17.67
Mugil cephalus AM 3.65 12.38 −14.21
Platycephalus indicus AM 4.56 15.11 −17.62
Pleuronectiformes AM ± SD 5.33 ± 1.39 14.47 ± 0.46 −17.80 ± 0.32
heterosomata Range 3.94 ~ 6.72 14.01 ~ 14.92 −18.12 ~ −17.47
Shellfish
Busycon canaliculatum AM ± SD 6.10 ± 0.11 11.18 ± 0.13 −18.62 ± 0.32
Range 5.99 ~ 6.21 11.05 ~ 11.31 −18.94 ~ −18.30
Loligo beka Sasaki AM ± SD 2.74 ± 0.43 14.81 ± 0.09 −18.53 ± 0.21
Range 2.30 ~ 3.17 14.72 ~ 14.91 −18.74 ~ −18.32
Scapharca subcrenata AM 1.78 9.62 −19.55
Crab
Portunus trituberculatus AM ± SD 2.71 ± 0.48 10.40 ± 2.24 −17.14 ± 0.66
Range 2.24 ~ 3.19 8.16 ~ 12.64 −17.80 ~ −16.49
Shrimp
Oratosquilla oratoria AM ± SD 1.71 ± 0.03 12.17 ± 0.78 −18.88 ± 0.67
Range 1.68 ~ 1.74 11.39 ~12.95 −19.55 ~ −18.21
Penneropenaeus chinensis AM 1.65 2.43 −16.03
AM, arithmetic mean; SD, standard deviation

Table 7.7 Vanadium concentrations (Mean ± SD) in some aquatic organisms (μg g−1
ww) reported in other regions
Commodity (city/country) n V Ref.
Fish (Pearl River Estuary, South China) 35 0.62±0.45 (Ip et al. 2005)
Fish (the East China Sea)a 42 0.15±0.33 (Asante et al. 2008)
Fish (Mekong Delta, South Vietnam)a 16 0.14±0.07 (Ikemoto et al. 2008)
Shrimp (Pearl River Estuary, South China) 13 0.25±0.10 (Ip et al. 2005)
Crab (Pearl River Estuary, South China) 7 0.32±0.09 (Ip et al. 2005)
Shellfish (Pearl River Estuary, South China) 3 0.97±1.44 (Ip et al. 2005)
a

Calculated wet weight for organisms, corresponding to 1/4 of the original dry weight

7.4.1.1 Geographical variation of V concentration

The geographical variation of V concentration in aquatic organisms is

commonly considered to be closely related to the distribution and characteristics of

 100

local pollution sources (Liu et al. 2017a). Sampling site L1 was near to the Yellow

River Delta Natural Reserve and DY Port Industrial Zone; sampling site L2 was

near to the estuary of the Xiaoqing River and L3 was close to the WF Port Industrial

Zone. In this study, Lateolabrax japonicas was the only species collected from all

sampling sites, and the highest concentration of V in Lateolabrax japonicusis was

found in sampling site L2, which may result from the heavy contamination of the

Xiaoqing River. The Xiaoqing River is considered the major source of

contamination and eutrophication in western Laizhou Bay, due to the smaller runoff

volume but higher nutrient and contaminant concentrations compared to the Yellow

River (Yu et al. 2017).

7.4.1.2 The differences of V concentrations among different species of aquatic

organisms

To evaluate the differences of V concentrations among different species of

aquatic organisms, concentrations of V in fish, shellfish, crab and shrimp from

Laizhou Bay were compared (Fig. 7.2). In Fig. 7.2, different distributions of V are

shown for different species. The highest concentrations of V were observed in

shellfish, suggesting that shellfish can more efficiently enrich trace metals from

water and sediment, as was also found by Ip et al. (2005). The significantly elevated

concentrations of V found in shellfish may result from the fact that the primary food

source of shellfish is rich in heavy metals (Ip et al. 2005). The order for V in this

study was shellfish > fish > crab > shrimp, as was also found by Ip et al. (2005).
 101

Fig. 7.2 Vanadium concentrations in fish, shellfish, crab and shrimp.

7.4.2 Stable isotope values of aquatic organisms from Laizhou Bay

The isotopic values for all species are illustrated in Table 7.6. Values of δ15N

ranged from 2.43‰ in Chinese shrimp (Penneropenaeus chinensis) to 15.71‰ in

one kind of carnivorous fish (Lateolabrax japonicas), and δ13C values ranged from

−19.55‰ in Mantis shrimp (Oratosquilla oratoria) to −14.21‰ in one kind of

omnivorous fish (Mugil cephalus). In Fig. 7.3, the data points of δ13C and δ15N are

densely distributed, indicating the existence of several primary food sources for

aquatic organisms at higher trophic levels.

 102

Fig. 7.3 Ratios of stable nitrogen (δ15N) and carbon (δ13C) isotopes in muscle tissues
of aquatic organisms in Laizhou Bay.

