Remediation of Chromium Contaminated Soil Theory and Practice 1st Edition Weichun Yang Liyuan Chai Zhihui Yang Feiping Zhao Qi Liao Mengying Si

Remediation of Chromium
Contaminated Soil Theory and Practice

1st Edition Weichun Yang Liyuan Chai
Zhihui Yang Feiping Zhao Qi Liao
Mengying Si
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Environmental Science and Engineering
Weichun Yang · Liyuan Chai ·

Zhihui Yang · Feiping Zhao · Qi Liao ·
Mengying Si
Remediation
of Chromium-
Contaminated Soil:
Theory and Practice
Series Editors
Ulrich Förstner, Buchholz, Germany
Wim H. Rulkens, Department of Environmental Technology, Wageningen
The Netherlands
The ultimate goal of this series is to contribute to the protection of our environment,
which calls for both profound research and the ongoing development of solutions
and measurements by experts in the field. Accordingly, the series promotes not only a
deeper understanding of environmental processes and the evaluation of management
strategies, but also design and technology aimed at improving environmental quality.
Books focusing on the former are published in the subseries Environmental Science,
those focusing on the latter in the subseries Environmental Engineering.
Weichun Yang · Liyuan Chai · Zhihui Yang ·
Feiping Zhao · Qi Liao · Mengying Si
Remediation
of Chromium-Contaminated
Soil: Theory and Practice
Weichun Yang Liyuan Chai
Central South University Central South University
Changsha, China Changsha, China
Zhihui Yang Feiping Zhao

Qi Liao Mengying Si
ISSN 1863-5520 ISSN 1863-5539 (electronic)

ISBN 978-981-99-5462-9 ISBN 978-981-99-5463-6 (eBook)
https://doi.org/10.1007/978-981-99-5463-6
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
Singapore Pte Ltd. 2023
This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
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Preface
Chromium (Cr) is a hard, steel-gray metal. Its free form is extremely rare and
chromite ore in earth’s crust is the common form in nature. It is widely utilized
in many industries, such as ferrous and non-ferrous alloy metal fabrication, leather-
tanning, chrome-plating and pigment industries. 90% of the total chrome production
is consumed by metallurgical industry. Chromium has also been recognized as a toxic,
mutagenic and carcinogenic metal. It is toxic to microorganism, plants, animals and
humans. Anthropogenic activities, especially industrial production of chromate, elec-
troplating and tanning leather directly and indirectly, cause Cr-pollution in wastew-
ater, air and soil, and soil and underground water serve as the sink of Cr-pollutants.
With the rapid increasing demand of Cr, the chromium pollution in soil is becoming
more and more serious, which has become one of the severe factors that restrict
the sustainable development of industry and harm the public health. Therefore, it
is an urgent and huge challenge to effectively remediate the soils contaminated by
chromium and its associated pollutants.
Two stable valence states of Cr in the environment usually are Cr(III) and Cr(VI).
Cr(III) has lower toxicity and mobility than Cr(VI). One of the potential treatments
is to transform Cr(VI) to Cr(III). Reductive materials and microorganisms have been
used to remediate Cr(VI) pollution in soil. According to the global needs of the
remediation of soil contaminated by chromium, this book systematically introduces
the latest theories and technical achievements of microbial and chemical treatments
for the chromium pollution in the chromium slag and chromium-contaminated soil,
combined with the author’s research achievements over the decades. The book
focuses on the biological and chemical behaviors of chromium in soil, microbial
and chemical remediation for the chromium-contaminated soil and the cases of
chrome-contaminated site remediation project. This book can be used by the scien-
tific researchers and engineering technicians engaged in chromium chemical industry
and environmental protection. It can also be used as a teaching and reference book
for graduate students in the majors of environmental science and engineering, soil
science, chemistry and chemical engineering, et al.
v
vi Preface
This work was supported by the Key Project of Chinese National Research
Programs (2021FYC1809203 and 2018YFC1802204), Chinese National High Tech-
nology Research and Development Program (2006AA06Z374), National Natural
Science Foundation of China (20477059 and 51304250), Chinese National Science
and Technology Benefit Program (2013GS430203), Hunan Provincial Science and
Technology Key Project (2009FJ1009 and 2008SK2007) and Natural Science
Foundation of Hunan Province (2021JJ30829).
The authors also sincerely thank the graduate students for their contribution to
publish this book. They are Dr. Wenjie Zhu, Dr. Zemin Ma, Dr. Shunhong Huang,
Dr. Zhenxin Wang, Dr. Yangyang Wang, Dr. Chunlian Ding, Canwen Sheng, Tengfa
Long, Xiong Li, Rong, Deng, Kun Zhao, Lijuan Chen, Zeyou Xu, Bing Wnag,
Changqing Su, Yingping Liao, Hangbin Li, Xiaoming Zhang, Qi Li, Dongdong Xi,
Xiaomin Li and Jiaqi Tang, et al.
Changsha, China Weichun Yang

Liyuan Chai
Zhihui Yang
Feiping Zhao
Qi Liao
Mengying Si
Contents
1 Contamination Characteristics of Soils and Biological

and Chemical Behavior of Chromium in Soil . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Sources of Soil Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Chromium Pollution from the Chromium Salt Industry . . . . 2
1.1.2 Chromium Pollution in the Electroplating Industry . . . . . . . . 4
1.1.3 Chromium Pollution in the Tanning Industry . . . . . . . . . . . . . 5
1.1.4 Chromium Pollution from Other Industries . . . . . . . . . . . . . . 5
1.2 Characteristics of Chromium Pollution in Soil . . . . . . . . . . . . . . . . . . 6
1.2.1 Chromium Concentrations in Chromium Pollution
in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.2 Vertical Distributions of Total Cr and Water-Soluble
Cr(VI) in the Soil Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.3 Chromium Fractions in the Contaminated Soils . . . . . . . . . . . 13
1.3 Microbial Communities in Chromium-Contaminated Soil . . . . . . . . 16
1.3.1 Bacterial Structural Diversity in the Contaminated
Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.2 Isolation and Identification of Hexavalent
Chromium-Resistant Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.3 Bacterial Genetic Diversity on the Basis
of Rep-Polymerase Chain Reaction Fingerprints . . . . . . . . . . 19
1.3.4 Hexavalent Chromium Reduction by Cr(VI)-Reducing
Bacterial Strains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.4 Adsorption of Cr(VI) on Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.4.1 Adsorption Kinetics of Cr(VI) . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.4.2 Adsorption Thermodynamics of Cr(VI) . . . . . . . . . . . . . . . . . 25
1.5 Cr(VI) Migration in Chromite Ore Processing Residue
(COPR)-Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.5.1 Diffusion of Cr(VI) in Chromium-Containing Slag . . . . . . . . 28
1.5.2 Cr(VI) Migration in Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
vii
viii Contents
2 Mechanisms of Cr(VI) Reduction by Microorganisms . . . . . . . . . . . . . 41

2.1 Cr(VI)-Reducing Bacteria Pannonibacter Phragmitetus BB
Isolated from Chromium-Contaminated Soil . . . . . . . . . . . . . . . . . . . . 42
2.1.1 Isolation and Identification of Cr(VI)-Reducing
Bacterial Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.1.2 Cr(VI) Reduction by Pannonibacter Phragmitetus BB . . . . . 43
2.1.3 Morphology of Pannonibacter Phragmitetus BB . . . . . . . . . 44
2.1.4 Elemental Composition of the Cr(VI)-Reduction
Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.1.5 Identification of Cr(VI)-Reduction Product . . . . . . . . . . . . . . 46
2.2 The Cr(VI)-Reducing Bacteria Leucobacter sp. CRB1
Isolated from Chromium-Containing Slag . . . . . . . . . . . . . . . . . . . . . . 47
2.2.1 Physiological and Biochemical Characteristics
of the Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.2.2 The Phylogenetic Tree of Strain . . . . . . . . . . . . . . . . . . . . . . . . 47
2.2.3 Evaluation of Chromium Tolerance . . . . . . . . . . . . . . . . . . . . . 48
2.2.4 Identification of Cr(VI)-Reduction Product . . . . . . . . . . . . . . 50
2.3 Behavioral Characteristics of Cr(VI) Reduction by Bacteria . . . . . . 52
2.3.1 Cr(VI) Reduction Characteristics of Pannonibacter
Phragmitetus BB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.3.2 Cr(VI) Reduction Characteristics of Leucobacter sp.
CRB1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.4 Electrochemical Characteristics of Cr(VI) Reduction
by Leucobacter sp. Ch-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.4.1 Effect of Initial pH Values on the Growth
of Leucobacter sp. Ch-1 and Reduction of Cr(VI) . . . . . . . . . 58
2.4.2 Effect of Applied Potentials on the Growth
of Leucobacter sp. Ch-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.4.3 Effect of Applied Potentials on the Reduction of Cr(VI) . . . 60
2.4.4 The Range of Initial pH and Eh for Leucobacter sp.
Ch-1 Growth and Cr(VI) Reduction . . . . . . . . . . . . . . . . . . . . . 63
2.4.5 Potential-pH Diagram for “Leucobacter sp.
Ch-1-Cr-H2 O” System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.5 Molecular Mechanisms of Bacterial Reduction of Cr(VI) . . . . . . . . . 65
2.5.1 Multiomics Response of Pannonibacter Phragmitetus
BB to Hexavalent Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.5.2 Discerning Chromate Reduce and Transport Genes
of Highly Efficient Pannonibacter Phragmitetus BB . . . . . . 96
2.5.3 Dynamic Proteome Responses to Sequential
Reduction of Cr(VI) and Removal of Coexisting
Heavy Metals by PannonibacterPhragmitetus BB . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Contents ix
3 Microbial Remediation of Chromium-Polluted Soil . . . . . . . . . . . . . . . . 133

3.1 The Microbial Remediation Efficacy of Soil Contaminated
with Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
3.1.1 Microbial Remediation of Cr(VI) in Soil . . . . . . . . . . . . . . . . 134
3.1.2 Kinetics of Cr(VI) Microbial Reduction . . . . . . . . . . . . . . . . . 135
3.1.3 Changes in pH and ϕh During Cr(VI) Microbial
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.1.4 Changes in Concentrations of Fe2+ , Mn2+ , SO4 2−
and NO3 − . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.2 Optimization of Cr(VI) Bioremediation in Polluted Soil . . . . . . . . . . 141
3.2.1 Effect of Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.2.2 Effect of Spray Intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.2.3 The Impact of the Initial Cr(VI) Content . . . . . . . . . . . . . . . . . 145
3.2.4 Effect of Depth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.5 Effect of Circulation Mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.3 Stability of Chromium in the Microbial Remediation Soil
Under Simulated Acid Rain Leaching . . . . . . . . . . . . . . . . . . . . . . . . . 149
3.3.1 The pH Values of the Leachate in the Soils Subjected
to Simulated Acid Rain Leaching Exhibited Variations . . . . 150
3.3.2 Releases of Chromium in Soils Under Simulated Acid
Rain Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3.3.3 Risk to Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3.4 Changes in the Bacterial Community During
the Bioremediation of Cr(VI)-Contaminated
Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.4.1 Phylogenetic Analysis of 16 rRNA Clone Libraries . . . . . . . 156
3.4.2 Real-Time Quantitative PCR Analysis . . . . . . . . . . . . . . . . . . 158
3.5 The Impact of Microbial Remediation on the Physicochemical
and Biological Qualities of Cr(VI)-Contaminated Soils . . . . . . . . . . 160
3.5.1 Chemical Characteristics of Soils After Remediation . . . . . . 161
3.5.2 Changes in Enzyme Activity in Soils After
Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
3.5.3 Quality of Soil Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
4 Mechanism of Chemical Reduction of Cr(VI) . . . . . . . . . . . . . . . . . . . . . 171
4.1 Chemical Reductive Materials for Cr(VI) . . . . . . . . . . . . . . . . . . . . . . 172
4.1.1 Organic Amendments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
4.1.2 Iron-Bearing Reductants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
4.1.3 Sulfur-Based Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
4.2 Enhanced Cr(VI) Removal by an “In Situ Synthesized”
Iron-Based Bimetal Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
4.2.1 Activity Toward Cr(VI) Removal . . . . . . . . . . . . . . . . . . . . . . . 194
4.2.2 Enhancement of Coexisting Cations on Cr(VI)
Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
x Contents
4.2.3 In Situ Synthesized Fe-Cu Bimetal During Cr(VI)

Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
4.2.4 Electrochemical Behaviors and Contribution of in Situ
Synthesized Fe–Cu Bimetal on Cr(VI) Removal . . . . . . . . . . 205
4.2.5 Enhanced Cr(VI) Removal Mechanism by in Situ
Synthesized Fe–Cu Bimetal . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.3 Interaction Between Pyrite and Zerovalent Iron that Has
a Higher Ability to Reduce Through Fe(II) Regeneration . . . . . . . . . 211
4.3.1 Incorporation of Sulfur into Fe0 . . . . . . . . . . . . . . . . . . . . . . . . 213
4.3.2 Removal Activity of FeS2 /ZVI Toward Cr(VI) . . . . . . . . . . . 216
4.3.3 Mechanism of Cr(VI) Removal by FeS2 /ZVI . . . . . . . . . . . . . 221
4.3.4 Sulfur Speciation Affects the Electron Transfer
of FeS2 /ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
4.4 Synergistic Cr(VI) Reduction and Organic Pollutant
Oxidative Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
4.4.1 Simultaneous Cr(VI) Reduction and Phenol Oxidation . . . . 231
4.4.2 The Evolution of Cr(VI) in the FeS2 /Fe0 + PS System . . . . 233
4.4.3 The Roles of Surface-Bound Fe2+ . . . . . . . . . . . . . . . . . . . . . . 236
4.4.4 The Roles of SO4 2− in the FeS2 /Fe0 + PS System . . . . . . . . 239
4.4.5 Reactive Species for Phenol Degradation . . . . . . . . . . . . . . . . 240
4.4.6 Synergistic Redox Conversion Mechanism . . . . . . . . . . . . . . . 243
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
5 Chemical Remediation of Chromium-Contaminated Soil . . . . . . . . . . . 257
5.1 Kinetics, Thermodynamics And Long-Term Effects
in Remediation of Cr(VI)-Contaminated Soil . . . . . . . . . . . . . . . . . . . 257
5.1.1 Factors Affecting Remediation
of Cr(VI)-Contaminated Soil . . . . . . . . . . . . . . . . . . . . . . . . . . 258
5.1.2 Kinetics and Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . 260
5.1.3 Soil pH Variation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.1.4 Soil Cr Speciation Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
5.1.5 Long-Term Stability of Cr in Remediated Soil . . . . . . . . . . . . 265
5.2 Remediation of Cr(VI) and Organic Pollutant Cocontaminated
Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.2.1 Factors Affecting the Remediation of Cr(VI)
and Organic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
5.2.2 Remediation Performance Comparison of Different
Reaction Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
5.2.3 Soil Cr(VI) Speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
5.3 Synergistic Remediation of Cr(VI) and Cationic Metal
Co-contaminated Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
5.3.1 Factors Affecting the Remediation
of Cr–Cu–Ni–Co–Contaminated Soil . . . . . . . . . . . . . . . . . . . 272
5.3.2 Sequential Extraction, Followed by an Evaluation
of Risk Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Contents xi
5.4 Chemical-Microwave Combined Remediation of Strongly

