Tempus IV

International Joint Master Programme on Material and Energy Flow Management

544364-TEMPUS-1-2013-DE-TEMPUS-JPHES

ENVIRONMENTAL MONITORING Dr Zoran Todorović, Dr Dragan Cvetković and Dr Milorad Cakić

University of Niš, Faculty of Technology Leskovac

2015

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This written material was developed as part of project activities within the Tempus project 544634-TEMPUS-1-2013-1-DE-TEMPUS-JPHES “International Joint Master programme on Material and Energy Flows management”. The course ENVIRONMENTAL MONITORING is held on the master level and mailnly aimed to engineers. The authors of the book are the creator of their idea and are fully responsible for the content of the written material.

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The basic teaching material for the course entitled ENVIRONMENTAL MONITORING

prepared by Zoran Todorović, Dragan Cvetković and Milorad Cakić based mainly on the following literature sources

EPA-600/4-79-020, Methods for Chemical Analysis of Water and Wastes, Washington, 1983;

Z. Todorović, Zaštita životne sredine, Tehnološki fakultet u Leskovcu, 2014.

V. Rekalić, Analiza zagađivača vazduha i vode, TMF Beograd, 1989;

M. Laušević, Analiza zagađivača vazduha i vode – praktikum, publikacija Katedre za analitičku hemiju TMF Beograd, 2000;

Monitoring ambient air quality for health impact assessment, World Health Organization Regional Office for Europe Copenhagen, Text editing: David Breuer, WHO Regional Publications, European Series, No. 85, 1990;

Quality Assurance Handbook for Air Pollution Measurement Systems Volume II Ambient Air Quality Monitoring Program, U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Air Quality Assessment Division, 2013;

W. Spangl, J. Schneider, L. Moosmann, C. Nagl, Representativeness and classification of air quality monitoring stations, Vienna, 2007;

Guidelines for Ambient Air Quality Monitoring, CENTRAL POLLUTION CONTROL BOARD (Ministry of Environment & Forests, Govt. of India), Parivesh Bhawan, East Arjun Nagar, Delhi;

P. Bruckmann, H.U. Pfeffer, Air Quality Monitoring, Encyclopedia of Ocupational Health & Safety, 2011.

P.K. Basu, Soil Testing in India, Methods Manual, Department of Agriculture and Cooperation Ministry of Agriculture Government of India, New Delhi, January, 2011.

World Meteorological Organization (WMO), Planning of water quality monitoring systems, WMO-No. 1113, Chair, Publications Board World Meteorological Organization (WMO) 7 bis, Avenue de la Paix, PO Box 2300, CH-1211Geneva 2, Switzerland, 2013.

J. Bartram, R. Balance, Water Quality Monitoring - A Practical Guide to the Design and Implementation of Freshwater Quality Studies and Monitoring Programmes, Published on behalf -of United Nations Environment Programme and the World Health Organization, 1996.

A. Dedijer, M. Mitrović-Josipović, E. Radulović, B. Dimić, L. Marić, M. Krunić-Lazić, G. Špegar, D. Vidojević, M. Jovanović, N. Veljković, M. Jovičić, N.Redžić, S. Popović, N. Pajčin, D. Lekić, T. Popović, A. Mijović, ENVIRONMENT in Serbia: an indicator – based review, Ministarstvo nauke i zaštite životne sredine Republike Srbije, 2007 (Beograd : Grafički centar). – [III] 154 str., taken 3.10.2015. at internet address:

www.sepa.gov.rs/download/Environment_in_Serbia_Full.pdf.

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COURSE BASIC DATA Name of the Course ENVIRONMENTAL MONITORING Study Program Material and Energy Flow Management Type and level of study Master Academic Degree Status of Course elective Credits (ECTS) 5 Semester I Aims of the Course Students gain basic knowledge of the environmental monitoring techniques and technology used in sampling, characterizing, remediating and post-remediation monitoring of site-specific environmental projects; and monitoring geographic areas to assess status and trends in environmental conditions/indicators.

Learning Outcomes/Competences of the Course: Students are able to prepare sampling plans for air, surface water, groundwater and soils characterization, remediation, and post-remediation monitoring of site-specific environmental projects. Understand physical, chemical and biological processes that govern contaminant transport, fate and exposure in the air, soils, groundwater and surface waters. Be able to assess compliance with relevant federal, state and local regulations using statistically valid sampling data.

Lessons Theory 30 Practice: 30

Teaching Methods Interactive lectures, group discussions, case studies, seminar paper

Students activities Case studies, Presentations, Seminar Paper, Report writing, Book reviews, Group discussions

List of course material Presentations, Teaching material, Further readings

Further readings 1. EPA-600/4-79-020, Methods for Chemical Analysis of Water and Wastes, Washington,

1983. 2. V. Rekalić, Analiza zagađivača vazduha i vode, TMF Beograd 1989; 3. M. Laušević, Analiza zagađivača vazduha i vode – praktikum, publikacija Katedre za

analitičku hemiju TMF, 2000;

Grade (maximal number of points: 100) Pre-exam duties Points Final exam Points

Activity during the lectures 10 Oral exam 30 Test I and Test II 40 Seminar paper 20

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CONTENTS PREFACE ..................................................................................................................................................................... 11 List of Figures ............................................................................................................................................................ 13 List of Tables .............................................................................................................................................................. 13 1. ANALYTICAL QUALITY ASSURANCE ................................................................................................................... 14