7.4.2.1 The variance of stable isotope ratios among the studied species

The δ15N values varied greatly among the studied species. Mean δ15N values in

each species were as follows: fish (13.57‰) > shellfish (12.32‰) > crab

(10.40‰) > shrimp (8.92‰). A large δ15N value range is likely to indicate

additional trophic levels within a food web (Borrell et al. 2016). Mean δ13C values

did not differ significantly among the studied species: crab (−17.14‰) > fish

(−17.42‰) > shrimp (−17.93‰) > shellfish (−18.77‰), suggesting a similar dietary

composition and ultimately a similar origin of organic matter (Kaehler et al. 2000).

This finding is similar to the results obtained in previous studies in other aquatic

ecosystems (Cui et al. 2011). Researchers found that δ13C values are generally

higher in coastal or benthic than in offshore food webs (Das et al. 2004; Hobson

1999; Kwon et al. 2012). Lower values of δ13C in the shellfish suggest that they feed
 103

primarily on offshore prey with a low δ13C signature.

7.4.2.2 Correlation of concentrations of V with δ15N and δ13C

A non-significant correlation between V and δ15N (R2 = 0.038, p = 0.396) or

δ13C (R2 = 0.023, p = 0.509) was observed, implying that V is not biomagnified or

biodiluted through the food chain. The same results were found in the aquatic food

chain in the Mekong Delta (Ikemoto et al. 2008). Asante et al. (2010) found that

δ13C in demersal fish from the Sulu Sea were negatively correlated with V. Similarly,

that V increases with decreasing δ13C was also reported in fish muscle in a lake

(Ofukany et al. 2014).

7.4.3 Estimated daily intake of V via aquatic organism consumption

The daily intake of V for an average person weighing 70 kg was calculated by

considering the metal concentrations observed in this study and aquatic organisms

consumption rates reported by the National Bureau of Statistics of China (CSY,

2016). The calculated intakes for V were further compared with its corresponding

oral reference dose (RfD) (Table 7.8) (USEPA 2013). The mean EDI calculated for

V was 1.421 μg kg−1bw day−1, lower than the ones reported as RfD (USEPA 2013).

The Target Hazard Quotient (THQ) of V from all samples was lower than 1,

implying that consumption of the analyzed aquatic organisms with regard to V poses

no health risk to consumers (Table 7.8).

 104

Table 7.8 Estimated Daily Intake (EDI) and Target Hazard Quotient (THQ) of V
from the samples
Trace Estimated Daily Oral Reference Dose Target Hazard
elements Intake (EDI) (RfD) Quotient (THQ)
(μg kg−1bw day−1) (μg kg−1bw day−1)
V 1.421 9a 0.16
(0.69 ~ 2.94) (0.08 ~ 0.33)
a
USEPA (2013)

7.5 Summary

(1) The average concentration of V in soils from the Yellow River Delta is slightly

higher than that of Chinese soil background, and high V was found in soil near the

oil field, which may be attributed to the exploitation and utilization of petroleum.

The results of ecological risk assessment showed that all soil samples had no V

pollution.

(2) This study provides data on the concentration of V in fish samples from the

Yellow River Estuary and assessment of the health risk that could arise from fish

consumption. The relatively higher V concentrations in the Yellow River Estuary

compared to studies in other regions might imply a certain relationship between V in

fish and their geographical environment. Relatively higher V was possibly related to

the petroleum industry around the Yellow River Estuary. The concentrations of V

dramatically differed across fish species, which might be attributed to the different

foraging habitats and dietary habits of the studied fish. Correlation analysis showed

that V is positively correlated with body weight and length. The obtained results also

showed low levels of toxicity regarding V, implying no risk from consuming fish

from the Yellow River Estuary for the Chinese population

(3) Vanadium concentrations in aquatic organisms collected from Laizhou Bay of

the Bohai Sea were found higher than those from many previous studies. Among
 105

fish, shrimp, crab, and shellfish, shellfish were found to have the highest

concentrations of V. Through the correlation analyses with δ15N, V was found to

have no biodilution effect or biomagnification effect in the marine food web. No

health risks of V could arise from the consumption of aquatic organism from

Laizhou Bay.
 106

Chapter 8 – Major conclusions and innovations

8.1 Major conclusions

This study aimed to investigate the environmental geochemistry of V in coal

mining areas based on research of V in soils, sediments and aquatic organisms

collected from the Anhui coal mining area. The V in soils, sediments and aquatic

organisms collected from the Yellow River Delta (a petroleum-producing area) was

also determined for comparison. The major conclusions of this study are listed

below.

