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Biohydrometallurgical Recycling of Metals from Industrial Wastes 1st Edition Hong Hocheng
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Chapter 1 Toxicity, Sources, and Control of Copper (Cu), Zinc (Zn), Molybdenum (Mo), Silver (Ag), and Rare Earth Elements in the Environment .......................................... 1
O. Sarafadeen Amuda, A. Olanrewaju Alade, Yung-Tse Hung, Lawrence K. Wang, and Mu-Hao Sung Wang
Chapter 2 Nano-Bioremediation: Applications of Nanotechnology for Bioremediation ............ 27
S. Raj Kumar and P. Gopinath
Chapter 3 Recycling of Filter Backwash Water and Alum Sludge from Water Utility for Reuse 49
Mu-Hao Sung Wang, Lawrence K. Wang, Nazih K. Shammas, and Milos Krofta
Chapter 4 Selection of Remedial Alternatives for Soil Contaminated with Heavy Metals 75
Nazih K. Shammas
Chapter 5 Removal of Heavy Metals by Low-Cost Adsorption Materials 127
Siew-Teng Ong, Sie-Tiong Ha, Pei-Sin Keng, Siew-Ling Lee, and Yung-Tse Hung
Chapter 6 Sulfide Precipitation for Treatment of Metal Wastes ............................................... 185
Nazih K. Shammas and Lawrence K. Wang
Chapter 7 Stabilization of Cadmium in Waste Incineration Residues by Aluminum/IronRich Materials .......................................................................................................... 239
Kaimin Shih and Minhua Su
Chapter 8 Arsenic in the Environment: Source, Characteristics, and Technologies for Pollution Elimination ............................................................................................... 255
Yu-Ming Zheng, Jiaping Paul Chen, and Qing Liu
Chapter 9 Simultaneous Removal of Chromium and Arsenate: A Case Study Using Ferrous Iron 289
Xiaohong Guan and Haoran Dong
Chapter 10 E-Waste Recycling: Environmental and Health Impacts ......................................... 339
Rajasekhar Balasubramanian and Obulisamy Parthiba Karthikeyan
Chapter 11 Site Assessment and Cleanup Technologies of Metal Finishing Industry ............... 365
Nazih K. Shammas
Chapter 12 Adsorptive Removal of Arsenic from Water Sources Using Novel Nanocomposite Mixed Matrix Membranes 413
R. Jamshidi Gohari, Woei Jye Lau, Takeshi Matsuura, and Ahmad F. Ismail
Chapter 13 Treatment of Photographic Processing Waste 439
Irvan Dahlan, Hamidi Abdul Aziz, Yung-Tse Hung, and Lawrence K. Wang
Chapter 14 Toxicity, Source, and Control of Barium in the Environment ................................. 463
Hamidi Abdul Aziz, Miskiah Fadzilah Ghazali, Yung-Tse Hung, and Lawrence K. Wang
Chapter 15 Toxicity, Sources, and Control of Selenium, Nickel, and Beryllium in the Environment ............................................................................................................. 483
Joseph F. Hawumba, Yung-Tse Hung, and Lawrence K. Wang
Chapter 16 Safety and Control for Toxic Chemicals and Hazardous Wastes 513
Nazih K. Shammas and Lawrence K. Wang
Chapter 17 Biological Treatment of Poultry Processing Wastewater 539
Nazih K. Shammas and Lawrence K. Wang
Chapter 18 Treatment of Wastewater, Storm Runoff, and Combined Sewer Overflow by Dissolved Air Flotation and Filtration ..................................................................... 577
Lawrence K. Wang, Mu-Hao Sung Wang, and Nazih K. Shammas
Chapter 19 Waste Treatment and Management in Chlor-Alkali Industries 611
Hamidi Abdul Aziz, Miskiah Fadzilah Ghazali, Mohd. Suffian Yusoff, and Yung-Tse Hung
Chapter 20 Dissolved Air Flotation (DAF) for Wastewater Treatment ...................................... 657
Puganeshwary Palaniandy, Hj. Mohd Nordin Adlan, Hamidi Abdul Aziz, Mohamad Fared Murshed, and Yung-Tse Hung
Chapter 21 Restaurant Waste Treatment and Management ........................................................ 695
Jerry R. Taricska, Jaclyn M. Taricska, Yung-Tse Hung, and Lawrence K. Wang
Chapter 22 Treatment of Textile Industry Waste ........................................................................ 719
Siew-Teng Ong, Sie-Tiong Ha, Siew-Ling Lee, Pei-Sin Keng, Yung-Tse Hung, and Lawrence K. Wang
Chapter 23 BOD Determination, Cleaning Solution Preparation, and Waste Disposal in Laboratories 797
Mu-Hao Sung Wang, Lawrence K. Wang, and Eugene De Michele
Chapter 24 Pr inciples, Procedures, and Heavy Metal Management of Dichromate Reflux Method for COD Determination in Laboratories 809
Mu-Hao Sung Wang, Lawrence K. Wang, and Eugene De Michele
Chapter 25 Environment-Friendly Activated Carbon Processes for Water and Wastewater Treatment 819
Wei-chi Ying, Wei Zhang, Juan Hu, Liuya Huang, Wenxin Jiang, and Bingjing Li
Chapter 26 Treatment of Wastes from the Organic Chemicals Manufacturing Industry 839
Debolina Basu, Sudhir Kumar Gupta, and Yung-Tse Hung
Chapter 27 Toxicity and Sources of Pb, Cd, Hg, Cr, As, and Radionuclides in the Environment 855
Ghinwa M. Naja and Bohumil Volesky
Chapter 28 Environmental Behavior and Effects of Engineered Metal and Metal Oxide Nanoparticles ............................................................................................................ 905
Bernd Nowack
Chapter 29 Heavy Metal Removal with Exopolysaccharide-Producing Cyanobacteria 931
Roberto De Philippis and Ernesto Micheletti
Chapter 30 Environmental Geochemistry of High-Arsenic Aquifer Systems 965
Yanxin Wang and Yamin Deng
Chapter 31 Na notechnology Application in Metal Ion Adsorption 997
Shu Guang Wang, Xue Fei Sun, Wen Xin Gong, and Yue Ma
Chapter 33 Treatment of Metal-Bearing Effluents: Removal and Recovery ............................ 10 67
Ghinwa M. Naja and Bohumil Volesky
Chapter 34 Co ntrol, Management, and Treatment of Metal Emissions from Motor Vehicles ......................................................................................................... 1113
Rajasekhar Balasubramanian, Jun He, and Lawrence K. Wang
Chapter 35 Removal of Heavy Metals from Industrial Effluents by Chemical Precipitation and Chemical Coagulation 1129
Nazih K. Shammas, Lawrence K. Wang, and Mu-Hao Sung Wang Index ............................................................................................................................................. 1141
Preface
Environmental managers, engineers, and scientists who have had experience with industrial and hazardous waste management problems have noted the need for a handbook series that is comprehensive in its scope, directly applicable to daily waste management problems of specific industries, and widely acceptable by practicing environmental professionals and educators.
Many standard industrial waste treatment and hazardous waste management texts adequately cover a few major industries, for conventional in-plant pollution control strategies, but no one book, or series of books, focuses on new developments in innovative and alternative environmental technology, design criteria, effluent standards, managerial decision methodology, and regional and global environmental conservation.