1.1. Quality assurance ...................................................................................................................................... 16 1.2. Components of quality assurance ........................................................................................................... 16 1.3. Management ............................................................................................................................................. 16 1.4. Training ...................................................................................................................................................... 17 1.5. Standard Operating Procedures ............................................................................................................. 17 1.6. Laboratory facilities .................................................................................................................................. 18 1.7. Equipment maintenance and calibration ............................................................................................... 18 1.8. Sampling .................................................................................................................................................... 19 1.9. Sample receipt, storage and disposal ..................................................................................................... 19 1.10. Reporting of results ................................................................................................................................ 19 1.11. Implementation of quality assurance ................................................................................................... 20 1.12. Checking compliance ............................................................................................................................. 20 1.13. Internal quality control .......................................................................................................................... 21 1.14. Choice of analytical method .................................................................................................................. 21 1.15. Validity checking .................................................................................................................................... 21 1.16. Calibration check .................................................................................................................................... 21 1.17. Use of blanks ........................................................................................................................................... 22 1.18. Recovery checking .................................................................................................................................. 22 1.19. Precision and accuracy checks ............................................................................................................... 22 1.20. Control by duplicate analysis ................................................................................................................ 22 1.21. Precision control using pooled reference material ............................................................................. 22 1.22. Accuracy control using certified reference materials ......................................................................... 23 1.23. Summary of an internal quality control program................................................................................ 24 1.24. Remedial action ...................................................................................................................................... 24 1.25. External quality control ......................................................................................................................... 24 1.26. Use and reporting of monitoring data .................................................................................................. 25 1.27. Quality assurance of data ...................................................................................................................... 26 1.28. Basic data checks .................................................................................................................................... 26 1.29. Departure from expected values .......................................................................................................... 27 1.30. Anomalous results .................................................................................................................................. 27 1.31. Analytical feasibility ............................................................................................................................... 27 1.32. Data handling and management .......................................................................................................... 27

2. SOILS ....................................................................................................................................................................... 28 2.1. Soil Profile .................................................................................................................................................. 29 2.2. Soil properties ........................................................................................................................................... 29 2.3. Physical properties of soil ........................................................................................................................ 29 2.4. Chemical properties of soil ...................................................................................................................... 30 2.5. Biological properties of soil ..................................................................................................................... 31 2.6. Testing soil................................................................................................................................................. 31 2.7. Soil sampling procedure .......................................................................................................................... 32 2.8. Soil sampling designs ............................................................................................................................... 32

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2.9. Soil samples collecting ............................................................................................................................. 33 2.10. Soil sample preparation ......................................................................................................................... 33 2.11. Soil post drying care ............................................................................................................................... 34 2.12. Soil color .................................................................................................................................................. 34 2.13. Determination of textures and mechanical composition of soil ........................................................ 34 2.14. Bulk density test ..................................................................................................................................... 35 2.15. Soil porosity ............................................................................................................................................ 36 2.16. Determination of hygroscopic moisture .............................................................................................. 36 2.17. Determination of ignition loss .............................................................................................................. 36 2.18. Determination of mineral matter content ............................................................................................ 36 2.19. Determination of soil acidity ................................................................................................................. 36 2.20. Soil lime requirement ............................................................................................................................. 37 2.21. Determination of soil specific conductivity ......................................................................................... 37 2.22. Humus determination ............................................................................................................................ 37 2.23. Determination of soil buffering capacity ............................................................................................. 38 2.24. Free carbonate test analysis .................................................................................................................. 39 2.25. Ion-exchange properties of soils ........................................................................................................... 39 2.26. Determination of exchangeable calcium and magnesium ................................................................. 40 2.27. Calcium plus magnesium EDTA method .............................................................................................. 40 2.28. Determination of total and readily available phosphorus in the soil ................................................ 40 2.29. Determination of nitrogen in the soil ................................................................................................... 41 2.30. Determination of total nitrogen ............................................................................................................ 42 2.31. Nitrate by phenoldisulfonic acid method ............................................................................................ 42 2.32. Determination of ammonia nitrogen ................................................................................................... 43 2.33. Ammonium by indophenol blue method ............................................................................................. 43 2.34. Determination of total nitrate and nitrite nitrogen ............................................................................ 43 2.35. Determination of total nitrate ............................................................................................................... 43 2.36. Determination of sulfur in the soil ........................................................................................................ 43 2.37. Determination of readily available potassium in the soil ................................................................... 44 2.38. Micronutrients ........................................................................................................................................ 44 2.39. Available zinc, copper, iron and manganese ....................................................................................... 44 2.40. Available boron....................................................................................................................................... 44 2.41. Determination of heavy metals (microelements) contents in the soil by atomic absorption spectrophotometry .......................................................................................................................................... 45 2.42. Sequential extraction ............................................................................................................................. 45 2.43. The phases of sequential extraction ..................................................................................................... 46 2.44. Sorptive (adsorptive and ion exchange bonded) phase ..................................................................... 47 2.45. The carbonate phase .............................................................................................................................. 47 2.46. Easily reducible phase ............................................................................................................................ 47 2.47. Moderately reducible phase .................................................................................................................. 47 2.48. Organic-sulfide phase ............................................................................................................................ 47 2.49. Residual phase ........................................................................................................................................ 47 2.50. The selectivity of extraction agents and their effect on the major heavy metals substrates ......... 47 2.51. Reference material.................................................................................................................................. 48

3. WATER MONITORING ........................................................................................................................................... 50 3.1. Processes affecting water-quality and their effects .............................................................................. 50

3.1.1. Effects of natural phenomena on water quality ............................................................................. 50 3.1.2. Anthropogenic pressures ................................................................................................................. 51

3.2. Point loading and non-point loading ..................................................................................................... 51

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3.3. Spatial and temporal variations .............................................................................................................. 51 3.4. Variability of water quality ...................................................................................................................... 52 3.5. Main purposes of a water quality monitoring program ........................................................................ 52 3.6. Key elements of a water-quality monitoring program ......................................................................... 53 3.7. Establishment of objectives of the monitoring program ..................................................................... 54 3.8. Definition of information needs .............................................................................................................. 54 3.9. Legislation and administrative setting ................................................................................................... 54 3.10. Design of a monitoring program ........................................................................................................... 54

