Recent Advances in Trace Elements E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1301

Veröffentlichungsjahr: 2018

Beschreibung

Comprehensive and multidisciplinary presentation of the current trends in trace elements for human, animals, plants, and the environment

This reference provides the latest research into the presence, characterization, and applications of trace elements and their role in humans, animals, and plants as well as their use in developing novel, functional feeds, foods, and fertilizers. It takes an interdisciplinary approach to the subject, describing the biological and industrial applications of trace elements. It covers various topics, such as the occurrence, role, and monitoring of trace elements and their characterization, as well as applications from the preliminary research to laboratory trials.

Recent Advances in Trace Elements focuses on the introduction and prospects of trace elements; tackles environmental aspects such as sources of emission, methods of monitoring, and treatment/remediation processes; goes over the biological role of trace elements in plants, animals, and human organisms; and discusses the relevance of biomedical applications and commercialization.

• A compendium of recent knowledge in interdisciplinary trace element research
• Uniquely covers production and characterization of trace elements, as well as the industrial and biomedical aspects of their use
• Paves the way for the development of innovative products in diverse fields, including pharmaceuticals, food, environment, and materials science
• Edited by well-known experts in the field of trace elements with contributions from international specialists from a wide range of areas

Unique in presenting comprehensive and multidisciplinary information of the key aspects of trace elements research in a digestible form, this book is essential reading for the novice and expert in the fields of environmental science, analytical chemistry, biochemistry, materials science, pharmaceutical science, nutraceutical, and pharmaceutical sciences. It is also valuable for companies that implement new products incorporating trace elements to the market.

Leseprobe

Table of Contents

Cover

Title Page

List of Contributors

1 Introduction

1.1 Introduction

1.2 Definition of Trace Elements (TEs)

1.3 Sources of Trace Elements for Humans

1.4 Analytical methods

1.5 Toxicity

1.6 Trace Elements in Agriculture

1.7 Environmental Aspects

1.8 Biomonitoring of Trace Metals in Surface Water

1.9 Conclusions

References

2 Historical Aspects

2.1 Introduction

2.2 Definitions of Trace Elements According to the Branch of Science

2.3 The Role of Analytical Methods in the Research on Trace Elements

2.4 The History of Research on Trace Elements

2.5 Conclusions

References

3 Modern Analytical Methods of Speciation and Determination of Trace Elements in Inorganic, Organic, and Biological Samples

Abbreviations

3.1 Overview of Selected Aspects of Modern Toxicology of Elements

3.2 Methodologies and Strategies of Sample Preparation in Toxicological Analyses of Elements

3.3 Comprehensive Review of Classical Analytical Techniques Applied in Current Studies Related to Determination and (Bio)Imaging/Mapping of Elements

3.4 Separation, Hyphenated, and Special Analytical Techniques in Current Studies Related to the Determination of Elements

3.6 Acknowledgments

References

4 Trace Elements in the Environment – Law, Regulations, Monitoring and Biomonitoring Methods

4.1 When New Meets Old – The Concept of Monitoring as a Way of Understanding the Information from Ecosystems

4.2 An Overview of Basic Terms Related to Bioindication – Classification Methods for Organisms and Communities

4.3 State of the Art in the Analysis of Plant Material for Monitoring Purposes – Possibilities and Difficulties

4.4 The Bioavailability Concept as a Key for Fully Understanding and Assessing Potential Risk

4.5 Hair Mineral Analysis – Telling History with Hair

4.6 Occupational Exposure to Metals – Monitoring at a Workplace

4.7 How the Law can Help in the Protection of the Environment and Human Health – European Union

4.8 Minamata Convention on Mercury – A Global Risk Assessment Tool?

References

5 Problems of Trace Elements in Water and Wastewater Treatment

5.1 Drinking Water

5.2 Wastewater

5.3 Water Treatment

References

6 Trace Elements in Agricultural and Industrial Wastes

6.1 Introduction

6.2 Trace Elements in Agricultural Wastes

6.3 Industrial Production

6.4 Conclusions

Acknowledgments

References

7 Trace Elements in Aquatic Environments

7.1 Introduction

7.2 Sources of Trace Elements

7.3 Distributions of Trace Elements

7.4 Conclusions

References

8 Trace Metals in Soils

8.1 Introduction

8.2 Analytical Methods for Monitoring Trace Metals in Soils

8.3 Assessing Soil Contamination

8.4 Conclusions

References

9 The Role of Trace Elements in Living Organisms

9.1 Introduction

9.2 Iron

9.3 Zinc

9.4 Copper

9.5 Manganese

9.6 Cobalt

9.7 Molybdenum

9.8 Vanadium

9.9 Nickel

9.10 Selenium

9.11 Iodine

9.12 Boron

9.13 Silicon

9.14 Chromium

9.15 Fluorine

9.16 Aluminum

9.17 Cadmium

9.18 Mercury

9.19 Lead

9.20 Arsenic

9.21 Conclusions

References

10 Fluorine and Silicon as Essential and Toxic Trace Elements

10.1 Introduction

10.2 Fluorine

10.3 Silicon

10.4 Conclusions

References

11 Biological Functions of Cadmium, Nickel, Vanadium, and Tungsten

11.1 Introduction

11.2 Cadmium

11.3 Nickel

11.4 Vanadium

11.5 Tungsten

11.6 Conclusions

References

12 Biosorption of Trace Elements

12.1 Introduction

12.2 Cobalt Biosorption

12.3 Copper Biosorption

12.4 Iron Biosorption

12.5 Manganese Biosorption

12.6 Nickel Biosorption

12.7 Vanadium Biosorption

12.8 Conclusions

References

13 Bioaccumulation and Biomagnification of Trace Elements in the Environment

13.1 Introduction – How to Address Environmental Issues in One Shot

13.2 A Journey of a Thousand Miles Begins with a Single Step: Basic Concepts Relating to Bioconcentration and Biomagnification Issues