Alkaline High Cr(VI)-Contaminated Soil . . . . . . . . . . . . . . . . . . . . . . 278
5.4.1 Comparison of Remediation Effect by Various
Amendments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
5.4.2 Factors Affecting Microwave Irradiation-Assisted
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.4.3 Mechanism of Microwave Irradiation Accelerating
Cr(VI) Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.4.4 Cr Speciation and Phase Transformation Under
Microwave Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
5.4.5 Long-Term Stability of Cr in Remediated Soil . . . . . . . . . . . . 292
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
6 Case of Chrome-Contaminated Site Remediation Project . . . . . . . . . . 299
6.1 Project Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
6.2 Remediation Technology and Route . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
6.3 Project Photos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
6.4 Remediation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Chapter 1
Contamination Characteristics of Soils
and Biological and Chemical Behavior
of Chromium in Soil
Chromium salt and chromium metal are the important industrial raw materials and
chemicals that are widely applied in electroplating, metallurgy, anticorrosion, leather,
dye and other industries. 10% of the commodity species in China are related to
chromium salt products, which are mainly used in electroplating, tanning, printing
and dyeing, pharmaceuticals, pigments, catalysts, organic synthesis oxidants and
metal corrosion inhibition. Chromium metal is also used for superalloys, selectro-
resistance alloys, precision alloys and other nonferrous alloys. Superalloys containing
10–25% Cr are mainly used for manufacturing jet engines, aerospace machinery
and materials, rocket engines and heat exchangers. As chromium can improve the
toughness, abrasive resistance and corrosion resistance of steel, chromium is also
an indispensable element in stainless steel, tool steel, bearing quality steel and other
steel types. The manufacture of chromium salt and chromium metal plays a key role
in the construction of the national economy but also produces serious environmental
problems, such as soil and groundwater contamination [1, 2].
1.1 Sources of Soil Chromium
Because of its extensive usage and potential for negative environmental impacts,
the heavy metal chromium is contaminating soil ecosystems at an alarming rate.
Chromium salt manufacturing, ore refining, steel and alloy production, pigment
manufacturing, corrosion inhibition, leather tanning, wood preservation, and coal
and oil combustion are mostly responsible for discharging chromium into the envi-
ronment. The majority of Cr industry activities lack proper disposal facilities, and
leaching has frequently occurred as a result of inadvertent discharges of wastes
containing Cr. Yet, it has the potential to gravely harm groundwater. As a result,
there are many different causes of chromium contamination in soils.
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 1
W. Yang et al., Remediation of Chromium-Contaminated Soil: Theory and Practice,
Environmental Science and Engineering,
https://doi.org/10.1007/978-981-99-5463-6_1
2 1 Contamination Characteristics of Soils and Biological and Chemical …
1.1.1 Chromium Pollution from the Chromium Salt Industry
The production of chromium salts in China has experienced a history of 40 years,

and the production and consumption of chromium compounds has become the first
in the world. More than 70 units have produced chromium salts in China, and the
total production of chromium slag is approximately 6 million tons. Chromium salt
production has grown from small to large, and its processes are constantly being
improved. However, the production and use of chromium salt products produce
chromium-containing wastewater, exhaust gas and slag emissions, resulting in soil
and groundwater contamination of the surrounding sites.
Chromium salt production is divided into two major technologies, calcium
roasting and calcium-free roasting. The process and the main equipment are gener-
ally similar. The biggest difference is that calcium-free roasting does not use calcium
filler, with calcium roasting slag discharge, high hexavalent chromium content, and
pollution being a concern. In the production process of calcium roasting, finely
ground chromite, dolomite and soda ash are mixed in a certain ratio, the mixture is
added to the rotary kiln to oxidize and roast the chromium trioxide in chromite into
sodium chromate, and the residual solid waste is chrome slag. Every 1 ton of sodium
red alum will discharge 1.7–4.2 tons of chrome slag, and every 1 ton of chromium
metal will discharge 7 tons of chrome slag.
The composition and properties of chromium slag vary greatly due to the differ-
ence in raw material composition and production conditions. The main composition
of chromium slag with calcium roasting is approximately 30% CaO, 20% MgO,
10% Fe2 O3 , 10% Al2 O3 , 10% SiO2 , 4.5% total chromium, 0.3% water-soluble
Cr(VI), and 0.5% acid-soluble Cr(VI) [3]. Therefore, the chromium slag produced
under the calcium roasting process has a very high alkalinity and contains a large
amount of incompletely leached hexavalent chromium, which is toxic and classi-
fied as hazardous waste. The main phase composition of chromium slag is listed in
Table 1.1, and the X-ray diffraction analysis pattern is shown in Fig. 1.1.
Cr(VI) in chromium slag can be classified into two types: water-soluble chromium
and acid-soluble chromium. The process involves finely grinding the chromium slag
and subjecting it to extensive washing with hot water to extract the Cr(VI) present,
which is then referred to as water-soluble chromium in the resulting washout water.
The Cr(VI) obtained after the washing filter cake is dissolved by heating with dilute
sulfuric acid which is called acid-soluble chromium. There is no strict boundary
between water-soluble chromium and acid-soluble chromium, and the acid-soluble
chromium will be slowly changed to water-soluble chromium when the chromium
slag is heated with water for a long time or by the long-term effect of outdoor rain
and carbon dioxide. Water-soluble Cr mainly refers to the remaining Na2 CrO4 due
to incomplete leaching of roasting products during the production process. Acid-
soluble Cr(VI) refers to the free CaCrO4 and the Cr(VI) presenting in the lattice
of calcium silicate and calcium iron aluminate in the form of calcium chromium
aluminate—calcium chromate, calcium silicate—calcium chromate, calcium iron
aluminate—calcium chromate solid solution. Upon conducting an investigation into
1.1 Sources of Soil Chromium 3
Table 1.1 Phase composition of chromium slag

Phase Molecular formula Content (%)
Magnesite MgO ~20
Dicalcium silicate β-2CaO·SiO2 ~25
Calcium ferroaluminate 4CaO·Al2 O3 ·Fe2 O3 ~25
Calcium chromite CaCr2 O4 5–10
Chrome spinel (Mg,Fe)Cr2 O4
Calcium chromate CaCrO4 1
Sodium chromate tetrahydrate Na2 CrO4 ·4H2 O 2–3
Calcium chromium aluminate 4CaO·Al2 O3 ·CrO3 ·12H2 O 1–3
Alkaline ferric chromate Fe(OH)CrO4 0.5
Calcium carbonate CaCO3 2–3
Calcium aluminate hydrate 3CaO·Al2 O3 ·6H2 O ~1
Fig. 1.1 X-ray diffraction analysis of chromium slag
the leaching behavior of Cr(VI) from chromium slag, James et al. discovered a signif-
icant correlation between the leaching behavior and the dissolution characteristics
of acid-soluble CaCrO4 in the surrounding environment. Consequently, the persis-
tent contamination of chromium slag and the challenges associated with achieving
complete detoxification can be primarily attributed to the presence of acid-soluble
Cr(VI).
The wastewater containing chromium in chromium salt production mainly
consists of chromic anhydride production plant wastewater, ground and equipment
cleaning wastewater, laboratory wastewater and boiler discharge wastewater. The
wastewater produced by the chromium salt production system is very small, but
the flushing water produced by the washing of equipment and site and evaporation
with froth due to material and slag loss, valve leakage, etc., is large and has a high
chromium concentration.
Chromium-containing waste gas pollutants are mainly generated in rotary kilns,
chrome slag drying, grinding, neutralization, acidification, chromic anhydride
heating furnaces and coal-fired boiler sections. The main pollutants are soot and
dust, and Cr(VI) and total chromium contained in the soot (dust), while gaseous
pollutants such as SO2 , nitrogen oxides, chromic acid mist, HCl and chlorine gas are
also generated due to fuel combustion and evaporation.
1.1.2 Chromium Pollution in the Electroplating Industry
With the advancements in mechanical manufacturing, chromium plating has been

witnessed widespread adoption owing to its array of exceptional properties. As a
result, the demand for chromium coatings has been steadily increasing. A large
number of strong acids, strong alkalis, heavy metal solutions, and even toxic and
harmful chemicals such as cyanide and chromic anhydride have been applied in
the electroplating industry. These toxic and harmful substances are discharged into
the environment through wastewater and waste residues, which makes chromium
plating a heavily polluting industry. Only approximately 1/3 of chromic anhydride is
used for chromium plating, and the other 2/3 of chromic anhydride is consumed in
wastewater or waste gas during chromium plating, which has caused serious pollution
to the environment.
The chromium plating solution widely used in industry consists of chromic anhy-
dride supplemented by a small number of anions. Chromic acid, derived from the
aqueous solution of chromic anhydride, serves as the sole source for chromium
coating. The concentration of chromic anhydride can span a broad range. When
employing a high-concentration chromic acid electrolyte, there is a tendency for
plating bath loss upon withdrawal of the workpiece. This leads to unnecessary
material consumption and introduces certain environmental pollution. Conversely,
a low-concentration plating bath is susceptible to impurity metal ions and exhibits
inadequate coverage.
The existing form of Cr(VI) in the plating solution varies according to the concen-
tration of chromic anhydride, generally in the form of chromic acid (CrO4 2− ) and
dichromatic acid (Cr2 O7 2− ). When the pH < 1, Cr2 O7 2− is the main form; when the
pH = 2–6, Cr2 O7 2− and CrO4 2− have the balance as follows: Cr2 O7 2− + H2 O =
2H2 CrO4 − + 2CrO2 − + 2H+ . When the pH > 6, CrO4 2− is the main form in chromic
anhydride. Therefore, the chromate ions in the chromium plating electrolyte are
Cr2 O7 2− and CrO4 2− .
In the chromium plating solution, Cr(III) is generated through the cathodic reduc-
tion of Cr(VI), while simultaneously being reoxidized at the anode. The concentration
of Cr(III) quickly reaches equilibrium, and the equilibrium concentration is contin-
gent upon the cathode-to-anode area ratio. The colloid film formed by the cathode
predominantly comprises Cr(III) ions, and successful chromium deposition occurs
only when the plating solution contains a specific quantity of Cr(III).
Sulfate, fluoride, fluorosilicate, fluoroborate, and their combinations are
frequently employed as catalysts in chromium plating. Insufficient catalyst content
results in the formation of minimal or no coating, primarily resulting in a brown oxide
1.1 Sources of Soil Chromium 5
layer. Conversely, excessive catalyst levels lead to inadequate coverage, diminished

current efficiency, and the possibility of partial or complete absence of the coating.
At present, sulfuric acid is widely used as a catalyst. Therefore, Cr2 O7 2− , CrO4 2− ,
H+ and SO4 2− exist in the chromium plating electrolyte.
1.1.3 Chromium Pollution in the Tanning Industry
Tanning is the most important process in the leather industry. Chrome tanning was
invented in the middle of the nineteenth century. After more than 100 years of devel-
opment, the modern leather industry has formed a complete set of tanning process
systems based on chrome tanning. Due to its simple operation, easy control, and high
moisture and heat resistance, chrome tanning is suitable for making various light
leathers, such as shoe upper leather, garment leather, glove leather, furniture leather,
etc. Soon, it was widely applied in the leather industry and occupied a dominant
position.
The utilization rate of chromium in the conventional chrome tanning method is
only 65–75%, and the remaining chromium is left in the waste liquid. The concen-
tration was up to 25 g L−1 (Cr2 O3 ). Therefore, the main cause of chromium pollution
in the leather industry is the incomplete utilization of chromium and its elution in
the subsequent process, which not only places great pressure on the ecological envi-
ronment but also causes the waste of chromium resources. In particular, chromium
retention is carried out on the basis of leather having almost saturated absorption
of chromium. Hence, the chromium absorption rate is lower, and the elution rate is
higher.
Chrome tanning mainly causes Cr(III) pollution. According to the current treat-
ment method for Cr(III) in the leather industry, except for the separated chrome
tanning waste liquor, which is precipitated into chromium-enriched sludge by alkali,
other Cr(III) basically enters the integrated sludge. The Cr(III) in tannery integrated
sludge mainly exists in the form of Cr(OH)3 , which is easily converted into chromic
acid and forms chromic acid mist under high-temperature and aerobic conditions.
With the development of pollution control and clean tanning technology, chrome
tanning technology will develop toward high absorption, waste liquid sectional throt-
tling and recycling. The research and development of chrome-free tanning technology
will receive increasing attention.
1.1.4 Chromium Pollution from Other Industries
In addition to chromium salt production, the electroplating industry and industrial