8.1.1 The environmental geochemistry of V in coals

(1) By analyzing > 2900 data from the published papers, V in Chinese coals

was estimated to have an average concentration of 35.81 μg/g. According to the

concentration coefficient of V in coals from individual provinces, three regions were

divided across Chinese coal deposits: depleted (0 < CC < 0.5), normal (0.5 < CC <

2), and slightly enriched (2 < CC <5). Among different coal-forming periods, the V

concentration in Late Permian was the highest with mean value of 115.59 μg/g, and

in Jurassic was the lowest (17.71 μg/g). The descending order of V in coals from

different coal ranks was: anthracite (58.29 μg/g) > lignite (54.58 μg/g) > bituminous

coal (39.34 μg/g). A large variation of V concentration was observed in Chinese

coals of different regions, coal-forming periods and maturation ranks. Vanadium in

Chinese coals was probably influenced by the sediment source and sedimentary

environment, supplemented by late-stage hydrothermal fluids. Specifically,

hydrothermal fluids had a relatively more significant effect on the enrichment of V

in local coal seams.

(2) Through the study of 21 coal samples from nine Chinese provinces based
 107

on the sequential chemical extraction and combustion experiments, the results

showed that V was mainly associated with silicate matter (40-50%), followed by

organic matter (~30%). With increasing coal rank, the proportions of water

leachable and ion exchangeable V increase and organic-bound V decrease. The

simulated coal combustion experiment at 950 °C showed that 9.23% of V was

volatilized. The volatilization ratio for V decreases as the coal rank increases. There

were close relationships between the chemical speciation of V and combustion

behavior of V in coals, and the low volatilization ratio of V might related to V

mainly associated with silicate matter.

(3) The Chinese V emission inventory generated by coal combustion was

estimated to be 4,906 mt in 2014, accounting for 50.55% of global emissions. V

emission inventories from transport, power plants, industry and other sectors during

1990-2035 were also estimated. Power plants were the largest contributor to V

emissions, which was estimated to account for 63.43% of global emissions in 2035.

8.1.2 Contamination level and potential risk of V in coal mining areas

(1) The average concentration of V in 41 surface soil samples near the coal

gangue in Huaibei area was 80.87μg/g, lower than the soil background of V in China.

The result of geoaccumulation index showed that only one soil sample B2-5

presented possible V pollution. The order of V concentration in the soil of four coal

mines was almost in accordance with the order of the age of the corresponding coal

mine.

(2) The V enrichment factors of surface sediments collected from sampling

sites A, B and D showed slight V pollution. In the sediment core of D, all the EFs

were over 1, indicating that the sediment core collected from D might have been

slightly polluted. The results of geoaccumulation index showed a practically

 108

uncontaminated status of V in surface sediment from the Huai River and no

contamination or moderately contamination by V at the depth of 12, 16, 18, 20, and

22 cm of sediment core D. The enrichment degrees of V in corresponding sediments

were inconsistent with the leached V from the coal gangues.

(3) The concentration of V in Carassius auratus from the subsidence pond

near four coal mines in the Huaibei coal mining area was about 0.4 μg/g dw. The

concentration of V in Carassius auratus may relate to the coal mining history. The

results of THQ of V from all fish samples were below 1, implying that consumption

of the analyzed fish from Huaibei subsidence ponds poses no health risk to

consumers.

8.1.3 Comparison of the environmental geochemistry of V between

petroleum-producing areas and coal mining areas

The average concentration of V in soil samples from the Yellow River delta

was slightly higher than that in the soil from the Huaibei coal mining area. Only one

soil sample from the Huaibei mining area might suffer from V pollution, while other

soil samples had no sign of V pollution. The V concentrations higher than 100 μg/g

in the soils near some oil fields indicated that the exploitation of oil and the

combustion of fossil fuels might have led to the aggravation of V pollution. The

concentrations of V in coal and coal gangue in the Huaibei coal mining area were

much lower than those in Chinese soil background, indicating that the exploitation

and utilization of coal have little or no influence on V in the soil.

The concentration of V in Carassius auratus in the subsidence ponds near four

coal mines was about 0.4 μg/g dw, far lower than the concentration of V in

Carassius auratus from the Yellow River Estuary (8.5 μg/g dw). This may indicate

that the exploitation of petroleum has a greater effect on the V concentration in

 109

aquatic organisms.

8.2 Innovations

(1) The distribution of V in different regions, different coal ranks and different

coal forming periods were studied. The average concentration of V in Chinese coals

was updated as 35.81 μg/g. The distribution of V in Chinese coals was categorized

into depleted, normal, and slightly enriched regions based on concentration

coefficients. Based on sequential extraction and combustion, the positive correlation

between V and Cr was found, and the impact of the mode of occurrence of V on the

combustion behavior of V was further revealed.

(2) The mobility of V in coal gangue was revealed, so as to improve the

knowledge of spatio-temporal characteristics and the fractionation of V in sediments

collected from coal concentrated areas, which might further reveal the migration and

transformation of V in the coal gangue, soils, sediments and aquatic organisms.

(3) Stable isotope ratios were used to study the bioaccumulation of V in aquatic

organisms from petroleum-producing areas. The relationship between V in aquatic

organism and trophic level were investigated to reveal the accumulation of V in

aquatic organism based on the stable isotope ratios.

 110

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