3.10.1. Planning a monitoring network ..................................................................................................... 55 3.11. Monitoring alternatives ......................................................................................................................... 55 3.12. Selection of sampling stations .............................................................................................................. 55 3.13. Documentation ....................................................................................................................................... 55 3.14. Selection of water-quality variables ..................................................................................................... 55 3.15. Categories of WQ parameters ............................................................................................................... 56 3.16. Selection of variables in relation to pollutant sources ....................................................................... 56 3.17. Selection of variables for early warning systems ................................................................................ 56 3.18. Hydrological variables ........................................................................................................................... 57 3.19. Selection of water-quality monitoring methods and techniques ...................................................... 57 3.20. WQM equipment ..................................................................................................................................... 57 3.21. Automatic measurements ...................................................................................................................... 58 3.22. Environmental monitoring .................................................................................................................... 58 3.23. Remote-sensing ...................................................................................................................................... 58 3.24. Frequency of sampling ........................................................................................................................... 59 3.25. Time of sampling .................................................................................................................................... 60 3.26. Collection of samples, types of samples ............................................................................................... 60 3.27. Water sampling methods ....................................................................................................................... 61 3.28. Sample containers .................................................................................................................................. 61 3.29. Sample volumes ...................................................................................................................................... 62 3.30. Sample storage and preservation ......................................................................................................... 62 3.31. Sample storage before analysis ............................................................................................................ 62 3.32. Time interval between water sampling and analysis .......................................................................... 63 3.33. Preservation techniques for water samples ......................................................................................... 63 3.34. General water variables testing methods ............................................................................................ 64

3.34.1. Temperature .................................................................................................................................... 64 3.34.2. Water colour .................................................................................................................................... 64 3.34.3. Water taste and odours .................................................................................................................. 64 3.34.4. Water residue and total suspended solids .................................................................................... 65 3.34.5. Suspended matter, turbidity and transparency ........................................................................... 65 3.34.6. Conductivity .................................................................................................................................... 66 3.34.7. pH, acidity and alkalinity ................................................................................................................ 66 3.34.8. Oxygenation conditions ................................................................................................................. 66

3.35. The Winkler method for dissolved oxygen determination with azide modification ....................... 67 3.36. Membrane electrode method for dissolved oxygen determination ................................................. 67 3.37. Carbon dioxide ........................................................................................................................................ 68 3.38. Chlorophyll .............................................................................................................................................. 69 3.39. Salinity ..................................................................................................................................................... 69 3.40. Nutrients .................................................................................................................................................. 69 3.41. Phosphate ................................................................................................................................................ 70 3.42. Stannous chloride method for phosphate determination ................................................................. 71

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3.43. Nitrogen (Ammonia) ............................................................................................................................... 71 3.44. Nitrogen (Nitrite) .................................................................................................................................... 72 3.45. Nitrogen (Nitrate) ................................................................................................................................... 72 3.46. Organic matter ........................................................................................................................................ 72 3.47. Chemical oxygen demand (COD) .......................................................................................................... 73 3.48. Biochemical oxygen demand (BOD) ..................................................................................................... 74 3.49. Total organic carbon (TOC) .................................................................................................................... 75 3.50. Combustion-infrared method for Total Organic Carbon determination .......................................... 75 3.51. Phenols .................................................................................................................................................... 75 3.52. Oil and grease ......................................................................................................................................... 76 3.53. Major ions ................................................................................................................................................ 76 3.54. Total hardness determination ............................................................................................................... 77 3.55. Calcium determination .......................................................................................................................... 77 3.56. Magnesium determination .................................................................................................................... 77 3.57. Sulfate ...................................................................................................................................................... 78 3.58. Turbidimetric method for sulphate determination ............................................................................ 78 3.59. Chloride ................................................................................................................................................... 78 3.60. Argentometric method for chloride determination ............................................................................ 78 3.61. Chlorine (Residual) ................................................................................................................................. 79 3.62. Silica ......................................................................................................................................................... 79 3.63. Fluoride .................................................................................................................................................... 80 3.64. Boron........................................................................................................................................................ 80 3.65. Cyanide .................................................................................................................................................... 81 3.66. Metals ....................................................................................................................................................... 81

3.66.1. Preliminary digestion for metals ................................................................................................... 81 3.66.2. Colorimetric method for chromium determination ..................................................................... 82 3.66.3. Neocuproine method for cuprous determination ........................................................................ 82 3.66.4. Zincon method for zinc determination ......................................................................................... 82 3.66.5. Phenanthroline method for iron determination .......................................................................... 82 3.66.6. Persulphate method for manganese determination ................................................................... 83 3.66.7. Dithizone method for lead determination.................................................................................... 83

3.67. Organic contaminants ............................................................................................................................ 83 3.67.1. Pesticides ......................................................................................................................................... 83

3.68. Biological variables ................................................................................................................................ 84 3.69. Microbiological indicators ..................................................................................................................... 85 3.70. Sedimentation ........................................................................................................................................ 86

4. AIR MONITORING .................................................................................................................................................. 88 4.1. Air pollutant sources and emissions ....................................................................................................... 88 4.2. Health and demographic information .................................................................................................... 88 4.3. Meteorological information .................................................................................................................... 88 4.4. Topographical information ..................................................................................................................... 89 4.5. Previous air quality information ............................................................................................................. 89 4.6. Monitoring network design ..................................................................................................................... 89 4.7. Measurement planning ............................................................................................................................ 89

4.7.1. Area measurement: ........................................................................................................................... 89 4.8. Number and distribution of monitoring locations ................................................................................ 91 4.9. Selection of monitoring location ............................................................................................................. 92 4.10. Representative site ................................................................................................................................. 92 4.11. Proper air sampling ................................................................................................................................ 93

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4.12. Comparability ......................................................................................................................................... 94 4.13. Topographical and meteorological factors .......................................................................................... 95 4.14. Sampling duration and frequency ........................................................................................................ 95 4.15. Measurement methods .......................................................................................................................... 96 4.16. Selection of technique for air measurement ........................................................................................ 96 4.17. Monitoring methods .............................................................................................................................. 97

4.17.1. Continuous monitoring .................................................................................................................. 97 4.17.2. Optical long-distance measurement procedures ......................................................................... 98 4.17.3. Passive monitoring ......................................................................................................................... 98

4.18. Mobile air quality monitoring laboratory (MAML) .............................................................................. 99 4.19. Meteorological measurements ............................................................................................................. 99 4.20. Laboratory requirements ....................................................................................................................... 99 4.21. Selection of pollutants ......................................................................................................................... 100 4.22. Methods for solid and liquid particles analysis ................................................................................. 100 4.23. Measuring wet depositions ................................................................................................................. 103 4.24. Methods of gases and vapors analysis ............................................................................................... 104 4.25. Measurement procedures for inorganic gases .................................................................................. 104 4.26. Automated procedures ........................................................................................................................ 106 4.27. SO2 measurements ............................................................................................................................... 106 4.28. NO2 Measurements ............................................................................................................................... 107 4.29. RSPM/PM10 Measurements ................................................................................................................. 107 4.30. SPM Measurements .............................................................................................................................. 107 4.31. CO measurements ................................................................................................................................. 107 4.32. Ozone measurements........................................................................................................................... 108 4.33. Ammonia measurements ..................................................................................................................... 108 4.34. Measurement procedures for organic air pollutants ........................................................................ 109 4.35. Hydrocarbons measurements ............................................................................................................. 111

4.35.1. Formaldehyde (CH2O) ................................................................................................................... 111 4.35.2. Benzene (C6H6) ............................................................................................................................... 111 4.35.3. Toluene (C7H8) ................................................................................................................................ 112 4.35.4. Polycyclic aromatic hydrocarbons measurements .................................................................... 112

4.36. Oxides of nitrogen measurements ...................................................................................................... 112 4.37. Volatile organic compounds measurements .................................................................................... 112 4.38. Particulate monitoring ......................................................................................................................... 112 4.39. Data handling and presentation ......................................................................................................... 113 4.40. Reporting data ...................................................................................................................................... 114

5. BASIC STATISTICAL ANALYSIS .......................................................................................................................... 115 5.1. General considerations .......................................................................................................................... 115 5.2. Outline of statistical techniques ............................................................................................................ 116

5.2.1. Analysis of data distributions ........................................................................................................ 116 5.2.2. Testing assumptions about data sets ............................................................................................ 116 5.2.3. Specifying data magnitudes and variability ................................................................................. 116 5.2.4. Estimating reliability of data statistics .......................................................................................... 116 5.2.5. Comparisons of data sets ................................................................................................................ 117 5.2.6. Associations between data sets ..................................................................................................... 117 5.2.7. Identifying trends and seasonality within data sets .................................................................... 117 5.2.8. Testing theories relating to the quality data ................................................................................ 117

5.3. Use of data and the need for supporting information ........................................................................ 117 5.4. Environmental quality standards and indices ..................................................................................... 118

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5.5. Simple graphical presentation of results ............................................................................................. 118 5.6. Reporting ................................................................................................................................................. 119

5.6.1. Types of report ................................................................................................................................. 119 5.6.2. Study plan report ............................................................................................................................ 119 5.6.3. Protocol and methods report ......................................................................................................... 119 5.6.4. Data report ....................................................................................................................................... 120 5.6.5. Interpretative report ....................................................................................................................... 120 5.6.6. Structuring a report ........................................................................................................................ 120

6. ENVIRONMENT IN SERBIA .................................................................................................................................. 122 6.1. Energy ...................................................................................................................................................... 122 6.2. Mining ...................................................................................................................................................... 122 6.3. Industry .................................................................................................................................................... 123 6.4. Air quality monitoring ............................................................................................................................ 123 6.5. Water quality monitoring ...................................................................................................................... 124 6.6. Soil quality monitoring .......................................................................................................................... 126 6.7. Waste ........................................................................................................................................................ 127

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PREFACE

This teaching material related to the mandatory course Environmental Monitoring is prepared for the students of the master academic studies Material and energy flow management, in the frame of the international project International Joint Master program on Material and Energy Flows management, TEMPUS IV, number 544364-TEMPUS-1-2013-DE-TEMPUS-JPHES.

Environmental Monitoring and Assessment discusses technical developments and data arising from environmental monitoring and assessment, principles in the design of monitoring systems, and the use of monitoring data in assessing the consequences of natural resource management and pollution risks.

A comprehensive literature review was conducted to identify possible monitoring methods and determine data that were available. In gathering this information special consideration was given to the suitability and practicality of monitoring and assessment methods to adequately fulfill the information requirements of the stated delisting goals. Several factors were accounted for in selecting the suggested methods: Quality of data; ease of implementation; specialized equipment or personnel needed; historical use; and cost. Greater weight was given to methods that have been field-tested or were already in use, but novel methods were also considered when deemed beneficial.

This publication presents recommended testing procedures for making determinations of the soil properties to be used in the design of civil works projects. It is not intended to be a text book on soils testing or to supplant the judgment of design engineers in specifying procedures to satisfy the requirements of a particular project. This publication discusses the monitoring of the quality of inland waters, including rivers and streams of all sizes, from their source to tidal limit (i.e. the influence of saltwater intrusion), canals and interconnecting river systems, lakes of all types and sizes, including marshes and swamps, reservoirs and river impoundments and groundwater. These water bodies comprise inland water resources which may be subject to anthropogenic influences or are intentionally used for municipal or industrial supply, irrigation, recreation, cooling or other purposes.

The main emphasis is on the strategies and objectives of the program and general criteria for the design of the monitoring network. Also described are the kinds of variables needed when water quality is to be monitored for different purposes (such as agriculture/irrigation, drinking-water

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sources, industrial water demand, livestock needs, etc.). Guidance on the selection of main monitoring methods and techniques for the different variables is then provided.

For setting up of any ambient air quality monitoring station, the most important thing to be considered prior to commencement of actual monitoring is to collect its background information. The background information that needs to be collected includes details of sources and emissions, health status, demography, population growth, landuse pattern, epidemiological studies. Such prior information will provide immense help to identify the likely effects and in particular health impacts resulting from population exposure to air pollutants.

This is followed by the definition of the resources required for the monitoring program (laboratory facilities, field stations, equipment and instruments, office and field staff and the estimation of costs of the program). Finally, the essential operational issues of quality assurance and data handling, leading to the reporting and dissemination of results and findings, are also covered.

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List of Figures Figure 1. Kjeldahl apparatus for total nitrogen content determination

List of Tables Table 1. Definitions associated with analytical quality assurance

Table 2. Necessary checks to be carried out when a problem is detected with an analytical method

Table 3. Parameters for measurement planning in measuring ambient air pollution concentrations (with example of application)

Table 4. Long-distance measurement procedures

Table 5. Measurement procedures for suspended particulate matter (SPM)

Table 6. Manual measurement procedures for inorganic gases

Table 7. Automated measurement procedures for inorganic gases

Table 8. Overview of common chromatographic air quality measurement procedures of organic compounds (with examples of applications)

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1. ANALYTICAL QUALITY ASSURANCE1 This chapter outlines the various techniques that may be employed in analytical quality assurance, and the reasons why they should be used. Reliability of data for a environmental quality monitoring program depends on strict adherence to a wide range of operating procedures for environmental sampling and analysis. It is the consistent application and monitoring of these procedures that is referred to as quality assurance. The subject can be confusing, especially if more than one reference work is used as an information source. Different authors may use different terms to describe the same thing or the same term to describe different things. The definitions are based on the vocabulary approved by the International Organization for Standardization (ISO) but may not have been universally adopted by those involved in analytical quality assurance. In order to demonstrate that a laboratory is producing data of adequate precision, accuracy and sensitivity it is necessary to assess all laboratory procedures at all stages from sampling to reporting. This is a time consuming and costly process and, for this reason, it is important to ensure that the necessary standards of performance are clearly defined and adhered to. In most laboratories, analytical quality assurance will start with the examination and documentation of all aspects of laboratory management. This will include clearly identifying lines of communication and responsibility, the description and documentation of all procedures which are carried out, and the documentation of instrumental and analytical checks. Within this there should be specific control and assessment procedures designed to monitor quantitatively the accuracy and precision of specific assays. Analytical quality assurance procedures should be based on a system of traceability and feedback. Traceability, in this context, requires that all steps in a procedure can be checked, wherever possible, by reference to documented results, calibrations, standards, calculations, etc. For example, where a balance is used in a laboratory, the accuracy of measurement must be regularly checked. The weights used for this purpose should either have a certificate demonstrating that they conform to a standard, or the balance must be regularly checked against such standards by the regular use of check weights which are well documented and thus can be linked within the

1 Taken from:

1. Todorović Z. Zaštita životne sredine, Tehnološki fakultet u Leskovcu, 2014. and 2. Bartram J., Balance R. Water Quality Monitoring - A Practical Guide to the Design and

Implementation of Freshwater Quality Studies and Monitoring Programmes, Published on behalf of United Nations Environment Programme and the World Health Organization, 1996.

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laboratory to the calibration standard. This principle also applies to the calibration of other equipment. Feedback is the principle that problems or omissions in the analytical quality assurance system should be brought to the attention of management. Where standards in the laboratory fall below acceptable limits, procedures should ensure that this is easily recognized and corrected. Criteria for recognition and correction of poor performance, as well as responsibilities for corrective be clearly established.

Statistically based assay control systems, as used in internal and external quality control programs, should also conform to the principles of traceability and feedback to ensure that correct criteria for adequate quality are adopted, and that any problems are quickly recognized and corrected.

Properly implemented analytical quality assurance should demonstrate the standard to which a laboratory is working, ensure that this standard is monitored effectively and provide the means to correct any deviations from that standard. It is sometimes argued that the value of quality assurance does not justify its cost but, without it, the reliability of data is doubtful and money spent on producing unreliable data is wasted. If 10 per cent of a laboratory’s budget is spent on quality assurance, the number of samples that can be analyzed will be about 90 per cent of that possible if there were no quality assurance program. However, the results obtained for that 90 per cent will be accurate, reliable and of consistent value to the monitoring program.

Table 1 Definitions associated with analytical quality assurance

Term Definition

Quality The totality of characteristics of an entity that bear on its ability to satisfy stated and implied needs.

Quality policy The overall intentions and direction of an organization with regard to quality, as formally expressed by top management. The quality policy forms one element of corporate policy and is authorized by top management.

Quality assurance

All the planned and systematic activities implemented within the quality system and

demonstrated as needed, to provide adequate confidence that an entity will fulfill requirements for quality.

Quality system Organizational structure, procedures, processes, and resources needed to implement quality management.

Organizational structure

The responsibilities, authorities and relationships through which an organization performs its functions.

Procedure A specified way to perform an activity. When a procedure is documented, the terms “Standard Operating Procedure “written procedure” or “documented procedure and are frequently used’. A documented procedure usually contains the purposes and scope of an activity; what shall be done and by whom; when, where and how it shall be done; what materials, equipment and documents shall be used; and how it shall be controlled and recorded.

Process A set of inter-related resources and activities that transform inputs into outputs.Resources may include personnel, finance, facilities, equipment, techniques and methods.

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2. SOILS2 Soil may be defined as a thin layer of earth’s crust which serves as a natural medium for the growth of plants. It is the unconsolidated mineral matter that has been subjected to, and influenced by genetic and environmental factors – parent material, climate, organisms and topography all acting over a period of time. Soil differs from the parent material in the morphological, physical, chemical and biological properties. Also, soils differ among themselves in some or all the properties, depending on the differences in the genetic and environmental factors. Thus some soils are red, some are black; some are deep and some are shallow; some are coarse-textured and some are fine-textured. They serve in varying degree as a reservoir of nutrients and water for crops, provide mechanical anchorage and favorable tilth. The components of soils are mineral material, organic matter, water and air, the proportions of which vary and which together form a system for plant growth; hence the need to study the soils in perspective. Rocks are the chief sources for the parent materials over which soils are developed. There are three main kinds of rocks: (i) igneous rocks, (ii) sedimentary rocks and (iii) metamorphic rocks. The rocks vary greatly in chemical composition and accordingly the soil differs in their properties because they are formed from the weathering of rocks. Weathering can be physical or chemical in nature. The agents of physical weathering are temperature, water, wind, plant and animals while chemical processes of weathering are hydration, hydrolysis, carbonation, oxidation and reduction. A developed soil will have a well defined profile which is a vertical section of the soil through all its horizons and it extends up to the parent materials. The horizons (layers) in the soil profile which may vary in thickness may be distinguished from morphological characteristics which include colour, texture, structure etc. Generally, the profile consists of three mineral horizons – A, B and C.

The A horizon may consist of sub-horizons richer in organic matter intricately mixed with mineral matter. Horizon B is below A and shows dominance of clay, iron, aluminum and humus alone or in combination. The C horizon excludes the bedrock from which A and B horizon are presumed to have been formed. A study of the soil profile is important from crop husbandry point of view, since it reveals the surface and the sub-surface characteristic and qualities namely, depth, texture,

2 Taken from:

1. Todorović Z. Zaštita životne sredine, Tehnološki fakultet u Leskovcu, 2014. and 2. Basu P.K., Soil Testing in India, Methods Manual, Department of Agriculture and Cooperation

Ministry of Agriculture Government of India, New Delhi, January, 2011.

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3. WATER MONITORING3 3.1 Processes affecting water-quality and their effects Access to clean water for drinking and sanitary purposes is a precondition for human health and well-being. Unpolluted water is also essential for ecosystems. Plants and animals in lakes, rivers and seas react to changes in their environment caused by changes in chemical water quality and physical disturbance of their habitat.

3.1.1 Effects of natural phenomena on water quality While the degradation of water quality is almost invariably the result of human activities, certain natural phenomena can result in water quality falling below the standard required for particular purposes. Natural events such as torrential rainfall and hurricanes lead to excessive erosion, landslides and mudflows, which, in turn, increase the content of suspended material in affected rivers and lakes. Seasonal overturn of the water in some lakes can bring water with little or no dissolved oxygen to the surface. These events may be frequent or occasional and have increased as a result of climate change.

Permanent natural conditions in some areas may make water unfit for drinking or for specific uses, such as irrigation. Additionally, there are naturally occurring areas of high nutrients, trace metals, salts and other constituents that can limit the use of water. Common examples are the salinization of surface waters through evaporation in arid and semi-arid regions and the high salt content of some aquifers under certain geological conditions. Many aquifers are naturally high in carbonates (alkalinity), thus necessitating their treatment before use for certain industrial applications. They may also contain specific ions (such as fluoride) and toxic elements (such as arsenic IV, V) and selenium) in quantities that are harmful to health, while others contain elements or compounds that cause other types of problems (such as the stainingof sanitary fixtures by iron and manganese). The nature and concentration of chemical elements and compounds in a freshwater system are subject to change by various types of natural processes – physical, chemical, hydrological and biological – caused by climatic, geographical and geological conditions.

3 Taken from:

1. Todorović Z. Zaštita životne sredine, Tehnološki fakultet u Leskovcu, 2014. and 2. World Meteorological Organization (WMO), Planning of water quality monitoring systems, WMO-

No. 1113, Chair, Publications Board World Meteorological Organization (WMO) 7 bis, avenue de la Paix, Geneva 2, Switzerland, 2013.

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4. AIR MONITORING4 4.1 Air pollutant sources and emissions Sources in a city include vehicles, industries, domestic etc. In an industrial area, information should be obtained on the type of industries including their number, fuel used, composition of fuel, pollutants emitted etc. Information on number and distribution of sources should be collected. This information will help in identifying which pollutants can be expected in an area and thus should be measured. In case of industrial stacks, locations of maximum ground level concentrations should be determined by modeling. The stations should be located at locations where maximum ground level concentrations are expected. Information on type and number of vehicles should be obtained. Information on domestic fuel that is used in household should be obtained. Pollution load emanating from these sources should be estimated so as to identify sources that are generating significant amount of pollution.

4.2 Health and demographic information Investigations shall be carried out based on the public complaints received from an area related to air pollution. If the results of such investigations reveal that the level is high that area can be considered for ambient air quality monitoring.

Areas where population density is high (more than one million) can be considered for locating monitoring stations. Information on age and socio-economic status of population is also important for making a decision on initiation of ambient air quality monitoring. Location of monitoring station in such areas will help in finding exposure levels to population which can be used further in epidemiological studies to evaluate health effects of air pollutants.

4.3 Meteorological information Meteorological data with respect to temperature, relative humidity, wind speed and direction should be collected. Predominant wind direction plays an important role in determining location of monitoring stations. Due to effects such as land and sea breezes, valley effects etc. it is important to collect local meteorological data specific to the site. The monitoring stations should

4Taken from:

1. Todorović Z. Zaštita životne sredine, Tehnološki fakultet u Leskovcu, 2014. and 2. Bruckmann P., Pfeffer H.-U., Air Quality Monitoring, Encyclopedia of Ocupational Health & Safety,

2011. Guidelines for Ambient Air Quality Monitoring, CENTRAL POLLUTION CONTROL BOARD (Ministry of Environment & Forests, Govt. of India), Parivesh Bhawan, East Arjun Nagar, Delhi, 2003.

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be located in areas that are downwind from the sources. Mixing height data should also be collected. Mixing height data can be collected from Indian Meteorological Department. Information on duration of various seasons in a year is also important. Measurement frequency should be such that monitoring is done in all the seasons so that all seasonal variations are included in computing annual average.

4.4 Topographical information Local winds and stability conditions are affected by topography. In river valleys there is increased tendency of developing inversions. More number of monitoring stations should be located in areas where spatial variations in concentrations are large. Mountains, hills, water bodies also affect dispersion of pollutants.

4.5 Previous air quality information Any previous information collected on ambient air quality can serve as a basis for selecting areas where monitoring should be conducted and previous studies may include data collected for any health studies etc. Previous studies can be used to estimate the magnitude of the problem. Once the background information is collected, the ambient air quality monitoring is to be initiated and selection of type of pollutant to be measured, number and distribution of monitoring stations etc. should be made.

4.6 Monitoring network design The development of a monitoring network of sites for a specific pollutant requires:

1. Understanding the monitoring objective. 2. Identifying the spatial scale most appropriate for the monitoring objective. 3. Identifying the general locations where the monitoring site should be placed in order

to collect a representative pollutant measurement. 5. Identifying specific monitoring sites.

5.1 Measurement planning The first step in measurement planning is to formulate the purpose of the measurement as precisely as possible. Important questions and fields of operation for air quality monitoring include:

5.1.1 Area measurement: - representative determination of exposure in one area (general air monitoring) - representative measurement of pre-existing pollution in the area of a planned facility

(permit, TA Luft (Technical instruction, air)) - smog warning (winter smog, high ozone concentrations) - measurements in hot spots of air pollution to estimate maximum exposure of

receptors (EU-NO2 guideline, measurements in street canyons, in accordance with the German Federal Immission Control Act)

- checking the results of pollution abatement measures and trends over time - screening measurements - scientific investigations - for example, the transport of air pollution, chemical

conversions, calibrating dispersion calculations.

Facility measurement: - measurements in response to complaints - ascertaining sources of emissions, causal analysis - measurements in cases of fires and accidental releases - checking success of reduction measures - monitoring factory fugitive emissions.

The goal of measurement planning is to use adequate measurement and assessment procedures to answer specific questions with sufficient certainty and at minimum possible expense.

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An example of the parameters that should be used for measurement planning is presented in Table 3, in relation to an assessment of air pollution in the area of a planned industrial facility. Recognizing that formal requirements vary by jurisdiction, it should be noted that specific reference here is made to German licensing procedures for industrial facilities.

Table 3. Parameters for measurement planning in measuring ambient air pollution concentrations (with example of application)

Parameter Example of application: Licensing procedure for industrial facilities in Germany

Statement of the question Measurement of prior pollution in the licensing procedure; representative random probe measurement

Area of measurement Circle around location with radius 30 times actual chimney height (simplified)

Assessment standards (place and time dependent): characteristic values to be obtained from measurement data

Threshold limits IW1 (arithmetic mean) and IW2 (98th percentile) of TA Luft (Technical instruction, air); calculation of I1 (arithmetic mean) and I2 (98th percentile) from measurements taken for 1 km2 (assessment surface) to be compared with IW1 and IW2

Ordering, choice and density of measurement sites

Regular scan of 1km2, resulting in “random” choice of measurement sites

Measurement time period 1 year, at least 6 months

Measurement height 1.5 to 4 metres above ground

Measurement frequency 52 (104) measurements per assessment area for gaseous pollutants, depending on the height of the pollution

Duration of each measurement 1/2 hour for gaseous pollutants, 24 hours for suspended dust, 1 month for dust precipitation

Measurement time Random choice

Measured object Air pollution emitted from the planned facility

Measurement procedure National standard measurement procedure (VDI guidelines)

Necessary certainty of measurement results

High

Quality requirements, quality control, calibration, maintenance

VDI guidelines

Recording of measurement data, validation, archiving, assessment

Calculation of quantity of data I1V and I2V for every assessment area

Costs Depend on measurement area and objectives

The example in table 1 shows the case of a measurement network that is supposed to monitor the air quality in a specific area as representatively as possible, to compare with designated air quality

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limits. The idea behind this approach is that a random choice of measurement sites is made in order to cover equally locations in an area with varying air quality (e.g., living areas, streets, industrial zones, parks, city centres, suburbs). This approach may be very costly in large areas due to the number of measurement sites necessary.

Another conception for a measurement network therefore starts with measurement sites that are representatively selected. If measurements of differing air quality are conducted in the most important locations, and the length of time that the protected objects remain in these “microenvironments” is known, then the exposure can be determined. This approach can be extended to other microenvironments (e.g., interior rooms, cars) in order to estimate the total exposure. Diffusion modelling or screening measurements can help in choosing the right measurement sites.

A third approach is to measure at the points of presumed highest exposure (e.g., for NO2 and benzene in street canyons). If assessment standards are met at this site, there is sufficient probability that this will also be the case for all other sites. This approach, by focusing on critical points, requires relatively few measurement sites, but these must be chosen with particular care. This particular method risks overestimating real exposure.

The parameters of measurement time period, assessment of the measurement data and measurement frequency are essentially given in the definition of the assessment standards (limits) and the desired level of certainty of the results. Threshold limits and the peripheral conditions to be considered in measurement planning are related. By using continuous measurement procedures, a resolution that is temporally almost seamless can be achieved. But this is necessary only in monitoring peak values and/or for smog warnings; for monitoring annual mean values, for example, discontinuous measurements are adequate.

The following section is dedicated to describing the capabilities of measurement procedures and quality control as a further parameter important to measurement planning.

5.2 Number and distribution of monitoring locations Knowledge of existing air pollutants levels and pattern within the area are essential for deciding number and distribution of stations. Isopleths distribution of ambient concentrations determined from modeling or previous air quality information can be used to determine number and distribution of stations. When isopleths maps are not available information of emission densities and land use pattern may be used with wind rose data to determine areas of expected higher concentrations. The number of monitoring stations in a city can be selected based on background information collected on sources and emissions, Population figures which can be used as indicators of region variability of the pollutants concentration

The number of sampling sites depends on: - Size of the area to be covered, - The variability of pollutant concentration over the area to be covered, - The data requirements, which are related to the monitoring, - Pollutant to be monitored and - Population figures which can be used as indicators of criticality both from view

For other monitoring objectives, particularly in relation to epidemiological studies, the number of samples will have to be increased. There are several other modifying factors as follows:

- In highly industrialized cities the no. of stations for SPM and SO2 must be increased. - In areas, where large amounts of heavy fuels are used the no. of stations for SO2

should be more or vice-versa. - In regions with irregular terrain, increase the no. of stations. - In cities with extremely heavy traffic the no. of stations for NOX, Oxidants and CO may

need to be doubled.

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6. BASIC STATISTICAL ANALYSIS5 Producing meaningful information from raw data normally requires an initial statistical analysis of that data; for example, to determine the magnitudes of variables, their variability, any time trends, etc. It is also necessary to be able to give some indication of the “confidence” the user may have in the statistical outputs. For example, if a sample average is 50 per cent greater than a previous estimate, could that be expected as a reasonable chance occurrence, or is it indicative of real change? In order that such results are valid, it is essential that only statistical tests which are suited to the data (defined by its type, manner and frequency of collection, etc.) are used. With the ready availability of computerized statistical packages it can be too easy to apply inappropriate analysis to data, especially when they can be automatically collected, stored and presented for analysis. This handbook does not aim to provide detailed methods for statistical analysis, but only to show the potential of such analysis and of effective presentation of data.

6.1 General considerations Many powerful, traditional statistical tests rely on the data conforming to an underlying pattern or frequency distribution. Most commonly, this is the “normal” distribution, or variants thereof. Such statistical tests are termed parametric to indicate the requirement that the data conform to some understood and describable (by its parameters) distribution. The mean and standard deviation, for example, are of this type. Another fundamental class of statistical tests are non-parametric (or distribution-free) which, as their description implies, make no assumptions about the data to which they may be applied. The median and the percentiles are examples of non-parametric tests. When data conform to the appropriate distribution requirements, the parametric statistical tests are usually more powerful than their non-parametric counterparts (where they exist). However, any advantage can be swiftly eroded once the data distribution becomes distorted and cannot be corrected by transformations, for example by using logarithms of the data instead of the raw data. Water quality data sets are often not easily definable, therefore there has been much recent development of non-parametric statistics, both to provide complementary tests to their parametric counterparts and to improve their power. An important, early step in program design is, therefore, to assess which statistical tests would best (and most simply) serve the information

5 Taken from:

1. Bartram J., Balance R. Water Quality Monitoring - A Practical Guide to the Design and Implementation of Freshwater Quality Studies and Monitoring Programmes, Published on behalf of United Nations Environment Programme and the World Health Organization, 1996.

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7. ENVIRONMENT IN SERBIA6 In 2004 the Serbian Government established the Environmental Protection Agency, within the Ministry of Science and Environmental Protection. Main priority of the Serbian Environmental Protection Agency is to collect and to process the data on all environmental components in Serbia, and to disseminate reliable information to policy makers and to widest spectrum of public. The Agency uses the central data bank to issue periodic reports on the environment in Serbia.

7.1 Energy Serbia is not rich in energy resources. With the current level of production, which provides for only 25% of the country’s needs, Serbia (excluding Kosovo) is expected to exhaust its coal supplies within the next 55 years, and oil and gas within 20 years. Current hydroelectric power capacity is 10,200 GWh per annum, while potential capacity has been estimated at 14,200 GWh per annum. The potentials of other, renewable energy resources, including biomass, small hydroelectric power plants, geothermal, wind and solar energy are very significant and exceed 3.8 Mtoe. Some 63% (2.4 Mtoe) of the potential renewable energy resources described lie in the utilization of biomass (wooden and agricultural biomass). Energy potential of the existing geothermal springs in Serbia is nearly 0.2 Mtoe, and that of small hydroelectric power plants 0.4 Mtoe. There are 50 city heating plants in Serbia with total heat energy capacity of 6,597 MW. The main characteristics of Serbia’s heating plants are low operating readiness due to insufficient maintenance and outdated equipment, financial exhaustion and an inability to perform urgent intervention on sources and grids. Heating is poor and there is a need for additional capacity. Over the 1990-2005 period, the structure of energy consumption changed significantly. The highest increase in energy consumption was achieved in the transport sector - 29.5%, slightly lower in the sectors of households, agriculture, public and commerce – 10.4%, while a decline of 36.7% was recorded in the industrial sector. Considering all facts, it is evident that a drop in industrial production was the primary cause of such decrease in energy consumption in Serbia.

7.2 Mining Mining is the cornerstone of Serbia’s industry and, consequently, of Serbian economy in general. The mining comprises four extraction sectors: coal; crude oil and gas; metal ores; other ores and 6 Taken from:

Dedijer, A., Mitrović-Josipović, M., Radulović, E., Dimić, B., Marić, L., Krunić-Lazić, M., Špegar, G., Vidojević, D., Jovanović, M., Veljković, N., Jovičić, M., Redžić, N., Popović, S., Pajčin, N., Lekić, D., Popović, T., Mijović, A., ENVIRONMENT in Serbia: an indicator – based review, Ministarstvo nauke i zaštite životne sredine Republike Srbije, 2007 (Beograd: Grafički centar). – [III] , 154 str., taken 3.10.2015. at internet address: www.sepa.gov.rs/download/Environment_in_Serbia_Full.pdf.

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samples were contaminated by PAHs in the quantity that exceeded the MAC. This practically means that the soil can potentially be a source of underground water contamination by polycyclic aromatic hydrocarbons. Examination of soil quality in urban zones is conducted in some of the larger towns and cities and it is mainly associated with accidents.

During the conflict NATO had reportedly deployed weapons containing depleted uranium. According to NATO data 112 locations in Kosovo were contaminated with depleted uranium and 31000 30-mm projectiles, equivalent to 10 tons of depleted uranium were fired. Outside the borders of Kosovo, 3000-5000 projectiles were fired too, mostly on the south of Serbia. The clean-up of the radioactive pollutants has been completed at a major site in southern Serbia.

The occurrence and progress of erosion processes is one of the major causes of soil degradation and its deteriorated quality. It is estimated that erosion processes (of various degrees) affect up to 80% of agricultural soil in Serbia. While in central regions and the hilly-mountainous regions the predominant type is water erosion, the predominant type in Vojvodina is eolic erosion. Approximately 85% of agricultural soil in Vojvodina is affected by wind erosion with an annual loss of over 0.9 ton material per ha.

7.7 Waste Poor standard of waste management has been identified as one of the pressing environmental issues in Serbia, resulting mainly from an inadequate social treatment of this issue so far. High-cost, uneconomical organization, poor quality of service and inadequate care for the environment are the result of a devastatingly poor organization of waste management. The existing relevant legislation in the Republic of Serbia defines local municipalities as the administrative and spatial entities responsible for managing communal waste. The only method of managing waste that is currently practiced in Serbia is disposal in landfills, which mostly fails to meet the most basic requirements of hygiene, as well as technical and technological standards, and some of them are already filled to full capacity.

Data on the distance between landfills and water resources give us a bleak picture as 25 landfills (15.2%) are situated within 50 m from a river, stream, lake or reservoir. Of this number, 14 landfills are practically located on the very bank of a waterway or in its channel. Eleven landfills (or 6.7%) are situated within 500 m from waterworks zones, and another 28 (12.2%) within 1000 m. Organized recycling of waste in Serbian landfills is practically non-existent as 160 of them (97.6%) have no processing of waste developed in any form.

There are neither reliable data on the total number of sources generating hazardous wastes nor the total number of sources generating waste that could be recycled as secondary raw materials. There is no facility for treatment of hazardous waste, or one for treatment of car waste and other specific types of waste, or indeed any permanent disposal site for hazardous waste complying with relevant legal provisions, so that temporary disposal is mostly done inside the company fence, and very often inadequately. For all these reasons, hazardous waste is being stored temporarily prior to export for further treatment.