chrome tanning, chromium pollution also widely exists in metallurgy, building mate-
rials, medicine, anticorrosion, dyes and the use of agrochemicals. In metallurgy,
chromium pollution generally originated from chrome ore smelters, whose washing
wastes contained 136 mg L−1 of total chromium, the majority of which was Cr(VI) at
112 mg L−1 and Cr(III) at 24 mg L−1 on average. During the zinc smelting operation,
chromium pollution in the zinc smelting dust reached an average of 42 mg kg−1 , while
the content of Cr(III) in the spray tower-emitted water and ferrochromium-silicon
alloy smelter slag processing waste effluents reached 4.4 and 1964 mg L−1 , respec-
tively. Chromium pollution in the field of building materials came from the use of
high temperature resistant magnesium-chromium bricks and hexavalent chromium, a
byproduct of cement production. The dissolution of chromium in cement was obvi-
ously influenced by the change in pH. Under alkaline conditions, the amount of
Cr(VI) dissolution was small, but when the pH dropped to 6–8, the chromium disso-
lution increased dramatically, reaching 2.0–2.5 mg L−1 , which greatly exceeded the
normal drinking water standard of chromium content below 0.05 mg L−1 . With the
advancement of urbanization, paint sludge was also produced in large quantities,
bringing chromium pollution even as high as 1500 mg kg−1 . Chromium pollution in
the pharmaceutical industry mainly came from the organic synthesis reaction in drug
synthesis, and it has been the core concern of heavy metal pollution control in the
pharmaceutical industry that chromium pollution from sodium dichromate used in
the oxidation reaction of chromic anhydride. Relatively speaking, it was convenient
to recycle the chromium in a unified manner because of the relatively small amount
of chromium used in anticorrosion. In textile printing and dyeing, chromium was
generally applied as a dyeing aid and mordant, and the total amount of chromium in
its wastewater reached 600 mg L−1 , among which contained Cr(VI) and Cr(III). The
waste gas, slag and wastewater generated by the production process of chromium-
related industries caused serious pollution threats to the area where the enterprises
were located and the surrounding soil.
1.2 Characteristics of Chromium Pollution in Soil
The discharge of waste containing chromium is the primary contributor to the accu-
mulation of chromium in soils. China stands out as one of the major producers of
chromate. During a period of more than 30 years, the metallurgical and chemical
sectors collectively released more than 6 million tons of chromium-containing slag
[4]. As most Cr manufacturing activities lack suitable disposal facilities, significant
volumes of chromium-containing slag may be deposited there without adequate safe-
guards against leaching, which may lead to soil contamination with the heavy metal
Cr. Slag that contains chromium has a high concentration of soluble Cr(VI), which
seeps into groundwater from the soil. Therefore, it is crucial to assess the extent
of chromium contamination in soils impacted by chromium-containing slag and to
examine the transport of Cr into the subsoil, as well as the levels of total Cr and
water-soluble Cr(VI) in both bulk soil and soil profiles.
1.2 Characteristics of Chromium Pollution in Soil 7
1.2.1 Chromium Concentrations in Chromium Pollution

in Soil
Since soil Cr(VI) contamination in China mainly resulted from chromium salt manu-
facturing, a site of chromium-containing slag heap was chosen for investigation of
chromium pollution in soil. The sites containing chromium-containing slag, along
with the surrounding area, are situated within a steel alloy factory in central Hunan
Province, located in the central and southern parts of China (latitude 27°75' N, longi-
tude 112°50' E). This region experiences a subtropical warm-moist climate, with an
average annual temperature of 17 °C. Monthly mean temperatures range from 29.7 °C
in July to 4.1 °C in January. The average annual precipitation in the area is 1300 mm.
1.2.1.1 The Total Cr Concentrations in Topsoils Contaminated

by Chromium-Containing Slag
Table 1.2 provides an overview of the total Cr content in the topsoil across different
sites. The concentration of total Cr in the soil exhibits significant variations depending
on the distance from the location of the chromium slag. The soils beneath the slag
heap exhibit total Cr concentrations ranging from 1248.4 to 2130.3 mg kg−1 . In
the area directly surrounding the slag heap, the total Cr concentrations range from
656.1 to 3500.1 mg kg−1 , with a mean value of 2239.5 mg kg−1 . The soils adjacent
to the sewage channel display a mean total Cr concentration of 995.3 mg kg−1 ,
with a range of 208.6 to 6207.6 mg kg−1 . In contrast, the total Cr concentrations
in the control location, representing uncontaminated soil located 5 km away from
the chromium-containing slag heap, exhibit minimal variation, ranging from 90.0 to
117.5 mg kg−1 . The total Cr concentrations in the soils beneath the slag heap, around
the slag heap, and near the sewage channel are 15, 21, and 9 times higher, respectively,
compared to the control location. These results clearly indicate the severe pollution
caused by the chromium-containing slag in the investigated areas. Among the three
selected locations, the soil in proximity to the slag heap displays the highest level of
contamination, while the contamination level is lowest near the sewage channel. The
total Cr contents in the soils beneath the slag heap are slightly lower than those in the
vicinity of the slag heap. This discrepancy can be attributed to the natural leaching
and mobility of the chromium-containing slag, which contributes to the majority of
the total Cr in the surface soils beneath the slag heap. However, the overall enrichment
of Cr in the topsoil around the slag heap can be attributed to runoff, leaching, and
diffusion of Cr(VI) released by the chromium-containing slag. It is important to note
that high Cr concentrations in soils can enhance plant adsorption and have adverse
effects on ecosystems, as well as the health of animals and humans if ingested through
food sources [5, 6]. Given that the soil samples collected along the sewage channel
were paddy soils, it is reasonable to anticipate that the elevated levels of total Cr in
this area could potentially contaminate the food chain. These findings underscore the
Table 1.2 Total Cr and water-soluble Cr in topsoil (mg/kg)

Sampling site N Mean Minimum Maximum SD
Total Cr
Under slag heap 3 1589.3 1248.4 2130.3 473.5
In the vicinity of slag 5 2239.5 656.1 3500.1 1413.5
heap
Near the sewer 23 995.3 208.6 6207.6 1643.1
channel
Control site 10 104.9 90.0 117.5 13.9
Water soluble
Cr(VI)
Under slag heap 3 123.8 49.5 252.7 112
In the vicinity of slag 5 36.9 0.5 101.8 38.9
heap
Near the sewer 23 0.6 0.2 1.7 0.3
channel
Control site 10 0.7 0.1 1.1 0.5
Note N = number of samples; SD = standard deviation
Reprinted from Ref. [4], Copyright 2009, with permission from the Nonferrous Metals Society of
China and Elsevier
significant detrimental impact of chromium released from the ferroalloying factory

on the soil ecosystem.
1.2.1.2 Water-Soluble Cr Concentrations in Topsoils Contaminated

by Chromium-Containing Slag
Table 1.2 also presents the concentrations of water-soluble Cr(VI) at various sampling
locations. The soils beneath the slag heap exhibited an average water-soluble Cr(VI)
concentration of 123.8 mg kg−1 , ranging from 49.5 to 252.7 mg kg−1 . The soils
surrounding the slag heap had an average water-soluble Cr(VI) concentration of
36.9 mg kg−1 , with a range of 0.5–101.8 mg kg−1 . The average water-soluble Cr(VI)
concentrations beneath the slag heap and in the vicinity of the slag heap were 176.9
times and 52.7 times higher, respectively, compared to the unpolluted soils at the
control site. In contrast, the water-soluble Cr(VI) levels in the soils near the sewage
channel were similar to those observed at the control site. These results clearly
indicate significant chromium contamination at the slag site of the ferroalloy plant.
Furthermore, the soil beneath the slag heap exhibited the highest concentration of
water-soluble Cr(VI). It was worth noting that although the water-soluble Cr(VI)
concentration in the soil along the sewer channel was low, the total Cr concentration
exceeded the critical limit set by the Secondary Environmental Quality Standard for
Soil in China. In the presence of MnO2 , Cr(III) can be transformed into Cr(VI) [7]. As
soil properties, such as pH and organic matter content, undergo changes, other forms
of Cr, such as exchangeable Cr and carbonate-bonded Cr, can also be converted into
water-soluble Cr(VI) [8]. It is important to note that even low levels of water-soluble
Cr(VI) in soils near the sewer channel may have potential health implications.
1.2.2 Vertical Distributions of Total Cr and Water-Soluble

Cr(VI) in the Soil Profiles
1.2.2.1 The Distributions of Total Cr in the Soil Profiles
Figures 1.2, 1.3, 1.4 and 1.5 show the vertical profile distributions of total Cr in
the studied locations. Beneath the slag heap, total Cr concentrations in profiles 1
and 3 steadily rose with soil depth within 60 cm before declining again. The results
indicated that total Cr accumulated at a depth of 60 cm. This most likely contributed
to Cr immobilization by additional Fe and Mn molecules. Nevertheless, a greater
Cr content was discovered in profile 2 at depths of 20–40 cm. Due to the limited
number of profiles, there was no consistent distribution pattern of total Cr observed
in the soil profiles near the slag heap (Fig. 1.2). However, in the vicinity of the sewer
channel, the profiles 6, 7, 8, and 9 in Fig. 1.4 exhibited a decreasing trend of total Cr
concentration with decreasing depth.
In comparison to the highly contaminated soils beneath and surrounding the
slag heap, the chromium pollutant originating from chromium-containing slag was
predominantly immobilized in the topsoil layers (Fig. 1.3). With the exception of
profile 12, which exhibited considerably higher total Cr accumulations at the surface
level, there was no discernible change in total Cr concentrations in the uncontam-
inated soil profiles (profiles 10 and 11) (Fig. 1.5). Generally, the mean total Cr
concentrations at different soil depths beneath the slag heap followed this order: 40–
60 cm (2236.8 mg kg−1 ) > 20–40 cm (2210.9 mg kg−1 ) > 0–20 cm (1589.3 mg kg−1 )
> 60–100 cm (1258.4 mg kg−1 ) > 100–150 cm (623.1 mg kg−1 ). A similar trend was
observed in the soil profiles surrounding the slag heap. These findings clearly demon-
strate a significant retention of Cr in the intermediate soil depths at the chromium-
containing slag sites of the iron alloy factory (under the slag heap and in the vicinity
of the slag heap). Previous studies have shown that the vertical distribution of total
Cr in the soil profiles surrounding the slag heap exhibited an accumulation pattern
towards the intermediate depths [9]. At intermediate depths, the observed leaching
and modest accumulation of Cr can be primarily attributed to the retention of the
element by iron compounds [1]. In geological environments, the solubility of Cr(III)
is commonly regulated by the solid solution (Cr, Fe)(OH)3 . This solid solution, which
forms in the presence of Fe(III), plays a significant role in controlling the solubility
of Cr(III) since Cr exists in two oxidation states, Cr(III) and Cr(VI) [10–12]. The
soil profile studied in this research was collected from the Quaternary red earth
region in southern China, known for the accumulation of iron-manganese nodules
in intermediate-depth soil. This phenomenon could potentially explain the observed
Fig. 1.2 The distributions of total Cr and water-soluble Cr(VI) in soil profiles under the chromium-
containing slag heap. Reprinted from Ref. [4], Copyright 2009, with permission from the Nonferrous
Metals Society of China and Elsevier
Fig. 1.3 The distributions of total Cr and water-soluble Cr(VI) in soil profiles in the vicinity of
chromium-containing slag heaps. Reprinted from Ref. [4], Copyright 2009, with permission from
the Nonferrous Metals Society of China and Elsevier
Fig. 1.4 The distributions of total Cr and water-soluble Cr(VI) in soil profiles near the sewer
channel of the manufactory. Reprinted from Ref. [4], Copyright 2009, with permission from the
Nonferrous Metals Society of China and Elsevier
accumulation of total Cr in the intermediate-depth soils beneath the slag heap and
in its surrounding areas. On the other hand, the vertical distribution profiles near the
sewage channel exhibited distinct patterns of total Cr compared to those beneath the
slag heap and in its vicinity. In these profiles, the highest concentrations of total Cr
were found in the topsoil, followed by a rapid decrease with depth. These variations
are likely influenced by changes in land use and human factors. The areas along the
sewage channel were primarily used for farming activities, where the application
of fertilizers and organic manure was common. This resulted in the accumulation
of organic matter in the topsoil. It was possible that this organic matter played a
contributing role in the substantial enrichment of total Cr in the topsoil along the
sewage channel. The high concentration of organic matter also suggested the forma-
tion of metal–organic complexes, which could lead to the accumulation of metals in
the soil. Therefore, the distribution of total Cr in the studied soil profile exhibited
different patterns, with the intermediate-depth soils showing accumulation related to
the presence of iron-manganese nodules, while the topsoil along the sewage channel
exhibited higher concentrations potentially influenced by organic matter and metal–
organic complex formation [10]. According to several publications, the buildup of
total Cr in contaminated soils may vary depending on the amount of organic matter
in the soils since chromium may be absorbed by organic matter.
The study findings indicated that Cr has the ability to penetrate the soil and reach
considerable depths of up to 150 cm. In fact, one sample taken at a depth of 150 cm
Fig. 1.5 The distributions of total Cr and water-soluble Cr(VI) in soil profiles at uncontaminated
sites. Reprinted from Ref. [4], Copyright 2009, with permission from the Nonferrous Metals Society
of China and Elsevier
beneath a slag heap exhibited the Cr levels that were three times higher than the
critical limit specified by the Secondary Environmental Quality Standard for Soil in
China (Fig. 1.2). Moreover, the total Cr concentrations in the profile soil beneath
and near the slag heap consistently exceeded the standard limit, ranging from two to
six times higher. However, along the sewage channel, the mean Cr contents below a
depth of 40 cm were within the standard limit, except for samples obtained from the
surface soil (0–20 cm) and subsurface soil (20–40 cm), which exceeded the standard
limit. Notably, there were significant variations in mean concentrations across the
three sites, with the contamination severity following the sequence of under the slag
heap > vicinity of the slag heap > along the sewage channel. These findings highlight
the potential for chromium migration into the subsoil from the slag heap, despite the
soil’s role in retaining chromium. Consequently, the study suggests that chromium
poses a substantial risk to the groundwater system.
1.2.2.2 The Distributions of Water Soluble Cr(VI) Content in Soil