13.3 A History of Food Web Research: Godfathers of Food Web Ecology

13.4 We are what we Eat: a General Model of Food Web Structure

13.5 Emission of Pollutants to the Environment: Origin of Trace Elements in the Environment

13.6 Bioaccumulation and Biomagnification of Trace Elements in the Terrestrial Environment

13.7 Bioaccumulation and Biomagnification of Trace Elements in the Marine Environment

13.8 Mercury Accumulation in Food Webs

References

14 Hydrometallurgy and Bio‐crystallization of Metals by Microorganisms

14.1 Introduction

14.2 Bacteria in Bioleaching

14.3 The Physicochemical Base of Bioleaching

14.4 Bioleaching Kinetics

14.5 Bioleaching Mechanisms

14.6 Bioleaching of Individual Minerals

14.7 Engineering Aspects of the Bioleaching Process

14.8 Modeling of Heap Bioleaching

14.9 Biopretreatment of Refractory Gold Ores

14.10 Reductive Dissolution Minerals

14.11 Bioprecipitation and Biomineralization

14.12 Conclusions

References

15 Trace Elements as Fertilizer Micronutrients

15.1 Introduction

15.2 Fertilizers as a Source of Trace Elements – The Positive and Negative Aspects

15.3 Effect of Trace Elements on Plant Growth and Development

15.4 Forms of Trace Elements

15.5 Conclusions

Acknowledgments

References

16 Trace Elements in Animal Nutrition

16.1 Introduction

16.2 Chromium

16.3 Cobalt

16.4 Copper

16.5 Iodine

16.6 Iron

16.7 Manganese

16.8 Molybdenum

16.9 Selenium

16.10 Zinc

16.11 Conclusions

Acknowledgments

References

17 Trace Elements in Human Nutrition

17.1 Iodine (I)

17.2 Selenium (Se)

17.3 Fluorine (F)

17.4 Molybdenum (Mo)

17.5 Iron [Fe]

17.6 Copper (Cu)

17.7 Manganese (Mn)

17.8 Zinc (Zn)

References

18 Trace Elements in Human Health

18.1 Introduction

18.2 Boron (B)

18.3 Cobalt (Co)

18.4 Chromium (Cr)

18.5 Copper (Cu)

18.6 Fluorine (F)

18.7 Iodine (I)

18.8 Iron (Fe)

18.9 Manganese (Mn)

18.10 Molybdenum (Mo)

18.11 Selenium (Se)

18.12 Zinc (Zn)

18.13 Conclusions

References

19

Spirulina

as a Raw Material for Products Containing Trace Elements

19.1 Introduction

19.2

Spirulina

Biomass as a Source of Trace Elements

19.3

Spirulina

as a Source of Zinc

19.4

Spirulina

as a Source of Iron

19.5

Spirulina

as a Source of Chromium

19.6

Spirulina

as a Source of Copper

19.7

Spirulina

as a Source of Selenium

19.8 Conclusions

References

20 Dietary Food and Feed Supplements with Trace Elements

20.1 Introduction

20.2 The Need for Trace Element Supplementation in Humans and Animals

20.3 Specific Roles of Trace Elements in Antioxidant Defenses

20.4 Feed Supplements

20.5 Human Side of Trace Mineral Supplementation

20.6 From Trace Minerals to Functional Food – the Case for Selenium

20.7 Conclusions

Acknowledgements

21 Biofortification of Food with Trace Elements

21.1 Introduction

21.2 Biofortification of Plant Foodstuff

21.3 Cereals

21.4 Biofortification of Animal Foodstuffs

21.5 Conclusions

22 Biomarkers of Trace Element Status

22.1 Introduction

22.2 Biomarkers

22.3 Human Biomonitoring

22.4 Exposure to Trace Elements

22.5 Matrices

22.6 Interpretation of Biomarker‐based Results

22.7 Conclusions

References

23 Human Exposure to Trace Elements from Dental Biomaterials

23.1 Introduction

23.2 Biocompatibility

23.3 Definition of Biomaterials

23.4 Regulations and Standards for Dental Biomaterials

23.5 Types of Biomaterials Used in Dentistry

23.6 The Oral Cavity as an Environment for Metallic Biomaterials

23.7 Release of Trace Metals from Dental Biomaterials: In Vitro and In Vivo Studies

23.8 Conclusions

References

24 Industrial Use of Trace Elements and their Impact on the Workplace and the Environment

24.1 Introduction

24.2 Health Risks Associated with Handling Fertilizers in the Workplace

24.3 Trace Elements in Inorganic Fertilizers

24.4 Trace Elements in other Industrial Activities

24.5 Effects of Heavy Metals on Human Health

24.6 Conclusions

25 Speciation of Trace Elements and its Importance in Environmental and Biomedical Sciences

25.1 The Need for Speciation Analysis – Do We Know Enough?

25.2 Speciation Analysis Development – How Far We Have Come?

25.3 Defining Undefined – Basic Terms Related to Speciation

25.4 Speciation as the Analytical Challenge – Problems to be Solved

25.5 Sequential Fractionation – an Introduction to Elemental Speciation Analysis

25.6 Hyphenated Techniques in Speciation Analysis – How Far We Can Reach?

25.7 Analytical Relevance of Trace Element Speciation in Environmental and Biomedical Sciences – Speciation of As, Se, Cr, Hg, and Sb

References

26 Trace Elements – A Threat or Benefit?

26.1 Introduction

26.2 Trace Elements as Plant Micronutrients

26.3 Trace Elements as Toxic Elements to Plants

26.4 Trace Elements as Micronutrients in Humans and Animals

26.5 Trace Elements as Toxic Elements to Humans and Animals

26.6 Beneficial and Unfavorable Roles of Trace Elements in the Environment

26.7 Trace Elements as Pharmaceuticals

26.8 Conclusions

Index

End User License Agreement

List of Tables

Chapter 01

Table 1.1 Trace elements and their toxicity [5, 13].

Chapter 03

Table 3.1 Summary of modern analyses of trace elements.

Chapter 04

Table 4.1 Emission limits of pollutants into air [82, 84], chemical parameters of drinking water [85], derived concentrations for radioactivity in water intended for human consumption [87], environmental quality standards for priority substances and some other pollutants for surface waters [89].

Table 4.2 Indicative occupational exposure limit values for heavy metals, trace elements, and their compounds at workplaces [103–105].

Chapter 05

Table 5.1 A comparison of limit values in potable water.

Table 5.2 Anthropogenic sources of trace elements in water and wastewater.

Chapter 06

Table 6.1 Agricultural wastes rich in trace elements.

Table 6.2 Industrial wastes rich in trace elements.

Chapter 07

Table 7.1 General information concerning distribution, residence time, and average content of trace elements in water [16].

Table 7.2 Average concentrations of trace elements in water bodies [19].

Table 7.3 Average concentrations of trace elements in the Indian Ocean [20].

Table 7.4 Average concentrations of trace elements in the Atlantic and Pacific Oceans [21].

Table 7.5 Average concentrations of trace elements in the Bay of Bengal [22].

Table 7.6 Average concentrations of trace elements in the Yellow Sea, Middle Red Sea, and Gulf of Aqaba [23, 24].

Table 7.7 Average concentrations of trace elements in Lake Michigan (USA), Lake Villarrica (Chile), Lake Caviahue (Argentina), and Rapel Reservoir (Chile) and in specific Eastern European regional lakes [15, 19, 25].

Table 7.8 Average concentrations of trace elements in selected Western European rivers [19, 25–27].

Table 7.9 Trace element concentrations in in Central European wellsprings, the Amazon, Yukon, and Yellow rivers, and mean concentrations of elements across all rivers in the world [25–27].

Table 7.10 Average concentrations of trace elements in the Tarim River, China [25–27].

Chapter 08

Table 8.1 Total digestion for trace metals in soil.

Table 8.2 Single extraction methods for trace metals in soil.

Table 8.3 Various sequential extraction procedures used on different environmental samples for speciation of heavy metals.