In 2004, CRC Press published its First Handbook in the handbook series, Handbook of Industrial and Hazardous Wastes Treatment. That First Handbook emphasized (1) in-depth presentation of environmental pollution sources, waste characteristics, control technologies, management strategies, facility innovations, process alternatives, costs, case histories, effluent standards, and future trends for each industrial or commercial operation (such as pharmaceutical industry, oil refineries, metal plating and finishing industry, photographic processing industry, soap and detergent industry, textile industry, phosphate industry, pulp and paper mills, dairies, sea food processing factories, meat processing plants, olive oil processing plants, potato production operations, pesticide industry, livestock industry, soft drink factories, explosive chemical plants, rubber industry, timber industry, and power industry) and (2) in-depth presentation of methodologies, technologies, alternatives, regional effects, and global effects of each important industrial pollution control practice that may be applied to all industries (such as industrial ecology, pollution prevention, in-plant hazardous waste management, site remediation, groundwater decontamination, and stormwater management).
In 2010, CRC Press published its Second Handbook in the handbook series, Handbook of Advanced Industrial and Hazardous Waste Treatment. That Second Handbook emphasized a different in-depth presentation of waste minimization, cleaner production, legislation and regulations for hazardous wastes, hazardous industrial wastes characteristics, soil remediation, brownfield sites restoration, bioremediation, enzymatic process, underground storage tank releases, biological treatment processes, deep well injection, methyl tertiary-butyl ether (MTBE), fuel oxygenates, evapotranspiration, landfill cover, hazardous leachate treatment, secondary flotation, solid waste treatment, etc. The 2010 Second Handbook also gives in-depth presentation of hazardous industrial treatment and management technologies used in many new industries or operations that are not covered in the previous 2004 First Handbook, such as, aluminum forming industry, coil coating industry, nickel-chromium plating plants, porcelain enameling industry, pentachlorophenol processing facilities, pulp and paper industry, and inorganic chemical industry. Many industries are covered for the very first time.
In a deliberate effort to complement both the 2004 First Handbook and the 2010 Second Handbook as well as other industrial waste treatment and hazardous waste management texts, this 2018 Handbook of Advanced Industrial and Hazardous Wastes Management (i.e., the Third Handbook), covers many new advances in the field of industrial and hazardous waste treatment, such as the toxicity, sources and/or control of various heavy metals (copper, zinc, molybdenum, barium, arsenic, silver, selenium, nickel, beryllium, chromium, cadmium, mercury, lead, etc.) and rare metals in the environment; applications of nanotechnology for bioremediation; remediation of heavy metal-contaminated soil; removal of heavy metals by low-cost adsorbents; stabilization of cadmium in waste incineration residues by aluminum/iron-rich materials; treatment of metal wastes by sulfide precipitation; simultaneous removal of chromium and arsenate; environmental and health impacts of e-waste disposal and recycling; site assessment and cleanup technologies of metal finishing industry; adsorptive removal of arsenic from water sources using novel nanocomposite mixed matrix membranes; treatment and management of photographic processing
wastes, poultry processing wastes, storm-runoff, combined sewer overflows, chlor-alkali industrial wastes, restaurant wastes, textile wastes, organic chemicals manufacturing wastes, and laboratory wastes; recycling of filter backwash water and alum sludge from water utility for reuse; safety and control for toxic chemicals and hazardous wastes; industrial water and wastewater treatment using dissolved air flotation, activated carbon adsorption, nanotechnology, granular sludge biosorption, exopolysaccharide-producing cyano-bacterial process, etc.; and control, treatment, and management of metal emissions from motor vehicles.
Special efforts were made to invite experts to contribute chapters in their own areas of expertise. Since the field of industrial hazardous waste treatment is very broad, no one can claim to be an expert in all industries; collective contributions are better than a single author’s presentation for a handbook of this nature.
This 2018 Handbook of Advanced Industrial and Hazardous Wastes Management, is a collection of the existing chapters from three small CRC Press books: (1) Heavy Metals in the Environment, (2) Remediation of Heavy Metals in the Environment, and (3) Waste Treatment in the Service and Utility Industries. The publisher prints this 2018 Handbook as well as its two accompanying handbooks (the 2004 Handbook of Industrial and Hazardous Wastes Treatment, and the 2010 Handbook of Advanced Industrial Hazardous Wastes Treatment) in very small quantities mainly for the university library collection worldwide. Three handbooks together (2004, 2010, and 2018) form a complete set of reference handbooks for the environmental professionals. They feature the major industries and hazardous pollutants that have significant effects on the environment. Professors, students, and researchers in environmental, civil, chemical, sanitary, mechanical, and public health engineering and science will find valuable educational materials here. The extensive bibliographies for each industrial waste treatment or management should be invaluable to environmental managers or researchers who need to trace, follow, duplicate, or improve on a specific industrial hazardous waste treatment practice.
A successful modern hazardous industrial waste treatment and management program for a particular industry will include not only traditional water pollution control but also air pollution control, noise control, soil conservation, site remediation, radiation protection, groundwater protection, hazardous waste management, solid waste disposal, and combined industrial– municipal waste treatment and management. In fact, it should be a total environmental control program. Another intention of this handbook series is to provide technical and economical information on the development of the most feasible total environmental control program that can benefit both industry and local municipalities. Frequently, the most economically feasible methodology is a combined industrial–municipal waste treatment and management.
Lawrence K. Wang
Newtonville, New York, USA
Mu-Hao Sung Wang Newtonville, New York, USA
Yung-Tse Hung Cleveland, Ohio, USA
Nazih K. Shammas Pasadena, California, USA
Jiaping Paul Chen Singapore
Editors
Lawrence K. Wang has over 28+ years of experience in facility design, environmental sustainability, natural resources, resources recovery, global pollution control, construction, plant operation, and management. He has expertise in water supply, air pollution control, solid waste disposal, water resources, waste treatment, and hazardous waste management. He is a retired dean/director/VP of the Lenox Institute of Water Technology, Krofta Engineering Corporation, and Zorex Corporation, respectively, in the United States. Dr. Wang is the author of over 700 papers and 45 books, and is credited with 24 U.S. patents and 5 foreign patents. He earned his BSCE degree from National Cheng-Kung University, Taiwan, ROC, his two MS degrees from the Missouri University of Science and Technology and the University of Rhode Island, USA, and his PhD degree from Rutgers University, USA. Currently he is the chief series editor of the Advances in Industrial and Hazardous Wastes Treatment series (CRC Press of Taylor & Francis Group) and the Handbook of Environmental Engineering series (Springer).
Mu-Hao Sung Wang has been an engineer, an editor, and a professor serving private firms, governments, and universities in the United States and Taiwan for over 25 years. She is a licensed professional engineer, and a diplomate of American Academy of Environmental Engineers. Her publications have been in the areas of water quality, modeling, environmental sustainability, waste management, NPDES (National Pollutant Discharge Elimination System), flotation, and analytical methods. Dr. Wang is the author of over 50 publications and an inventor of 14 US and foreign patents. She earned her BSCE degree from National Cheng Kung University, Taiwan, ROC, her MSCE degree from the University of Rhode Island, USA, and her PhD degree from Rutgers University, USA. She is the co-series editor of the Handbook of Environmental Engineering series (Springer), and a member of American Water Works Association, New England Water Works Association, Water Environment Federation, and Overseas Chinese Environmental Engineers and Scientists Association.
Yung-Tse Hung has been a professor of civil engineering at Cleveland State University since 1981. He is a fellow of the American Society of Civil Engineers, and has taught at 16 universities in 8 countries. His research interests and publications have been involved with biological processes and industrial waste treatment. Dr. Hung is credited with over 470 publications and presentations on water and wastewater treatment. He earned his BSCE and MSCE degrees from National ChengKung University, Taiwan, and his PhD degree from the University of Texas at Austin, USA. He is the editor of International Journal of Environment and Waste Management, International Journal of Environmental Engineering, and International Journal of Environmental Engineering Science.