Profiles
The presence of water-soluble Cr(VI) in profile 1 and profile 2, located under the slag
heap, exhibited an initial increase within the top 40 cm of depth (Fig. 1.2), followed
by a subsequent decline. Notably, the concentration of water-soluble Cr(VI) was
significantly higher at the surface depth (0–20 cm) compared to other levels, while
profile 3 demonstrated relatively consistent levels of water-soluble Cr(VI) throughout
(Fig. 1.2). Similarly, profiles 4 and 5, situated in the vicinity of the slag heap, displayed
a decreasing trend in water-soluble Cr(VI) concentrations with increasing depth
(Fig. 1.3). Along the sewage channel, all profiles showed extremely low levels of
water-soluble Cr(VI), close to the background level (Figs. 1.4 and 1.5).
Across all test sites, the average concentrations of water-soluble Cr(VI) in the soil
profiles decreased as the depth increased. The soil beneath the slag heap consistently
exhibited significantly higher water-soluble Cr(VI) levels compared to the vicinity of
the slag heap, followed by the sewage channel and control sites. These findings indi-
cate extensive contamination by chromium from chromium-containing slag heaps,
particularly beneath and near the slag heaps. Furthermore, the persistence of elevated
water-soluble Cr(VI) levels at depths of 100–150 cm suggests a substantial release
and migration of this form of chromium from the slag heap. This transfer of Cr(VI)
raises concerns about potential risks to the groundwater system in the area.
1.2.3 Chromium Fractions in the Contaminated Soils
The concentration of various chromium fractions in soils collected from different

depths at three different locations, under chromium slag, near the slag heap and
unpolluted land, are presented in Table 1.3. The mean Cr values of the water soluble,
exchangeable, carbonate-bonded fractions in soils under chromium slag were 97.5,
3.0 and 16.3 mg kg−1 , accounting for 6.26%, 0.19% and 1.05% of the total Cr,
respectively. Near the slag heap, the Cr contents in the water-soluble, exchangeable,
carbonate-bonded fractions were 16.8, 11.5 and 5.7 mg kg−1 , accounting for 1.93%,
1.32% and 0.65% of the total Cr, respectively. In the unpolluted soil, the Cr concen-
trations in the water soluble, exchangeable, carbonate-bonded fractions were 1.8,
1.5 and 2.5 mg kg−1 , accounting for 2.1%, 1.7% and 2.9% of the total Cr, respec-
tively. Because the chromium slag in the current study has a high pH value, the high
percentage of carbonate-bonded Cr in soils under chromium slag and near chromium
slag was higher than that in unpolluted soil profiles. The vertical variation in water-
soluble Cr in the soil profiles was not consistent in the different locations. The Cr
amount of the water-soluble and exchangeable fractions in the soil profiles. There
was no obvious difference in carbonate-bonded Cr observed in the soil profiles.
Fe- and Mn-bonded Cr, organic-bonded Cr and residual Cr were generally higher
than water-soluble Cr, exchangeable Cr and carbon-bonded Cr (Table 1.3). The mean
values of Fe and Mn-bonded Cr in profile soils under chromium slag heap ranged from
269.4 to 1679 mg kg−1 . The equivalent values for soils near slag heaps varied from
59.8 to 439.9 mg kg−1 and from 9.9 to 20.78 mg kg−1 in unpolluted soils. Relatively
high amounts of Fe- and Mn-bound Cr were found in the subsoil and 40–60 cm soil
depth. The mean values of organic-bounded Cr in soils beneth chromium slag near
slag heaps and unpolluted land were 273.2, 201.2 and 16.2 mg kg−1 , respectively.
Table 1.3 Chromium fractions in soil profiles (mg kg−1 )

Soil depth (cm) Soil under the Soil in the vicinity of the Uncontaminated soil (n
chromium-containing chromium-containing = 3)
slag heap (n = 3) slag heap (n = 3)
Water soluble Cr (Mean ± SD)
0–20 123.8 ± 112.0 33.3 ± 40.5 2.5 ± 1.0
20–40 132.7 ± 145.8 24.1 ± 38.7 1.8 ± 0.5
40–60 91.2 ± 112.9 18.9 ± 30.7 1.4 ± 0.2
60–100 76.2 ± 90.8 6.8 ± 8.0 1.6 ± 0.3
100–150 63.7 ± 100.2 0.8 ± 0.6
Exchangeable Cr (Mean ± SD)
0–20 3.9 ± 3.1 18.6 ± 22.3 1.6 ± 1.1
20–40 3.0 ± 0.2 16.2 ± 23.9 1.4 ± 0.6
40–60 2.9 ± 2.3 11.9 ± 15.9 1.5 ± 0.3
60–100 3.2 ± 1.9 6.3 ± 5.8 1.4 ± 0.7
100–150 1.9 ± 0.4 4.6 ± 4.2
Carbonate-bonded Cr (Mean ± SD)
0–20 12.1 ± 8.7 7.7 ± 8.4 2.4 ± 0.1
20–40 20.7 ± 16.6 10.4 ± 13.7 2.5 ± 0.1
40–60 21.8 ± 17.7 4.1 ± 3.5 2.5 ± 0.1
60–100 16.0 ± 14.6 3.8 ± 2.9 2.6 ± 0.2
100–150 10.8 ± 7.7 2.3 ± 0.0
Organic-bonded Cr (Mean ± SD)
0–20 291.6 ± 385.8 403.6 ± 618.2 20.3 ± 12.5
20–40 390.6 ± 270.1 374.9 ± 572.7 17.7 ± 6.1
40–60 453.5 ± 215.6 83.7 ± 67.1 15.1 ± 3.6
60–100 172.2 ± 103.2 124.3 ± 125.4 11.7 ± 2.1
100–150 58.2 ± 36.2 28.9 ± 20.5
Fe and Mn-bonded Cr (Mean ± SD)
0–20 471.4 ± 434.1 301.4 ± 343.4 20.8 ± 7.9
20–40 1459.2 ± 582.9 439.9 ± 557.5 17.2 ± 9.1
40–60 1679.4 ± 622.2 137.9 ± 112.6 10.9 ± 1.5
60–100 792.3 ± 406.5 228.0 ± 267.7 9.9 ± 2.5
100–150 269.4 ± 140.2 59.8 ± 70.3
Residue Cr (Mean ± SD)
0–20 326.7 ± 161.7 683.8 ± 742.7 57.4 ± 20.2
20–40 240.7 ± 241.9 677.5 ± 770.6 44.4 ± 21.7
40–60 113.0 ± 19.1 249.9 ± 50.3 57.6 ± 13.1
(continued)
Table 1.3 (continued)

Soil depth (cm) Soil under the Soil in the vicinity of the Uncontaminated soil (n
chromium-containing chromium-containing = 3)
slag heap (n = 3) slag heap (n = 3)
60–100 208.7 ± 195.1 224.2 ± 73.4 40.4 ± 16.4
100–150 276.6 ± 420.8 169.9 ± 135.8
Reprinted from Ref. [4], Copyright 2009, with permission from the Nonferrous Metals Society of
China and Elsevier
Regarding residual Cr, its mean content in soils under chromium slag in the vicinity
of slag heap and unpolluted land was 233.1, 389.7 and 49.9 mg kg−1 , respectively.
The assessment of potential risks associated with heavy metals in soils requires
considering their bioavailability rather than relying solely on total metal concentra-
tions. This is because metals exhibit complex distribution patterns among different
chemical fractions or solid phases, making it difficult to accurately gauge their
bioavailability. The bioavailability of heavy metals is predominantly influenced by
their chemical forms, particularly those related to solubility. Of particular concern
are the exchangeable and carbonate forms, which are prone to leaching and can pose
a threat to groundwater contamination. These forms play a crucial role in deter-
mining heavy metal uptake by plants and are thus of utmost importance in assessing
environmental hazards [8].
In comparison to unpolluted land, soils under chromate slag and near slag heaps
had greater levels of water-soluble Cr, exchangeable Cr, and carbonate forms. The
results suggest that the solubility and mobility of chromium were high in the polluted
soils, particularly in the subface soil. The analysis shows that the environmental
danger posed by the metal chromium released by the Steel-Alloy factory poses a
significant risk to the environment. In conclusion, the mean contents of various Cr
fractions were in the order Fe and Mn-bonded Cr > residual Cr > organic-bonded
Cr > water-soluble Cr > carbonate-bonded Cr > exchangeable Cr. In soil profiles
contaminated by chromate slag, the concentration of water-soluble Cr generally
decreased with profile depth. The subsoil and the first 40–60 cm of the soil were
found to contain rather significant concentrations of o Fe- and Mn-bonded Cr and
organic-bonded Cr. In the profile layers, there was no discernible difference between
exchangeable Cr and carbonate-bonded Cr. Topsoil beneth chromate slag and in
the vicinity of the slag heap contained relatively high levels of water soluble Cr in
comparison to unpolluted soils.
1.3 Microbial Communities in Chromium-Contaminated

Soil
The recycling of essential nutrients for plants, the preservation of soil structure,
and the detoxification of toxic substances are all significant functions carried out
by microbes. Heavy metals are hazardous to soil biota, affecting essential microbial
processes and reducing the quantity and activity of soil microorganisms [13]. The
microbial community has often been presented as a simple and sensitive indicator
of anthropogenic influences on soil ecology. Elevated levels of Cr(VI) have been
found to alter the composition of soil microbial communities and adversely affect
the metabolic activity of microbial cells [14]. As a result, it is critical to look at
the microbial communities in hexavalent chromium-contaminated soil, as well as
the genetic diversity of hexavalent chromium-resistant bacteria. Soil samples were
obtained from six chromite ore processing residue (COPR) disposal sites in China
(D: Hunan; G: Henan; H: Shanxi; J: Shaanxi; N: Hebei; R: Yunnan). Since the 1960s,
chromite ore processing residue has been disposed of at these locations, producing
serious chromium pollution in the local ecosystem. Microbial communities were
discovered in chromium-contaminated soil (Table 1.4).
1.3.1 Bacterial Structural Diversity in the Contaminated Soils
Soil samples D, G, H, J, N, and R showed 17, 17, 20, 12, 15, and 21 DNA bands,
as shown in Fig. 1.6a. Moreover, distinct discrepancies in the locations of the DNA
bands in each lane suggested that the bacterial communities in these soils were
distinct. The DICE similarity coefficient was used for cluster analysis (Fig. 1.6b).
The bacterial cummunities’ similaritiey coefficient in the six soils varied The from
0.52 to 0.81. Further, soils G and J had the greatest similarity coefficient (0.81).
The presence of high hexavalent chromium content did not have a significant
impact on the structural diversity of bacteria in the soil samples. Soil R had the highest
hexavalent chromium concentration (481.27 mg kg−1 ) among the six soils, but it also
exhibited the most diverse bacterial community with 21 DNA bands. Conversely, Soil
N had the lowest hexavalent chromium concentration (23.60 mg kg−1 ) and showed
only 15 DNA bands. Correlation analysis revealed a strong relationship between the
diversity of soil bacterial communities and soil pH (correlation coefficient of − 0.874,
p < 0.05), while the correlation coefficient between the diversity of soil bacterial
communities and soil hexavalent chromium concentration was not significant.
The results indicated that soil pH had a more significant influence on the diver-
sity of soil bacterial communities in polluted areas compared to the concentration
of hexavalent chromium. This suggests that the variation observed in the bacte-
rial communities was primarily driven by soil pH rather than the specific levels of
hexavalent chromium present.
Table 1.4 Source and properties of different soil samples (mg kg−1 )
Soil Location pH Cr(VI) Pb Cd Cu Hg As
D Hunan 9.0 ± 0.1a 151.8 ± 3.5 350.2 ± 5.4 9.5 ± 0.3 101.5 ± 2.5 10.16 ± 0.7 31.0 ± 2.3
G Henan 8.6 ± 0.2 243.9 ± 4.2 99.8 ± 6.2 3.1 ± 0.6 64.6 ± 3.0 4.38 ± 0.6 14.4 ± 1.7
H Shanxi 8.7 ± 0.1 176.5 ± 2.8 104.7 ± 3.5 5.3 ± 0.4 540.0 ± 5.3 11.10 ± 0.4 6. 3 ± 2.0
J Shaanxi 9.2 ± 0.3 135.8 ± 2.0 83.2 ± 2.7 2.7 ± 0.1 57.8 ± 4.0 9.86 ± 0.4 13.2 ± 2.7
N Hebei 8.9 ± 0.1 23.6 ± 2.2 88.4 ± 3.4 3.0 ± 0.3 44.5 ± 3.6 5.19 ± 0.6 10.4 ± 2.1
R Yunnan 8.1 ± 0.1 481.3 ± 2.5 57.6 ± 4.5 2.0 ± 0.4 72.1 ± 2.9 6.94 ± 0.5 27.1 ± 4.0
1.3 Microbial Communities in Chromium-Contaminated Soil
aMean value ± standard deviation

Reprinted from Ref. [15] by permission of Taylor & Francis Ltd
17
Fig. 1.6 a DGGE banding

patterns of the 16S rRNA
gene extracted from soil
bacterial populations.
b Dendrogram constructed
using the coefficient method
from DGGE profiles of
bacterial communities. Lanes
D, G, H, J, N, and R
represent soil samples
contaminated with
hexavalent chromium.
Reprinted from Ref. [15] by
permission of Taylor &
Francis Ltd.
In terms of heavy metal toxicity, several mechanisms have been associated with
their adverse effects. These mechanisms include direct interactions with proteins,
the generation of reactive oxygen species, and the displacement of essential cations
from specific binding sites. These processes contribute to the overall toxicity of heavy
metals and their detrimental impact on biological systems [16].
1.3 Microbial Communities in Chromium-Contaminated Soil 19
1.3.2 Isolation and Identification of Hexavalent

Chromium-Resistant Bacteria
A total of twenty-two bacterial strains resistant to hexavalent chromium were

isolated from sample D. Analysis of the 16S rRNA gene sequences of these isolates
revealed a diverse range of bacterial strains, including Brevundimonas, Micrococcus,
Exiguobacterium, Alcaligenes, and Pannonibacter genera. The nucleotide sequences
of these strains were submitted to GenBank, and their corresponding accession codes
and genotypic characteristics can be found in Table 1.5. Furthermore, a phylogenetic
analysis of the sequences of these strains and their closest matches from GenBank
is presented in Fig. 1.7. This analysis provides insights into the genetic relatedness
of the isolated strains and their relationships with other known bacterial species.
1.3.3 Bacterial Genetic Diversity on the Basis

of Rep-Polymerase Chain Reaction Fingerprints
Figure 1.8 displays the banding patterns obtained from the BOX-, ERIC-, and REP-
polymerase chain reactions. The BOX-polymerase chain reaction produced complex
banding patterns with 4 to 10 DNA bands ranging from 500 to 3000 bp. The ERIC-
polymerase chain reaction generated two to six polymorphic bands varying from
200 to 2500 bp, while the REP-polymerase chain reaction produced two to ten poly-
morphic bands ranging from 200 to 3000 bp. Among the three primers, the BOX-
polymerase chain reaction yielded the most intricate patterns, making it ideal for
assessing the genotypic diversity of hexavalent chromium-resistant bacteria. Each
primer set produced nine distinct genotypic patterns (Table 1.5), providing valuable
insights into the genetic variations among the bacteria under investigation.
1.3.4 Hexavalent Chromium Reduction by Cr(VI)-Reducing

Bacterial Strains
In the hexavalent chromium reduction test conducted at an initial dosage of