Chapter 12

Table 12.1 Examples of biosorption of trace elements using different types of biological sorbents.

Chapter 14

Table 14.1 Sulfide mineral‐oxidizing bacteria and archaea [16–18].

Chapter 17

Table 17.1 Recommended dietary allowances (RDA) of iodine [4–6].

Table 17.2 Iodine content in selected foods [10, 11, 19].

Table 17.3 Iodine content in selected foods (µg/100 g food product) [8].

Table 17.4 Recommendations of selenium dietary intake [4].

Table 17.5 Upper tolerable intake levels (UL) of selenium recommended by the Scientific Committee on Food in the European Union (SCF); Food and Nutrition Board, Institute of Medicine (FNB IM USA); Expert Group on Vitamins and Minerals (EVM) UK [26, 27].

Table 17.6 Food sources of selenium [4, 41, 42].

Table 17.7 Upper tolerable intake levels (UL) of fluoride recommended by the Scientific Committee on Food in the European Union (SCF EU) and the Food and Nutrition Board (FNB), Institute of Medicine (IM) USA (FNB IM USA) [4, 45].

Table 17.8 Recommendations of fluoride dietary intake by the Food and Nutrition Board at the Institute of Medicine, National Health and Medical Research Council, and Institute of Food and Nutrition (IFN) (Poland) [4, 44].

Table 17.9 Content of fluorine in food products from the United States Department of Agriculture (USDA) database [56].

Table 17.10 Content of fluoride cations (F

−

) in natural mineral water, spring water, table water, and treatment water in Poland (mg/l) [8].

Table 17.11 Recommended Dietary Allowance (RDA) and Estimated Average Requirement (EAR) of molybdenum for children and adults [57, 61, 62].

Table 17.12 The average content of molybdenum in food products [57, 66, 72].

Table 17.13 Recommended Dietary Allowances (RDA) of iron according to the National Food and Nutrition Institute, Poland (IZZ) [4].

Table 17.14 Daily requirement for iron in the diet according to the World Health Organization (WHO) [74].

Table 17.15 The iron content of animal foods [78].

Table 17.16 The iron content of plant foods [78].

Table 17.17 Recommended Dietary Allowances of copper according to the National Food and Nutrition Institute, Poland (IZZ) and the World Health Organization (WHO) [4, 80].

Table 17.18 The copper content in selected food products [78].

Table 17.19 Adequate Intake (AI) of manganese according to the Food and Nutrition Board of the National Academy of Sciences [80].

Table 17.20 Manganese content in selected foods [78].

Table 17.21 Recommended Dietary Allowances of zinc according to the National Food and Nutrition Institute (IZZ) [4].

Table 17.22 Food sources of zinc [78].

Chapter 18

Table 18.1 Symptoms of Menkes’ disease and Wilson’s disease [23–25].

Table 18.2 A summary of major iodine deficiency and overload symptoms [36].

Table 18.3 A summary of the major symptoms of iron (Fe) imbalance [48].

Table 18.4 A summary of possible outcomes of deficiency and overexposure to zinc [80, 81].

Chapter 19

Table 19.1 The content of mineral elements in the composition of

Spirulina

(

Arthrospira platensis

) biomass of different origins.

Chapter 20

Table 20.1 Selenoprotein functions in avian species.

Table 20.2 Zinc‐associated proteins involved in antioxidant defenses (adapted from [14]).

Table 20.3 Copper‐containing enzymes in animals and humans (adapted from [2]).

Table 20.4 Some characteristics of food choice for Selenium (Se)‐enrichment (adapted from [12]).

Chapter 22

Table 22.1 Classes of biomarkers [6, 16].

Chapter 23

Table 23.1 Chemical composition of chosen alloys used in dentistry.

Chapter 24

Table 24.1 Trace elements in selected inorganic fertilizers and limes.

Table 24.2 Comparison of trace metal concentrations (ppm) in industrial areas reported worldwide.

Chapter 25

Table 25.1 A review of different methods proposed for sequential extraction in solid matrices (adapted from [60]).

Table 25.2 A list of the most commonly occurring selenium forms found in environmental and biological systems [82, 87, 89].

Chapter 26

Table 26.1 Biological role and deficiency effect of Cu, Fe, and Zn in animals and humans.

Table 26.2 Toxic properties of Fe, Zn, and Cu both with maximum tolerable levels (A); Toxic properties of Mo, Se, and F both with LD

50

and maximum tolerable levels; (B) Beneficial properties of Al, As, Cd, Pb, and Hg both with LD

50

and maximum tolerable levels (C).

List of Illustrations

Chapter 03

Figure 3.1 Schema of laser ablation inductively coupled plasma mass spectrometry LA‐ICP‐MS.

Figure 3.2 Scheme of an apparatus for capillary electrophoresis.

Figure 3.3 Scheme of separation by CZE and CITP techniques.

Figure 3.4 Cross section of SPLITT channel; left picture: CS mode, right picture FFD mode.

Figure 3.5 Schematic presentation of online coupling SPLITT‐FAAS/ICP.

Figure 3.6 Modern analytical techniques in trace elements analysis.

Chapter 07

Figure 7.1 Main distributions profiles of trace elements in water environment: A – conservative, B – scavenged, C ‐ nutrient

Chapter 09

Figure 9.1 MoCo, a molybdopterin cofactor.

Figure 9.2 Lewisite and British Anti‐Lewisite (BAL; 2,3 dimercaptopropanol).

Chapter 11

Figure 11.1 The most commonly known Ni‐dependent metalloenzymes. (Enzyme (active site): UR, urease (high‐spin Ni(II) dimer); HG, hydrogenase (center); SOD, superoxide dismutase (4–5 coordinate Ni site); LarA, lactate racemase (5 coordinate Ni site); Glx I, glyoxolase I (6‐coordinate Ni site), CODH, CO dehydrogenase (cluster); ACS, acetyl‐CoA synthase (cluster); MCR, methyl‐CoM reductase (Ni tetrapyrrole); ARD, acireductone dioxygenase (6‐coordinate Ni site). Other abbreviations: CA, carbonic acid; LA, lactic acid; LA

−

, lactate; MGO, methylglyoxal; AR, acireductone (1,2‐dihydroxy‐3‐oxo‐5‐(methylthio)pent‐1‐ene); MMP, methylthiopropionate [18–22].)

Figure 11.2 Vanadium‐derived compounds showing antidiabetic, antitumor and/or anticancer activity. (VDC, vanadocene dichloride; VDAc, vanadocene acetylacetonate; IBV, benzyl‐substituted vanadocene; VD Y, vanadocene Y; ISV, indole‐substituted vanadocene; MtlV, methyl‐substituted vanadocene; MTxV, methoxy‐substituted vanadocene; NGLV, naglivan; VAc, vanadyl acetylacetonate; BMOV, bis(maltolato)oxovanadium(IV); BEOV, bis(ethylmaltolato)oxovanadium(IV); BKOV, bis(kojato)oxovanadium(IV); VN, other inorganic and organic derivatives of vanadate; VL, other inorganic and organic derivatives of vanadyl [82, 85–89].)