Nazih K. Shammas is an environmental consultant and professor for over 45 years. He is an exdean/director of the Lenox Institute of Water Technology, and an advisor to Krofta Engineering Corporation, USA. Dr. Shammas is the author of over 250 publications and 15 books in the field of environmental engineering. He has experience in environmental planning, curriculum development, teaching, scholarly research, and expertise in water quality control, wastewater reclamation and reuse, physicochemical and biological processes and water and wastewater systems. He earned his BE degree from the American University of Beirut, Lebanon, his MS degree from the University of North Carolina at Chapel Hill, and his PhD degree from the University of Michigan, USA.
Jiaping Paul Chen has been a professor in the Department of Civil and Environmental Engineering in the National University of Singapore (NUS) since 1998. His research interests are physicochemical treatment of water and wastewater and modeling. He has published three books, more than 150 journal papers and book chapters with citations of above 6000, and H-index of 43. He holds seven
patents in the areas of adsorption and membrane technologies, and ballast water management systems. He has received various honors and awards, including the Sustainable Technology Award from the IChemE, Guest Professor of the Huazhong University of Science & Technology and Shandong University, China, and Distinguished Overseas Chinese Young Scholar of National Natural Science Foundation, China. He has been recognized as an author of hot papers and highly cited papers (Web of Science). Professor Chen earned his MEng degree from Tsinghua University and his PhD degree from Georgia Tech., USA in 1991 and 1997, respectively. He is a chartered chemical engineer (UK).
Contributors
Hj. Mohd Nordin Adlan
School of Civil Engineering
Universiti Sains Malaysia Pulau Pinang, Malaysia
A. Olanrewaju Alade
Department of Chemical Engineering
Ladoke Akintola University of Technology Ogbomoso, Nigeria
O. Sarafadeen Amuda
Department of Pure and Applied Chemistry
Ladoke Akintola University of Technology Ogbomoso, Nigeria
Hamidi Abdul Aziz
School of Civil Engineering
Universiti Sains Malaysia Pulau Pinang, Malaysia
Rajasekhar Balasubramanian
Division of Environmental Science and Engineering
National University of Singapore
Singapore
Debolina Basu
Department of Civil Engineering
Motilal Nehru National Institute of Technology Allahabad Allahabad, Uttar Pradesh, India
Changlun Chen
Institute of Plasma Physics
Chinese Academy of Science Beijing, China
Jiaping Paul Chen
Division of Environmental Science and Engineering
National University of Singapore
Singapore
Irvan Dahlan
School of Chemical Engineering
Universiti Sains Malaysia Pulau Pinang, Malaysia
Roberto De Philippis
Department of Agricultural Biotechnology
University of Florence Florence, Italy
Yamin Deng
School of Environmental Studies and MOE
Key Laboratory of Biogeology and Environmental Geology
China University of Geosciences Beijing, China
Haoran Dong
Key Laboratory of Environmental Biology and Pollution Control
Hunan University Changsha, China
Miskiah Fadzilah Ghazali
School of Civil Engineering
Universiti Sains Malaysia Pulau Pinang, Malaysia
R. Jamshidi Goharl
Advanced Membrane Technology Research Centre
University Teknologi Malaysia
Johor, Malaysia and
Department of Chemical Engineering
Islamic Azad University Bardsir, Iran
Wen Xin Gong
School of Environmental Science and Engineering
Shandong University
Shandong, China
P. Gopinath
Centre for Nanotechnology
Indian Institute of Technology
Roorkee, Uttarakhand, India
Xiaohong Guan
State Key Laboratory of Pollution Control and Resources Reuse
Tongji University Shanghai, China
Sudhir Kumar Gupta
Centre for Environmental Science and Engineering
Indian Institute of Technology Bombay Mumbai, Maharashtra, India
Sie-Tiong Ha
Universiti Tunku Abdul Rahman Perak, Malaysia
Joseph F. Hawumba
Biochemistry Department Makerere University Kampala, Uganda
Jun He
Division of Environmental Science and Engineering
National University of Singapore Singapore
Juan Hu
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology Shanghai, China
Liuya Huang
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology Shanghai, China
Yung-Tse Hung
Civil and Environmental Engineering Department
Cleveland State University Cleveland, Ohio
Ahmad F. Ismail
Advanced Membrane Technology Research Centre
University Teknologi Malaysia Johor, Malaysia
Wenxin Jiang
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology Shanghai, China
Obulisamy Parthiba Karthikeyan
Department of Civil and Environmental Engineering
National University of Singapore Singapore
Pei-Sin Keng
Department of Pharmaceutical Chemistry
International Medical University Kuala Lumpur, Malaysia
Milos Krofta
Lenox Institute of Water Technology Lenox, Massachusetts
S. Raj Kumar
Centre for Nanotechnology
Indian Institute of Technology Roorkee, Uttarakhand, India
Woei Jye Lau
Advanced Membrane Technology Research Centre
University Teknologi Malaysia Johor, Malaysia
Siew-Ling Lee
Ibnu Sina Institute for Scientific and Industrial Research
Universiti Teknologi Malaysia Johor, Malaysia
Bingjing Li
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology Shanghai, China
Qing Liu
Institute of Urban Environment
Chinese Academy of Sciences
Xiamen, Fujian, China
Yue Ma
School of Environmental Science and Engineering
Shandong University Shandong, China
Takeshi Matsuura
Advanced Membrane Technology Research Centre
University Teknologi Malaysia Johor, Malaysia and Department of Chemical and Biological Engineering
University of Ottawa Ottawa, Ontario, Canada
Eugene De Michele
Technical Services and Committee Liaison Water Environment Federation Alexandria, Virginia
Ernesto Micheletti
Department of Agricultural Biotechnology University of Florence Florence, Italy
Mohamad Fared Murshed School of Civil Engineering Universiti Sains Malaysia Pulau Pinang, Malaysia
Ghinwa M. Naja
Research Associate and Environmental Engineering Consultant McGill University Montreal, Quebec, Canada
Bernd Nowack
Empa – Swiss Federal Laboratories for Materials Testing and Research D übendorf, Switzerland
Siew-Teng Ong
Universiti Tunku Abdul Rahman Perak, Malaysia
Puganeshwary Palaniandy
School of Civil Engineering
Universiti Sains Malaysia Pulau Pinang, Malaysia
Nazih K. Shammas
Lenox Institute of Water Technology Pasadena, California and
Yanxin Wang School of Environmental Studies and MOE Key Laboratory of Biogeology and Environmental Geology
China University of Geosciences Beijing, China
Wei-chi Ying
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology
Shanghai, China
Mohd. Suffian Yusoff School of Civil Engineering Universiti Sains Malaysia Nibong Tebal, Penang, Malaysia
Wei Zhang
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process
East China University of Science and Technology
Shanghai, China
Yu-Ming Zheng Institute of Urban Environment
Chinese Academy of Sciences Xiamen, Fujian, China
1 Toxicity, Sources,
and Control of Copper (Cu), Zinc (Zn), Molybdenum (Mo), Silver (Ag), and Rare Earth Elements in the Environment
O. Sarafadeen Amuda, A. Olanrewaju Alade, Yung-Tse Hung, Lawrence K. Wang, and Mu-Hao Sung
ABSTRACT
There are more than 20 heavy metal toxins contributing to a variety of adverse health effects in humans. Exposed individuals experience different behavioral, physiological, and cognitive changes depending on the type of the toxin and the degree of exposure by the individual. This chapter presents the sources of exposure, toxicity, and control technologies of Cu, Zn, Mo, Ag, and rare earth elements in the environment.
1.1 INTRODUCTION
Toxic substances are generally poisonous and cause adverse health effects in both man and animals. Some chemical substances can be of use at certain concentrations, beyond which they become toxic. The toxicity of a substance is based on the type of effect it causes and its potency. Exposure to such toxic substance is via inhalation, ingestion, or direct contact. Both long-term exposure (chronic) and short-term exposure (acute) may cause health effects that manifest immediately or later in life. The concentration of trace metals is increasing as a result of releases into the air and water as well as their heavy use in products for human consumption. The impact of these heavy metals at toxic concentration produces behavioral, physiological, and cognitive changes in an exposed individual. These impacts are well documented based on reports of accidental human exposure and animal studies (1–120). Most agencies that specialize in the study of toxicity of substances, which are either consumed or not consumed by human, terrestrial, and aquatic animals as well as plants, have set lower and upper allowable concentrations of the substances. Concentrations above the upper limit and beyond exposure time are toxic and exhibit health effects ranging from intestinal and neurotic to death.
In this chapter, the toxicity, sources, environmental issues (121–134), and
nologies (121–141)
1.2 COPPER
1.2.1 Copper and Its Compounds
Copper is a malleable light reddish-brown metallic element. It is represented by the symbol “Cu” and assigned with atomic number of 29 and atomic weight of 64 on the periodic table of elements (1,2). Copper occurs naturally in rock as a wide range of mineral deposits either in its pure or compound form. It has also been found in soils, water, and sediments (3,4). It can also be found in areas designated for municipal incineration, metal smelting sites (4), foundries, and power plants as a result human activities (1).
Copper sulfate and copper oxide are the most widely distributed naturally form of copper compound, Table 1.1, however, it combines with other metals like zinc and tin to form alloys such as brass and bronze, respectively (1,2).
1.2.2 CharaCterIstICs of Copper
Copper is a solid metal at room temperature and possesses good electrical and thermal conductivity. It does not react with water but reacts slowly with oxygen present in the air to form a thin film of dark-brown copper oxide. It does not react in sulfide, ammonia, and chloride media. There are 29 identified isotopes of copper ranging from 52 to 80. Only two of these, 63Cu and 65Cu, are stable and occur naturally. 63Cu shows a predominant existence (69%).
1.2.3 IndustrIal produCtIon of Copper
About 35% of world’s copper is produced in Chile, while 11% is produced in the United States and the remaining percentage comes from Indonesia, the former Soviet Union, Peru, Zambia, China, Poland, and the Democratic Republic of Congo (1). Copper ore is often extracted from large open pit mines as copper sulfides.
1.2.4 IndustrIal applICatIons of Copper
Copper is widely used in pure form or as an alloy, in the production of electrical conductors and wires, sheet metals, pipe and plumbing fixtures, coins, cooking utensils, and other metal products (3,5). Copper compounds have received wide application in the agricultural sector where they are being used as fungicides. It is also used in the treatment of water, particularly, to eliminate algae. Other applications include production of preservative lumbering, tannery, and textiles. Copper also
TABLE 1.1
Concentration and Distribution of Copper in Environment
Distribution Concentration (ppm)
Earth’s crust
Plants (dry weight basis)
Source: US EPA. Environmental Technology Verification Report Environmental Bio-detection Products Inc. Toxi-chromotest. Washington DC: US Environmental Protection Agency, June, 2006. EPA/600/R-06/071 and NTIS PB2006-113524
form an essential component in ceramic, glaze, and glass works. In the form of Fehling’s solution, copper compounds have application in chemistry for the determination of reducing sugars.
1.2.5 toxICIty and related hazards
Copper is an essential micronutrient that is required by plants and animals for growth and other body metabolisms. Higher concentrations of copper in both animals and plants are toxic and result in adverse health effects and stunted growth, respectively (7).
1.2.5.1 Route of Exposure
Environmental pollution due to copper is mostly anthropogenic ranging from mining, smelting, incineration, and water treatment processes, while pollution through natural origin is as a result of wind and rain erosion and through eruption of volcanoes (2), animals are expose to copper through inhalation of contaminated air, ingestion of contaminated water and food, and through skin contact with soil that is contaminated with copper (5). Exposure to copper can occur in plant through deposition on leaves and stem and through absorption of contaminated water in the soil.
1.2.5.2 Toxicity of Copper
The toxicity of copper can be traced to its ability to accept and donate single electrons while undergoing the change of oxidation state (8). The health effects of the acute ingestion of copper or copper compounds by man and animals include gastrointestinal ulcerations and bleeding, acute hemolysis and hemoglobinuria, hepatic necrosis, nephropathy, cardiotoxicity, tachycardia, and tachypnea. Other effects include dizziness, headache, convulsions, lethargy, stupor, and coma, all of which are central nervous system related effects.
Recent cases of accident and research-based studies of copper toxicity are reported in Table 1.2 , based on the effect experienced by the victims.
Copper bioavailability in water is always higher than in other environmental media particularly in diets where it is a function of its solubility as well as the types of complexes in which it is present. These complexes often inhibit copper absorption (12). Chronic toxicity in human often results in liver and liver related diseases ( Table 1.3), such as Wilson, hepatic, and renal diseases (13). Wilson disease impacts cases of acute toxicity of copper leading to liver disease (14).
Information on the studies of toxicity of copper in animals is sparsely available and these cover mainly physiological, biochemical, and pathological aspects of copper metabolism or chronic toxicity of copper in comparison to the copper concentration standard in human diets. As such the level of acute copper toxicity demonstrated in these animals cannot be adopted as standard for humans. The maximum contaminant level goal (MCLG) for copper is given as 1.3 mg/L (21,22); this concentration indicates gastro intestinal symptoms. The International Programme on Chemical Safety, (IPCS) (23), stipulated 2–3 mg Cu per day as the upper limit of acceptable range of copper intake and these values have received World Health Organization (WHO) acceptance (24) ( Table 1.4).
TABLE 1.2
Health Effects of Chronic Toxicity of Copper in Humans and Animals
Health Effect Victims References
Acute hemolytic anemia
Humans; sheep (13)
Cessation of menstruation and osteoarthritisHumans (14)
Neurological abnormalities
Prevention of embryogenesis
Enhancement of endogenous
Rats (15,16)
Women (17,18)
Oxidative reaction leading to DNA damageHumans (19,20)
TABLE 1.3
Acute Copper Toxicosis Resulting from Oral Exposure (Ingestion)
Exposure Cases Health Effect
Copper Exposure Measurement (mg/L)References
43 individuals in single point source contact in hotelAcute illness 4.0–70 (9)
5 drank water with over night build up of copperAbdominal symptoms >1.3 (10)
60 adult women of low socio-economics status Gastrointestinal effect ≥3 No symptoms >5 (11)
TABLE 1.4
Maximum Limits of Copper for Environmental Releases and Human Exposure
Dietary (RDA) Children (0–3 years)0.34 mg/day NAIM
Dietary (RDA) Children (4–8 years)0.44 mg/day NAIM
Source: The facts on copper, Dartmouth College, Hanover, NH, http://www.dartmouth.edu/, 2015.
Note: US EPA—US Environmental Protection Agency; OSHA—Occupational Safety and Health Administration; NIOSH—National Institute for Occupational Safety and Health; and NAIM— National Academics Institute of Medicine.
1.2.6 InteraCtIon of Copper wIth other elements
Many divalent cations such as copper, cadmium, cobalt, lead, and zinc influence the synthesis of metallothionein as a result of their binding properties. However, this competition often leads to the physiological regulation of these elements in relation to the presence and concentration of the other (25). The effects of interaction of copper with other elements are as shown in Table 1.5
1.3 ZINC
1.3.1 zInC and Its Compounds
Zinc, one of the most common elements in the Earth’s crust, is found in the air, soil, and water and is present in all foods. Zinc in its pure elemental (or metallic) form is a bluish-white, shiny metal. Zinc is commonly used in the industry to coat steel and iron as well as other metals to prevent rust and corrosion; this process is called galvanization. Metallic zinc, when mixed with other metals forms alloys such as brass and bronze. A zinc and copper alloy is used to make pennies in the United States. Metallic zinc is also used to make dry cell batteries (33).
Zinc can combine with other elements, such as chlorine, oxygen, and sulfur, to form zinc compounds such as zinc chloride, zinc oxide, zinc sulfate, and zinc sulfide. Most zinc ore found naturally
TABLE 1.5
Effect of Interaction of Copper with Other Essential Elements
Combination
Zinc and copper
Effects
References
Induction of intestinal metallothionein synthesis leading to poor systemic absorption of copper (26)
Reductions in erythrocyte superoxide dismutase in women (27)
Molybdenum and copperDecrease in copper uptake leading to copper utilization and toxicity (28,14)
Ferrous iron and copperDecrease in copper absorption in intestine (12,29)
Stannous tin and copperDecrease in copper absorption in the intestine (12,30)
Selenium and copperNo significant hepatic and histological alterations in rats subjected to study(31,32)
in the environment is present in the form of zinc sulfide. Zinc sulfide and zinc oxide are used to make white paints, ceramics, and other products. Zinc enters the air, water, and soil as a result of both natural processes and human activities. Zinc, in most cases enters the environment through mining, purifying of zinc, lead, and cadmium ores, steel production, coal burning, and burning of wastes. These activities can increase zinc levels in the environment. Waste streams from zinc and other metal manufacturing and zinc chemical industries, domestic waste water, and run off from soil containing zinc can discharge zinc into waterways. The level of zinc soil increases mainly from disposal of zinc wastes from metal manufacturing industries and coal ash from electric utilities (33). Zinc is present in the air mostly as fine dust particles, which eventually settles over land and water. Zinc in lakes or rivers may settle on the bottom, dissolve in water, or remain as fine suspended particles. Fish can ingest zinc in from the water and from their feeding habits. Depending on the type of soil, some zinc from hazardous waste sites may percolate into the soil and thus cause contamination of groundwater. Zinc may be ingested by animals through feeding or drinking of water containing zinc.
1.3.2 CharaCterIstICs of zInC
Zinc is not found in its free state in nature but can be processed from its ore. This bluish-white element has melting and boiling points of 419.5°C and 908°C, respectively (34). It tends to form a covalent bond with sulfide and oxides (35) and show amphoteric characteristics (36). On exposure to air, it forms a coat of zinc oxide, which covers the underlying metal and gives it anti-corrosion properties. In anaerobic condition, it may form zinc sulfide. Zinc influences membrane stability in humans and plants and plays a role in the metabolism of proteins and nucleic acids (37).
1.3.3 produCtIon of zInC
Zinc is essentially produced from its ore excavated from both underground and open pits through an electrolytic process involving the leaching of zinc oxide, from calcined ore, with sulfuric acid, leading to the formation of zinc sulfate solution. The solution is then subjected to electrolysis after which zinc deposits are collected on cathode electrodes (38). About 90% of the zinc production comes from zinc sulfide, ZnS (sphalerite) (35). In 2001, world production of zinc was 8,850,000 metric tons and the United States contributed about 799,000 metric tons (39).
1.3.4
applICatIon of zInC
Industrially, zinc is widely used as protective coating on metals such as iron and steel that are highly susceptible to corrosion. It is also used in the production of zinc-based alloys involving other metals
such as aluminum, copper, titanium, and magnesium. In 2002, over 50% of the zinc produced in the United States was used for galvanizing, while about 20% was used for zinc-based alloys, and the remaining specifically went for the production of bronze and brass (40). Other applications of zinc include production of campaigned zinc which is used in a wide range of industries as an essential material for production (35,37,38).
1.3.5 toxICIty and related hazard
Zinc has been reported to play important roles in plants and humans, particularly in the metabolism of proteins and nucleic acids (37). It, however, affects human and animals when taken in higher concentration and for a prolonged time thus resulting in adverse health effects (33).
1.3.5.1 Route of Exposure
Principal human activities leading to the release of zinc and zinc compounds into the environment are zinc mining, purification, and decomposition. Run off from ore, production, and waste sites distribute zinc into water ways and over soil. Leaching of waste sites and other areas contaminated with zinc eventually contaminate underground water. Fine dust particles from the production sites are often bound to aerosols (41) and are later washed down by rain, snow, or wind onto land, water, and vegetation. In water, zinc is present in suspended form, dissolved form or bound to suspended matter (42). Human and animals are exposed to zinc and its compound through ingestion of food, water, and soil. Use of zinc-plated and zinc-based products such as paints and batteries are other sources of exposure in addition to occupation exposure which involves inhalation, food consumption, and skin contact. Zinc accumulates in aquatic organisms which invariably form human diets (33). Plant species, soil pH, and the composition of the soil greatly influence the accumulation of zinc in plants (43).
1.3.5.2
Toxicity
The exposure of animals and humans to acute concentration of zinc and its compounds often results in adverse health effects. The inhalation of a high concentration of zinc dust for a prolonged periods of time results in flu like symptoms, fever, sweating, headache, and subsequent weakness (44). Oral exposure to zinc often interferes with the essential body metabolism of copper and this may result in hematological and gastrointestinal effects as well as decrease in cholesterol levels in the body. Zinc is often absorbed in the small intestine and its uptake from a normal diet ranges from 26% to 33% when taken with food (45,46). Zinc in animal blood does not undergo metabolism, but interacts with protein or forms soluble chelating complexes. Recent cases of accident and research-based studies of zinc toxicity are reported in Table 1.6
Generally ingestion of zinc at a high concentration causes decrease in cholesterol levels and copper metalloenzyme activity (51,52) and other health effects such as hematological gastrointestinal and immunotoxicity (53) ( Table 1.7).
Inhalation of zinc, in the form of zinc oxide fumes or zinc chloride from the smoke of bombs, shows different adverse health effects including dryness and irritation of the throat, and other effects, which manifest after hours when exposure persists for 1 or 2 days (35) (Table 1.8).
Zinc is essentially needed in human nutrition; the recommended dietary allowance (RDA) is given in Table 1.9.
1.3.6
InteraCtIon of zInC wIth other elements
Metabolism leading to toxicity is often activated or deactivated by the presence of other elements in both plant and animal. For a particular element under study, many studies have shown the interaction between zinc and other metals to be of significant reaction. Few of these studies are summarized in Table 1.10
TABLE 1.6
Zinc Toxicity Resulting from Oral Exposure
Exposure Cases Health Effect
21 men and 26 woman fed with zinc for 6 weeks
31 men and 38 women fed with zinc for 1 year
9 men and 11 women fed with zinc for 8 weeks
Abdominal cramps, nausea, and vomiting
Lower mean serum certainties, lower total serum protein, lower serum curare acid and higher mean corpuscular hemoglobin (Hb)
Zinc Exposure (mg/day)References
2–15(47,48)
20–150(49)
Increase in plasma zinc concentration and decrease in DNA oxidation 45 (50)
TABLE 1.7
Health Effect of Chronic Toxicity of Zinc in Animals
Health Effects
Decrease in erythrocytes and Hb levels; total and differential leukocyte levels. Percentage increase in reticulocytes and polychromatophilic erythrocytes
Species References
13 males and 16 females and Wistar rats (62)
Decrease in Hb level and serum capper. Increase in serum and tissue7–8 male New Zealand white rabbits (63)
Negative effect on retention of learned behavioral response
Increase in lavage fluid parameters
A group of 9–12 male and female Swiss mice (64)
Hartley Guinea pigs and 344 Fischer rats (57)
Distortion of chromosome structure of sperm 10 male Sprague-Dawley rats(65)
TABLE 1.8
Zinc Toxicity Resulting from Inhalation Exposure
Exposure Case Health Effect
Shipyard workers who sprayed zinc onto steel surfaces
Workers exposed to zinc oxide fumes
Aches and pains, dyspnea, dry cough, lethargy, and fever
Impaired lung function
Concentration of ZincReferences
(54)
(55,56)
4 adults exposed to zinc oxide fumes for 2 hChills, muscle/joint pain, chest tightness, dry throat, and headache 5 mg/m3 (57)
A group of 13 healthy nonsmoking individuals exposed to zinc oxide fumes for 2 h Fatigue, muscle ache, and cough0–5 mg/m3 (58)
20 Chinese workers exposed to zinc oxide over a single 8 h workday
13 soldiers exposed to zinc chloride smoke during combat exercise
No significant health effect detected or reported 0–36.3 mg/m3 (59)
Decrease in lung diffusion capacity, plasma level of fibrinogen elevated at 1–8 weeks postexposure
3 patients exposed to zinc chloride for 1–5 minTwo died of edema, pulmonary sepsis, emphysematic changes, and necrosis. The third revealed severe restrictive pulmonary dysfunction
Unknown(60)
Unknown(61)
TABLE 1.9
Recommended Dietary Allowance (RDA) Requirement of Zinc at Various Life Stages and Gender
Source: US EPA. Toxicological Review of Zinc and Compound. Washington, DC: US Environmental Protection Agency, 2005. EPA/635/R-05/002.
TABLE 1.10
Effects of Interaction of Zinc with Other Essential Elements
Combination
Effect
References
Copper and zincInduction of intestinal metallothionein synthesis leading to poor systemic absorption of copper (67)
Calcium and zincNo significant interference with absorption of zinc nor changes in hair or serum zinc(68,69)
Iron and zincSignificant lower percentage zinc absorption particularly in pregnant women (70)
Increased dietary iron intake result in diminished absorption of zinc (71)
Cadmium and zincLikely decrease of toxicity and carcinogenicity of cadmium (72,73)
Inhibition of zinc absorption toxic at level of cadmium is possible (44,68)
Lead and zincNo significant evidence of possible interference of absorption of zinc by lead and vice versa (74,75)
Cobalt and zincStudy animals (rats) demonstrated protection against the testicular toxicity of cobalt in the presence of zinc (76)
1.4 SILVER
1.4.1 sIlver and Its Compounds
Silver is a ductile and white metallic element represented by the symbol Ag and assigned with atomic number 47 and atomic weight 247.8014 on the periodic table of the element. It is found in the environment mostly as silver sulfide (AgS) or in combination with other metals (77). Its primary source is the ore while other sources include new scrap generated in the manufacturing of silvercontaining products (Table 1.1). The anthropogenic sources of silver in the environment include smelting operations, coal combustion, production and disposal of silver-based photographic and
TABLE 1.11
Maximum Concentration of Silver Distribution in the United States
Destination ConcentrationSitesReferences
Air near smelter
Seawater
36.5 ng/m3 Idaho(78)
8.9 μg/L Galveston(79)
Soil 31 mg/kgIdaho(78)
Liver of marine mammals1.5 mg/kg–(80)
Mushrooms 110 mg/kg–(81)
electrical materials, and cloud seeding (78). The larger percentage of the lost silver is immobilized in the form of minerals, metals, or alloys in the terrestrial ecosystem which serve as their destination (Table 1.11). About half of the emitted silver into the environment is precipitated some kilometers away from its point source (77).
1.4.2 CharaCterIstICs of sIlver
Silver is a solid metal at room temperature but occurs naturally in several oxidation states, which include Ag0, Ag+, Ag2+, and Ag3+ (77) and forms compounds with sulfide, bicarbonate, and sulfate (77). Ag2+ and Ag3+ are more effective oxidizing agents than Ag0 and Ag+ but are relatively unstable in an aqueous environment with a temperature close to 100°C. Silver exists as silver sulfhydrate (AgSH) or as a polymer HS Ag S Ag SH at the lowest concentration in the aqueous phase. However, at higher concentration, it exists as colloidal silver sulfide or polysulfide complexes (82). Only two isotopes of silver, 107Ag and 109Ag are stable and exist naturally, the other 20 isotopes do not exist naturally. Some compounds of silver, like silver oxalate (AgC2O 4), silver acetylide (Ag2C2) and silver azide (Ag N3) are potential explosives.
1.4.3 produCtIon of sIlver
The current world estimate of mine production of silver is given as 15.5 million kg (83) and their distribution is given in Table 1.12
TABLE 1.12
World Major Mine Producers of Silver
Source: Eisler R. Silver Hazards to Fish, Wildlife and Invertebrates: A Synoptic Review. Washington, DC: US Department of the Interior, National Biological Service, 44pp. (Biological Report 32 and Contaminant Hazard Reviews Report 32), 1997.
The open pit or underground mining methods are the predominantly used methods for the mining of silver. The excavated ore is upgraded through floatation, smelting, and a series of other processes; the pure silver is extracted using an electrolytic process (electrolysis) (77).
1.4.4 applICatIon of sIlver
The use of silver has been dated back to the historical period of man’s civilization where it was used in ornamental materials, utensils, coinage, and even as basis of wealth. It has, however, been used in recent times as raw material for the production of a variety of other products. The industrial use of silver in the United States is summarized in Table 1.13.
Silver is also used in the water purification process because of its bacteriostatic property; it has equally been employed in food and drugs processing (77). Silver is used medically for the treatment of burns and as an antibacterial agent. It is also used as catalyst in the industrial production of some chemicals such as formaldehyde and ethylene oxide.
1.4.5 toxICIty and related hazards
Silver has been reportedly used in food and for medical purposes by man (77); however, its release and eventual contact with both plants and animals in the environment in toxic concentrations results with adverse health consequences.
1.4.5.1 Route of Exposures
Silver from anthropogenic sources is often transported over a long range and reaches the soil through wet and dry deposition and eventual sorption to soils and sediments. Silver reaches underground water through leaching which is influenced mostly by the decreasing pH of the soil (77). The presence of silver in marine environments is also influenced by salinity, as a result of its strong affinity for chloride ions (84). The presence of silver in some aquatic organisms varies considerably with the ability of such organisms to bioaccumulate silver (85). Animals and humans can be exposed to varying concentrations of silver as a result of occupation, skin contact, ingestion, and inhalation. Skin contact and inhalation are generally occupational exposure; however, further contact occurs through the use of ornaments and other domestic products made of silver, and the use of silver utensils leads to ingestion (77).
1.4.5.2 Toxicity of Silver
Exposure to a high concentration of silver through different routes resulted in adverse health effects in people. Inhalation of dust containing a high concentration of silver compound, like AgNO3 or
TABLE 1.13
Use of 50% of Refined Silver Produced in the United States (1990)
Product
Source: ATSDR. Toxicological Profile for Silver. Atlanta, GA: US Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry (TP-90-24), 1990.
TABLE 1.14
Acute Silver Toxicosis Resulting from Exposure
Exposure Cases
112 workers exposure to work place silver nitrate and silver oxide
Rise in blood silver 0.6 μg silver/100 mL blood 0.039–0.378 mg silver/m3
Workers at photographic facilityPresence of silver in blood, urine, and fecal samples0.001–0.1 mg/m3
Source: ATSDR. Toxicological Profile for Silver. Atlanta, GA: US Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry (TP-90-24), 1990.
TABLE 1.15
Effect of Toxicity of Silver on Terrestrial Plants
Plant Species Effect
Lettuce
Rye grass
Seeds of corn, oat, turnip, soybean, spinach in silver rich soil
Exposure LevelReferences
Adverse effect on germination0.7 mg silver/L (88)
Adverse effect on germination7.5 mg silver/L (88)
No adverse effect on germination106 mg silver/kg dry soil(89,90)
Seed of Chinese cabbage and lettuceAdverse effect on germination106 mg silver/kg dry soil(89,90)
AgO, may cause trachea-related problems like lung and throat irritation as well as stomach pain. Skin contact with silver demonstrates rashes, swelling, and inflammation (77). Silver demonstrates high level of toxicity to aquatic plants and animals particularly in its ionic state (86,87). Recent cases of accident and research-based studies of silver toxicity are reported in Table 1.14 Generally, the accumulation of silver is higher in aquatic media than in soils and thus, aquatic animals are expected to be more affected by the toxicity of silver than terrestrial animals (87,88). Most aquatic organisms demonstrate a high accumulation of silver at nominal concentration of 0.5–4.5 μg/L and corresponding health effects include stunted growth, muting, and histopathology (78). Studies have shown that silver accumulations in aquatic organisms such as marine algae are due mainly to adsorption rather than uptake (88). Accumulation of silver by terrestrial plants is relatively slow and only affects the plant growth but higher concentration may eventually lead to the plant’s death. Tables 1.15 through 1.17 report cases of toxicity of silver in terrestrial plants.
1.4.6 InteraCtIons of sIlver wIth other elements
Interaction of silver and other metals usually influences absorption, distribution, and excretion of one or more of the metals (77). Though silver demonstrates good dissociation in water media, its interaction with other elements is sparsely documented in the literature. However, studies show interaction between silver and selenium increases deposition of insoluble silver salt in body tissue (77).
1.5 MOLYBDENUM
1.5.1 molybdenum and Its Compound
Molybdenum is a transition metallic element existing in five oxidation states (II–VI). It has a silvery white color in its pure metal form and is more ductile than tungsten (101). It has a melting point of 2623°C (102) but boils at a temperature above 600°C (103). Molybdenum largely exists in association with other elements and molybdate anion (MoO 4 2 ) is its predominant form found in soil and
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Title: Kyllikki ja Lemminkäinen Laulurunoja
Author: Hilja Liinamaa-Pärssinen
Release date: April 1, 2024 [eBook #73309]
Language: Finnish
Original publication: Helsinki: E. E. Sundvall, 1902
Credits: Tapio Riikonen *** START OF THE PROJECT GUTENBERG EBOOK KYLLIKKI JA LEMMINKÄINEN ***
KYLLIKKI JA LEMMINKÄINEN
Laulurunoja
Kirj.
HILJA LIINAMAA [Hilja Pärssinen]
Helsingissä, E. E. Sundvall, 1902.
SISÄLLYS:
Alkutunnelma.
Kyllikin lauluja.
Kyllikin kuolo.
Loppusanat.
ALKUTUNNELMA.
Majan pienen porraspuulla istun monta iltaa. Luokseni käy unten immet sinerväistä siltaa.
Leiniköt ja sinikellot mulle nyökkii päitään. Keltaperhot riemuitsee ja hyppelevät häitään.
Käki kukkuu kaihojansa, hohtaa ilman pieli. Poskilleni rusko nousee, herkkyy hellä mieli.
On kuin suru suistuisi, ja murenisi murhe. Unhoittuisi ikävä ja elon tyhjä turhe.
I.
II.
Oi pihlaja, mun pihlajain sä valkokukkainen. Sä laulun puu ja unelmain ja suvimuistojen.
Mä nään sun kukkas hohtavat ja latvas lahean. Ja kuulen sadat soitelmat ja lehväis huojunnan.
Oi pihlaja, mun pihlajain Sun lemmin varjoas.
Mä tahdon luonas olla ain’ ja kuulla kuiskeitas.
III.
Etsin elämästä sovun suurta rauhaa, vaivain viihtymystä, sulomieltä lauhaa. Etsin päivästä ja yöstä, etsin levosta ja työstä.
Uurastin ja raastin, vaikka koski rintaa. Elämä se nosti kärsimyksen hintaa, kunnes ratkes suru silloin, itkin yöni, itkin illoin.
Vihdoin kanteloisen polvelleni nostin. Helkynnällä soitin kohtaloni kostin. — Ja mun soittaissani saavat hoivaa rinnan verihaavat.
KYLLIKIN LAULUJA.
I.
Mä pakenen rannalle lahdekkeen, kun sulhoja tuvassa liikkuu.
Täällä eessäni nään minä vapahan veen ja allin, mi aalloilla kiikkuu.
Ne turhaan tarjovat kihlojaan Kuu, Päivä ja Illantähti.
Mun mielen’ on allina aalloilla vaan, jo ammoin se sinne lähti.
Mun mieleni lähtihe uneksimaan siitä suuresta sankarista, joka kerran saapuvi kertomaan mulle oudoista rantamista.
Pois vieköhöt kihlansa sulhot nuo, pois helmyet, huivit ja soijet; kenen sydän jo kammoten luotaan luo, hällä kolkot on vuotehen oljet.
III.
Mä vuottelen aikoa armasta, kun saapuvi satujen seppä, josta kertovi aaltonen liikkuva ja rannan tuomi ja leppä.
Kas silloin pyynä mä pyrähtelen hänen lietensä lämpimille. Ah kerran, kerran mä matkannen satusaarille kaukaisille.
Milloin tulet toivojeni kulta, unten urho uljahin. Tulet hehkuin taivahista tulta, kiidät kotkan lentimin. Kutsut, viehätät mun valtavasti, tempaat Pävätärten karkeloon, sinne missä pilvet hartahasti kietoo, hurmaa huumioon.
Milloin tuletkaan sä uneksuttu sulho, säihkysilmäinen, aatoksilleni niin outo — tuttu, jota odotan mä arkaillen. — Katso, rusoittaapi taivonkaari hattaroiden harjalla. Siintää silmihini satusaari tuolla, tuolla kaukana.
Päivä on kirkas, ja notkuu vain kangaspuissani niidet. Lemmenkaihossa vuoteellain valvonut yöt olen viidet.
Valvonut yöt olen nähtyäin Kaukon sulhoista parhaan.
II.
Oon kuni eksynyt mielessäin lempeni kukkaistarhaan.
Lentäös syöstävä sukkelaan, ottaos vauhtia uutta.
En minä lemmestä riudukaan, valvo en yötä mä kuutta.
En minä jouda kuihtumaan Kaukoni silmien nähden.
Kukkana mielin notkua vaan, kun minä kisoihin lähden.
Päivä on kirkas, ja kimmoilee helskyen kankaassa pirta.
Hopean hohtavaks’ vaikenee mieleni vierivä virta.
— 10 —
IV.
Tapiolan valkopirttiin pieni polku johtaa. Metsä soi, ja taivon ranta ruskopilvin hohtaa.
Tapiolan talosehen pieni polku johtaa. Metsä soi, ja taivon ranta ruskopilvin hohtaa.
Oi te aallot autuaat sopuisesti soliskaat. Soikaa heljät haapapuut. Soikaa leivot laulusuut, kunis vaihemieli vaihtuis, levottomuus multa haihtuis.
Kaksi ääntä kuulen mä, Yks' on lemmen hyminä, toinen vieraan varoitus: "Kiellä Ahdin rakkaus, sill' on mieli tuulen Turjan, ajatuskin aallon hurjan." —
VI.
Oi te aallot autuaat sopuisesti soliskaat. Virittäkää virsi uus’, sopusointu, suloisuus — Sydämeni voitti Ahti. Suun, suur’ on lemmen mahti.
Kullankukkaa omaa heruttelen hiljaa vain. Valkolehmää somaa varoellen lypsän ain’.
Yhyy, kullankukka etpähän sä arvaakaan, minne tyttörukka luotasi pois kutsutaan.
Kauvas, kauvas täältä kohta käypi Kyllikki. — Kysy ilman säältä, minne tieni kulkevi.
Tutki tuulosilta, missä lehti levon saa. Kysy lainehilta maininkien satamaa.
Yhyy, ystäväni et sä mua ymmärrä. Voi mun sydäntäni, sieill' on outo ikävä.
Lypsän kotikarjaa, lypsän kerran viimeisen. — Tuolla aallon harjaa kulkee Kaukon venonen.
VII.
Jää hyvästi nyt metsäpolkuni ja vaahtera ja raitarukka. Jää hyvästi sä kedon orvokki ja neilikka ja aurankukka.
Ja jääös hyvästi sä mettinen, mi mettä keräät kukkasista.
Ja sulle viime kiitos leivonen sun lauluistasi ihanista.
Myös hyvästi nyt äiti armahin, ja veljyet ja sisarukset.
Mä vaikka vaeltelen kauvaskin, tok' aina muistan kodin ukset.
Mä muistan kotitalon rakkahan sen pihamaalla ruohonkorret ja tyttö-aittani niin puhtoisan, sen valkeaiset seinät, orret.
Oi hyvästi nyt kaikki jääkätte, ja sulo muistot saakoot meille.
Nyt viljoin vieriköhön kyynele, kun kuljen kohtaloni teille.
VIII.
Kaukon tupaan astelen yli kuulun kynnyksen. Painuu kiinni tuvan ovi. Mulla sykkäileepi povi.
Mikä kumma kärsimys on mun rintan väristys.
Miksi pelkään sydäntäni?
Miksi värjyn lemmessäni?
Kuule, Kauko ojenna
mulle kätes tukeva. —
Ymmärrätkö kulta, kulta minun sydämeni tulta?
IX.
Viherjällä niemellä on Ahdin pieni maja.
Tänne saaret siintelee ja metsänrannan maja.
Ahti kutoo verkkoja, ja minä paitaa neulon.
Lemmen tuhat tunteina mielessäni seulon.
Kuule kulta, kaihoni mä rinnastani riivin.
Otsaas hiljaa suutelen ja sylihisi hiivin.
Sull’ laulan ylistystä kesä-ilta mä jolloin lahtuella viivähdin. Kuun hopea se hohti taivahilta. Yö varjojaan loi rannan lehtoihin.
Ja nuotalta me tultiin joukkuella ja laitettihin kalanuotio.
Ol’ äsken saatu työssä tarpoella, siks’ tuntui herttaiselta lepo jo.
Niin siinä lepäelen leutomiellä yövilkon vienoisessa tuokseessa. Ja aatos ailakoitsi ilmantiellä, ja silmä seurasi veen varjoja.
Ja poskuelle poikan’ vetrehisen yö heitti rauhaisata ruskoaan, kun rantamalla saaren terhenisen hän hiljaa hyräeli laulujaan.
Hän viihtymyksen virttä lauleskeli, mä lemmen ikuisuutta aattelin.
Kuun kulta lainehilla leikitteli, ja yöhyt varjojaan loi rantoihin.
XI.
Minä miekkoinen miniä vierellä hyvän anopin Ahdin liettä leyhyttelen puhun tulta Tuiskumielen.
Anopill’ on lämmin silmä, siksi mielellä hyvällä villalangan vierittelen, kehreän kotoisen rihman, kaiken kankahan kutoilen.
Anopill’ on puhe hellä, siksi suurella ilolla valkaisen mä vaattehia, pesen paitoja paraita veden valko vaahtosessa.
Minä miekkoinen miniä vierellä hyvän anopin yhtä vainen vaikertelen, tuiskumieltä Lemminkäisen, joka aaltona ajaikse,
hyökynä on hyrskyävi, meren voimalla valuvi.
Jos mä voisin viihdytellä urhoni uhmamielen, sotakaihon Kaukoltani, jos mä voisin laulullani lauhduttaa sen rinnan polton, jos mä voisin lemmelläni soinnuttaa sen soraäänet, asetella meren aavat, tyynnytellä Turjan tuulet, silloin lintuna lepäisin kaulassa kotoisen Kaukon, suloisessa suudelmassa lemmen lauhassa levossa.
XII.
Jo poista Kauko sun vuotees’ luota tuo säilärautasi säihkyinen. Ei meille onnea miekka tuota, sen hurmehaava on hirmuinen.
Oi ellös kättäsi tahraelko, en tuota itkutta nähdä vois.
Mun öitän’ valtaisi synkkä pelko, ja lempi luotani hiipis pois.
Ja haava syömehen syttyis syvä, kun lentäis vainojan nuolet nuo. Oi Kauko olkosi hellä, hyvä ja poista seinältä miekka tuo.
XIII
Mä kuulen humun karkelosta nuorten, kun loppunut on päivän aherrus. Se kaikuu yli vainioin ja vuorten, ja siin’ on ilon-ääni, riemahdus.
Ja mieleni kuin kantamana tuulen se kirpoo irralleen ja karkaa pois. Ja keijuna mä liitäväni luulen, ja on kuin harput hopeaiset sois.
Niin keijusena illan kuutamalla nyt notkuu karkelossa Kyllikki. Mut Ahti ulkona on ulapalla ja yksin verkkojansa vetävi.
XIV.
Etpä sä Kaukoni arvaakaan, kuinka mä itken salaa. Nuoruus pois, pois haipuvi vaan, eikä se koskaan palaa.
Miksi, oi miksi mun ryöstitkään, vielä mä leikkinyt oisin. Taaton tanhuet muistossa nään, sinne jos palata voisin.
Sielläpä kahleitta karkeloi
Kyllikki tyttöraisu. Miksi mun kisoista kiellät, oi liekö lempesi vaisu?
Miksi on katsehes kaihtiva, mistä on silmies uhka?
Itkisit Kyllikin nuoruutta, kohta se kylmä on tuhka.
Oi illan rusko ihana, mi leimut lännen taivaalla mun surujan’ et suistaa voi et voi.
Kuin meren aalto pohjaton, niin musta mureheni on, ja kivunkannel mulle soi se soi.
Mun murtui nuori elämän kuin kevään kukan kelmeän, min ensi halla korjaa pois niin pois. Nyt surren rantahiekalla mä kaipaan kuolon kutsua, kai suruuni ne hoivan tois kai tois.
XVIII.
Voi minua virpi vieno, vesa valju, vaimeloinen povella poloisen luonnon. Jo mä kurja kuihtunenki, kuivun korreksi kulolla, tuskan tuiman polttehessa.
Voi minua virpi vieno erämaassa ehtyneessä, miss’ ei lankea satehet, vieri vilpoiset vetoset. Täällä painuu pääni hento, vaipuu varteni varaton, elon lanka laukeaapi.