300 mg L−1 , a total of 22 bacterial strains were evaluated. The results, presented in
Table 1.5, revealed a significant reduction in the proportion of hexavalent chromium
across these strains, ranging from 0.87 to 99.9%. Particularly, the isolates WY20 and
WY21 were exhibited exceptional performance by effectively lowering 300 mg L−1
of hexavalent chromium within a mere 24-h period. These findings highlight the
potential of these bacterial strains as highly efficient agents for hexavalent chromium
remediation. WY20 and WY21 are Pannonibacter phragmitetus, according to the
phylogenetic analysis (Fig. 1.9). Bacillus [17], Pseudomonas aeruginosa [18],
Ochrobactrum [19] and Microbacterium [20] are among the bacterial strains with
Table 1.5 Genotypic characterization and hexavalent chromium reducing capacity of hexavalent
chromium resistant isolates
Isolates Hexavalent REP BOX ERIC Closest identified strain (similarity
(access chromium type type type and accession number)
number) reduction (%)
WY1 4.0 R1a B1a E1a Brevundimonas sp. PL46b_S4
(KC203066) (100% and JF274919.1)
WY2 40.9 R2 B2 E2 Alcaligenes faecalis strain KZJ01
(KC203067) (100% and FJ436432.1)
WY3 5.5 R3 B3 E3 Micrococcus sp. HEXBA04 (99%
(KC203068) and JQ658423.1)
WY4 7.9 R4 B4 E4 Brevundimonas sp. SGJ (100% and
(KC203069) HM998899.1)
WY5 1.5 R5 B5 E5 Exiguobacterium sp. ERGBD-1
(KC203070) (99% and HM854020.1)
WY6 0. 9 R5 B5 E5 Exiguobacterium sp. AFB-18 (99%
(KC203071) and HQ848274.1)
(KC203072) (100% and FJ436432.1)
WY8 37.9 R2 B2 E2 Alcaligenes sp. C8 (100% and
(KC203073) EU563336.1)
(KC203074) (100% and FJ436432.1)
WY10 9.0 R1 B6 E1 Brevundimonas sp. PL46b_S2
(KC203075) (100% and JF274917.1)
(KC203076) (100% and FJ436432.1)
(KC203077) (100% and FJ436432.1)
(KC203078) (100% and FJ436432.1)
WY14 11.3 R4 B6 E1 Brevundimonas diminuta strain
(KC203079) 3P04AD (100% and EU977701.1)
WY15 7.5 R1 B1 E6 Brevundimonas sp. 183 (100% and
(KC203080) EU593764.1)
WY16 2.6 R6 B7 E5 Exiguobacterium sp. AFB-18 (99%
(KC203081) and HQ848274.1)
WY17 12.1 R7 B8 E7 Brevundimonas sp. PL46b_S4
(KC203082) (100% and JF274919.1)
WY18 40.7 R7 B8 E7 Brevundimonas sp. LSH-3 (100%
(KC203083) and DQ825665.1)
WY19 7.5 R7 B8 E7 Brevundimonas diminuta strain 764
(KC203084) (100% and EU430091.1)
WY20 99.7 R8 B9 E8 Pannonibacter sp. W1 (100% and
(KC203085) EU617334.1)
(continued)
1.4 Adsorption of Cr(VI) on Soils 21
Table 1.5 (continued)

Isolates Hexavalent REP BOX ERIC Closest identified strain (similarity
(access chromium type type type and accession number)
number) reduction (%)
WY21 99.9 R8 B9 E8 Pannonibacter sp. W1 (100% and
(KC203086) EU617334.1)
WY22 44.3 R9 B1 E9 Micrococcus sp. M10 (100% and
(KC203087) JN596114.1)
a R, B and E refer to the abbreviation of fingerprint patterns of REP-, BOX- and ERIC-PCR,
respectively. The initial Cr(VI) concentration and pH were 300 mg. L−1 and 9.0, these bacterial
strains were incubated at 30 °C for 24 h
Reprinted from Ref. [15], Copyright © 2015 managed by Taylor & Francis
hexavalent chromium-reducing activity that have been described in the previous liter-
atures. At concentrations ranging from 10 to 2000 mg L−1 , these bacterial strains may
totally eliminate hexavalent chromium [18–21]. The 22 isolates used in this investi-
gation expanded the number of bacteria know to be capable of reducing hexavalent
chromium.
1.4 Adsorption of Cr(VI) on Soils
The adsorption behavior of Cr(VI) on soils is an essential property for forecasting its
current condition and giving significant information for its migration and manage-
ment. Traditionally, most chromium-soil adsorption experiments have focused on the
behavior of pure Cr(VI) solutions in uncontaminated soils. However, it is crucial to
gain insights into the kinetics and thermodynamics of Cr(VI) adsorption in soils. This
understanding is essential for comprehensively assessing the adsorption processes
and their environmental implications.
1.4.1 Adsorption Kinetics of Cr(VI)
Figure 1.10 depicts the quantites of Cr(VI) adsorption as a function of sorption time
The Cr(VI) concentration in the soil-free blank solutionsdid not change during10
h. The tendencies of Cr(VI) adsorption over time in soil samples were constant at
the three distinct temperatures (15, 25, 35 °C). The adsorption capacity of soil for
Cr(VI) rose gradually with increasing soil temperature, as illustrated in Fig. 1.10, and
eventually reached the equilibrium state of adsorption. Particularlly, the adsorption
amounts of Cr(VI) increase fast during the first 2.5 h. After that, the adsorption
quantities gradually rise until they reach equilibrium after 5 h.
Fig. 1.7 Phylogenetic tree generated by 16S rRNA gene sequences for 22 hexavalent chromium-
resistant bacterial strains and similar strains. Accession numbers of the bacterial isolates in this
study and others are shown in brackets. Reprinted from Ref. [15] by permission of Taylor & Francis
Ltd
Fig. 1.8 Rep-PCR genomic fingerprints of 22 isolates generated with the BOX, ERIC, REP primer
set. Lanes 1–22 represent isolates WY1 to WY22, respectively. Lane M is the DNA marker. Lane
B is a negative control (PCR without DNA template). Reprinted from Ref. [15], Copyright © 2015
managed by Taylor & Francis
Fig. 1.9 Phylogenetic tree showing the genetic diversity of 22 hexavalent chromium-resistant
bacteria based on the combined fingerprint patterns of BOX-, ERIC- and REP-PCR. Reprinted
from Ref. [15] Copyright © 2015 managed by Taylor & Francis
Fig. 1.10 The effects of agitation time and temperature on the adsorption of Cr(VI) by soil.
Reprinted from Ref. [22], Copyright 2019, Springer-Verlag GmbH Germany, part of Springer Nature
Fig. 1.11 Pseudo-first-order kinetics (a) and pseudo-second-order kinetics (b) for the adsorption
of Cr(VI) onto soil at different temperatures. Reprinted from Ref. [22], Copyright 2019, Springer-
Verlag GmbH Germany, part of Springer Nature
The kinetic data collected were analyzed by the pseudo-first-order kinetics model
and pseudo-second-order kinetics model to research the mechanism of Cr(VI) adsorp-
tion on soil and assess the rate-controlling stage of the adsorption process [23].
Figure 1.11 shows the pseudo-first-order and pseudo-second-order kinetics of Cr(VI)
adsorption onto soil at varies temperatures are shown in. In comparision to pseudo-
first-order kinetics (Fig. 1.11a), the pseudo-second-order kinetics (Fig. 1.11b) model
gives a good match to the adsorption kinetic data of Cr(VI) at different temperatures
(15, 25, and 35 °C),with correlation coefficients R2 of 0.9998, 0.9999, and 0.9997,
respectively. The equilibrium adsorption capacities (qe ) are 232.56, 286.53, and
312.20 mg kg−1 , respectively, andare extremely similar to the actual amount of equi-
librium adsorption (229.62 mg kg−1 , 281.67 mg kg−1 , and 309.21 mg kg−1 ), respec-
tively. The pseudo-first-order mode’s R2 values for Cr(VI) adsorption are 0.8593,
0.9548, and 0.9043, respectively, and the equilibrium adsorption capacities (qe ) are
39.06, 66.98, and 78.20 mg kg−1 (Table 1.6). The estimated adsorption capacity of
Cr(VI) is significantly lower than the actual equilibrium adsorption quantity. These
findings indicate that the pseudo-second-order kinetic model provides a more suit-
able description of the Cr(VI) adsorption kinetics. Moreover, the pseudo-second-
order model assumes that the rate-limiting step involves chemical sorption, which
entails valence force interactions through electron sharing or exchange between the
adsorbent and the adsorbate [24]. Hence, the good fitting of the pseudo-second-order
model implies that the Cr(VI) sorption onto soil may undergo a chemical adsorption
process.
1.4.2 Adsorption Thermodynamics of Cr(VI)
The calculation of thermodynamic parameters, including the change in standard

free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), were performed using the
Table 1.6 Predicted kinetic parameters for Cr(VI) adsorption on soil at different temperatures
T °C Pseudo-first-order kinetic Pseudo-second-order kinetic
qe (mg/kg) k 1 (min−1 ) R2 qe (mg/kg) k 2 (kg mg−1 min−1 ) R2
15 39.06 0.0090 0.8593 232.56 0.0006 0.9998
25 66.98 0.0095 0.9548 286.53 0.0004 0.9999
35 78.20 0.0074 0.9043 312.20 0.0003 0.9997
following equations [25]:
ΔS ◦ ΔH ◦
ln K c = − (1.1)
R RT
ΔG ads = ΔHads − T ΔSads (1.2)
The thermodynamic parameters (ΔG°) for the adsorption process of Cr(VI) onto
the soil were determined to be −2.78, −3.36, and −3.94 kJ mol−1 at the temperatures
of 15 °C, 25 °C, and 35 °C, respectively, as presented in Table 1.7. The negative values
of ΔG° indicate that the adsorption of Cr(VI) onto the soil occurs spontaneously,
suggesting a favorable adsorption process. Additionally, the positive value of ΔH°
confirms that the adsorption of Cr(VI) is an endothermic process, indicating that heat
is absorbed during the adsorption reaction [26]. The positive value of ΔS° indicates
that adsorption is feasible, and enhanced unpredictability at the sorbent/solution
interface occurs in the internal structure of Cr(VI) adsorption onto soil. A positive
result for value of ΔH° (14.01 kJ mol−1 at 15 °C) implies an endothermic process
of adsorption [27].
Table 1.8 shows the values of the Langmuir and Freundlich parameters, as well
as and R2 . Both Langmuir and Freundlich isotherms had a strong correlation with
the observed data (Fig. 1.12). Yet, the regression coefficient R2 revelaed that the
Langmuir isotherm model was much superior to the Freundlich isotherm model
in characterizing adsorption processes (R2 of Langmuir isotherm 0.975, 0.990 and
0.977 vs Freundlich isotherm 0.845, 0.882 and 0.980). The Langmuir isotherm is
a typical adsorption isotherm for determining an adsorbent’s potential application.
The adsorption of Cr(VI) onto soil generally follows Langmuir isotherms with the
Table 1.7 Thermodynamic parameters for the adsorption of Cr(VI) by soil

Temperature (K) ΔG° (kJ mol−1 ) ΔH° (kJ mol−1 ) ΔS° (kJ mol−1 K−1 )
288 −2.78 14.01 58.33
298 −3.36
308 −3.94
maximum adsorption capacity (qm ) of the soil being 175, 200, and 310 mg kg−1 at
temperatures of 15 °C, 25 °C, and 35 °C, respectively. The values of b, a measure of
heat of adsorption, are 0.043, 0.087, and 0.038.
The dimensionless separation factor (RL ) was developed baseeedon additional
investigation of the Langmuir equation to predict the breakthrough behavior of Cr(VI)
adsorbed on the soil bed [28].
1
RL = (1.3)
(1 + bC0 )
where C 0 represents the initial Cr(VI) concentration (mg/L) and b represents the
Langmuir isotherm constant. Four idealized types of equilibrium behavior may be
identified using the value of RL . Unfavorable adsorption equilibrium is represented by
RL > 1; linear adsorption equilibrium is represented by RL = 1; favorable adsorption
equilibrium is represented by RL = 1; and irreversible adsorption equilibrium is
represented by RL = 0. The value of RL in the current investigation varied between
0.054–0.535 (RL 1), confirming soil’s preferential adsorption of Cr (VI).
Table 1.8 Parameters of Langmuir and Freundlich isotherms at different temperatures

T Langmuir parameters Freundlich parameters
b qmax R2 Kd 1/n R2
15°C 0.043 175.44 0.975 14.60 0.513 0.845
25°C 0.087 200.40 0.990 33.13 0.384 0.882
35°C 0.038 310.56 0.977 39.39 0.391 0.980
Fig. 1.12 Langmuir isotherm (a) and Freundlich isotherm (b) for Cr(VI) adsorption in soil at
different temperatures. Reprinted from Ref. [22], Copyright 2019, Springer-Verlag GmbH Germany,
part of Springer Nature
1.5 Cr(VI) Migration in Chromite Ore Processing Residue

(COPR)-Soil
The hexavalent chromium in the chromium-containing slag may be separated into

water-soluble and acid-soluble hexavalent chromium based on its solubility. The
water-soluble hexavalent chromium is made up of Na2 CrO4 from the leaching
and baking processes. The acid-soluble hexavalent chromium mostly consistes
of the dissociated CaCrO4 , Ca2 SiO4 and 4CaO·Al2 O3 ·Fe2 O3 . While CaCrO4 is
dissociated from chromium-containing slag, the majority of chromium compo-
nents are dispersed within the particles rather than only as surface contam-
inants [29]. Ca2 SiO4 and 4CaO·Al2 O3 ·Fe2 O3 occur in the crystal lattice, for
example. Because of the aforesaid features of Cr(VI) components, Cr(VI) is persis-
tently leached from chromium-containing slag. The solubility leaching behavior
of acid-soluble CaCrO4 in the outside environment was greatly reliant on Cr(VI)
leaching behaviour [30]. In aqueous or acidic media, Na2 CrO4 ·4H2 O, CaCrO4 ,
4CaO·Al2 O3 ·CrO3 ·12H2 O, Fe(OH)CrO4 , and adsorbed Cr(VI) have rapid diffusion
rates, while CaCrO4 ·Ca2 SiO4 ·CaCrO4 and 4CaO·Al2 O3 ·Fe2 O3 ·CaCrO4 have slower
diffusion rates [3]. The rate of Cr(VI) diffusion from slag direct impact on the soil
contamination process.
1.5.1 Diffusion of Cr(VI) in Chromium-Containing Slag
1.5.1.1 The Deposition Potential of Cr(VI) Reduction
Samples of chromium-containing slag were obtained from the former Changsha