Figure 11.3 Well‐known enzymes either activated or inhibited by tungsten. (Enzyme: FDH

HTA

, formate dehydrogenase in hyperthermophilic archaea; FDH

B

, formate dehydrogenase in bacteria; FMDH, formyl methanofuran dehydrogenase; CAR, carboxylic reductase; AOR, aldehyde ferredoxin oxidoreductase; FOR, formaldehyde ferredoxin oxidoreductase; GAPOR, glyceraldehyde 3‐phosphate ferredoxin oxidoreductase; ADH, aldehyde dehydrogenase; NR

F

, fungal nitrate reductase; XO

CH

, chicken xanthine oxidase; SOX

R

, rat sulfite oxidase; AOX, aldehyde oxidase. Other abbreviations: FmA

−

, formate; MFR, methanofuran; CHOMFR,

N

formyl methanofuran; GAP, glyceraldehyde 3‐phosphate; PG, phosphoglycerate; PvA

−

, pyruvate; AcoA, acetyl coenzyme A; Xnt, xanthine; UrA, uric acid [104–110].)

Chapter 13

Figure 13.1 Transfer of biomass and energy through the trophic levels of an ecosystem in the simple grazing type food chain where plants constitute the first trophic level

Figure 13.2 The graphical representation of the grazing based‐chain (left side) and detritus food chain (right), where solid arrows show grazing while dashed ones excretion and/or death

Figure 13.3 Geochemical cycle of mercury, where B ‐ includes reaction catalysed by bacteria in sediment; C ‐ low sulphide concentration; D ‐ direct or indirect accumulation through food web; Hg

0

‐ undissociated mercury

Figure 13.4 Biological cycle for mercury in a lake, where A – abiotic; B – bacteria; P ‐ phytoplancton

Chapter 14

Figure 14.1 A diagram of the bioleaching sulfate minerals.

Figure 14.2 The electrochemical mechanism of pyrite–chalcopyrite mineral system bioleaching.

Figure 14.3 The migration direction of leaching solution and gas within the heap.

Figure 14.4 Flow velocities of the leaching solution between ore particles.

Figure 14.5 A typical BIOX process flow sheet.

Figure 14.6 Ferredox: a reductive dissolution process.

Figure 14.7 Flow sheet showing the use of the BioSulphide® process for copper recovery.

Chapter 15

Figure 15.1 Plant growth dependent on the nutrient supply of soil.

Figure 15.2 Factors affecting the availability of anions and cations of trace elements to plants.

Figure 15.3 A graph that represents how ionic potential (IP) influences the chemical form of trace elements in the soil.

Chapter 18

Figure 18.1 Recommended daily intake (RDI) of essential trace elements in food [1].

Figure 18.2 The dynamics of iron‐involving processes in the body. Adapted by Renata Mozrzymas [45].

Figure 18.3 Changes in the major tests available for the diagnosis of iron status.

Chapter 19

Figure 19.1 Zinc (Zn) accumulation in

Spirulina

biomass grown on a standard medium (control) and on media with the addition of coordination compounds of zinc (Zn) with amino acids. (a) Zinc in spirulina biomass grown on a medium with complexes in concentrations of 20 mg/L: 1 – [Zn(D‐Ala)

2

]; 2 – [Zn(D‐Ser)

2

]; 3 – [Zn(D,L‐Ser)

2

]; 4 – [Zn(Gly, D‐Ser)]; 5 – [Zn(D,L‐Ala)

2

]; 6 – [Zn(L‐Ser)

2

]; 7 – [Zn(L‐Ala)

2

]; 8 – [Zn(Gly D, L‐Ser)]; 9 – [Zn(Gly, L‐Ser)]). (b) Distribution of zinc on fractions (% of total quantity) of

Spirulina

biomass grown on a medium with [Zn(Gly, L‐Ser)], 20 mg/L.

Figure 19.2 Iron (Fe) accumulation in

Spirulina

biomass cultivated on a standard medium (control) and in media supplemented with Fe three nuclear coordinative compounds. (a) Iron in

Spirulina

biomass obtained by cultivation on a medium supplemented with compounds at concentrations of 50 mg/L: 1 – [Fe

3

O‐Val]; 2 – [Fe

3

O‐Ala], 3 – [Fe

3

O‐Gly], 4 – [Fe

2

CaO], 5 – [Fe

2

BaO], 6 – [Fe

2

NiO], 7 – [Fe

2

ZnO], 8 – [Fe

2

CoO], 9 – [Fe

2

MgO]. (b) Iron distribution in biomass fractions (% of total quantity) of

Spirulina

cultivated in a medium supplemented with [Fe

3

O‐Gly], 50 mg/L.

Figure 19.3 The chromium (Cr) accumulation in

Spirulina

biomass cultivated in a standard medium (control) and in media supplemented with chromium compound. (a) Chromium in

Spirulina

biomass cultivated in a medium supplemented with compounds in concentration 40 mg/L: 1 – [Cr(HEDTA)(H

2

O)]; 2 – [K

2

Cr

2

(SO

4

)

4

]·12H

2

O; 3 – K

2

[Cr(NTA)(C

2

O

4

)(H

2

O)]·2H

2

O; 4 – [Cr(ur)

6

](NO

3

)·6H

2

O; 5 – [Cr(ur)

6

]Cl

3

·3H

2

O; 6 –[Cr(ADTA)(H

2

O)]·3H

2

O – 40 mg/L. (b) Chromium distribution in biomass fractions (% of total quantity) of

Spirulina

cultivated in a medium supplemented with [K

2

Cr

2

(SO

4

)

4

]•12H

2

O 40 mg/L.

Figure 19.4 Accumulation of copper (Cu) in

Spirulina

biomass grown in a standard medium (control) and in media with the addition of coordination compounds with Cu(II). (a) Copper in

Spirulina

biomass grown on a medium with the addition of coordination compounds in concentrations of 6 mg/L: 1 – [Cu(L

9

‐H)NO

3

]; 2 – [Cu(L

10

‐H)Cl]; 3 – [Cu(L

11

‐H)Br]; 4 – [Cu(L

12

‐H)NO

3

]; 5 – [Cu(L

9

‐2H)]; 6 – [Cu(L

10

‐H)Cl]; 7 – [Cu(L

11

‐H)Br]; 8 –[Cu(L

12

‐H)NO

3

]. (b) The distribution of copper on biomass fractions (% of total quantity) of

Spirulina

grown on a medium with the addition of [Cu(L

11

‐H)Br] – 6 mg/L.

Figure 19.5 Selenium (Se) accumulation in

Spirulina

biomass cultivated in a standard medium (control) and in media supplemented with selenium compounds. (a) Selenium in

Spirulina

biomass cultivated in a medium supplemented with compounds in concentrations of 30 mg/L: 1 – [(NH

4

)

2

SeO

3

]; 2 – [Na

2

SeO

3

]; 3 – [ZnSeO

3

]; 4 – [GeSe

2

]; 5 –[Fe

3

Se

3

O

9

°6H

2

O]]; (b) Selenium distribution in biomass fractions (% of total quantity) of

Spirulina

cultivated in a medium supplemented with [Fe

3

Se

3

O

9

°6H

2

O] – 30 mg/L.

Chapter 25

Figure 25.1 The most frequently used hyphenated techniques for trace element speciation analysis

Figure 25.2 Diagram presenting the contributions of various aspects of speciation analysis in different fields of research

Figure 25.3 Chromium circulation in the polluted environment

Figure 25.4 Selenium circulation in the polluted environment

Figure 25.5 The biogeochemical cycle of arsenic in the environment

Guide

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Recent Advances in Trace Elements

Edited by

Katarzyna Chojnacka

Wrocław University of Science and Technology, Poland

Agnieszka Saeid

Wrocław University of Science and Technology, Poland

This edition first published 2018© 2018 John Wiley & Sons Ltd

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List of Contributors

Ludmila BatirState University of Moldova, Chisinau, Republic of Moldova

Barbara Ortega BarceloUniversity of Granada, Department of Chemical Engineering, Granada, Spain

Valentina BulimagaState University of Moldova, Chisinau, Republic of Moldova

Bogusław BuszewskiDepartment of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Interdisciplinary Centre for Modern Technologies, Nicolaus Copernicus University, Toruń, Poland

Liliana CepoiInstitute of Microbiology and Biotechnology of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Tatiana ChiriacInstitute of Microbiology and Biotechnology of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Katarzyna ChojnackaWrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

Bartłomiej CieślikDepartment of Analytical Chemistry, Faculty of Chemistry, Gdańsk University of Technology, Gdańsk, Poland

Anna Dawiec‐LiśniewskaWrocław University of Technology, Department of Chemistry ul. Norwida, Wrocław, Poland

Agnieszka DmytrykGrupa Azoty Zakłady Azotowe Kędzierzyn S.A., Kędzierzyn‐Koźle, Poland

Svetlana DjurInstitute of Microbiology and Biotechnology of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Daniela ElenciucUniversity of Academy of Sciences of Moldova, Chisinau, Republic of Moldova

Katarzyna GodlewskaDepartment of Horticulture, The Faculty of Life Sciences and Technology, Wrocław University of Environmental and Life Sciences, Wrocław, Poland

Henryk GóreckiWrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

Mateusz GramzaGrupa Azoty Zakłady Azotowe Kędzierzyn S.A., Kędzierzyn‐Koźle, Poland

Elżbieta Gumienna‐KonteckaUniversity of Wrocław, Faculty of Chemistry, Wrocław, Poland

Piotr KonieczkaDepartment of Analytical Chemistry, Faculty of Chemistry, Gdańsk University of Technology, Gdańsk, Poland

Klaudia KonikowskaDepartment of Dietetics, Medical University of Wrocław, Wrocław, Poland

Tomasz KowalkowskiDepartment of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Interdisciplinary Centre for Modern Technologies, Nicolaus Copernicus University, Toruń, Poland

Marek ŁuczkowskiUniversity of Wrocław, Faculty of Chemistry, Wrocław, Poland

Elżbieta MaćkiewiczInstitute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University of Technology, Lodz, Poland

Anna MandeckaDepartment of Dietetics, Medical University of Wrocław, Wrocław Poland

Joseph M. MatongDepartment of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Johannesburg, South Africa

Izabela MichalakWrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

Marzena Mikos‐SzymańskaNew Chemical Syntheses Institute, Pulawy, Poland

Marcin MikulewiczDepartment of Dentofacial Orthopedics and Orthodontics, Division of Facial Abnormalities, Medical University of Wrocław, Wrocław Poland

Renata MozrzymasDepartment of Pediatrics, Regional Specialist Hospital, Research and Development Centre, Wrocław, Poland

Tshimangandzo S. MunondeDepartment of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Johannesburg, South Africa

Jacek NamieśnikDepartment of Analytical Chemistry, Faculty of Chemistry, Gdańsk University of Technology, Gdańsk, Poland

Philiswa N. NomngongoDepartment of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Johannesburg, South Africa

Athanasios C. PappasDepartment of Nutritional Physiology and Feeding, Faculty of Animal Science and Aquaculture, School of Agriculture, Engineering, and Environmental Science, Agricultural University of Athens, Athens, Greece

Aleksandra PawlaczykInstitute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University of Technology, Lodz, Poland

Macarena Rodriguez‐Guerra PedregalUniversity of Granada, Department of Chemical Engineering, Granada, Spain

Wojciech PiekoszewskiDepartment of Analytical Chemistry, Faculty of Chemistry, Jagiellonian University in Kraków, Kraków, PolandandFar Eastern Federal University (FEFU), School of Biomedicine, Vladivostok, Russia

Daria PodstawczykWrocław University of Technology, Department of Chemistry ul. Norwida, Wrocław, Poland

Karol PokomedaWrocław University of Technology, Department of Chemistry ul. Norwida, Wrocław, Poland

Paweł PomastowskiDepartment of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Interdisciplinary Centre for Modern Technologies, Nicolaus Copernicus University, Toruń, Poland

Agnieszka PawlowskaFaculty of Chemistry, Wrocław University of Science and Technology, Wrocław, Poland

Katarzyna RafińskaDepartment of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Interdisciplinary Centre for Modern Technologies, Nicolaus Copernicus University, Toruń, Poland

Magdalena Rowińska‐ŻyrekUniversity of Wrocław, Faculty of Chemistry, Wrocław, Poland

Ludmila RudiInstitute of Microbiology and Biotechnology of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Valery RudicInstitute of Microbiology and Biotechnology of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Piotr RusekNew Chemical Syntheses Institute, Pulawy, Poland

Zygmunt SadowskiFaculty of Chemistry, Wrocław University of Science and Technology, Wrocław, Poland

Agnieszka SaeidWrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

Mateusz SamorajGrupa Azoty Zakłady Azotowe Kędzierzyn S.A., Kędzierzyn‐Koźle, Poland

Mateusz SugajskiDepartment of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Interdisciplinary Centre for Modern Technologies, Nicolaus Copernicus University, Toruń, Poland

Peter F. SuraiDepartment of Microbiology and Biochemistry, Faculty of Veterinary Medicine, Trakia University, Stara Zagora, Bulgaria;Moscow State Academy of Veterinary Medicine and Biotechnology named after K.I. Skryabin, Moscow, Russia;Department of Animal Nutrition, Faculty of Agricultural and Environmental Sciences, Szent Istvan University, Gödöllo, Hungary;Department of Veterinary Expertise and Microbiology, Faculty of Veterinary Medicine, Sumy National Agrarian University, Sumy, UkraineandOdessa National Academy of Food Technology, Odessa, Ukraine