Chromate Factory for the purpose of estimating the apparent diffusion coefficient of
Cr(VI) in the slag. Two distinct methods were employed for this estimation. In the
first procedure, the deposition potential of Cr(VI) reduction was assessed through
linear scan voltammetry. Subsequently, the changes in current resulting from Cr(VI)
reduction were monitored using single potential step chronoamperometry, which
allowed the generation of a current-time course curve. By applying Fick’s laws to
this curve, the apparent diffusion coefficients of Cr(VI) originating from the initial
chromium-containing slag were calculated. These experimental approaches provide
valuable insights into the diffusion behavior of Cr(VI) within the slag samples.
The linear scan voltammetry curve in 0.1 mol L−1 Na2 SO4 baseline solution and
0.1 mol L−1 Na2 SO4 + 0.02 mol L−1 K2 Cr2 O7 solution at 0.05 V s−1 across the
potential range of 0 to −1.0 V is shown in Fig. 1.13. At −0.75 V, there was a major
shift in the electric current in the basal solution(Fig. 1.13a). Since protons are engaged
in redox reactions in the basal solution, this inflexion potential might be termed the
hydrogen deposition potential. Nevertheless, in 0.1 mol L−1 Na2 SO4 and 0.02 mol
L−1 K2 Cr2 O7 solution, a quickly increasingcurrent was recorded at around −0.5 V,
suggesting the startof Cr(VI) reduction on the lead electrode surface (Fig. 1.13b).
1.5 Cr(VI) Migration in Chromite Ore Processing Residue (COPR)-Soil 29
Fig. 1.13 Curve of linear scan voltammetry. Reprinted from Ref. [31], Copyright 2009, with
permission from Elsevier
Following the initial stage, the current exhibited a gradual increase, accompanied
by multiple waves. These findings indicated that the deposition process occurred in
distinct steps. The calculated potential for Cr(VI) reduction was determined to be
−0.5 V (vs. SCE). In comparison, the calculated potential for Cr(VI) reduction on
the standard hydrogen electrode (SHE) was −0.26 V, which closely approximated its
standard potential of −0.13 V. The slight disparity between the standard and calcu-
lated potentials resulted in an overpotential. This outcome confirmed that the first
peak observed in the linear scan voltammetry curve corresponded to the deposition
potential of Cr(VI) reduction.
1.5.1.2 Apparent Diffusion Coefficient of Cr(VI)
To determine the diffusion coefficient of metal ions, electrochemical methods have

been frequently employed [32, 33]. It was supposed that the diffusion of Cr(VI) is an
immediate and unstable diffusion process. As a result, Fick’s second law may be used
to charaterize Cr(VI) diffusion. Cr(VI) diffusion in slag occurs inside the fluid-filled
pores and empty spaces. The presence of other ions in the pore fluid influences Cr(VI)
diffusion. Meanwhile, the chemical and physical binding force must be dispelled by
Cr(VI) diffusion in slag. Slag is the most essential factor in Cr(VI) binding. As a
result, the diffusion coefficient of Cr(VI) became known as the apparent diffusion
coefficient.
The apparent diffusion coefficient of Cr(VI) from the original and detoxified
chromium-containing slag to the boundary surface was investigated using single
potential step chronoamperometry in this study (Fig. 1.14). According to Fig. 1.15,
The deposition potential of Cr(VI) reduction was −0.5 V. As a result, the step poten-
tial was kept under control at −0.5 in the zone of the limit current density. For
the original chromium-containing slag and detoxified, the variations in current were
measured whthin 5000 and 2500 s, respectively, (Fig. 1.16). A linear line was drawn
between ln (it 1/2 ) and t −1 (data not shown). In this equation, i defines the current
density, and t defines time. The apparent diffusion coefficient may be stated using
the slope of the above straight line and the following equation derived from Fick’s
first law and Fick’s second law [34]:
L2
D α (1.4)
4tg
where D is the apparent diffusion coefficient of Cr(VI), L is the thickness of the slag
plate (5 mm) and tgα is the slope of the straight line between ln (it1/2 ) and t−1 .
The apparent diffusion coefficient of Cr(VI) distributed from the original
chromium-containing slag was 4.40 × 10–9 m2 s−1 , as shown in Table 1.9, whereas
the comparable value for the detoxified slag treated with Achromobacter sp. CH-1
for 16 h was 2.62 × 10–8 m2 s−1 . According to the results, there was a six-times
increase in Cr(VI) apparent diffusion conffcient in the detoxified slag compared the
original slag. The increase in porosity and hydraulic permeability may be to blame for
this Cr(VI) increase. The original slag and the detoxified slag had porosities that were
63.4% and 64.1%, respectively. The original slag’s hydraulic permeability coefficient
was 8.5 × 10–5 cm s−1 ; the detoxified slag’s was 9.8 × 10–4 cm s−1 . Due to the greater
apparent diffusion coefficients of Cr(VI) in the detoxified slag, bacterial were able
to queckly submerge, which caused chromium-containing materials to dissolve and
the slag to be destroyed. As a consequence of the recurrent destruction, additional
pores formed. Cr(VI) is generally related with chromium-containing compounds
in the crystal lattices, such as CaO·Al2 O3 ·CrO3 ·12H2 O, CaCrO4 ·Ca2 SiO4 ·CaCrO4
and CaO·Al2 O3 ·Fe2 O3 ·CaCrO4 . Cr(VI) was converted to Cr(III) as detoxification
progressed, and the disruption of the crystal lattices might also contribute to the fast
diffusion of Cr(VI) in slag.
1.5.1.3 Cr(VI) Diffusion in Chromium-Containing Slag as Affected

by Cr(VI) Reduction Strain
A mixture was prepared by combining 2 g of the aforementioned original chromium-

containing slag with a total volume of 20 mL of bacterial cultures that had been grown
overnight. The mixture was then horizontally shaken at a speed of 150 rpm and a
temperature of 30 °C until no traces of Cr(VI) were detected. Microbial detoxification
increased Cr(VI) diffusion in chromium-containing slag in the ongoing study. While
the result would be negative in temrs of environmental protection, it may be used
CE
Electrochemical
WE
RE workstation
7
8
3 5 9
2 1
Computer
1
6 4
Chromium-containing
slag plate
lead sheet electrode
polymethyl methacrylate clapboard

with a square hole of 20×20×4 mm
(1. Water bath; 2. electrobath; 3. counter electrode (CE); 4. slag plate; 5. clapboard; 6. lead flake
(working electrode (WE)); 7. salt bridge; 8. reference electrode (RE))
Fig. 1.14 Set-up of potential step chronoamperometry. Reprinted from Ref. [31], Copyright 2009,
with permission from Elsevier
to effectively and quickly detoxify chromium-containing slag. The decreased water-

soluble Cr(VI) content in the leachate after the detoxification operation of chromium-
containing slag by Achromobacter sp. CH-1 revealed that Cr(VI) was efficiently
reduced rather than persisting in the ambient environment. As a result, it is possible
to infer that the detoxification of chromium-containing slag increased rather than
decreased Cr(VI) diffusion. Meanwhile, Achromobacter sp. CH-1 has the potential
for use in Cr(VI) biodetoxification in chromium-containing slag.
Fig. 1.15 The pattern of single potential step chronoamperometry of the original chromium-
containing slag. Reprinted from Ref. [31], Copyright 2009, with permission from Elsevier
Fig. 1.16 The pattern of single potential step chronoamperometry of detoxified chromium-
containing slag. Reprinted from Ref. [31], Copyright 2009, with permission from Elsevier
Table 1.9 Diffusion coefficients of Cr(VI) released from chromium-containing slag