Małgorzata Iwona SzynkowskaInstitute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University of Technology, Lodz, Poland

Łukasz TuhyGrupa Azoty Zakłady Azotowe Kędzierzyn S.A., Kędzierzyn‐Koźle, Poland

Anna Witek‐KrowiakWrocław University of Technology, Department of Chemistry ul. Norwida, Wrocław, Poland

Aneta WiśniewskaWrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

Inga ZinicovscaiaJoint Institute for Nuclear Research, Joliot‐Curie, Dubna, Russian FederationandHoria Hulubei National Institute for R&D in Physics and Nuclear Engineering, Bucharest – Magurele, RomaniaandInstitute of Chemistry of the Academy of Science of Moldova, Chisinau, Republic of Moldova

Liliana ZosimState University of Moldova, Chisinau, Republic of Moldova

1Introduction

Katarzyna Chojnacka

Wrocław University of Science and Technology, Faculty of Chemistry, Department of Advanced Material Technologies, Wrocław, Poland

1.1 Introduction

Trace elements (TEs), although present in low quantities, can have significant effects in living organisms. Although the role of trace elements in the human body is not yet fully understood, it is known that their effect on human health can be essential, neutral, or detrimental [1]. Trace elements play a role in many chemical, biochemical, and enzymatic reactions; biological and physiological, catabolic and metabolic processes of living organisms [2]. Their role relies on the unique property of them forming complexes and binding with macromolecules (e.g., proteins) [1]. Frequently mentioned trace elements or micronutrients are: Cr, Co, Cu, F, I, Mn, Mo, Se, V, and Zn. The main sources of these elements for humans are drinking water, food and food supplements, and the general environment. There are trace elements that are essential, but there are also those that are non‐essential or potentially toxic: Al, As, Cd, Hg, and Pb [2].

Humans are exposed to trace elements from atmospheric suspended particles in street and house dust to soil and are exposed through different routes such as inhalation, ingestion, or dermal adsorption. The establishment of emission standards for trace elements is important when considering the potential impact on society from urban areas, taking into account toxicity and the degree of human exposure [3].

1.2 Definition of Trace Elements (TEs)

Trace elements were first described at the beginning of the twentieth century as elements present at very low levels in different matrices. In actual fact, different branches of science (e.g., geochemistry, medicine, agriculture, and chemistry) have different understandings of TEs. The word “trace” is usually related to abundance, and includes elements with different chemical properties: elements and metalloids, including the micronutrients group, essential elements, and toxic elements. In geochemistry, TEs are chemical elements that occur in the earth’s crust in amounts less than 0.1% and to biological sciences TEs are elements present in trace concentrations in living organisms [4]. The result of these differences is that, until now, no precise definition of TEs has been provided. Elements that are trace in biological materials are not necessarily trace in terrestrial environments (e.g., iron) [4]. Early research theorized that these elements do not play important functions due to their low abundance [1] but, more recently, it has been shown that this is not the case.

1.3 Sources of Trace Elements for Humans

There are beneficial effects of TEs in food. However, in some cases, impurities in the food chain and in the general environment has been observed to have detrimental effects [1]. The relation between bioavailability and speciation in food is an important factor here, especially concerning iron, selenium, or chromium [1].

Vincevica‐Gaile et al. [2] reviewed the trace metal content in foods from plant (vegetables: carrots, onions, potatoes) and animal origin (cottage cheese, eggs, honey). Environmental factors (e.g., geographical location or seasonality), botanical origin, agricultural practices, product processing, and storage were all found to influence the content of TEs. The level of TEs in food depends on the environmental conditions of specific sites such as the composition of soil and water [2].

Tea plants contain high levels of TEs because they are grown in acidic soils where metal ions are more available for uptake by the root system. Some of the TEs (Al, Cu, Cd, Cr, Mn, and Ni) are beneficial; others are harmful for human health and are transferred through tea infusion. The content of tea has been assessed and found to show nutritional value, but also adverse health effects [5]. Tea contains 4–9% of inorganic matter, 30% of which is extracted. Polyphenolic compounds (flavonoids) bind metal ions, especially Fe and Cu [5]. The reported TE contents in fresh tea leaves are as follows (mg/kg): for example, Chinese tea [6]: Al 2034–3322, Cd 0.03–0.08, Cu 9.68–18.82, As 0.024–0.066, and Pb 0.31–3.42 [7] and Turkish tea: Mn 2617–3154 and Ni 6.60–11.7 [5, 8].

A good dietary source of TEs (Fe, Cu, Zn, and Mn) comes from seaweed. For instance, Porphyra vietnamensis can be added to foods to improve the content of essential minerals and trace elements. The strong flavor of seaweeds is related to the presence of TEs, the content of which is higher than in terrestrial vegetables. An example content of TEs in seaweed is: Fe 1260 mg/kg and Cu 7.46 mg/kg. The consumption of 8 g of green, brown, or red seaweed contains more than 25% of a daily Dietary Recommended Intake [9].

1.4 Analytical methods

Pollution of the environment with trace metals has generated the need for finding suitable analytical methods that are sensitive, rapid, effective, and reliable. Several analytical techniques; inductively coupled plasma‐atomic emission spectrometry (ICP–AES), inductively coupled plasma‐mass spectrometry (ICP–MS), atomic absorption spectrometry (AAS), x‐ray fluorescence (XRF), total reflection x‐ray fluorescence (TXRF) spectroscopy, and neutron activation analysis (NAA) have been developed to analyze and monitor trace elements in environmental and food samples, as well as in the human body [10]. The determination methods ICP‐OES, NAA, and ICP‐MS are techniques with high sensitivity and multi‐element capability [11]. TXRF is a quantitative analysis technique for liquid samples which can be deposited as thin films on clean reflectors. The sensitivity and detection limits of TXRF are better than XRF [10].

The unique chemical properties and coherent behavior of TEs means that their environmental distribution reflects geographical location and aquatic factors (e.g., source input and water–rock interaction). Similarities between trace metals and their very low concentrations do, however, make determination difficult. Problems appear if a particular element is evaluated in a mixture with other elements as interferences and coincidences can occur [11]. The matrix and elements that are to be analyzed dictate the how difficult an analysis may be. For example, the direct determination of REEs (Rare Earth Elements) in high‐salt groundwater, because the concentrations of REEs are close to the detection limit of ICP‐MS and there are high concentrations of matrix ions (K, Na, Ca, and Mg) which defocus the extracted ion beam due to space charge effects, means that significant losses of analyte sensitivity are produced [11].

For this reason, pre‐concentration techniques are used and separation from the matrix elements is required before ICP‐MS analysis takes place. Solid phase extraction (SPE) or solvent extraction (SE) techniques are employed for the pre‐treatment of high‐salt samples (e.g., seawater). This removes the matrix components and enriches the samples with analytes. Of course, this can generate a new matrix and new interferences [11].

Speciation of TEs is important in the analysis of food, quality of products, health, and environment. Mobility, bioavailability, storage, retention, and toxicity of TEs depends on their chemical form. Biochemical and geochemical pathways depend on speciation [1]. Of particular importance is characterizing speciation of TEs in samples related to the chemistry of life. This requires the elaboration of separation techniques, sensitive enough to determine elements, as well as the identification of metallo‐compounds [12]. The problem with speciation analysis is related to the low total concentration of TEs, for example, ng/L in serum. The level of given species can even be several times lower. Another problem lies within non‐covalent bonds that are formed by TEs in different matrices such as tissue, blood, urine, sediment, water, and sludge, that are unstable especially after sampling [1].

1.5 Toxicity

The toxicity of TEs depends not only on their concentration (dose), but also on their speciation. Safe and adequate daily intake (SAI), and acceptable daily intake (ADI) have been defined as important toxicological measures. Table 1.1 summarizes the important toxicological issues related to TEs together with guidelines for drinking water and daily intake.

Table 1.1 Trace elements and their toxicity [5, 13].

WHO prescribed guideline value in drinking water, mg/L

The estimated maximum intake, as FAO/WHO for provisional tolerable weekly intake (PTWI) µg/kg body weight (µg/person per week)

ADI (Acceptable Daily Intake) (mg/d, safe and adequate daily intake)

Toxic properties

As

0.001

15 (900)

—

Mutagenic and carcinogenic, highly toxic to plants and animals.

Cd

0.003

0.004 (420)

—

Human carcinogen. Origin in cropped soil: phosphate fertilizers – 50 % input. Phytotoxic, inhibits plant growth, affects assimilation of nitrates, disturbs plant balance of water and ions. Impairs photosynthesis.

Cr

0.05

—

—

Essential, but also poses adverse effects. In soil 10–50 mg/kg as Cr(III) and (VI) – plants take up both forms. Toxicity in plants: reduced root and phytomass growth, impairment of photosynthesis, chlorosis, stunting and plant death, lower yield, inhibition of enzymatic activity, and mutagenesis. Because of complex chemistry, it is difficult to identify toxicity mechanisms. Metal speciation influences mobilization, uptake and toxicity.

Cu

—

—

2.5

Micronutrient, but highly toxic at higher levels. Content in foods and beverages is controlled on daily basis.

Pb

0.01

—

—

Food and beverages are the main source of Pb in human body. Allowable level in foods/beverages in Europe – 5 mg/kg.

Mn

0.4

—

2–5

Adverse effects are seen with deficiency and overexposure. Neurological effects seen after inhalation or exposure from drinking water. Tea drinking is the major dietary source.

Ni

—

—

<1

Toxic to plants and animals. Source: mining and agriculture. Essential for plant growth at low concentrations.

1.6 Trace Elements in Agriculture

Trace metals from soil can accumulate in less soluble forms and enter the food chain migrating from the soil and plant biota to humans and can move to watersheds through leaching and erosion [14]. Trace elements are taken up by plants and re‐enter the food chain or leach through the soil profile to groundwater. Organic matter in soil may increase the mobility of TEs [15]. Continuous harvesting of crops from fields interrupts the cycling of organic matter and depletes nutrients in the soil [15]. The level of TEs can be partially replenished by adding mineral fertilizers or composts. The addition of TEs to soil is regulated by guidelines recommending maximum levels in fertilizers and soils.

1.6.1 Trace Elements in Soil

Soils are sinks for TEs because many species of trace ions are fixed, a characteristic which determines how they are cycled in the soil [4]. The behavior of TEs in soil is fundamentally defined by their association with different soil components and phases [4]. Uptake by plants depends on the rate and amount of TEs applied as fertilizer, as well as soil and plant characteristics [16]. There are permanent physical, chemical, and biological processes occurring in soils that cause the evolution of parent materials, determine sorption, speciation, redistribution, mobility, and bioavailability of TEs. Weathering relies on the dissolving of primary minerals and hydrolysis of released elements [17].

A biohazard risk in soils is associated with the presence of trace metals, but not necessarily their total content. It is more relevant to determine fractions that describe their mobility and therefore whether real dangers to the abiotic and biotic elements of the environment are posed. Rao et al. [18] presented a review of the extraction schemes for trace metal fractionation in environmental samples (soil, sewage sludge, road dust and run off, waste, and miscellaneous materials) and recommended the use of chemometric methods in sequential extraction analysis [18].

1.6.2 Trace Elements in Fertilizers

Trace elements in fertilizers are categorized as either non‐essential in plant metabolism (Cd, Cr, Hg, Ni, Pb) or essential in trace quantities (Cu, Fe, and Zn). If TEs are found together with organic matter, they become organically‐bound and are less available to plants than mobile mineral forms [19]. Also, soil adsorptive properties determine bioavailability to plants. Many reports describe the impact of TEs on crop plants [19].

The aim of increasing agricultural productivity is the primary reason for using agricultural fertilizers containing TEs that might be toxic, can contaminate soils, and reach food products [20]. Concerns over food security are related to agricultural supplements and subsequent soil contamination which causes chemicals to accumulate in grocery products [20]. Quality control of fertilizers used in agricultural production is essential, since they can become contaminated by raw material, especially if they are recycled or are waste materials. The maximum permitted limits for contaminants (As, Cd, Cr, Hg, and Pb) in mineral fertilizers are regulated by law [20]. The general risk model for establishing safe levels of TEs in fertilizers includes evaluating: the content in fertilizer product, application rate, level in soil, uptake by plants, food ingestion rate for crops, established acceptable level in diet (toxicity), and the calculation of an acceptable upper limit of a specific TE in fertilizer products [16].

Many TEs are also fertilizer micronutrients. In the past, they have been introduced to soil mainly in the form of mineral salts. More recently, innovative, controlled released products have been designed. The idea is to supplement micronutrients in highly bioavailable and nontoxic form with minimum losses to the environment (leaching to groundwater). Biologically important TEs (Cu, Co, Mo) can be leached slowly from granulated phosphogypsum. Leachability depends on the presence of urea or urea phosphate [22].

Liu et al. [21] produced fertilizers with TEs chelated by amino acids, based on proteins of bacteria from sewage sludge. The method relied on hydrolysis by mineral acids and further chelation with TEs (Fe, Cu, Zn, Mn, Mom and B) [21].

Nziguheba and Smolders [14] analyzed 200 samples of phosphate fertilizers in order to estimate the input of trace metals to soils. The average concentrations (mg/kg) determined in fertilizers were: 14.8 (Ni), 7.4 (Cd), 166 (Zn), 2.9 (Pb), 7.6 (As), and 89.5 (Cr) [14]. A linear and positive correlation between the level of P and trace metal content was found. It was concluded that trace metal application using fertilizers was comparable to atmospheric deposition from the air [14].

Long‐term phosphate fertilizers contribute to the level of TEs in soil, in particular As, Cd, and Pb, and consequently the level seen in cultivated crops [16]. The levels of As, Cd, and Pb in phosphate fertilizers falls within the following ranges (respectively): 8–15, 3–12, 3–30 mg/kg [16]. Additional factors contributing to the level of TEs in soil include atmospheric deposition, incorporation of crop residues, and harvesting. However, there is a substantial difficulty in evaluating TEs inputs and outputs [16].

1.7 Environmental Aspects

1.7.1 Fuels

Trace elements are present in various types of fuel. During the combustion process they are transferred to either the ash or are emitted with flue gases.

Trace metals in petroleum products occur either in organic or inorganic form. Their presence is either of natural origin or may be added during refinery processing. The concentration of TEs can be determined by ICP‐OES and ICP‐MS techniques. Important issues in analysis include sample preparation, speciation, and total content analysis. The ratios between the levels of given metals are a sort of fingerprint that reflects the age of the oil and its origin (the V/Ni ratio in particular). The content of metals determines environmental risk and defines the use of a refining procedure (demetallization). The presence of metals can cause problems for engines, in particular for electronic sensors involved in the control of the combustion process. Some compounds of trace metals are added as antioxidants, anti‐icing agents, anti‐knock agents, or metal deactivators. Trace metals are added as additives or catalysts (Co, Cr, Mn, Mo, Ni, Sn, V, Zn), whereas others form contaminants during the refining process (Cr, Cu, Fe, Mn, Ni, Zn) or are of natural origin (Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Sn, V, Zn) [23].

Coal is a source of TEs. The composition of mineral matter in coal determines the environmental hazards associated with the emission of toxic TEs during coal combustion and utilization. The composition of coal is determined by how it formed. For example, peat which has accumulated and been influenced by seawater has a different composition than peat accumulated in a freshwater environment. The subsequent composition of elements is therefore connected to the peat‐swamp environment. Reports have been carried out on geochemical data using mineralogical studies (SEM, XRD) identifying the origin of TEs in coals [24].

1.7.2 Emissions from Waste

It is important to determine the content, mobility, and chemical association of TEs, as well as the chemical characteristics of various waste fuel incineration ashes, as these are important in predicting the migration behavior of TEs [25]. The release of TEs from waste incineration is a problem that limits its use or disposal. Another problem related to the presence of TEs in waste is their release which is affected by various geochemical characteristics: mineral composition, acid neutralization ability, weathering conditions, and the intrinsic properties of the elements themselves. Leachability is affected by leachate pH, liquid—solid ratio (L/S), extractant type and concentration, contact time, and solid matrix [25].

Charlesworth et al. [3] report on the sources, transport pathways, and sinks of particulate TEs in urban environments, paying particular attention to the atmosphere, soil, street and indoor dusts. The new discipline of urban biochemistry focuses on these aspects. The research shows that emissions of Pb, As, Cd, Hg, Zn, and Cu have significantly decreased in urban environments over the last few decades.

Saqib and Bäckström [25] investigated bottom ashes from different waste fuels and wood for the total content of TEs. This included looking at leaching behavior using a standard leaching procedure (EN 12457‐3) and the chemical association of TEs using sequential extraction. It was found that the type of fuel determined the level of TEs. The content, in decreasing order, was as follows: Cu > Zn > Pb > Cr > Ni > Sb > As [25].

1.7.3 Trace Elements in Sewage Sludge

Sewage sludge is being used as an alternative fuel in mono‐ or co‐combustion with coal. The retention and emission of TEs during combustion was investigated [28]. Fly ash was found to consist of very fine particles which provided sufficient specific surface area for TEs such as Pb, Cu, Zn, Cr, As, and Cd [26]. The research found that TEs can leach out from fly ash and cause soil and groundwater contamination, posing a great risk to human health and the environment. It is crucial therefore to control the mobility of TEs [26].

The content of the following TEs has been studied in sewage sludge: As, Cd, Co, Cr, Cu, Ni, Pb, Zn. The TEs are involved in chemical reactions and phase transition and therefore become enriched in the ash. In this process, Pb and Zn may undergo volatilization. For example, during co‐combustion of sewage sludge with coal gangue, crystalline kaolinite is broken into semi‐crystalline metakaolinite and then to mullite. The decomposition and transition of the crystal structure causes a charge imbalance and the elements become chemically bonded to the aluminosilicate structure. A result of this is that co‐combustion can facilitate the prevention of TEs emission [27].

The migration of TEs from fly ash from waste incineration is a problem for use and in landfill. The average total content of TEs in most fly ashes decreases in the order Zn > Cu > Pb > Sb > Cr > As > Cd. The most mobile elements that present excessive leaching are Cd, Pb, Zn, Cu, and Sb, as determined by sequential extraction [25].

1.8 Biomonitoring of Trace Metals in Surface Water

In environmental water biomonitoring studies, the following are considered as TEs: As, Ba, Cd, Cr, Cu, Ni, Pb, V, and Zn. The origin of these elements in coastal areas could be due to industrial activity: chemical and petrochemical plants, oil refineries, or harbor activities. Trace elements present in water reach marine ecosystems and pose ecological risks. The behavior of TEs in marine water is complex as these TEs can occur in different phases: colloidal, particulate, or dissolved phases. The latter is found in the lowest levels [27]. Monitoring programs have been established to track changes in the levels of trace metals in water environments. The presence of these metals affects fish and wildlife [28]. Biomonitoring techniques enable assessment of the biologically available levels of pollutants in ecosystems and, simultaneously, their effect on living organisms and their response to different environmental conditions over long periods of time.

Upwelling and the formation of geochemical provinces influence the presence, or not, of biogenic and other elements in surface waters. These are seen in the mineral composition of organisms living in these waters. The content of TEs (Fe, Mn, Zn, Cu, Cd, Pb, Ni, Cr) in brown algae, bivalves, and gastropods, as well as other organisms that inhabit water environments and foul navigation buoys has been studied and shown that the existence of biogeochemical provinces in the sea can be identified through the observation of higher concentrations of TEs in organisms [29].

Trace metals not only undergo bioaccumulation and biomagnification, but also biotransformation. Macrobenthic biomonitors fulfill the criteria for good biomonitors of TEs because of their limited mobility [27]. For instance, in aquatic environments Hg(II) is microbiologically converted to methylmercury, resulting in elevated concentrations in fish. Mercury concentration in the edible muscle of fish in many cases exceeds health guidelines for human consumption and may also be toxic to the fish itself [28].

Various organisms have developed protective mechanisms. For example, hepatocytes (cells in the liver) contain high levels of intracellular binding proteins and peptides which help to bind non‐essential metals, thus preventing their interaction with metabolic processes. It is possible to isolate subcellular fractions and investigate trace metal content there in order to investigate intracellular distribution. If non‐essential metals are found in potentially sensitive subcellular compartments, this could signify potential toxicological effects [28, 30].

1.9 Conclusions