Treatment Slope (tgαa ) Diffusion coefficient correlation p value
coefficient
(m2 s−1 ) (rb )
Raw slag −1419.5 4.40 × 10–9 0.9953 <0.01
Detoxified slag −238.1 2.62 × 10–8 0.9942 <0.01
a tgα is the slope of the straight line between ln (it1/2 ) and t−1
in the patterns of single potential step
chronoamperometry
b r is the correlation coefficient between ln (it1/2 ) and t−1
Reprinted from Ref. [31], Copyright 2009, with permission from Elsevier
1.5.2 Cr(VI) Migration in Soils
Leachate from chromium slag can lead to soil contamination, and the presence of
deposited Cr(VI) in the soil can have detrimental effects on soil ecosystems, both
in the short term and over a prolonged period [35]. More critically, it has the poten-
tial to cause considerable harm to groundwater, limiting its usage in many regions.
However, owing to the constant release of Cr(VI) from chromium slag, testing the
contamination level of the soil and groundwater. As a result, studying the Cr(VI)
transport properties in soil has both theoretical and practical implications.
1.5.2.1 Migration Characteristics of Cr(VI) in Soils
In general, a graph of C t /C 0 versus t will produce the ion concentration plot’s break-
through curve. Cl− was identified in the outflow from the bottom of the soil column
after one hour of continuous infusion of Cl− solution. Cl− in the effluent rapidly rose
after 1.5 h of incection, as seen in the black curve in Fig. 1.17, and became the curve
steep. The curve is then a straight line. At this time, the Cl− content in the effluent is
99% of that in the influent concentration. Totally, it took 5.5 h for Cl− to reach steady
state conditions. Similarly, Cr(VI) was found after 5.5 h of continuous infusion of
Cr(VI) solution. After approximately 7 h of injection, the Cr(VI) concentration grad-
ually increased, leading to a shift in the curve. By the 25th hour, the curve flattened,
indicating that the effluent Cr(VI) concentration had reached 99.5% of the influent
concentration. Compared to the breakthrough curve of the conservative tracer Cl-
in Fig. 1.17, the equilibrium time for Cr(VI) was 5 times longer than that for Cl-.
This prolonged penetration time indicated significant retardation phenomena during
Cr(VI) transport through the soil, suggesting various interactions such as adsorp-
tion, desorption, ion exchange, precipitation dissolution, oxidation, and reduction.
For instance, soil humic acids can firstly reduce Cr(VI) to Cr(III), which can subse-
quently precipitate as chromium hydroxide (Cr(OH)3 ) or iron-chromium hydroxide
((Fe,Cr)(OH)3 ), or become immobilized through sorption onto the soil. As a result,
the total flow of Cr(VI) through the soil column decreases due to the reduction and
precipitation processes [36, 37].
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"Too bad. I wonder if it'll carry people."
"Darling," drawled Arden, "don't you think you'd better catch your
rabbit first?"
"Not too bad a thought," agreed Don. "Walt, have you got any rabbit
traps out?"
"A couple. I've been tinkering a bit. I know we can disintegrate matter
through a power-tube of slight modification, and reintegrate it with
another. At the present state of the art, it is a mess."
"A nice mess," laughed Don. "Go ahead, though. We'll pitch in when
the going gets hard."
"That's where I stand now. The going is tough."
"What's the trouble?"
"Getting a perfect focus. I want it good enough so that we can scan a
polished sheet of steel—and it'll come out as slick as the original."
"Naturally. We'd better get Wes Farrell on the job."
"I wonder what by-product he'll get this time?"
"Look, Walt. Quit hoping. If you get this thing running right, it'll put
your name in history."
"After all," grinned Walt, "I've got to do something good enough to
make up for that Channing Layer."
"Kingman is still fuming over the Channing Layer. Sometimes I feel
sorry that I did it to him like that."
"Wasn't your fault, Don. You didn't hand him the thing knowing that
the Channing Layer would inhibit the transmission of energy. It
happened. We get power out of Sol—why shouldn't they? They
would, except for the Channing Layer."
"Wonder what your idea will do."
"About the Channing Layer? Maybe your spaceline competition is
not as good as it sounds."
"Well, they use the power-transmission tubes all over the face of the
Solar System. I can't see any reason why they couldn't ship stuff
from Sydney to Mojave and then space it out from there."
"What an itinerary! By Franks' matter transmitter to Mojave.
Spacecraft to Luna. More matter transmission from Luna to Phobos.
Then trans-shipped down to Lincoln Head, and by matter transmitter
to Canalopsis. Whoosh!"
"Do we have time to go into the old yarn about the guy who listened
in and got replicas?" asked Arden.
"That's a woman's mind for you," grinned Channing. "Always making
things complicated. Arden, my lovely but devious-minded woman,
let's wait until we have the spry beastie by the ears before we start to
make rabbit pie."
"It's not as simple as it sounds," warned Walt. "But it's there to worry
about."
"But later. I doubt that we can reason that angle out."
"I can," said Arden. "Can we tap the power beams?"
"Wonderful is the mind of woman," praised Don. "Positively
wonderful! Arden, you have earned your next fur coat. Here I've
been thinking of radio transmission all this time. No, Arden, when
you're set up for sheer energy transmission, it's strictly no dice. The
crimped up jobs we use for communications can be tapped—but not
the power transmission beams. If you can keep the gadget working
on that line, Walt, we're in and solid."
"I predict there'll be a battle. Are we shipping energy or
communications?"
"Let Kingman try and find a precedent for that. Brother Blackstone
himself would be stumped to make a ruling. We'll have to go to work
with the evidence as soon as we get a glimmer of the possibilities.
But I think we have a good chance. We can diddle up the focus, I'm
certain."
Arden glowered. "Go ahead—have your fun. I see another couple of
weeks of being a gadgeteer's widow." She looked at Walt Franks. "I
could stand it if the big lug only didn't call every tool, every part, and
every effect either she or baby!"
Walt grinned. "I'd try to keep you from being lonely, but I'm in this,
too, and besides, you're my friend's best wife."
"Shall we drag that around a bit? I think we could kill a couple of
hours with it sometime."
"Let it lie there and rot," snorted Channing cheerfully. "We'll pick it up
later. Come on, Walt. We've got work to do."
Mark Kingman glowered at the 'gram and swore under his breath.
He wondered whether he might be developing a persecution
complex; it seemed as though every time he turned around, Venus
Equilateral was in his hair, asking for something or other. And he was
not in any position to quibble about it. Kingman was smart enough to
carry his tray very level. Knowing that they were waiting for a chance
to prove that he had been connected with the late Hellion Murdoch
made him very cautious. There was no doubt in any mind that
Murdoch was written off the books, but whether Murdoch had made
a sufficiently large impression on the books of Terran Electric to have
the connection become evident—that worried Kingman.
So he swore at each telegram that came in, but quietly, and followed
each request to the letter. Compared to his former attitude toward
Venus Equilateral, Mark Kingman was behaving like an honor
student in a Sunday school.
Furthermore, behaving himself did not make him feel good.
He punched the buzzer, told his secretary to call in the shop
foreman, and then sat back and wondered about the 'gram.
He was still wondering when the man entered. Kingman looked up
and fixed his superintendent with a fishy glance. "Horman, can you
guess why the Venus Equilateral crowd would want two dozen
gauge blocks?"
"Sure. We use Johannson blocks all the time."
"Channing wants twenty-four blocks. All three inches on a side—
cubes. Square to within thirty seconds of angle, and each of the six
faces optically flat to one-quarter wave length of cadmium light."
"Whoosh!" said Horman. "I presume the three-inch dimension must
be within a half wave length?"
"They're quite lenient," said Kingman bitterly. "A full wave length!"
"White of them," grunted Horman. "I suppose the same thing
applies?"
"We're running over thin ice," said Kingman reflectively. "I can't afford
to play rough. We'll make up their blocks."
"I wonder what they want 'em for?"
"Something tricky, I'll bet."
"But what could you use two dozen gauge blocks for? All the same
size."
"Inspection standards?" asked Kingman.
"Not unless they're just being difficult. You don't put primary blocks
on any production line. You make secondary gauges for production
line use and keep a couple of primaries in the check room to try the
secondaries on. In fact, you usually have a whole set of gauge
blocks to build up to any desired dimension so that you don't have to
stock a half-million of different sizes."
"It's possible that they may be doing something extremely delicate?"
"Possible," said Horman slowly. "But not too probable. On the other
hand, I may be one hundred percent wrong. I don't know all the
different stuff a man can make, by far. My own experience indicates
that nothing like that would be needed. But that's just one man's
experience."
"Channing and that gang of roughneck scientists have been known
to make some fancy gadgets," said Kingman grudgingly.
"If you'll pardon my mentioning the subject," said Horman in a
scathing tone, "you'd have been far better off to tag along with 'em
instead of fighting 'em."
"I'll get 'em yet."
"What's it got you so far?"
"I'm not too bad off. I've come up from the Chief Legal Counsel of
Terran Electric to controlling the company."
"And Terran Electric has slid down from the topmost outfit in the
system to a seventh rater."
"We'll climb back. At any rate, I'm better off personally. You're better
off personally. In fact, everybody that had enough guts to stay with
us is better off."
"Yeah—I know. It sounds good on paper. But make a bum move
again, Kingman, and we'll all be in jail. You'd better forget that hatred
against Venus Equilateral and come down to earth."
"Well, I've been a good boy for them once. After all, I did point out
the error in their patent on the solar beam."
"That isn't all. Don't forget that Terran Electric's patent was at error,
too."
"Frankly, it was a minor error. It's one of those things that is easy to
get caught on. You know how it came about?"
"Nope. I accepted it just like everybody else. It took some outsider to
laugh at me and tell me why."
Kingman smiled. "It's easy to get into easy thinking. They took power
from Sirius—believe it or not—and then made some there-and-back
time measurements and came up with a figure that was about the
square of one hundred eighty-six thousand miles per second. But
you know that you can't square a velocity and come up with anything
that looks sensible. The square of a velocity must be some concept
like an expanding area."
"Or would it be two spots diverging along the sides of a right angle?"
queried Horman idly. "What was their final answer?"
"The velocity of light is a concept. It is based on the flexibility of
space—its physical constants, so to speak. Channing claims that the
sub-etheric radiation bands of what we have learned to call the driver
radiation propagates along some other medium than space itself. I
think they were trying to establish some mathematical relation—
which might be all right, but you can't establish that kind of relation
and hope to hold it. The square of C in meters comes out differently
than the square of C in miles, inches, or a little-used standard, the
light-second, in which the velocity of light is unity, or One. Follow?
Anyway, they made modulation equipment of some sort and
measured the velocity and came up with a finite figure which is
slightly less than the square of one hundred eighty-six thousand
miles per second. Their original idea was wrong. It was just
coincidence that the two figures came out that way. Anyway," smiled
Kingman, "I pointed it out to them and they quick changed their
patent letters. So, you see, I've been of some help."
"Nice going. Well, I'm going to make those gauges. It'll take us one
long time, too. Johannson Blocks aren't the easiest things in the
world to make."
"What would you make secondary standards out of?"
"We use glass gauges, mostly. They don't dinge or bend when
dropped—they go to pieces or not at all. We can't have a bent gauge
rejecting production parts, you know, and steel gauges can be bent.
Besides, you can grind glass to a half wave length of light with ease,
but polishing steel is another item entirely."
"I'm going to call Channing and ask him about glass blocks. It may
be that he might use them. Plus the fact that I may get an inkling of
the ultimate use. They have no production lines running on Venus
Equilateral, have they?"
"Nope. Not at all. They're not a manufacturing company."
"Well, I'm going to call."
Kingman's voice raced across Terra to Hawaii, went on the
communications beams of the sky-pointing reflectors, and rammed
through the Heaviside Layer to Luna. At the Lunar Station, his voice
was mingled in multiplex with a thousand others and placed on the
sub-ether beams to Venus Equilateral.
Don Channing answered the 'phone. "Yes?"
"Kingman, Dr. Channing."
Don grunted. He did not like to be addressed by title when someone
who disliked him did it. His friends did not; Kingman's use of the title
made it an insult.
"Look," said Kingman, "what do you want to use those blocks for?"
"We've got a job of checking dimensions."
"Nothing more? Do you need the metal for electrical reasons?"
"No," said Don, "what have you in mind?"
"Our tool shop is nicely equipped to grind glass gauges. We can do
that better than grinding Jo-blocks. Can you use glass ones?"
"Hang on a minute." Channing turned to Walt. "Kingman says his
outfit uses glass gauges. Any reason why we can't?"
"See no reason why not. I've heard of using glass gauges, and
they've got some good reasons, too. Tell him to go ahead."
"Kingman? How soon can we get glass ones?"
"Horman, how soon on the glass blocks?"
"Two dozen? About a week."
"We'll have your blocks on the way within four days, Channing. Four
days minimum, plus whatever wait is necessary to get 'em aboard a
spacer."
"We'll check from this end on schedules. We need the blocks, and if
the wait is too long, we'll send the Relay Girl in for 'em."
Don hung up and then said: "Glass ones might be a good idea. We
can check the transmission characteristics optically. I think we can
check more, quicker, than by running analysis on steel."
"Plus the fact that you can get the blocks back after test," grinned
Walt. "Once you tear into a steel block to check its insides, you've
lost your sample. I don't know any better way to check homogeneity
than by optical tests."
"O.K. Well, four days for glass blocks will do better than a couple of
months on steel blocks."
"Right. Now let's look up Wes and see what he's come up with."
They found Farrell in one of the blister laboratories, working on a
small edition of the power transmission tubes. He was not dressed in
spacesuit, and so they entered the blister and watched him work.
"Have a little trouble getting the focus to stay sharp through the
trace," complained Wes. "I can get focus of atomic proportions—the
circle of confusion is about the size of the atom nucleus, I mean—at
the axis of the tube. But the deflection of the cone of energy
produces aberration, which causes coma at the edges. The corners
of an area look fierce."
"I wonder if mechanical scanning wouldn't work better."
"Undoubtedly. You don't hope to send life, do you?"
"It would be nice—but no more fantastic than this thing is now.
What's your opinion?"
Wes loosened a set screw on the main tube anode and set the
anode forward a barely perceptible distance. He checked it with a
vernier rule and tightened the screw. He made other adjustments on
the works of the tube itself, and then motioned outside. They left the
blister, Wes closed the air-tight, and cracked the valve that let the air
out of the blister. He snapped the switch on the outside panel and
then leaned back in his chair while the cathode heated.
"With electrical scanning, you'll have curvature of field with this
gadget. That isn't too bad, I suppose, because the restorer will have
the same curvature. But you're going to scan three ways, which
means correction for the linear distance from the tube as well as the
other side deflections and their aberrations. Now if we could scan the
gadget mechanically, we'd have absolute flatness of field, perfect
focus, and so forth."
Walt grinned. "Thinking of television again? Look, bright fellows, how
do you move an assembly of mechanical parts in quanta of one
atomic diameter? They've been looking for that kind of a gadget for
centuries. Dr. Rowland and his gratings would turn over in their
graves with a contrivance that could rule lines one atom apart."
"On what?" asked Don.
"If it would rule one atom lines, brother, you could put a million lines
per inch on anything rulable with perfection, ease, eclat, and savoir
faire. You follow my argument? Or would you rather take up this slip
of my tongue and make something out of it?"
"O.K., fella, I see your point. How about that one, Wes?"
Wes Farrell grinned. "Looks like I'd better be getting perfect focus
with the electrical system here. I hadn't considered the other angle at
all, but it looks a lot tougher than I thought."
He squinted through a wall-mounted telescope at the set-up on the
inside of the blister. "She's hot," he remarked quietly, and then set to
checking the experiment. Fifteen minutes of checking, and making
notes, and he turned to the others with a smile. "Not too bad that
way," he said.
"What are you doing?"
"I've established a rather complex field. In order to correct the
aberrations, I've got non-linear focussing fields in the places where
they tend to correct for the off-axis aberrations. To correct for the
height-effect, I'm putting a variable corrector to control the whole
cone of energy, stretching it or shortening it according to the needs. I
think if I use a longer focal length I'll be able to get the thing running
right.
"That'll lessen the need for correction, too," he added, cracking the
blister-intake valve and letting the air hiss into the blister. He opened
the door and went inside, and began to adjust the electrodes. "You
know," he added over his shoulder, "we've got something here that
might bring a few dollars on the side. This matter-bank affair
produces clean, clear, and practically pure metal. You might be able
to sell some metal that was rated 'pure' and mean it."
"You mean absolutely, positively, guaranteed, uncontaminated,
unadulterated, perfectly chemically pure?" grinned Don.
"Compared to what 'chemically pure' really means, your selection of
adjectives is a masterpiece of understatement," laughed Walt.
"I'm about to make one more try," announced Wes. "Then I'm going
to drop this for the time being. I've got to get up to the machine shop
and see what they're doing with the rest of the thing."
"We'll take that over if you wish," said Don.
"Will you? I'll appreciate it. I sort of hate to let this thing go when I
feel that I'm near an answer."
"We'll do it," said Walt, definitely.
They left the laboratory and made their way to the elevator that
would lift them high into the relay station where the machine shop
was located. As they entered the elevator Don shook his head.
"What's the matter?"
"Well, friend Wes is on the beam again. If he feels that we're close to
the answer, I'll bet a hat that we're hanging right on the edge. Also,
that kind of work would kill me dead. He likes to stick on one thing till
the bitter end, no matter how long it takes. I couldn't do it."
"I know. About three days of this and you're wanting another job to
clear your mind. Then you could tackle that one for about three
hours and take back on the first."
"Trying to do that to Farrell would kill both him and the jobs," said
Don. "But you and I can keep two or three projects going strong. Oh,
well, Wes is worth a million."
"He's the best we've got," agreed Walt. "Just because he has a
peculiar slant on life is no sign he's not brilliant."
"It's you and I that have the cockeyed slant on life," grinned Don.
"And frankly, I'm proud of it." He swung the elevator door aside and
they walked down the corridor. "This isn't going to be much to see,
but we'll take a look."
The machine shop, to the man, was clustered around the one
cabinet under construction. They moved aside to permit the entry of
Channing and Franks.
"Hm-m-m," said Don. "Looks like a refrigerator and incinerator
combined."
It did. It stood five feet tall, three feet square, and was sealed in front
by a heavy door. There was a place intended for the tube that Farrell
was tinkering in the blister, and the lines to supply the power were
coiled behind the cabinet.
"Partly wired?" asked Don.
"Just the power circuits," answered Warren, "We'll have this finished
in a couple of days now. The other one is completed except for Wes
Farrell's section."
Channing nodded, and said: "Keep it going." He turned to Walt and
after the passage of a knowing glance the pair left. "Walt, this is
getting on my nerves. I want to go down to Joe's and drink myself
into a stupor which will last until they get something cogent to work
on."
"I'm with you, but what will Arden say?"
"I'm going to get Arden. Self-protection. She'd cut my feet off at the
knees if I went off on a tear without her."
"I have gathered that," grinned Walt. "You're afraid of her."
"Yeah," drawled Don. "After all—she's the cook."
"I'm waiting."
"Waiting for what?"
"If and when. If you two go on as you have for another year without
one of you turning up with a black eye, I may be tempted to go forth
and track me down a babe of my own."
The cabinet stood in the north end of Venus Equilateral but it was not
alone. It may even be the record for all times; certainly no other
cabinet three by three by five ever had twenty-seven men all
standing in a circle awaiting developments. The cabinet at the south
end of Venus Equilateral was no less popular, though the number of
watchers was less by one. Here, then, were winner and runner-up of
inanimate popularity for the ages. The communicator system set in
the walls of the two rooms carried sounds from the north room to the
south, and those sounds in the south room could be heard in the
north room. Channing grinned boyishly at Arden.
"This, my love, is a device which may make it quite possible for me
to send you back to mother."
Arden smiled serenely. "No dice," she said. "Mother went back to
grandmother last week. When is this thing going to cook?"
"Directly."
"What are we waiting for?"
"Walt."
"I'm ready," came Walt's voice through the speaker.
"About time, slowpoke."
"Really, it was not his fault," objected Wes. "I wanted to check the
scanner-synchronization."
"He's precious," chortled Arden in Don's ear. "He wouldn't think of
letting Walt, the big bum, take the blame for anything that wasn't
Walt's fault."
"That's a good line," grinned Don. "Walt's faults. After we set this
thing aside as a finished project, we'll set that 'Walt's Faults' to
music. Ready, Walt?"
"Right. I am now slipping the block into the cabinet. The door is
closed. Have you got the preliminary synchronizing signal in tick?"
Channing called: "Wait a minute, I'm lagging a whole cycle."
"Cut your synchronization input and let the thing catch up."
"O.K. Um-m-m—Now, Walt."
"Has anyone any last words to say?" asked Walt.
No answer.
"Then since no one has any objections at this time, I assume that
everything may be run off. Silence, people, we are going on the air!"
"There was a very faint odor of corn in Walt's last remark," said Don.
"I think the corn was on his breath," said Arden.
"Done!" announced Walt. "Don, crack the door so that the rest of us
can laugh if it don't work."
Channing swaggered over and opened the door. He reached inside
and took out the—object.
He held it up.
"Walt," said he, "what are you giving me?"
"Huh?"
"I presume that you shipped me one of the cubes?"
"Right."
"Well, what we got at this end would positively scare the right arm off
of a surrealist sculptor."
"Hang onto it. I'll be right up."
"Hang on to it?" laughed Don. "I'm afraid to touch it."
It was three miles from one end of Venus Equilateral to the other and
Walt made it in six minutes from the time he stepped into the little
runway car to the time he came into the north-end laboratory and
looked over Channing's shoulder at the—thing—that stood on the
table.
"Um," he said. "Sort of distorted, isn't it?"
"Quite," said Don. "This is glass. It was once a three-inch cube of
precision, polish, and beauty. It is now a combination of a circular
stairway with round corners and a sort of accordion pleat. Hell's
bells!"
"Be not discouraged," gurgled Walt. "No matter what it looks like, we
did transmit matter."
Arden tapped Don on the shoulder. "May I say it now?"
"You do—!"
"Then I won't say it doesn't matter."
"I'm ignoring your crude remark. Walt, we did accomplish something.
It wasn't too good. Now let's figure out why this thing seems to have
been run over with a fourth dimensional caterpillar-tread truck."
"Well, I can hazard a guess. The synchronizing circuits were not
clamped perfectly. That gives the accordion-pleat effect. The starting
of the trace was not made at the same place each time due to
slippage. We'll have to beef up the synchronization impulse. The
circular staircase effect was probably due to phase distortion."
"Could be," said Don. "That means we have to beef up the
transmission band so it'll carry a higher frequency."
"A lower impedance with corrective elements?"
"Might work. Those will have to be matched closely. We're not
transmitting on a line, you know. It's sheer transmission-tube stuff
from here to there. Well, gang, we've had our fun. Now let's widen
the transmission band and beef up the sync. Then we'll try number
two."
Number two was tried the following afternoon. Again, everybody
stood around and watched over Don's shoulder as he removed the
cube from the cabinet.
"Nice," he said, doing a little war dance.
Franks came in puffing, took the cube from Don's fingers and
inspected it. "Not too bad," he said.
"Perfect."
"Not by a jug full. The index of refraction is higher at this edge than
at the other. See?" Walt held the cube before a newspaper and they
squinted through the glass block.
"Seems to be. Now why?"
"Second harmonic distortion, if present, would tend to thin out one
side and thicken up the other side. A sine-wave transmission would
result in even thickness, but if second harmonic distortion is present,
the broad loops at the top create a condition where the average from
zero to top is higher than the average from zero to the other peak.
Follow?"
"That would indicate that the distortion was coming in at this end. If
both were even, they would cancel."
"Right. Your scanning at one end is regular—at the other end it is
irregular, resulting in non-homogeneity."
"The corners aren't sharp," objected Arden.
"That's an easy one. The wave-front isn't sharp either. Instead of
clipping sharply at the end of the trace, the signal tapers off. That
means higher frequency response is needed."
"We need a term. Audio for sonics; radio for electronics; video for
television signals—"
"Mateo," said Arden.
"Um—sounds sort of silly," grinned Walt.
"That's because it's strange. Mateo it is," said Don. "Our mateo
amplifier needs higher frequency response in order to follow the
square wave-front. Might put a clipper circuit in there, too."
"I think a clipper and a sharpener will do more than the higher
frequency," said Farrell. He was plying a vernier caliper, and he
added: "I'm certain of that second harmonic stuff now. The
dimension is cockeyed on this side. Tell you what, Don. I'm going to
have the index of refraction measured within an inch of its life. Then
we'll check the thing and apply some high-powered math and see if
we can come up with the percentage of distortion."
"Go ahead. Meanwhile, we'll apply the harmonic analyzer to this
thing and see what we find. If we square up the edges and make her
homogeneous, we'll be in business."
"The space lines will hate you to pieces," said Arden.
"Nope. I doubt that we could send anything very large. It might be
more bother to run a huge job than the money it costs to send it by
spacer. But we have a market for small stuff that is hard to handle in
space because of its size."
"I see no reason why Keg Johnson wouldn't go for a hunk of it,"
offered Wes Farrell.
"I've mentioned it to Keg; the last time I was in Canalopsis," said
Walt. "He wasn't too worried—provided he could buy a hunk."
"Interplanet is pretty progressive," mused Don. "There'll be no
reason why we can't make some real handy loose change out of
this. Well, let's try it again tomorrow."
"O.K. Let's break this up. Will we need any more blocks from Terran
Electric?"
It was less than a month later that a newspaper reporter caught the
advance patent notice and swallowed hard. He did a double take,
shook his head, and then read the names on the patent application
and decided that someone was not fooling. He took leave and made
the run to Venus Equilateral to interview the officials. He returned not
only with a story, but with a sample glass block that he had seen run
through the machine.
The news pushed one hatchet murder, a bank robbery, a football
upset, and three political harangues all the way back to page seven.
In terms more glowing than scientifically accurate, the matter
transmitter screamed in three-inch headlines, trailed down across
the page in smaller type, and was embellished with pictures,
diagrams, and a description of the apparatus. The latter had been
furnished by Walt Franks, and had been rewritten by the reporter
because Walt's description was too dry.
The following morning Venus Equilateral had nine rush telegrams.
Three were from cranks who wanted to go to Sirius and set up a
restorer there to take people; four were from superstitious nuts who
called Channing's attention to the fact that he was overstepping the
rights given to him by his Creator; one was from a gentleman who
had a number of ideas, all of which were based on the idea of getting
something for nothing and none of which were legal; and the last one
was a rather curt note from Terran Electric, pointing out that this
device came under the realm of the power-transmission tube and its
developments and that they wanted a legal discussion.
"Have they got a leg to stand on?" asked Walt.
"I doubt it."
"Then to the devil with them," snapped Walt. "We'll tell 'em to go
jump in the lake."
"Nope. We're going to Terra and slip them the slug. If we clip them
now, they'll have nothing to go on. If we wait till they get started,
they'll have a fighting chance. Besides, I think that all they want to do
is to have the facts brought out. Are we or are we not under the
terms of that contract?"
"Are we?"
"We're as safe as Sol. And I know it. That contract pertained to the
use of the solar beam only, plus certain other concessions pertaining
to the use of the power-transmission tubes and other basic effects as
utilized in communications."
"Why can't we tell them that?"
"It's got to be told in a court of law," said Don. "Kingman's mind runs
to legal procedure like Blackstone."
"We'll take the gadgets?"
"Right. What are you using for power?"
"What other? Solar beams, of course. We don't bother about running
stuff around any more. We plug it in the 115-volt line, it energizes the
little fellows just long enough to make them self-sustaining from Sol.
All the 115-volt line does is to act as a starting circuit."
"You and Farrell had better dream up a couple of power supplies
then. We can't use the solar beam on Terra."
"I know. We're a little ahead of you on that. Wes and one of the
Thomas boys cooked up a beam-transducer power supply that will
get its juice from any standard 115-volt, sixty-cycle line socket.
We've got two of them—and they run the things easily."
"Good. I'll 'gram Terran Electric and let 'em know we're on our way
for the legal tangle. You load up the Relay Girl and we'll be on our
way. Stock up the usual supply of bars, blocks, gadgets, and traps.
Might include a bar magnet. When we show that it is still
magnetized, we'll gain a point for sure."
"If we take a magnet, we'd better take the fluxmeter to show that the
magnetic field hasn't dropped."
"Right. Take anything you can think of for a good show. We can
knock them dead!"
Mark Kingman put his assistant legal counsel on the witness stand.
"You will state the intent of the contract signed between Terran
Electric and Venus Equilateral."
"The contract holds the following intent: 'Use of the power-
transmission tubes for communications purposes shall fall under the
jurisdiction of Venus Equilateral. For power transmission, the tubes
and associated equipment shall be under the control of Terran
Electric. In the matter of the solar beam tubes, the contract is as
follows: Venus Equilateral holds the control of the solar beam in
space, on man-made bodies in space, and upon those natural
bodies in space where Venus Equilateral requires the solar power to
maintain subsidiary relay stations.'"
"Please clarify the latter," said Kingman. "Unless it is your intent to
imply that Terra, Mars, and Mercury fall under the classification of
'places where Venus Equilateral requires power.'"
"Their control on natural celestial objects extends only to their own
installations and requirements. Basically, aside from their own power
requirements, Venus Equilateral is not authorized to sell power. In
short, the contract implies that the use of the sub-etheric phenomena
is divided so that Venus Equilateral may use this region for
communications, while Terran Electric uses the sub-ether for power.
In space, however, Venus Equilateral holds the rights to the power
beam."
Frank Tinken, head legal man of Venus Equilateral, turned to Don
and said: "We should have this in a technical court."
Don turned his attention from the long discussion of the contract and
asked: "Why not change?"
"Judges hate people who ask for changes of court. It is bad for the
requestee—and is only done when the judge's disinterest is open to
question—and also when the suspicion of dislike is less dangerous
than the judge himself."
"Well, this should be in a technical court."
"Want to chance it?"
"I think so. This is more than likely to turn up with differential
equations, physics experts, and perhaps a demonstration of atom
smashing."
Kingman finished his examination and turned away. The judge
nodded sourly at Tinken. "Cross-examination?"
Tinken faced the witness, nodded, and then faced the court.
"The witness' statements regarding the contract are true. However,
Judge Hamilton, I will attempt to show that this case is highly
technical in nature and as such falls under the jurisdiction of the
Technical Court. May I proceed?"
"Counsel for the plaintiff assures me that this is not truly a technical
case," snapped Hamilton. "However, if you can definitely prove that
the case in point hinges on purely technical matters, what you say
may be instrumental in having this hearing changed. Proceed."
"Thank you." Tinken turned to the witness. "Exactly what is the point
in question?"
"The point in question," said the witness, "is whether or not the
matter transmitter falls under Terran Electric's contract or Venus
Equilateral's contract."
"Isn't the question really a matter of whether the basic effect is
technically communication or power transmission?"
"Objection!" barked Kingman. "The counsel is leading the witness."
"Objection permitted—strike the question from the record."
"I was merely trying to bring out the technical aspect of the case,"
explained Tinken, "I'll rephrase the question. Is it not true that the
contract between Terran Electric and Venus Equilateral is based
upon a certain technology?"
"Certainly."
"Then if the case is based upon technical aspects—"
"Objection!" marked Kingman. "More than half of all manufacturing
contracts are based upon technical background. I quote the case of
Hines versus Ingall in which the subject matter was the development
of a new type of calculating machine. This case was heard in a legal
court and disposed of in the same."
"Objection permitted."
"No further examination," said Tinken. He sat down and turned to
Don, "We're in trouble. Hamilton does not like us."
"Well, we still have the whip hand."
"Right, but before we get done we'll have trouble with Hamilton."
"Before we get done, Kingman will have trouble with us," said Don.

Remediation of Chromium Contaminated Soil Theory and Practice 1st Edition Weichun Yang Liyuan Chai Zhihui Yang Feiping Zhao Qi Liao Mengying Si

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Remediation of Chromium Contaminated Soil Theory and Practice 1st Edition Weichun Yang Liyuan Chai Zhihui Yang Feiping Zhao Qi Liao Mengying Si

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Remediation of Chromium

Contaminated Soil Theory and Practice

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Weichun Yang · Liyuan Chai ·

Zhihui Yang Feiping Zhao

ISSN 1863-5520 ISSN 1863-5539 (electronic)

Changsha, China Weichun Yang

1 Contamination Characteristics of Soils and Biological

2 Mechanisms of Cr(VI) Reduction by Microorganisms . . . . . . . . . . . . . 41

3 Microbial Remediation of Chromium-Polluted Soil . . . . . . . . . . . . . . . . 133

4.2.3 In Situ Synthesized Fe-Cu Bimetal During Cr(VI)

5.4 Chemical-Microwave Combined Remediation of Strongly

1.1 Sources of Soil Chromium

1.1.1 Chromium Pollution from the Chromium Salt Industry

The production of chromium salts in China has experienced a history of 40 years,

Table 1.1 Phase composition of chromium slag

Fig. 1.1 X-ray diffraction analysis of chromium slag

1.1.2 Chromium Pollution in the Electroplating Industry

With the advancements in mechanical manufacturing, chromium plating has been

layer. Conversely, excessive catalyst levels lead to inadequate coverage, diminished

1.1.3 Chromium Pollution in the Tanning Industry

1.1.4 Chromium Pollution from Other Industries

In addition to chromium salt production, the electroplating industry and industrial

1.2 Characteristics of Chromium Pollution in Soil

1.2.1 Chromium Concentrations in Chromium Pollution

1.2.1.1 The Total Cr Concentrations in Topsoils Contaminated

Table 1.2 Total Cr and water-soluble Cr in topsoil (mg/kg)

significant detrimental impact of chromium released from the ferroalloying factory

1.2.1.2 Water-Soluble Cr Concentrations in Topsoils Contaminated

1.2.2 Vertical Distributions of Total Cr and Water-Soluble

1.2.2.1 The Distributions of Total Cr in the Soil Profiles

1.2.2.2 The Distributions of Water Soluble Cr(VI) Content in Soil

1.2.3 Chromium Fractions in the Contaminated Soils

The concentration of various chromium fractions in soils collected from different

Table 1.3 Chromium fractions in soil profiles (mg kg−1 )

Table 1.3 (continued)

1.3 Microbial Communities in Chromium-Contaminated

1.3.1 Bacterial Structural Diversity in the Contaminated Soils

aMean value ± standard deviation

Fig. 1.6 a DGGE banding

1.3.2 Isolation and Identification of Hexavalent

A total of twenty-two bacterial strains resistant to hexavalent chromium were

1.3.3 Bacterial Genetic Diversity on the Basis

1.3.4 Hexavalent Chromium Reduction by Cr(VI)-Reducing

In the hexavalent chromium reduction test conducted at an initial dosage of

Table 1.5 (continued)

1.4 Adsorption of Cr(VI) on Soils

1.4.1 Adsorption Kinetics of Cr(VI)

1.4.2 Adsorption Thermodynamics of Cr(VI)

The calculation of thermodynamic parameters, including the change in standard

following equations [25]: