1 CONTENTS

INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY: REDESIGN AND FUTURE TRENDS 3 Antero Aitio CHEMICAL POLICY IN THE EUROPEAN UNION 7 Kyriakoula Ziegler-Skylakakis OECD AND CHEMICAL SAFETY 8 Rolf F. Hertel NATIONAL AUTOMATED SYSTEM FOR ENVIRONMENTAL MONITORING /NASEM/ 11 Dimitar Vergiev REGULATIONS RELATED TO CHEMICAL RISK ASSESSMENT IN HUNGARY 17 Gyula Dura CHEMICAL RISK ASSESSMENT IN THE USA 25 Herman Gibb PRIORITY TOXIC SUBSTANCES IN BULGARIA 29 Nikolai Rizov, Fina Kaloyanova, Yordan Simeonov, Ivan I. Benchev HEAVY METALS POLLUTION AROUND THE METALLURGY PLANTS IN SOME REGIONS IN BULGARIA 38 Ivan Grancharov, Siyka Popova CHEMICAL ACCIDENTS – ORGANIZATION OF THE PROTECTION, MEANS AND METHODS FOR MITIGATION OF THE CONSEQUENCES 48 Svetoslav Andonov BULGARIAN LEGISLATIVE FRAME FOR PREVENTING WATER POLLUTION BY CHEMICALS53 Veska Kambourova THE CONTRIBUTION OF THE SMALL ENTERPRISE “HYGITEST” LTD. – SOFIA TO THE ASSESSMENT OF CHEMICAL POLLUTION IN THE AMBIENT AND WORKPLACE AIR 59 Petko Vardev, Dimitar Dimitrov LIST OF PARTICIPANTS64

2 INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY: REDESIGN AND FUTURE TRENDS

ANTERO AITIO International Programme on Chemical Safety, Geneva, Zwitzerland

Environment and health are at the centre of strategies to promote sustainable development and an integrated approach is required whenever possible. IPCS is a collaborative body of three intergovernmental organizations (WHO, ILO and UNEP) which works scientifically to charac- terize the burden and impact of chemicals exposure on human health and the environment. Technical assistance to strengthen capacities for the sound management of chemicals at country, regional and global levels are built upon activities which promote a better awareness and under- standing of the risks of chemical exposure and best practice prevention and response. As a result of assessing the work of IPCS and changes in the world of chemical safety, IPCS is being redesigned. This redesign process is in progress, and below are presented some aspects of the new IPCS, noting especially that changes are likely to occure when the plan is finalised and before it is fully implemented. IPCS work can be devided to four elements; they are briefly discussed below. The long-term goal of IPCS is to reduce adverse effects of chemicals on human health and the environment. Element 1 Risk assessment and establishment of guidance values, as well as development and global harmonization of risk assessment methods Goals Identify health and environment problems arising from exposure to chemicals through food, water, air and other sources. Improve estimates of the magnitude of chemical-related health problems and environ- mental impacts. Risk assessment activities contribute to the establishment of scientifically-based guid- ance values. Improved use of observational data on human exposure to chemicals. Improve awareness and understanding of the adverse effects of chemicals and identify and promote appropriate preventive measures. Refine risk assessment methods, integrate procedures for the assessment of health and environmental effects of chemicals. Address emerging scientific issues, for example toxicogenomics, so that risk assessment tools can be continually improved. Outputs Assessments of the risk of chemicals to human health and the environment (including Concise International Assessment Documents (CICADs) and International Chemical Safety Cards (ICSCs). Chemical risk assessments for Codex Alimentarius and countries (JMPR, JECFA). Chemical risk assessments for WHO guidelines (including for water and air quality). Development and harmonization of methodologies for chemical risk assessments (in- cluding for chemicals in food and emerging health risks). Implementation of the Globally Harmonized System for Classification and Labelling of Chemicals in IPCS risk assessment products. Guidance for improving use and awareness of human toxicology data.

3 Impact at Countries are better able to identify and characterize exposure, hazards and risks Country and to identify and implement preventive and response activities. Level Improved communication on chemical risks is enabled by IPCS risk assessment products. Development of country-specific activities to eliminate/minimize exposure to hazardous chemicals. Countries are better able to set priorities and measure progress towards chemical management goals. Improved priority-setting for research related to chemical safety and selection of chemicals for assessment. Element 2 Poisons information, prevention and management and the collection, analysis, interpretation, reporting and of human toxicology and exposure data Goals Health professionals have timely access to information on the hazards of chemi- cals including pharmaceuticals and natural toxins, and on the diagnosis manage- ment of poisoning. Health professionals have timely access to analytical toxicology services. Relevant professionals have access to guidance materials on strategies for the prevention of poisoning. Members of the public have access to information on prevention, recognition, and the first aid treatment of poisoning. Better quality information on the incidence and severity of poisoning. Better systems for monitoring trends and providing early warning of health im- pacts of chemical exposures. More effective poisoning prevention, identification and treatment through im- proved exchange of toxicological information and the sharing of expertise. Improved quality of chemical risk assessment through better use of high-quality information on human poisoning cases. Recognition of the role of poison centres in chemical management. Improved quality and availability of observational and analytical and clinical toxi- cology information from human exposures to chemicals, including pesticides. Outputs Awareness raising through presentations and publications on the role of poisons centres in chemical safety. Guidelines and other material that can be used for poisons prevention activities. Internationally peer-reviewed documents on the management of poisoned pa- tients, including PIMs, treatment guides, and antidote monographs. INTOX network used for information exchange and problem solving. Increased number of members in the IPCS INTOX network. Improved dialogue between professionals engaged in chemical assessment and management and health care. Impact at Establishment of one or more poisons centres in countries where none exist and Country strengthening of existing poisons centres. Level Reduction in the incidence and severity of poisoning cases. Improved verification of cases of human poisoning. Improved public awareness regarding toxic chemical substances. Health professionals in countries become more actively involved in chemical assessment and management processes. Risk assessment priorities more closely aligned with identified public health priorities.

4 Element 3 Chemical incidents and emergencies: prevention, preparedness, surveillance, alert and response Goals Strengthen national public health response plans for chemical incidents and emergencies occurring naturally, accidentally or deliberately. Establish and maintain a global mechanism for the timely detection of, and the rapid response to, chemical incidents and emergencies of international concern. Improve the knowledge base for the sound management of chemicals, and environmental health policy and decision-making. Strengthen information exchange through global networks of partners. Strengthen collaboration and coordination of chemical incident and emergency activities. Ensure engagement in the process of review and implementation of the Interna- tional Health Regulations (IHR) to cover public health events of international importance, including those of chemical aetiology. Outputs Guidance and training material for countries. Global capacity building activities. A surveillance system for identifying chemical incidents and emergencies of international importance. A mechanism for mobilising WHO experts, international organizations and other resources to provide technical assistance where requested by countries. A roster of experts available to respond to chemical incidents or emergencies at short notice. An inventory of internationally-accessible resources for responding to chemical incidents and emergencies. Regular outbreak reports, a quarterly newsletter to network members, annual reports and presentations. Improved public health capabilities and capacities to respond to chemical incidents and emergencies of natural, accidental or deliberate origin. Impact at Improved surveillance and investigation of incidents of chemical aetiology. Country Improved national chemical safety and environmental health policy and Level decision-making. Improved access to internationally-available resources to respond to chemical incidents and emergencies.

5 Element 4 Capacity-building support, for the above activities Goals To provide advice and tools for the development of infrastructure and qualified local individuals in all countries/regions to implement elements 1-3. To promote and facilitate international collaborative research. To transfer knowledge and facilitate technology transfer. Outputs Expert Groups and teams for IPCS activities including experts from developing countries and countries with economies in transition, e.g. in expert groups developing risk assessment methodologies and chemical-specific risk assessments and in teams investigating chemical incidents. Chemical assessment products in local languages, e.g. ICSCs. Guidance and training materials to support poisons centre and chemical inci- dent response activities for chemicals including pesticides. Support for the establishment of poisons centres. Networks for communication between national experts and IPCS/WHO. Collection of locally-relevant human data, such as exposure data, pesticide epidemiology. Local training courses, e.g. in pesticide handling. Technical support to enable countries to fulfil obligations under international conventions such as those relating to Prior Informed Consent and Persistent Organic Pollutants. Technical support to enable implementation of the Globally Harmonized System for Classification and Labelling. Improved indicators of performance. Impact at National experts and agencies have information and skills for the assessment Country and safe management of chemicals, and for the prevention and management of Level poisoning. Improved public health capabilities and capacities to investigate chemical incidents and to respond to chemical incidents and emergencies of natural, accidental or deliberate origin. Establishment and strengthening of poisons centres. Improved access to internationally-available resources. Improved ability to make and implement chemical policies, including those in support of international obligations.

6 CHEMICAL POLICY IN THE EUROPEAN UNION

ZIEGLER-SKYLAKAKIS KYRIAKOULA European Commission, Employment and Social Affairs, Luxembourg

About 100 00 different substances are registered in the EU market of which 10 000 are marketed in volumes of more than 10 tonnes and a further 20 000 are marketed at 1-10 tonnes. The world chemical production in 1998 was estimated at € 1 244 billion, with 31 % for the EU chemical industry. In 1998, EU chemical industry was the world’s largest chemical industry, followed by that of the US with 28% of production value. The chemical industry is also Europe’s third largest manufacturing industry. It employs 1.7 million people directly and up to 3 million jobs are de- pendent on it. Therefore many legislative actions have dealt with chemicals in the past.

Increasing concern that current EU chemical policy - existing legislation- was not capable of responding adequately to public concern in Europe about impact of chemicals on health and environment led the Commission to propose a new policy for chemicals. In the White Paper on the Strategy for a Future Chemicals Policy the Commission outlined in 2001 the strategy to ensure a high level of chemicals safety through a system for Registration, Evaluation and Authorisation of Chemicals to be known as the REACH system. The White Paper is based on seven objectives that need to be balanced within the overall framework of sustainable develop- ment: – Protection of human health and the environment – Maintenance and enhancement of the competitiveness of the EU chemical industry – Prevention of fragmentation of the internal market – Increased transparency – Integration with international efforts – Promotion of non-animal testing – Conformity with EU international obligations under WTO The REACH system provides a single regulatory system for new chemicals and “existing” chemi- cals. All chemical substances produced or imported in volumes of 1 tonne or more per year, per manufacturer/importer have to be registered in REACH. There are special provisions for inter- mediates and polymers. Recently the Commission has prepared legislative proposals for the different blocks of the REACH system. In July 2003 the Commission launched an Internet consultation to consider the work- ability of the draft proposal for a Regulation concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH-Regulation).

7 OECD AND CHEMICAL SAFETY

ROLF F. HERTEL Federal Institute of Risk Assessment, Berlin / Germany

The Organisation for European Economic Co-operation (OEEC) was established in 1948 with the aim to support implement the Marshall Plan in Europe. This organisation was succeeded in 1961 by the Organisation for Economic Co-operation and Developement (OECD) with the aim of promoting economic growth and employment and track liberalisation thus improving the standard of living within all 30 member countries. Since 1971 the OECD has established work on environment, health and safety in the so-called Environmental Health and Safety (EHS) Programme. This programme focussed on specific in- dustrial chemicals with health or environmental impact. The aim of this programme was to share information about the risk of this chemicals by performing risk assessments and developing risk management options. In 1999 the programme was refocused by concentrations on hazard as- sessments instead of detailed risk assessments. As a consequence from that time on detailed exposure information gathering is carried out at the national/regional level and is no longer part of the OECD-initial assessment. Following the EHS-Programme, Member countries decided to undertake a systematic investiga- tion of existing chemicals. It was recommended that Member countries work together and „share the burden“ of investigating the potential hazards from priority chemicals. For reaching this goal, each Member country carries out a specific part of the total work and makes the information it has collected or generated available to other Member countries. Chemical industries in Member countries play a significant role in the conduct of this co-operative work. The Business and Industry Advisory Committee to OECD (BIAC) and national chemical indus- try associations promote the collection of information and help ensure that tests which need to be conducted are undertaken in a timely manner. The work is carried out in collaboration with the International Programme on Chemical Safety (IPCS) and the International Register of Po- tentially Toxic Chemicals (IRPTC). Since 1988, OECD Existing Chemicals activities have centered primarily on high production volume (HPV) chemicals, as an indicator of potential occupational, consumer and environmen- tal exposure. The first objective of this co-operative work is to ensure that the basic information necessary to undertake a first evaluation of potential hazards associated with HPV chemicals is either available or needs to be generated. A second objective is to undertake an initial assess- ment of this information and to draw conclusions on the potential hazards of the chemicals and make recommendations related to the need for further work. Finally, when complete data sets and hazard assessments are available, Member countries may decide to develop common, con- sistent or harmonized risk reduction actions. The OECD List of HPV Chemicals identified by Member countries serves as the overall priority list from which chemicals are selected for testing and/or assessment. In consultation with their chemical industries, Member countries identify chemicals for which, on a voluntary basis, they will act as a Sponsor country in the HPV programme. The overall number of chemicals which any Member country or group of Member countries (through, for example, the EU programme)

8 sponsors should, as a minimum, be proportional to its financial contribution to the OECD Chemi- cals Programme, which in turn is proportional to its (combined) Gross National Product. For the selected chemicals an initial screening is performed on the potential hazards to man and/ or the environment. Therefore data sets have been developed as a base for an informed assess- ment. The data elements needed for „screening“ were brought togehter as the Screening Infor- mation Data Set (SIDS), which comprises characterisation and effects data as well as elements of exposure information. The SIDS is regarded as the minimum information needed to assess an HPV chemical and to determine whether any further work should be carried out or not. Each Member country is responsible for generating and making available SIDS data for the selected chemicals. In return, it will benefit from receiving similar data on the chemicals from other Member countries. All SIDS elements are listed in the OECD Manual for investigation of HPV Chemicals. For any SIDS element on effects or characterisation for which no data are available or the data are not considered adequate, testing will in principle be carried out. Any testing to complete the SIDS is conducted according to the OECD Test Guidelines and the Principles of Good Labora- tory Practice (GLP), in order to ensure that generated data are mutually acceptable among Mem- ber countries. By written procedure via an „electronic discussion group“ forum (EDG), the SIDS Dossiers and SIDS Testing Plans are forwarded by the Sponsor country to all SIDS Contact Points, so that each country and the experts nominated by IPCS can study the proposals made by the Sponsor country. When a SIDS Testing Plan for a chemical is agreed by the other Member countries, the Sponsor country carries out the test(s) and/or the collection of information on exposure and effects. When all information is available the Sponsor country prepares the SIDS Initial Assessment Report (SIAR). The SIAR presents an evaluation including conclusions on the hazards identified and recom- mendations for further action, if appropriate. The SIARs are circulated with the updated SIDS Dossier, to SIDS Contact Points in a timely manner prior to the SIDS (prior to SIAM EDG) Initial Assessment Meeting (SIAM). At the SIAM the reports are discussed and consensus reached on the initial assessment and the conclu- sions and recommendations for each chemical. Participants in the SIAM include representatives of the Sponsor countries, representatives from other Member countries and the Commission of the European Union, experts from non-Member countries nominated by IPCS, secretariat staff from OECD, IPCS and IRPTC, experts nomi- nated by OECD’s Business and Industry Advisory Committee (BIAC) and Trade Union Advi- sory Committee (TUAC), representatives of companies which produce the chemical (for that part of the discussions which concerns their chemical), and further non governmental organiza- tions (NGOs) being engaged in animal welfare or environmental/consumer protection. Where a chemical has been reviewed at a SIAM with a recommendation that further information is required to assess identified concerns, any follow-up testing or information gathering is re- garded as „Post SIDS Work“. The SIAM will give an indication of what data need to be col- lected, generated and/or analysed; the overall responsibility for initiating and undertaking the work rests with industry. Finally during the OECD Joint Meeting, which is a policy body of OECD, Member countries discuss and agree on any follow-up actions on chemicals and discuss and confirm all conclu- sions and recommendations made on all chemicals which have been assessed in the SIDS programme.

9 OECD decided that Member countries shall make information obtained from the co-operative investigation of chemicals publicly available via IRPTC. Therefore all information, including test reports, SIDS dossiers and SIDS Initial Assessment Reports, are transmitted to IRPTC and the information is entered in the IRPTC database, thus being available to users throughout the world. Besides the work on investigation of Industrial Chemicals, including important work on prepar- ing test guidelines and developing „Good laboratory practice (GLP)“, OECD has established the Pesticide Programme focussing on pesticides used in agriculture and on a group of products called „non-agricultural pesticides“ and biocides. The Programme on Harmonization of Classification and Labelling Systems was successful in harmonizing the many different chemicals classification systems and is implemented through the United Nations in both OECD and non-member countries. Another activity of OECD is the Chemical Accidents Programme, which helps to prevent chemical accidents and to respond appropiately if one does occur. A further highlight in the EHS-programme are Pollutant Release and Transfer Registers (PRTRs), which are databases of pollutant emis- sions to air, water, soil and wastes transferred for treatment or disposal.To help Member coun- tries to evaluate the risks of particular uses of genetically modified organisms, OECD has estab- lished the Programme on the Safety of Novel Foods and Feeds and the Programme on the Har- monization of Regulatory Oversight in Biotechnology. The overall aims and procedures of the HPV Chemicals Programme are described on the OECD- website (http://cs3-hq.oecd.org/scripts/hpv/).

10 NATIONAL AUTOMATED SYSTEM FOR ENVIRONMENTAL MONITORING /NASEM/

DIMITAR VERGIEV Executive Environment Agency, Ministry of Environment and Water, Bulgaria

The Executive Environment Agency /ExEA/ is a structure under the Minister of Environment and Water, which carries out the management of the National Automatic System for Environ- mental Monitoring. The Agency is also a National Reference Center for the European Environ- ment Agency and methodological leader for the Regional Inspectorates for environment and water. Bulgaria has a long tradition of environmental monitoring, particularly monitoring of ambient air and water quality. Observing, measuring, collecting, processing and summarising environ- mental information is carried out through the NASEM, based on continuous or periodic moni- toring of qualitative and quantitative parameters. This system, which covers the whole country, is supported by an information database at the national and regional level. It comprises e.g. monitoring data on: – ambient air quality and emissions of pollutants to air; – surface and ground water quality; – subsurface (soil) quality; – noise from aviation as well as road and rail traffic; – ionising radiation; – hazardous, industrial, municipal and construction waste.

Air monitoring

Air quality monitoring comprises monitoring of ambient air quality and of emissions to air. The Clean Air Act, adopted in 1996 and amended in 2000, establishes the monitoring obligations of operators of stationary sources, as well as their reporting obligations. It provides the framework for an air quality monitoring management structure, with national and municipal networks. The operator of an installation can be required to monitor local air quality at source. a) Ambient air quality monitoring The network for ambient air quality monitoring, set up in 1972, has improved significantly over the past ten years. The network now consists of 66 stationary stations, operated by the ExEA and the Ministry of Health. There are 16 automated online stations, and 50 stations with manual sampling and chemical analysis. In addition, there are six mobile automated stations. The sam- pling frequency in the case of manually operated stations is four times a day, five days a week. Automated stations operate continuously. The stationary stations are located in 37 urban, indus- trial and rural settlements in different parts of the country. The basic measurements carried out are for TSP, Pb, aerosols, SO2, NO2 and H2S. In industrial areas NH3, phenols, THC, As aer.,

HCl, Cl2, CO, NO, O3, Cd and Mn are also measured. Tropospheric ozone is monitored at most

(i.e. 15) automatic stations and PM10 is measured at most stations.

11 The National Institute of Hydrology and Meteorology (NIHM) operates five air quality monitor- ing stations that mainly provide data for digital modelling of trajectories (dispersion models). Measurements from these stations are integrated into the national air quality monitoring system. The NIHM also has some 130 weather stations and some 250 stations that measure precipita- tion. Air quality is mostly monitored in urban areas. There is one background station for air quality monitoring, operated by one of the Regional Inspectorate for environment and water /RIEW/ - Smolian and situated on one of Bulgaria’s highest peaks (Rojen). The ExEA and the NIHM carry out monitoring of transboundary pollution jointly. An integrated system for air quality control and management developed under the PHARE pro- gram was put into operation in 2002 in Bulgarian and Rumanian transboundary towns in lower Danube. Seven automated stations for air quality control and two meteorological stations were installed on the territories of the two countries. The system is unique because the two coun- tries have completely identical systems. The used measurement equipment is also identical – Identical air pollutants are controlled in the mirror towns – Identical maximum admissible concentrations are used for the pollution level mea- surement. The measured pollutants are as follows: sulphur dioxide, nitrogen oxide, nitrogen dioxide, carbon monoxide, chlorine, hydrochloric acid, hydrogen sulfide, ozone, benzene, toluen, phenol, xylene, styrene, fine particulate matter. Fifty-two stations belong to the European air quality control network, EUROAIRNET. Mea- surement results are sent to the European Environment Agency /EEA/ in Copenhagen. The back- ground station in Rojen is part of the UNEP-GEMS, WMO and UNESCO networks. b) Air emissions monitoring Emissions monitoring has improved considerably since 1996, following adoption of the Clean Air Act, which provides for mandatory regular reporting of emissions by large enterprises and supports enforcement of regulations. Bulgaria’s 150 largest enterprises produce around 80% of air pollutant emissions. As part of their emissions control efforts, these enterprises must carry out self-monitoring on a periodic or continuous basis. Continuous emissions monitoring will be mandatory for large industrial plants as of the beginning of 2004. A list of enterprises obliged to undertake this type of self-monitoring according to the decision for Reporting on Environmental Impact Assessment is held by the Ministry of environment and water /MOEW/. Monitoring programmes for self monitoring of the emissions are approved by the ExEA. Self-monitoring activities are supervised and controlled by the MOEW, the RIEWs and municipal authorities. The operator submits self-monitoring data twice a year.

Emissions of TSP, soot, SO2, NO2 and other specific pollutants are directly measured in order to assess compliance with national emissions standards. This takes place twice a year, using four mobile automatic stations and eight mobile analysers. A list of enterprises to be monitored is approved every year by the MOEW. In the case of mobile sources, responsibility for emissions control lies with the State Automobile Inspectorate (SAI) of the Ministry of Transport and Communication (when the vehicle is mov- ing, control done by licensed car garages) and the Ministry of the Interior (when the engine is idling), which report back to the MOEW. The ExEA on the basis of motor fuel consumption data and of the CORINAIR methodology currently establishes annual inventories of national emis- sions from mobile sources. The Ministry of Interior is establishing a national register of motor vehicles, including exhaust emission data.

12 The MOEW provides the UN-ECE Convention on Long-range Transboundary Air Pollution with early emissions data on SO2, NO2, CH4, NMVOC, CO, NH3, Cd, Pb, Hg, PAH, PCBs, HCB, PCP and dioxins from 11 activity sector groups. Included are emissions from different types of energy production, industrial processes, extraction and distribution of fossil fuels, sol- vents use, road transport, other mobile sources and machinery, waste treatment and disposal, as well as from agriculture and nature. Data on SO2, NO2, CH4, NMVOC, CO and NH3 emissions from 34 large point sources are also reported to the UN-ECE in Geneva. Data on GHG emis- sions are reported annually to the Secretariat of the UN Framework Convention on Climate Change (UNFCCC). Data on ozone depleting substances are reported annually to the UNEP Ozone Secretariat.

Water monitoring

Water quality monitoring is carried out through a number of programmes co-ordinated under the NASEM. Bulgaria’s 78 river basins are covered. The environmental administration is respon- sible for physical, chemical and biological monitoring of fresh ground and surface waters and of coastal waters. The health administration is mainly responsible for monitoring water quality in sources supplying drinking water and for overseeing bathing waters (physical, chemical and microbiological analysis). According to the Water Act, the biggest water polluting enterprises are required to self-monitor the quantity and quality of their sewage water. a) Surface water monitoring The main purposes of the national surface water monitoring network are to: – obtain quantitative and qualitative data on the state of surface waters and assess trends with respect to their past, present and future development; – oversee compliance with national surface water quality standards; – assess the impacts of point sources on the receiving water body; – identify heavily polluted water areas (hot spots) where immediate action is needed; – provide public and private decision makers, academics and the general public with relevant information on the state of surface waters. Surface waters are divided into three categories, according to their use: water supply; leisure, fishing and industrial; irrigation. The national network for monitoring surface water quality comprises 253 stations covering all major river basins. Three of these stations, located on the rivers Struma, Mesta and Maritza, are automatic. Of the surface water stations, 185 are in rivers (ten in the Danube), eight in lakes, 26 in reservoirs and 24 in the Black Sea. Fresh water mea- surements are made for some 30 parameters, including quantity, temperature, DO, BOD, COD,

NH4, NO2, NO3, total N, PO4, total P, heavy metals, detergents and hydrocarbons. Measurements are taken once a month in rivers and lakes and seven times a year in the Black Sea. Biological monitoring of surface waters has been carried out since 1992. There are 1200 sam- pling points, located along rivers at a distance of 5-10 km. The method is based on analysis of sensitive benthic macroinvertebrates. Water quality is assessed according to the biotic index, using five levels. Microbiological parameters such as bacteria, pathogens and coliforms are monitored in three areas (Sofia, Stara Zagora, Smolyan) at the same sampling sites as those used for physical and chemical monitoring. Monitoring of the Black Sea takes place in connection with the Black Sea Convention

13 (Bucharest, 1992), which was signed by six bordering countries. Due to its hydrophysical and ecological characteristics, the Black Sea is highly sensitive to pollution by oil and oil products. Its basin was therefore declared a special area that benefits from systematic monitoring of the content of oil products in sea water, sediments and the bottom bio-indicators. According to the Convention on the Protection and Sustainable Use of the River Danube, five of Bulgaria’s water quality stations on the Danube and three on its Bulgarian tributaries belong to a transfrontier monitoring network. Data are regularly submitted to the Commission on the Protection of the River Danube in Vienna and to the data base of the ExEA in Bratislava.. Bulgaria reports monitoring results from 111 surface water stations to the EUROWATERNET system. b) Ground water monitoring The main purposes of the national ground water monitoring network are to: – obtain quantitative and qualitative data, as well as assess trends in the state of ground water; – control compliance with national standards for ambient ground water; – provide decision makers and interest groups with up to date information on the state of ground water. The national network for monitoring ground water quality is made up of 225 stations. They are sampled two or four times a year for about 30 parameters. Bulgaria reports monitoring results from 74 ground water stations to the EUROWATERNET system. c) Water resources and use The national network for monitoring water resources comprises 373 rainfall measuring stations, 236 hydrological stations and 595 hydrogeological stations. The headquarters for this network is based within the National Institute of Hydrology and Meteorology (NIHM) in Sofia. Meteoro- logical information is collected and received via satellite from 18 hydrological stations, which also serve to give warning in case of flood danger. Water quantity is monitored via the networks of other specialised administrations, such as the “Reservoirs and Cascades” administration, which operates 140 hydrometric stations and 40 rainfall measuring stations.

Lands, biodiversity and protected areas monitoring a) Land and soil quality monitoring, managed by the ExEA as part of the NASEM, includes: – monitoring and control of subsoil resources including abstraction waste and sewage sludge; – control and protection of soil from pollution with persistent organic pollutants (20 monitoring stations for PAH, PCB and pesticides, and 48 stations for pesticide moni- toring); – acidification (70 sampling plots); – salinisation (15 sampling plots); – erosion. Data on polluted soils are collected by ExEA, together with the Institute of Soil Science and Agroecology. Soil contamination of industrial sites is also monitored using EIA procedures and an environmental auditing system. This monitoring is associated with the liability issues ad- dressed as part of the privatisation process.

14 b) Biodiversity monitoring In some protected areas the number of certain endangered species is monitored by the environ- mental administration. Monitoring of species and habitats within the three National Parks is carried out by the National Parks Directorate of the MOEW, established in 1999. Monitoring of forest damage is carried out in the framework of the Convention on Long Range Transboundary Air Pollution (LRTAP) and the International Co-operation Programme on Forests led by the EU and UN-ECE. The ExEA acts as a focal point; field studies are carried out by University of Forestry and the Forest Research Institutes.

Waste monitoring

Data on municipal waste are directly obtained from the municipalities responsible for waste management. The NSI collects data on non-hazardous industrial waste from enterprises through annual statistical surveys. Data on hazardous waste compiled by the ExEA are transmitted to the Secretariat of the Basel Convention. Database on hazardous waste is currently functionning at the ExEA. The waste reporting system covers some 620 landfills; almost 2 000 other waste dumps operate without proper reporting on the quality and quantity of wastes deposited. It is expected that these dumps will be closed by 2007 and will be replaced by regional landfills. The National Waste Management Programme foresees the construction of 37 new landfills that would meet EU criteria by 2002 and that will cover approximately 33% of the country’s territory.

Radiation monitoring

The National Automatic System for Radiation Control in Real Time was set up in 1997 to meet international requirements for safe use of nuclear energy and monitoring of transboundary trans- missions of nuclear material. The system is completely automated and has a hierarchical struc- ture. It consists of 26 local gamma background monitoring stations (LMS) covering the entire country. The nuclear power plant “Kozlodouy” benefits from special monitoring through a higher density of monitoring stations around the plant. All LMS are supplied with measurement and communication equipment. Data are transmitted in real time to the ExEA where they are pro- cessed and stored in a database. They are then transmitted on to the authorities responsible for emergency situations and civil protection (i.e. the Civil Defence Department and the Committee on the use of Atomic Energy for Peaceful Purposes). The measurements taken are collected, processed and stored in the data base of the ExEA. They are then transmitted to the users of the system - the Civil Defence Department and the Commit- tee on the use of Atomic Energy for Peaceful Purposes. Radiation is also monitored as part of the air, soil, surface and ground water monitoring net- works. A mobile monitoring station is available in case of an accident “in situ”.

Public access to environmental information

Bulgaria is progressively implementing its laws regulating access to environmental information. The environmental administration provides public access to environmental information in vari- ous forms, using a wide range of information sources. Information is provided upon request through public information centres at the MOEW and the ExEA, via Green Phone lines within the MOEW and the RIEWs, and at regular press conferences. Certain types of environmental

15 information such as air quality and radiation levels are systematically made available to the Bulgarian Telegraphic Agency by the ExEA.

Providing information upon request The MOEW, the ExEA and the RIEWs provide environmental information to individuals and organisations upon request. Responses to requests are usually made within 14 days, correspond- ing to legal provisions.

Public information centres Both the MOEW and its ExEA have established public information centres on their premises where a large number of publications and studies are available, including reports on studies commissioned by the Ministry, environmental impact assessment reports and material from Eu- ropean and international environmental organisations.

16 REGULATIONS RELATED TO CHEMICAL RISK ASSESSMENT IN HUNGARY

GYULA DURA Fodor József National Public Health Centre, National Institute of Environmental Health, Budapest

Background

Hungary as other European countries is burden of chemicals. The chemical production and use in Hungary estimated about 14 million ton per year. Most of the firms belong to the group of SME. Small farms which are using chemicals enlarged to some hundred thousands. Recently in Hungary over 30 000 contaminated sites are registered by Na- tional Clean up Programme Office. Hungary prepared the National Profile of Chemical Substances in 1997. This called attention to the fact that the number of the decrees regulating chemical safety is much to high (exactly 163). The efficiency of many of these were near to zero. Different ministries were responsible for the different sectors of chemical safety, the co-operation was insufficient between these ministries. The institutional background of chemical safety was found to be fragmented and the profes- sional level was not perfect. Efficiency of former chemical legislation was very low and insuffi- cient due to the inconsequent authority control. The comprehensive re-regulation of chemical safety in Hungary was also justified by the 1. Expectations of EU 2. Commitments to OECD 3. Chapter 19 of Agenda 21 4. Recommendations of IFCS

New law on chemical safety

In the process of the approximation and implementation of national legislation to EU, Hungar- ian Parlament adopted Act No 25/2000 on Chemical Safety. Its content is the follow: Chapter 1 Definitions and Scope Chapter 2 Determination of Hazards of Dangerous Substances and Preparations to Man and the Environment; Hazard Identification Chapter 3 Classification of Substances and Preparations; Reporting and Notification of New Substances Chapter 4 Packaging, Labelling, Stockpiling, Transport and Advertisement of Dangerous Substances and Preparations Chapter 5 Risk Assessment, Risk Reduction Chapter 6 Risk Management Chapter 7 Risk Communication, Information Exchange

17 Chapter 8 Conditions of Activity with Dangerous Substances and Preparations; Supervision of Chemical Safety Chapter 9 Closing Provisions

The new act XXV/2000 overcomes the mentioned problems. Enforcement of the Act on chemi- cal safety is provided by the following orders and decrees: – Rules of procedure regarding dangerous substances and preparations – Rules and function of Interministerial Committee on Chemical Safety – Communication of Ministry of Health on list of dangerous substances classified in EU – Amercement /fine/ in case of chemicals load – Environmental and human health risk assessment – Restriction of use of some dangerous substances and preparates on PIC procedures – Chemical safety at work place – On prevention of adverse health effects of occupational carcinogens

Implementation of Chemical Law - institutional structure

covers Function Institutions Government minister of health new data collection intersectorial committee risk assessment National Public Health and Medical Officers Service and risk magement National Public Health Centre risk communication Institute of Chemical Safety existing inspection/controll Toxicological Information Centre chemicals Poison Centre penalitites County Public Health Institutes (21) Municipal Publ Health Institutes (136)

Hungarian regulations as stated above as well as the law on Public Health Service appoint pro- viding scientifically based information to decision makers on possible environmental and health consequencies of potential exposure to chemicals.

Activity of the National Public Health Service is focused on the protection of population, vul- nerable groups of population, consumers, workers, ecosystems from the adverse effects of chemi- cals at the same safety level in different situations. To reach this goal the Service should provide authority control. Some elements of inspection: – employee (manufacturer, importer, trader) is allowed to conduct any kind of activity only with registered or notified chemicals. Components of preparates aslo should be registered or notified – control of package, labelling, storage – control of report on risk assessment at workplace – control of MSDS Public Health Service should improve risk communication to make understandable in wider context the scientific findings according to the regulation of chemicals.

18 Legislation related to environmental and human health risks in aspects of environmental safety

1) Law on emergency preparednes and protection against major accidents involving dangerous substances (LXXIV/1999) 2) Governmental Decree on protection against major accidents involving dangerous substances (2/2001) 3) Governmental Decree on activities affecting the quality of subsurface waters (33/ 2000) 4) Ministerial order on limit values for the protection of subsurface waters and the soil (10/2000) 5) Governmental Decree on environmental impact assessment (20/2001) 6) Governmental Decree on the declaration of convention on the tranboundary effects of industrial accidents (128/2001)

Common features of the decrees listed above

- prevention w recognition and identification of hazards arising from possible major chemical ac- cidents w analysis of the different kinds of risks coming from contaminated environmental media w proactive protection of human health and of the environment w reduction of risks of chemicals to human health and the environment - intersectorial co-operation w involvement of all stakeholders - improvement of risk communication w public availability /access to information, safety cards, MSDS

Risk Assessment Practice

Risk assessment considered as universal tool for the integration of the large quantity of environ- mental, health, toxicological data. There is a need for use of internationally accepted methodol- ogy for evaluation on environmental and health impact of toxic substances. It follows from the above-mentioned that there is an increasing demand for wider and appropri- ate use of risk assessment in controlled manner. National Institute of Environmental Health performs quantitative environmental and health risk assessment to evaluate serious environmental and public health hazard situation arising from the polluted environment (hot spots). This resulted establishment of site specific soil and ground water higienic limit values, remediation (clean-up) concentrations for hot spots (see table of Hungarian cases studies). County Public Health authorities perform mainly expertise activities concerning impact of chemi- cals/pollutants/contaminants on human health. Common goal of central (national) and regional (county) public health institutes is strengthening decision making process (i.e. public health authority expertise, resolution, licensing) by efficient use of risk assessment.

19 and ground water on site site of the dump off specific values in swimming pools EPA IEUBK EPA CalDTSC Lead Risk Assessment software CALIFORNIA DEPART- CONTROL SUBSTANCES MENT OF TOXIC RBCA Risk Based Corrective Action, ASTM Standard, USA (5 thousand) specific limit values for soil and (over 300 thousands)Children(few) (few) management/treatment HESP CalDTSC RQ....? intoxication of children (No of exposed people) Case studies on Human Health Risk Assessment in Hungary PBPK model Physiologically-Based-Pharmaco-kinetic Model IEUBK Integrated Exposure Uptake Biokinetic Model for Lead US EPA USES Unified System for Evaluation of Substances Lead processing plantprocessing Lead (some hundreds)flooded area of home-gardens Adults Ministerial order on site RA RQ < 1 (Tetra-, penta-,(Tetra-, hexachlorobenzene), Dioxin (few) Population living near the site RA Joint ministerial order on site Soil andgroundwaterPAHBTEX, TPH, pipe-line, Oil mining, refinery, site,on Workers tank underground RBCAsite off inhabitants Clean-up values Ground anddrinking water Deep thermal Aswater BTEXSoil, Sediment S-E Hungary (natural occurence) Pb, Cd, As, ZnSoil S-E Hungary (natural occurence) Gyöngyösoroszi General populationSoil General population Pb Quality assessment Chlorobenzenes RAd.w. of Improvement Heves (illegal demolition of batteries) Gare, hazardous waste disposal site Children Workers Advice for using thermal water model, PBPK Investigation of lethal and heavy Potential risk on site Environmental media ContaminantsSoil Area/Site Pb, Cd, Zn, Cu Budapest-Nagytétény Population Children and adult Method/model HESP Results RQ > 1 validated (Pb-blood) RQ Risk Quatient RA Risk Assisstant software HESP Human Exposure to Soil Pollutant software

20 Legislation of environmental and human health risks arising from major chemical accidents (Seveso II.)

Emergency preparednes and protection against major accidents involving dangerous substances w lower threshold limit à safety analysis (480 industrial sites in Hungary) w upper threshold limit à safety report (180 industrial sites In Hungary) Safety report has to contain detailed data about items listed as follows: w characterization of the safety management of the facility w characterization of the environment surrounding the site (inhabitants; natural values; economic values; public institutions; public utilities) w other hazardous sites or activities near the facility w characterization of the health consequences and impacts on the natural environment due to an industrial accident w detailed description of the site by the meaning of manufacturing; production; use, quantity of dangerous substance; description of technologies; circumstances of safe operation; w the measures against a major accident involvig dangerous substances. For screening purposes RAPID ENVIRONMENTAL AND HEALTH RISK ASSESSMENT (REHRA) is applied. Development of REHRA was supported by WHO, Rome EH Office, de- veloped by ICARO, Cortona Italy and sponsored by Italian Ministry of the Environment an performed/implemented in Bulgaria, Hungary, Romania. Flowchart of the REHRA procedure is shown on the figure 1.

Regulation related to occupational risks

1) Law on occupational safety (1993/XCIII) 2) Decree on the chemical safety of workplaces (25/2000 EüM-SZCSM) 3) Decree on protection against occupational exposure to carcinogenic substances (26/ 2000 EüM) 4) Decree on the minimum requirements of protective measures at workplaces being in potentially explosive environment (3/2003 FMM-ESZCSM)

Common features of the regulations listed above

– protect health of employees for a long period of time by creating safe and adequate conditions for work which make possible the prevention of occupational accidents/injuries and occupational diseases. – duties of the employer: w if dangerous, carcinogenic or potentionally explosive materials are used at any work- places the employer is obliged to carry out a risk assessment and to take mea- sures on the basis of the results; w if possible the employer has to eliminate or reduce risk arising from dangerous sub- stances by replacing them with less harmful ones or with harmless ones; w if it is not possible the employer has to minimize the risks to harmless level by

21 Figure 1. RAPID ENVIRONMENTAL AND HEALTH RISK ASSESSMENT in tributaries of the lower Danube basin. Ranking hazardous facilites

QUESTIONAIRE DATABASES DATA 1. Identification of facility, 1. Industrial code,SIC code COLLECTION activity, 2. "SEVESO II." lists: threshold quantities, 2. Technology data, 3. EU classification list of 3. Hazardous substances, hazardous substances 4. Environmental data, (67/548/EEC), 5. Health data. INPUT 4. Other lists: water pollutants, 5. Toxicological databases.

SCORING in accordance with questionary

DATA PROCESSING

SITE INDEX DANGEROUS SUBSTANCE according to questioner 2. INDEX • type of activity according to questioner 3. • organization/automatization • Seveso II. lists • EU classification list of hazardous substances (67/548/EEC)

SUMMING-UP SCORES

ENVIRONMENT AND SURROUNDINGS: HEALTH DATA, • sourface and ground water, demografic characteristics • soil, (according to questioner 5.) • meteorology, • ecology (according to questioner 4.)

FINAL SITE HAZARD INDEX

CHEMICAL ACCIDENT RISK POPULATION RISK ( M A R S ) ( PEC / PNEC )

22 implementing collective and individual protection and by using the best available technology; w the employer has to take preventive measures to avoid accidents involving danger- ous substances w the employer has to inform and educate the employees appropriatelly and also execute regular medical examinations.

Implementation of workplace legislation:

Chemical safety of workplaces w the employer has to guarantee concentrations of dangerous substances in the work- place air under the level stated in this decree

Protection against occupational exposure to carcinogenic substances w lays down that carcinogenic substances are allowed to use only if they cannot be replaced with another substance suitable for the same purpose but having no carci- nogenic property w definition of the tolerable level of risk, which is less than 10-5 w list of carcinogenic substances; w list with the names of employers and employees working with carcinogenic sub- stances w regulations for working with asbestos w regulations for working with vinyl-chloride monomer

Accentuated tasks in chemical risk assessment in Hungary

Chemicals as public health challenge – problems & actions

Problems Actions insufficient knowledge on chemicals improve dissemination and exchange of information, tox. information centre safety of the unborn/new-born child focus on reproductive health, pre-, peri- and postnatal effects neurodevelopmental disorders lack of data on human exposure strengthening biomonitoring health risk of hazardous waste special attention to obsolete pesticides post marketing surveillance of chemicals biocides, pesticides, household chemicals site specific risk assessment of land/groundwater remediation, derivation of environmental former/abandoned industrial facilities and human health risk-based clean up values multi-exposure, multi-factorial, multi-outcome Good Modelling Practice approach in risk assessment procedure acceptability of risks (precautionary principle) uncertainties in risk assessment health, environment and safety in enterprises integrated risk assessment environmental health impact assessment populational risk assessment

23 Further promotion of implementation of chemical risk assessment at country level - harmonization of legislation (chemicals regulated via different legislation) - implementation of national action plans (e.g. as part of Natl.Env.Hlth Action Programme - NEHAP, Children Env.Hlth Action Programme -CEHAPE) - adaptation of public health services to chemical safety priorities - public concern/awareness as input for priority setting - improvement of education and training - development of coherent research plans - strengthening of databases on occupational accidents and poisonings, on ecotoxicology and env. fate)

Intersectorial activities in chemical safety - need for more transparency on mandates/responsibilities and for improved harmo- nization of actions and programmes - improved horizontal collaboration - improved communication as basis for action.

24 CHEMICAL RISK ASSESSMENT IN THE USA*

HERMAN GIBB, PH.D. National Center for Environmental Assessment U.S. Environmental Protection Agency

*The opinions expressed are those of the author and not necessarily those of the U.S. Environmental Protection Agency.

Risk Assessment

“Risk assessment is the use of a factual base to define the health effects of exposure of individu- als or populations to hazardous materials or situations” National Academy of Sciences, 1983

Purpose of a Risk Assessment

• To determine the need for action • To aid regulatory agencies and the public in understanding risks • To satisfy regulations which require risk assessments (e.g., Superfund, Air and Water Programs/EPA; Food Additives/FDA)

Risk Assessment vs Risk Management

• Risk assessment is based on science (fact and professional judgment) • Risk management is based on science, social issues, economics, and technical feasibility

U.S. Government Agencies Responsible for Regulating Human Exposure to Chemicals

• Food and Drug Administration • Environmental Protection Agency • Occupational Safety and Health Administration • Consumer Product Safety Commission

Regulation of Human Health Risks

• Food, Drug & Cosmetics Act (FD&C Act; 1938); Delaney Amendment (1958); Food Additives Act (1959); Color Additives Act (1960)

25 • Food Quality Protection Act (FQPA; 1996) • Children’s Health Initiative (CHI; 1997) • Clean Air Act (1970) • Federal Insecticide, Fungicide, & Rodenticide Act (FIFRA; 1972) • Safe Drinking Water Act (1974) • Toxic Substances Control Act (TSCA; 1976) • Resource Conservation & Recovery Act (RCRA; 1976) • Comprehensive Environmental Response, Compensation & Liability Act (CERCLA; Superfund; 1980) • Occupational Health & Safety Act (OSHA; 1970) • Consumer Product Safety Act (1972)

Government Justification to Regulate Human Exposure to a Chemical

The chemical is capable of harming persons who may be exposed and humans are likely to be exposed to the substance.

Chemical Categories

• Noncarcinogenic compounds (systemic or portal of entry toxicants) • Carcinogens (known or potential) • Current effort to harmonize toxicity nomenclature and quantitation methods

Concept of “Negligible Risk”

• FDA allows for some carcinogenic drugs to be administered to food-producing animals if no residue will be found in edible tissues OR if lifetime dietary risks will be less than one in a million • EPA and other agencies uses “de minimus risk” of one in a million as the point of departure for acceptable risk for exposure to environmental chemicals

De Minimus Risk

• De minimus risks are risks judged to me too small to be of social concern, or too small to justify the use of risk management resources for control • The point of departure for de minimus risk frequently used by government agencies (e.g., EPA, FDA, NASA) is a 1 in a million (0.000001 in 1 OR 1 x 10-6) increased risk of an adverse effect (e.g., cancer, death) occurring over a lifetime in a large population • Exposure to a substance associated with a risk of 1 x 10-6 would increase chances of developing cancer from all causes (1 in 3) by 0.0003%

26 Risk Comparisons for Involuntary Risks

RISK RISK OF DEATH/PERSON/YEAR Influenza 1 in 5000 Leukemia 1 in 12,500 Struck by automobile 1 in 20,000 Floods 1 in 455,000 Tornados (Midwest) 1 in 455,000 Earthquakes (California) 1 in 588,000 Nuclear power plant 1 in 10 million Meteorite 1 in 100 billion Source: JAMA, 244, 1126, 1980

Activities That Increase Risk of Death by One in a Million

Activity Cause of Death Smoking 1.4 cigarettes Cancer, heart disease Traveling 10 miles by bicycle Accident Traveling 300 miles by car Accident Flying 1000 miles by jet Cancer from radiation One chest X-ray Cancer from radiation Risk of accident by living Cancer from radiation within 5 miles of a nuclear reactor for 50 years Source: Technology Review, 81 (1979)

Evolution of Risk Assessment at EPA

• beginnings of the field (tools, approaches) 1970s • emphasis on oral route per FDA precedent

• guidelines 1980s • basic methods • dosimetry • data bases (IRIS) • peer review 1990s • dermal and inhalation routes • understanding mechanisms • cumulative risks • complex mixtures 2000s • susceptible subpopulations • uncertainty evaluations • new tools/approaches

27 Risk Assessment in the Federal Government (NRC, 1983)

• hazard identification • dose-response assessment • exposure analysis • risk characterization

Reference Values

• Definition: An estimation of an exposure for a given duration to the human popula- tion (including susceptible subgroups) that is likely to be without appreciable risk of adverse effects over a lifetime. • Reference Values (acute, less than lifetime, and chronic) - oral (RfD) - dermal (RfD) - inhalation (RfC)

Cancer Toxicity Values

oral slope factor – expressed as the estimate of cancer risk over a lifetime per mg chemical per body weight per day

inhalation unit risk - expressed as the estimate of cancer risk over a lifetime per mg/m3 air breathed

Estimated Lifetime Risk for Carcinogens

Risk is the probability of an individual developing cancer over a lifetime due to exposure to the chemical

Benzene in drinking water example: Risk = (4.1 x 10-3 mg/kg-day of exposure) x 5.5 x 10-2 (mg/kg-day) -1 = 2 x 10-4

Chemical risk assessments done by U.S. EPA may be found on the Integrated Risk Information System (IRIS) at www.epa.gov/iris.

28 PRIORITY TOXIC SUBSTANCES IN BULGARIA

NIKOLAI RIZOV, FINA KALOYANOVA, YORDAN SIMEONOV, IVAN I. BENCHEV National Center of Hygiene Medical Ecology and Nutrition, Sofia, Bulgaria

Introduction

During the last several decades the international organizations increased their concern to protect human health and environment from chemical pollution. This is associated with the increased use of chemicals in all kinds of human activities and growing scientific evidence for relation- ship between many chemicals and the most dangerous human diseases such as cancer, immune system modulation, including autoimmune diseases, nervous systems etc. directly or via endo- crine disruption and genetic damages. WHO and UNEP in cooperation with other organizations created specifically oriented units for chemical safety. Their principal goal was “to achieve that chemicals are used and produced in ways that lead to minimization of significant adverse effect on human health and environment, using transparent science-based risk assessment procedures and science-based risk management procedures, taking into account the precautionary approach, as set out the principle of the Rio Declaration on Environment and Development” (Rapport de la Conference 1992). In Bulgaria chemical safety had high priority in the preventive activity of the Ministry of Health starting in 1966 with the special regulations. At present the Ministry of Environment and other governmental, independent research and training institutions and NGO’s play a considerable role in chemical regulation and safety.

1. APPROACHES USED

The Intergovernmental Forum on Chemical Safety (IFCS) has requested the Inter-organization Programme for the Sound Management of Chemicals (IOMS) member organizations, to identify criteria for setting priorities for various types of risk assessments and to elaborate, on the basis of these criteria a list of priority chemicals for risk assessment. The global criteria for selection of chemicals for international assessment have been developed but additional criteria have been applied in selecting for IPCS EHC and CICAD programmes. It was noted that priority setting by countries was carried out within a national legal framework, which might involve additional criteria for selection of chemicals (IFCS/ISG3/98.08w, 8 June 1998). There are also international targeted risk assessments. Some of them may provide information on given endpoint like the International Agency for Cancer Research (IARC) evaluations of chemicals for their potential carcinogenicity, others provide assessment of chemicals present in given environmental media-drinking water, food (pesticides and food additives), air etc. Different priority setting mechanisms involving specific criteria exist for different types of docu- ments. In the report we stress to the criteria used for CICAD priorities chemicals in addition to the combined criteria with national significance. Of all CICAD criteria the most important ones for our country are:

29 – there is a probability of exposure, and/or significant toxicity/ecotoxicity, and/or significant international trade. – the substance has transboundary concern. – the use/production is high and the use is dispersive. – it is of concern for possible risk management. To select priority chemicals for risk assessment and management we tried to combine the glo- bally recognized criteria and used the most simple, but effective method - expert evaluation and scoring. Emphasis was given to the long-term effects, especially carcinogenicity. In this respect it was important but not easy and possible to take into account the recently defined new phenomenon known as a multiple chemical sensitivity (MCS). We took into consideration the necessity to evaluate the total combined carcinogenic load, but MCS required more knowledge and data. MCS is a poorly understood condition, on which some patients have severe reaction to chemi- cals at concentrations that most people can easily tolerate. Characterizing MCS is difficult due to the broad range of symptoms associated with it (Miller 1997). Modern epidemiological stud- ies have found that most known risk factors for breast cancer- the most common cancer among women, excluding radiation, are directly related to lifetime exposure to estradiol and other hor- mones. Researchers have reasoned that any environmental chemical, that has the ability to mimic human hormones or affect their metabolism, may be carcinogenic. (Forum 1997). Taking into account the big group of chemicals with endocrine disruption effects, we may see the magnitude of the problem and the pressing need of research in this field.

1. 1. Industrial chemicals Chemical production plants are the principal sources of environmental pollution. The chemical industry comprises production of acids, alkalis, salts, petrochemical products, synthetic fibers, plastics, pharmaceutical products, fertilizers, paints, pesticides and many other products. Metallurgical plants producing lead, zinc, copper, steel and other metals pose the most serious problem and have global significance because pollution with metals and their inorganic com- pounds has long term consequences for the environment. In large cities, transport vehicles and thermoelectric power stations are responsible for air pollution by lead, sulfur dioxide, dust and other contaminants. Metal pollution is one of the most important and to some extent well known problems Lead is the principle pollutant arising from non-ferrous metallurgy. A correlation exists between some pollutants and morbidity from certain diseases, especially respiratory system disorders, allergic reactions and anemia. Lead exposed individuals very often have an increased prevalence of cardiovascular and nervous system diseases. The study con- ducted during the period 1999/2000 in the region of a plant of non-ferrous industry near Plovdiv has shown unusually high levels (242 ± 78 mg/l) of lead in blood samples from a representative group of 129 children aged 3 - 13 years (cited by C. Willeke Wetstein). A major problem is soil pollution near metallurgical plants, due to sedimentation of metals from air. This pollution contributes considerably to the exposure of the general population. The most serious problem with a global significance is presented by the metallurgical plants producing lead and zinc near Plovdiv and Kurdjaly and the plant producing copper and rare metals in Srednogorie. An important and long lasting problem is the decontamination of soils polluted with metals because of the lack of practical and effective methods. Arsenic poses water pollution problems both due to its natural presence and as waste from the

30 metallurgical plants. Chromium is not well studied. There is no organized waste disposal of chromium containing chemicals. Cadmium is used in the electronic and electro-technical indus- try as yet there is no proper substitute. Lazer mass multielement analysis has been recommended for environmental samples (Simeonov, 1999; Simeonov and Managadze, 1999; Simeonov et al., 1996, 1998). Mercury pollution is mainly a result of uncontrolled waste deposition of out-of-use luminescent lamps and neon lighting. Organic lead compounds are still present in transport fuels. Organometals are local problems connected with activities in ship-yards and ship repair in sea and river ports. The measures undertaken for risk reduction should take into account cost/benefit analyses. In order to achieve effective results it will be necessary to identify and deal with the worst and the most easily controllable risk factors of global significance. Sources and emissions of hexachlorobenzene and polychlorinated biphenyls (PCBs) included in the POPs list need additional national inventory and monitoring. According to the data published in the Annual Bulletin of MOEW for 2000, 6 PCBs have been monitored in soil samples. The conclusion is that the concentrations measured are below the background values and there is no potential risk for soil contamination by PCBs). Polyaromatic hydrocarbons (PAHs) are widely dispersed and poorly investigated. Some PAHs have been found in soil samples in the vicinity of a plant producing carbamide, formaldehyde resins, aniline etc. in particular: benzo(b)fluoranthene 68-70 mmg/kg, benzo(k)fluoranthene 324 mmg/kg, benzo(ghi)perylene up to 49 mmg/kg, indeno(1,2,3-cd)pyrene from 0.1 to 55 mmg/kg In water samples the same substances have been detected in single samples and low concentra- tions (1-15 ng/l). The annual Bulletin of MOEW for 2000 reports that 16 substances of PAHs have been con- trolled; the general conclusion is that the values measured do not cause any adverse effect on soils, also in regions of high potential impact. 1,1-Dichlorethane presents a local problem for waters in the region of Varna due to the chemical industry in Devnja. Nitrobenzene is a regional problem associated with waste waters from the chemical production in Dimitrovgrad. Phenol presents water problems in regions with wood- working industry as well as in regions with petrochemical industry, such as Bourgas and Pleven. Chloroform is still widely used as a laboratory solvent. Cyanides are widely used in galvanothechnics and machinery. Cyanides are associated with some accidents registered in the following regions: – Slivnitza - road accident with cyanide containing substances; – Tran - unauthorized deposition of industrial wastes near water sources; and – Brjagovo - water contamination of river and terrace wells as a consequence of transboundary industrial pollution. Phtalate esters are mainly pollutants of the working environment.

31 Table 1. Different industrial chemicals

Name Scores Media of concern

PCBs 5 No data PAHs 5 Water, working environment, soil Cyanides 5 Working environment; water Phenol 5 Water, working environment Musk xylene 4 Working environment Nitrobenzene 4 Water, working environment Short chain chlorinated paraffins 3 Working environment 2,4,6-tris-(1,1-Dimethylethyl) phenol 1 Working environment Hexachlorobenzene 1 Water, working environment

Table 2. Chorinated organic chemicals

Name Scores Media of concern

Solvent Chloroform 5 Water, working environment Others Hexachlorobutadiene 3 Working environment Benzenes 1,2-Dichlorobenzene 2 Working environment 1,3-Dichlorobenzene 2 Working environment Solvent 1,1- Dichloroethane 2 Working environment Benzene 1,4-Dichlorobenzene 2 Working environment Solvent 1,1,1-Trichloroethane 1 Working environment Benzene 1,2,4-Trichlorobenzene 1 Working environment 1,2,4,5-Tetrachlorobenzene 1 Working environment Pentachlorobenzene 1 Working environment Others Octachlorostyrene 1 Working environment

Table 3. Metals and organometals

Name Scores Media of concern

Arsenic 5 Total environment Cadmium 5 Total environment Chromium 5 Working environment; water Lead 5 Total environment Organic lead 5 Working environment; food Mercury 5 Working environment; water; food Organic mercury 5 Water; food Antimony 4 Water; working environment Beryllium 4 Water; working environment Zinc 4 Working environment; water Organic tin 4 Working environment Nickel 4 Working environment; water Copper 3 Working environment; water; food Selenium 3 Working environment; water

Table 4. Phthalate esters

Name Scores Media of concern

Dibutyl phthalate 4 Working environment Butylbenzyl phthalate 4 Working environment Diethylhexylphthalate 2 Working environment Bis-(2-ethylhexyl)phthalate 1 Working environment

32 1. 2. Pesticides In Bulgaria only registered pesticides are applied for agricultural or public health use. The most used groups are pyrethroides, organophosphates, carbamates, thiocarbamates, dithiocarbamates, tricloracetic acid compounds, dipyridiliums, triazols, triazines, copper sulfate, methylbromide, aluminium and zink phosphate. The number of the registered active substances is about 320. Fungicides are 73, insecticides - 85, herbicides - 95, dessicants and defoliants - 9, plant growth regulators - 33, feromones - 23. The use of persistent organochlorine pesticides is very limited. Pesticides with high acute toxic- ity such as aldicarb, parathion etc. have not been used for many years. Some of the persistent pesticides such as DDT, aldrin, dieldrin and endrin have been registered in Bulgaria and consequently banned since 1969. DDT contributed significantly to the eradica- tion of insects in home and for vector control - mostly malaria. In 1969 it was concluded that, due to the complex measures taken, malaria was successfully controlled in the country. For this reason it was not necessary to look for alternatives for malaria control. It was very easy to exclude agricultural use of DDT due to the large number of alternative pesticides. The most important reason for the ban of DDT was food contamination. (Kambourova and Vassilev, 2001). Aldrin, dieldrin and endrin were used almost exclusively as raticides in very limited quantities and on small areas. Toxaphene was banned in 1985 and heptachlor in 1991. Mirex, HCB and chlordane have never been registered. Nevertheless, despite the limited use of persistent pesticides, the pollution problem is present due to different reasons. DDT was detected in the Danube River at concentrations of up to 0.002 µg/l in the Bulgarian section but up to 21.8 µg/l in some other Danube basin countries. Up to 8.13 µg/l DDT were found in the tributaries of some Danube basin countries. Lindane and atra- zine were also found in the Danube River in amounts of 0.033 µg/l and 0.04 µg/l respectively. (Kaloyanova-Simeoinova 1998; Kaloyanova et al 2001). In some accidents related to unattended stockpiles, DDT was found in soil samples in concentra- tions up to 1205 mg/kg almost four year after the event, while in water samples it ranges from 0.04 to 1.59 µmg/l (Kambourova et al., 2002). According to expert data 10 per cent of the samples from different water bodies were positive for lindane with maximum values of 0.2 µmg/l. Hexachlorobenzene and heptachlor were detected in water samples in a few cases in amount of 0.05 µmg/l. Residues of 15 pesticides have been found in 19% of the examined 176 water samples. The most positive findings were related to lindane (10%), and atrazzine (13%). The contamination levels ranged from 0.01 to 0.1 µmg/l for atrazine and from 0.01 to 0.06 µmg/l for lindane (Bratanova and Vassilev, 2001). Because of the permanent presence of triazines in the water environment, especially in ground water, it might be proposed to include triazines in the list of priority chemicals (Bratanova and Vassilev, 2001).

Table 5. Persistent Pesticides

Name Scores Media of concern

DDT 4 Water, soil BHC, including lindane 4 Water, food Heptachlor 1 Water

33 1. 3. Unintended by-products Dioxins Dioxins are a high priority for Bulgaria. The main known sources for dioxins in the country are: ferrous and nonferrous metallurgy, power generation and heating, mineral products outcome, petroleum industry, waste incineration, transport, uncontrolled combustion processes, etc. A national inventory of dioxin sources and their monitoring in the environment is an urgent need. Methods for analysis in air, water, soil, chemicals and food should be made available. Furans Furans are also a priority for Bulgaria as they have not been sufficiently studied. They are pro- duced unintentionally by many of the above mentioned processes producing dioxins. The main sources may be waste incineration and transport. Contaminated animal products may represent the major source of human exposure. According to the MOEW data (2000) the greatest part of the estimated emissions of dioxins and furans is due to the thermoelectric plants (46.9%) and the domestic burning processes (25%), followed by the non-burning industrial processes (9.2%). Within the framework of a Programme supported by WHO 30 breast milk samples (10 samples from three Bulgarian regions) were analyzed in Germany for presence of PCBs, dioxins and furans. The results obtained rank Bulgaria among the first four countries with the lowest concen- trations of those chemicals.

Table 6. Unintended by-products

Name Scores Media of concern

Dioxins 5 Total environment Furans 5 Total environment

2. PRINCIPAL PROBLEMS WITH NATIONAL SIGNIFICANCE

2.1. Decreasing of the exposure – Human exposure from: Residues in food; Contaminated drinking water; and occupational exposure. – Environmental exposure: Air pollution; Ground and surface water pollution; Soil fertility impairment; Ecotoxicity; and Contamination of marine water. Many of the sources are of transboundary and/or global dimension.

2.2. Management of mostly persistent and dispersed in the environement chemicals with highest priority, selected by expert judgment based on long term experience of specialists. Pesticides: DDT as historical contaminant, lindane and triazines. Metals: Mercury and mercury containing organic compounds, lead including organic lead, mercury, including organic mercury and lead containing organic compounds,

34 as well as compounds containing arsenic, chromium, cadmium and cyanide present health problems mainly due to environmental pollution. Dioxins and Furans are a danger to human health and the environment. They are dis- persed all over the country due to chronic pollution originating from transport and long term low temperature burning of wastes, especially chlorine containing poly- mers (PVC). PCBs are not well studied at present. PAHs are widely present in the environment as they are formed by burning processes and constitute health problems. Other industrial chemicals: phenol, cyanide, chloroform

2.3. Long term adverse health and environmental effects Carcinogenicity Chemical carcinogens have first priority due to the character of the effect they may produce directly or as co-carcinogens. They are found in all environmental media and the total carcino- genic load is considerable for all age groups including newborns, due to intrauterine exposure (Simeonov 2001a). From the industrial substances used in Bulgaria chemical carcinogens are: Human carcinogens: arsenic, (arsenic acid, arsenic oxide (V and III) hydrogen arsen- ate), cadmium, chromium ( chromium (VI) oxide, zinc chromate, zinc potassium chromate), lead, nickel (nickel trioxide, nickel dioxide, nickel monoxide (II) nickel disulfide, nickel sulfide, dinickel trioxide). Animal carcinogens: PCBs PAHs, dioxins, chloroform, berillium, lead and lead or- ganic compounds, cadmium chloride, cadmium sulfate, calcium chromate, dichro- mates (potassium, amonium, sodium), chromyl chloride, potassium chromate, hexachlorbenzens. Many others are suspected carcinogens.

3. FUTURE NEEDS

3. 1. Regulatory documents for management of toxic substances During the last 10 years considerable efforts have been made by the Ministry of Health, Ministry of Environment and Waters, and other organizations to harmonize Bulgarian regulatory docu- ments with the respective European legislation and to start their implementation (MEW 2000; MEW 2001).

Activities for the implementation of existing regulatory documents, International Conventions and related national plans Development and implementation of regulatory control Enforcement of regulatory control Technology transfer activities Supporting and introducing alternatives Implementation of outreach and information programmes Implementation of remedial action plans for stockpiles and contaminated sites Research and monitoring programmes on sources and movement Research and monitoring programmes on human and environmental impacts of chemi- cals

35 Table 7. Implementation of existing documents Implementation Evaluation score Legislative documents 4 Air/water monitoring (national and regional programmes) 4 Import and trade regulation 4 Financing 3 Training (all levels) 3 Workers protection 3 Stockpiles and transport 3 Scientific investigations 3 Safe use 3 Environmental protection 2 Quality assurance 2 Public protection by accidents 2 Obsolete stocks (inventory, removal, destruction) 2 Hazardous waste and treatment 2 Modelling 1 GIS 1

3. 2. Research programmes for solving the main problems Some topics for research and development are proposed below. A) Precise exposure and health risk assessment by means of biomonitoring surveys with stress to long term effects (cancer, reproductive and developmental toxicity). B) In-depth and long-term assessment of the consequences of incidents and accidents related to chemicals in Bulgaria. C) Establishment and development of environmental screening programmes of chemi- cals, included in EC and other international documents. D) Development of National GIS based information system for acute toxic and persis- tent chemicals (sources, polluted areas, sensitive groups and areas, accidents, reme- dial actions, monitoring data). Modelling of environmental pollution (Dura et al., 1998; Kambourova et al., 1998). E) Development and adaptation of analytical methods and quality assurance systems for chemical analyses in environmental media. F) Projects for decontamination of polluted sites by phytoremediation, bioremediation and other effective technologies should be encouraged. The existing data from labo- ratory experimental modeling (Simeonova and Simeonov, 1997) and field studies in Kremikovtzi metallurgic plant region, demonstrated that phytoremediation is a perspective approach in the land clean-up (Simeonov, 1997; Simeonov et al., 1999). International coordination and financial support are necessary, especially for analyses requiring expensive equipment, and for research on long terms effects especially carcinogenicity in hu- man in epidemiological studies (Simeonov 2001a, 2001b).

4. RISK REDUCTION

Risk reduction needs cost/benefit analysis. In order to achieve effective results it will be neces- sary to identify and deal with the worst and the most easily controllable risks related to sub- stances with national and global significance. Unrealistic optimism should be avoided i.e. there should be an appropriate time frame for achieve- ment of the plan. Alternatives should be well studied. There should be flexibility especially if health and serious environmental concerns exist. 36 References Bratanova Z. and K. Vassilev (2001). Pesticide Residues in Ground and Surface Water in Bulgaria. Fresenius Envi- ronmental Bulletin, 10 No 4, 401- 404. Dura Gy., G. Kamburova, K. Vassilev, M. Tasheva and L. Simenonov (1998). Estimating environmental concentra- tions of pesticides and hazard categories using exposure modeling. Cent. Eur. J. Occup. Environ. Med. 4, 328-342. Forum. Breast cancer and MCS in EHP. Environmental Health Perspectives, vol.105,/3 March 1997, 1-8. IFCS/ISG3/98.08w 8 June 1998. Criteria for setting priority for various types of International risk assessment and means to identify particular chemicals of Interest Prepared by: WHO-PCS and OECD for the third meeting of IG IFCS. Yokohama, Japan, 1-4 December 1998. Kaloyanova F. (1998) Pesticides in Danube River and Tributaries. In Proceedings of Subregional warness raising workshop on persistent organic pollutants (POPs). Kranjska Gora , Slovenia, 11-14 May 1998, IOMC,272-283. Kaloyanova F., Gy. Dura and V. Kambourova (2001). Results of the use of two environmental models for pesticides ranking by hazard. In: Modelling of Environmental Chemical Exposure and Risk, J.Linders ed. NATO Science Series IV. Earth and Environmental Sciences. Vol 2, Kluwer Academic Publishers, pp. 97-103. Kambourova V., L. Simeonov, Gy. Dura, K. Vassilev and M. Tasheva (1998). Comparative hazard assessment of pesticides to aquatic life using estimated concentrations. Cent. Eur. J. Occup. Environ. Med. 4, 343-353. Kambourova V. and K. Vassilev (2001). Application of USES for Estimation of PEC of Pesticides and Hazard Assessment for Aquatic Environment, in J.B.H.J.Linders (ed.) Modelling of Environmental Chemical Exposure and Risk, Kluwer Academic Publishers, 73-78. Kambourova V., Zl. Bratanova, J. Christova, J. Simeonov. Environmental Consequences of Incidents with pesti- cides in Bulgaria, Proceedings. International Conference on Rural Health in Mediterranean and Balkan Coun- tries, Bari (Italy), November 13-16, 2002, p.130. MEW (2000). Annual Bulletin of Executive Agency for Environment. State of Environment in Republic of Bulgaria for 1998. Ministry of Environment and Water. Sofia, Bulgaria. (In Bulgarian). MEW (2001). Annual Bulletin of Executive Agency for Environment. State of Environment in Republic of Bulgaria for 1999. Ministry of Environment and Water. Sofia, Bulgaria. (In Bulgarian). MEW (2000). Annual Bulletin of Executive Agency for Environment. State of Environment in Republic of Bulgaria for 2000. Ministry of Environment and Water. Sofia, Bulgaria. (In Bulgarian). Miller S.C. Toxicant-induced loss of tolerance - an emerging theory of disease? Environ. Health Perspect 105 (suppl. 2): 445-453 (1997). Rapport de la Conference des Nations Unies sur l’Environment et le deveoppment. Rio de Janeiro, 3-14 juin 1992. Resolution adopte par la Conference, resolution 1, annex II. Publ. Nations Unies: F.93.1.8 et rectificatifs. Simeonov L. (1997). Perspectives of Remediation of Argicultural Lands Polluted with Heavy Metals in the Kremikovtzi Region, Bulgaria. In Strategies to improve Occupational and Environmental Health in Central and Eastern Europe. Ed. R. Ungar and C. Slatin, University of Massachusett , Lowell, 67-69. Simeonov L. (1999). Express semi-quantitative multielement analysis of water solutions with the lazer mass analyser LASMA in Contemporary problems of Solar- Terrestrial Influences , Sofia, November.Publ. CLSTI, BAS, 195-198. Simeonov L. and G. Managadze (1999). Laser mass analysis of environmental samples with LASMA in Contempo- rary problems of Solar-Terrestrial Influences, Sofia, November. Publ. CLSTI, BAS 191-194. Simeonov L., K. Scheuermann and C. Schmidt (1996). Schnelle semiquantitative Multielement-analyse wabriger Losungen mit dem Laser-Massenanalysator LASMA. In Teratech Nov. Dez, 6, 29-31. Simeonov L. , G. Managadze, C. Schmidt and K. Scheuermann (1998). Ecology screening of heavy metal pollution of the soil with Laser mass spectrometry. Comptes rendus de l’Academie bulgare des Sciences, Tome 51, No 5- 6, 29-32. Simeonov L., B. Simeonova and J. Nikolova (1999). Phytoremediation of Industrially Polluted with Heavy Metals Lands in Bulgaria. (First trials). In Proceedings of Contaminated Site Remediation Conference, ed.I. D.Johnston, 21-25 March 1999 Premantle, Western Australia. Centre for Groundwater Studies, 551-557. Simeonova B. and L. Simeonov (1997). Phytoremediation of polluted with heavy metals agricultural lands In Sc. Works, vol. XLII, book 2; Higher School of Agriculture, Plovdiv, Agroeco 97; 253-258. Simeonov Y. (2001a). Cancer of offspring. In: Euroworkshop Proceedings Current Epidemiological Evidence ver- sus Experimental Data on Reproductive and Development Toxicity of Pesticides. T. Vergieva and F.Kaloyanova- Simeonova eds, Sofia, 175-180. Simeonov Y. (2001b). Analysis of studies relating pesticides to breast cancer risk in exposed persons and their offspring. In: Euroworkshop Proceedings Current Epidemiological Evidence versus Experimental Data on Re- productive and Development Toxicity of Pesticides. T. Vergieva and F.Kaloyanova-Simeonova eds, Sofia, pp. 193-216. Willee-Wetstein Ch., Health Risk of Heavy Metals in the Food Chain of Industrial Areas in Central and Eastern Europe. Annual Report 2002 (abstract), http://www.uni-giessen.de/~ghi5/incocop01.htm

37 HEAVY METALS POLLUTION AROUND THE METALLURGY PLANTS IN SOME REGIONS IN BULGARIA

IVAN GRANCHAROV, SIYKA POPOVA Department of Inorgnic Chemical Technology, University of Chemical Technology and Metalurgy, Sofia, Bulgaria

1. Introduction

The soil is a key component of terrestrial ecosystems, both natural and agricultural, being essential for the growth of plants and the degradation and recycling of dead biomass. It is a complex heterogeneous medium comprising mineral and organic solids, aqueous and gaseous components. The soil is a dynamic system, subject to short-term fluctuations, such as variations in moisture status, pH and redox conditions and also undergoing gradual alterations in response to changes in management and environmental factors. These changes in soil properties could affect the form and bioavailability of metals and need to be considered in decisions on the management of polluted soils. “Heavy metals” is a general collective term applying of metals and metalloids with an atomic density greater than 6 g/cm3. Although it is only a loosely defined term it is widely recognized and usually applied to the elements such as Cd, Cr, Cu, Hg, Ni, Pb and Zn which are commonly associated with pollution and toxicity problems. An alternative and theoretically more acceptable name for this group of elements is “trace metals” but it is not as widely used. Unlike most organic pollutants, such as organohalides, heavy metals occur naturally in rock-forming and ore minerals and so there is a range of normal background concentrations of these elements in soils, sediments, waters and living organism. Pollution gives rise to anomalously high con- centrations of the metals relative to the normal background levels (Alloway, 1990). There are different sources of heavy metals pollutants in soils. Some of the major sources of heavy metal pollutants in soils are: – Metallurgical industries can contribute to soil pollution in several ways: a/ by emissions of fumes and dusts containing metals which are transported in the air and eventually deposited onto soils and vegetation; b/ by effluents which may pollute soils when watercourses flood; c/ by creation of waste dumps ( and scrapyards ) from which metals may be leached and thus pollute underlying or nearby soils. The mining and smelting of non-ferrous metals has caused soil pollution. Metals are dis- persed in dusts, effluents and seepage water. Tailings discharged into water-courses have pol- luted alluvial soils downriver from mines. – Agricultural fertilizers and pesticides: several of these including phosphatic fertiliz- ers, slugs from iron manufacture, pesticides and herbicides contain various combi- nations of heavy metals, either as impurities or active constituents. – Organic manures: these include pig and poultry manures which may contain high concentrations of Cu or As fed to improve food conversion efficiency. Sewage sludge

38 usually contain relatively high concentrations of several metals, especially those from industrial catchments. – The deposit of urban and industrial wastes can lead to soil pollution from the depo- sition of aerosol particles emitted by the incineration of metal-containing materials. – Atmosphere pollution from motor vehicles: the use of leaded petrol has been re- sponsible for the global dispersion of Pb aerosols. – The combustion of fossil fuels: this results in the dispersion of many elements in the air over a large area. The disposal of ash is a further source of heavy metals. The major interrelationships affecting the dynamics of heavy metals between the soil and the plant are shown in Figure 1. The soil-plant system is an open system subject to inputs, such as contaminants, fertilizers and pesticides, and to losses, such as the removal of metals in har- vested plant material, leaching, erosion and volatilisation.

Fig. 1 The soil plant system showing the key components concerned with the dynamics of heavy metals

Whatever their sources, toxic elements can and do reach the soil, where they become part of the life cycle of soil ® plant, animal ® human (Figure 2). Unfortunately, once the elements become part of this cycle they may accumulate in animal and human body tissue to toxic levels. It should be noted that the content of metals in tissue generally builds up from left to right, indicating the vulnerability of humans to heavy metal toxicity.

2. Heavy metal pollutants in Bulgarian soils

Major source of heavy metal pollutants in our soils are non-ferrous and ferrous works and metal- ferrous mining: UMPC – Pirdop; NFM works – Plovdiv; Lead and Zinc Plant – Kurdjali; MME

39 Industrial products, Air Birds burned fuel, fertilizers, pesticides Soil Plants Domestic Humans animals

Rocks in earth crust Water Fish

Fig. 2 Sources of heavy metals and their cycling in the soil-water-air-organism ecosystem.

– Eliseina; Kremikovtzi company; Mining company “Asarel – Medet” (Table 1) (Ministry of Environment,1979a). The data presented in Table 1 show that heavy metal contaminated soils are quite a common and widespread in industrialized regions of Bulgaria, especially around the metallurgy plants. More than 35 years of unrestricted environmental pollution with heavy metals from mining and metallurgical activity have resulted in a contamination of approximately 200 000 decares with Cu, Pb, Zn, Cd and As.

Table 1. List of contaminated land with heavy metals in Bulgaria from industry

Region Living place Conta- Element Source of Minated Decares contaminated contamination areas, soils Total Including over 2 times of limits Vidin Total 1002 673 - - Bregovo 671 508 Cu, Zn river Timok /from Serbia/ Baley 45 45 Pb, As “ Vruv 286 120 Pb, As “ Vratza Total 1310 635 - - Ochin dol 390 15 As, Pb MME-Eliseina Zverino 300 - Pb “ Oselna 300 300 As, Pb “ Zli dol 40 40 As, Pb, Cu “ Eliseina 280 280 As, Pb “ Kurdjali Total 33500 11500 - - Kurdjali 9000 5000 Pb, Zn, Cd Lead and Zinc plant Shiroko pole 2700 1000 “ “ Vishegrad 1000 500 “ “ Tcherna skala 1000 500 “ “ Sedlovina 2000 1000 “ “

40 Table 1. List of contaminated land with heavy metals in Bulgaria from industry (continued)

Ostrovitza And another 3500 2000 “ “ 14 villages Pazardjk Total 22800 17800 - - Lesichevo 1500 1500 As, Cu UMPC-Pirdop Buta 3000 - As Asarel-Medet Oborishte 10000 10000 Cu, As, Pb “ Elshiza 2500 2500 Cu, As “ Rosen 800 800 Cu, As “ Poibrene 2000 - AS “ Plovdiv Total 71780 19620 - - Kuklen 10827 4885 Pb, Zn, Cd NFM Works- Plovdiv Dolni voden 7884 4505 “ “ Jagodovo 6800 2200 “ “ Krumovo 6800 2200 “ “ Katunitza 4350 1500 “ “ Gorni voden 3600 1320 “ “ Asenovgrd and “ “ another 4 14977 7306 villages Sofia town Total 11689 3314 - - Buhovo 2690 2217 Pb Kremikovtzi company Jelava 1090 - “ “ Kremikovzi 963 870 “ “ Seslavtzi 1944 - “ “ GorniBogrov 1564 202 “ “ Dolni Bogrov 357 - “ “ Jana 2893 25 “ “ Botunez 119 - Pb “ Chelopechene 69 - “ “ Sofia- Total 47400 11000 - - district Pirdop 15000 5000 Cu, As UMPC – Pirdop Zlatiza 12000 4000 “ “ Anton 6000 2000 “ “ Chelopech 5000 - “ “ Dushantzi and 1500 - Cu, As Kremikovtzi another 4 - Pb company villages Total for 193581 64542 - - the country

41 Having established that an area of soils is contaminated, it is necessary to make a decision about the action that needs to be taken in order to avoid unnecessary risk of health effects or of damage to structures. For this purpose, various sets of critical concentrations are in use around the world. The ranges of critical limit concentrations of heavy metals used in Bulgaria for the interpretation of contaminated land are given in Tables 2 and 3 (Ministry of Environment, 1979; 1997).

Table 2. Critical (limit) concentration of heavy metals in soils (Ministry of Environment 1979 b), (mg/kg)

Critical concentration of heavy metal, mg/kg soil Soil pH Pb As Cu Zn 4.0 < 25 < 25 < 20 <40 4.5 < 30 “ < 25 < 40 5.0 < 40 “ < 40 < 60 5.5 < 50 “ < 60 < 90 6.0 < 70 “ < 120 < 200 6.5 < 80 “ < 250 < 320 7.0 < 80 “ < 260 < 340 7.5 < 80 “ < 270 < 360 8.0 < 80 “ < 280 < 370

Table 3. Critical (limit) concentrations of heavy metals in soils (Ministry of Environment 1997), (mg/kg)

soil pH Cd Ni Cr Hg ≥ 4,0 0,4 25 150 1 ≥ 5,0 0,8 35 170 1 ≥ 5,5 1,0 50 180 1 ≥ 6,0 1,5 60 190 1 ≥ 7,0 3,0 70 200 1

3. Remediation of contaminated land

Once an area of land has been identified as been contaminated, it becomes necessary to decide what action ought to be taken with regard to restrictions on its use and, or, requirements for the amelioration or “clean-up” of the soil. There are several options available for the remediation of contaminated sites (Alloway 1990). The choice of option will depend on the nature of the con- taminants, the type of soil, the characteristics of the site, the intended use, the relative costs of the appropriate options and the regulations which apply in the country or region where the site is located. The remediation options can vary from the minimum of reducing the bioavailability of the contaminants, to the maximum of either complete clean-up of the soil or its removal from the site. Removal of the pollutant can be accomplished in the short-term by applying various me- chanical and chemical technologies. These engineering solutions are typically very expensive, which restricts their application only to small areas with high levels of contamination. In cases of low and medium pollution of agricultural lands with heavy metals, a wide spread situation in Bulgaria around the heavy industry plants, the only possible remediation technology seems to be phytoremediation. Phytoremediation is a new emerging technology, which uses the ability of specially selected higher terrestrial plants, called hyperaccumulators to extract and accumulate considerable amounts of heavy metals from polluted soil and water sites (Salt et al., 1995;

42 Simeonov,1997; Simeonov et al., 1999; Simeonova and Simeonov, 1997;, The hyperaccumulators extract with their root system toxic elements from the soil and translocated them to the shoot tissues in accumulator depots. The shoot-leaves and stalk biomass is further harvested and pro- cessed. The conventional procedures include excavation and transportation of the polluted soil for further processing (ex-citu), or the application of in-citu technologies, which are mainly chemical, such as stabilization and sodification. The technologies, available and widely used for soil remediation from heavy-metal contamina- tion have highly destructive character – the soil, which is regarded as a non-renewable resource, is thoroughly wasted. The interest in the application possibilities of phytoremediation is ex- panded by the expected economic (the overall costs for cleaning one unit of soil is many orders of magnitude less, than the cost, related to physicochemical technologies), aesthetic (soil nonde- structive and public accepted) and technical (a relatively low-tech method) advantages over traditional engineering solutions. In literature (Salt et al., 1995; Simeonov, 1997) hyperaccu- mulators are considered plants, that contain in their shoots 10 to 1000 times greater consider- ations of toxic metals, than ordinary plants, in figures, that would mean roughly > 100 mg/kg dry weight for Cd, > 1000 mg/kg for Ni, Cu, Co and Pb,> 10000 mg/kg for Zn and Mn. The number of plants, reported in the literature and classified as hyperaccumulators is nearly 400 species. Ni is extracted and accumulated by more, than 300 of them, Co by 26, Cu and Zn by nearly 20 each, and at the bottom of the table are Pb, Cd and As, or the metals of particular ecological “signifi- cance” (Salt et al., 1995). There are some problems in connection with realization of phyto-remediation of heavy metals contaminated soil: it is a time-consuming process, which makes it economically suitable for soils, contaminated at medium and low concentrations; - the process is strongly dependent on the soil, climate, and anthropogenic parameters and factors; - most of the reported hyperaccu- mulators are exotic wild African and Australian plants with small biomass and undefined growth requirements and characteristics in respect to European climate; - the process of phytoremediation depends greatly on the metal availability in soil. Only free metal ions and partially the soluble metal complexes are readily subjected to phytoremediation. Some increase of the bioavailable part of the metal content could be achieved by changing the pH level, by the application of special chelation agents and changing the fertilizers to exploit the metal competition in asolution or by parallel application of engineering remediation techniques such as electroosmosis (Simeonov,1997).

4. Heavy metals pollution around the metallurgy plants in Bulgaria

The biggest areas for heavy metals pollution of agricultural land in Bulgaria are in connection with industrial activities and are situated around the metallurgy plants (Table 1). Some environ- mental problems in activity of UMPC – Pirdop, Kremikovtsi Corp. and NFM Works – Plovdiv and information about current contamination with heavy metals of the soil around this plants and it remediation are presented and discussed.

UMPC – Pirdop The company is situated in the Zlatitsa – Pirdop valley. It is the biggest non-ferrous production plant in Bulgaria. The environmental problems, which are a result of the plant activity up to the privatization, can be summarized in the following order: – An influence over the atmospheric air in the region caused by organized sources of

SO2 and production dust;

43 – An influence over the surface waters in the region caused by the copper producing activity; – An influence over the soils and underground waters as a result of the uncoordinated storage of production and harmful waste materials. After the problems had been considered and analysed Compliance program for their solution were worked out. Realization of this program after 1999 by now has led to reduction of environ- mental contamination, including the soils. In the area of Zlatitsa – Pirdop hallow many studies have been carried out about the contamina- tion of the agricultural land, crops and animals. Surface contamination and acidification of the soils while studied the profile distribution of heavy metals in vicinity to the smelter have been established. On the basis of the spatial distribu- tion of heavy metals in the surface soil horizons, NSS-NCH “Spektroteh” assumes that the industrial contamination of the soils is due to several main sources. There is also a hypothesis for pedogenic (lithogenic) reasons for the increased concentration of heavy metals and arsenic in Zlatitsa – Pirdop hollow. A new field and analytical investigations on the soils and interpretation of the results and integration between available and new information. have been carried out ( Koulikov et al. (1997) According to the norms in Bulgaria, only 17% of the whole studied area of the agricultural lands (which are 25,7 thousand ha) are designated to the so called zone of “practically not contami- nated lands”, where there is not necessary to recommendation land use regime. The zone of so called “weakly contaminated agricultural lands” occupies 21%. In this zone, according to the instruction of the Ministry of Agriculture and Forestry, when contamination is in a progress “consumption of spies, leaf vegetables, and silage for the animals is not allowed” without control analyses when those are grown on such land. In the zone of “moderately contaminated agricultural lands”, occupying 22%, consumption of spies, leaf vegetables, peas, green onions, all kinds of vegetables for winter storage, beans, production for silage, leaf forage for animals is not allowed” without control analyses when those are grown on such land. In the zone of “strongly contaminated lands”, occupying 26% of the total studied area, “con- sumption of all kinds of vegetables, cereals and beans for food, strawberries, blueberries, black- berries, peaches, quinces, apricots, all kind of silage and forage for animals is not allowed” without control analyses when those are grown on such land. In the zone of “risky contaminated lands” that occupy 15% of the total area of the studied agri- cultural land, “growing crops which production is designated for a direct consumption, exclud- ing cherries, pie-cherries, apples, pears and grapes”. The results of this investigation confirmed already established information about the character of the industrial contamination of agricultural lands, spectrum of the heavy metals contamina- tion – Cu, As, Cd and Pb, the sources of contamination – smelting and ore dressing works (UMPC – Pirdop, Asarel – Medet company, NAVAN and BIMAK Co. – Chelopech), phitotoxicity caused by acidification of soils. Also, the results of this investigation gave a new information about the scale of industrial con- tamination of the holow and the location of the harmful areas, as well as give a basis for design of a melioration activity, related to immobilization of the contaminators and neutralization of the harmful acidity.

Kremikovtzi Corp. Kremikovtzi Corp. is the greatest industrial enterprise in Bulgaria, situated at about 17 kms from Sofia with over 35 years of production activities. Kremikovtzi Corp. is an enterprise with com- 44 plete metallurgical cycle from extraction of pig iron to production of steel. Taking into account the nature of the production and the general productive capability, Kremikovtzi Corp. presents a serious contamination of environment as a whole. From the productive activity of Kremikovtzi Corp., significant quantities of dust, SO2, NOx, CO, CO2, H2S, HCN, heavy metal etc. are emitted. The general quantity of the dust emission in the atmosphere for 1997 is 38 054 tons. The serious environmental problem, that cannot be easily solved, is the heavy-metal contamination of the soil. More, than three decades of unrestricted environmental pollution with heavy metals have resulted in a contamination of hundreds of hectares of originally very rich soil to values up to ten times the permissible levels for Cd, Pb, Mn and As. In table 4 is presented information for heavy metal content in soil profile around the Kremikovtzi (region 1 – 3 km distance from plant). The soil horizon analyses show a high concentrations of Pb, Mn, As and Cd. Higher concentration is observed in Jana and another areas, depending on distribution of dust, aerosols, water and wastes emission. Heavy metals in Sofia-field are reached significant concentrations. They will remain and accumulate in soil and are toxic for soil micro- organisms and plant. Improvement of technologies and implementation of new purifying equip- ment in Kremikovtzi Corp. may improve ecological condition of Sofia-region.

Table 4. pH and heavy metals content, mg/kg, in soil horizon, cm

Soil horizon, cm PH Cu Zn Mn Pb Cd As 0 – 40 6.90 46.50 320 2300 88.25 1.00 118 40 – 80 6.55 43.25 535 2050 70.25 0.75 131 80 – 120 7.01 48.75 335 2300 87.50 0.75 116 0 – 40 8.53 65.00 290 3500 177.25 1.50 122 40 – 80 7.90 49.25 345 2750 114.25 1.25 116 80 – 120 7.24 41.59 225 2250 95.00 0.75 91 0 – 40 7.72 30.25 180 1385 62.75 0.25 19 40 – 80 7.94 27.00 110 940 37.50 0.20 19 Average 0 – 40 7.38 47.24 263 2395 76.08 0.91 - 40 – 80 7.46 39.83 300 1913 74.00 0.73 - 80 – 120 7.12 45.12 280 2275 86.25 0.75 - Simeonov (1997), Simeonov et al. (1999) carried out a special investigation for laboratory mod- eling of phitoextraction of heavy metals from polluted lands in the Kremikovtzi region. Soil samples were collected at the depths 0 – 10 and 10 – 25 cm before and after the harvest of decorative low-height sunflower possessing big and rich root system. The process of extraction of the metals was monitored by AAS and semi-quantitatively by a mass analyses of accumulator depots by laser mass-spectrometry Simeonov (1999), Simeonov and Managadze (1999), Simeonov et al. (1996). The experimental materials show that the phytoremediation process could be completed in a few days. This outlines the rate of amendment application and the chemical manipulation of the soil for the increase of the bioavailable part. Successful phytoremediation is possible after a preci- sion site characterisation and selection of the appropriate hyperaccumulator plants.

NFM Works – Plovdiv The Works is situated in about 10 km far from Plovdiv, to the right of the highway to Asenovgrad, Smolyan and Kurdjali. The investigations have shown that the area around the plant is strongly contaminated with heavy metals – mainly Zn, Pb, Cd in less extent – Cu. The contamination with Cu is mainly due to the situated nearby plant “Agria” for pesticides production.

45 The most heavy metal pollution around the plant are these of the villages of Belashtiza, Brestnik, Kuklen, Dolno Voden, Gorno Voden, Branipole, Asenovgrad, Mavrudovo, Krumovo, Jagodovo, Plovdiv. The main phytotoxicant in this region is zinc. In regard with contamination area around the plant is divided in three zones: I – up to 1000 m, II – from 1000 to 3000 m, III – from 3 to 15 km. In table 5 are presented average heavy metal content in soil.

Table 5. Average heavy metals content (mg/kg) in soil

Zone Metal Average content in different years 1989 1991 1993 1994 1995 I Pb 1703 1305 1059 908.9 924 Zn 2040 1601 1275 1015 1091 Cd 22 17 12 9 8 II Pb 525 502 340 270 260 Zn 905 698 470 329 352 Cd 13 9 5 5.3 4.8 III Pb 214 201 148 131 140 Zn 251 227 204 184 130 Cd 7 4.5 3.5 2.8 2.3

There are suggestions of what kind of plants may be grown in each of these zones in order to use the land properly and ecologically sound agricultural production. Large-scaled and ecologically oriented research, design and investment activities of the “N.F.M.Works” Co. have begun since 1990. In the last years, to achieve essential improvements on the impact and pollution of the environment, a project is developed which realization is expected to become reality in the end of 2003. In this project, there are proposed two trends for modernization, reconstruction of the productions and solution of the ecological problems. From the analysis made and estimation, it is concluded that after the realization of the project, there will be achieved the acting standars accepted in our country, for emissions of harmful substances in the waste gases from the “N.F.M.Works” Co., and an essential improvement of the quality of the air in the region will be reached. From this, it should be expected a positive influence of the realization of the project, on the whole chain of anthropogenic influence on the way of the air upon the rest compounds of the environment – soils, plantation, livestock, health status of the population in the region.

5. Conclusion

The biggest areas for heavy metals pollution of agricultural land in Bulgaria are in connection with industrial activities and are situated around the metallurgy plants. Some environmental problems in activity of our ferrous and non-ferrous metallurgy plants and needs for moderniza- tion and reconstruction of the productions and solution of the ecological problems are presented. The serious environmental problem that cannot be easily solved, is the heavy-metal contamina- tion of the soil. More than three decades of unrestricted environmental pollution with heavy metals have resulted in a contamination of hundreds of hectares of very rich soil to values over permissible levels for Cd, Pb, Mn, Zn, As. There are suggestions of what kind of plants may be grown in different contaminated regions in order to use the land properly and ecologically sound agricultural production. A new method for phytoextraction of heavy metal from soil are presented and discussed.

46 References

1. Alloway B. J. (1990), Heavy Metal in soils Halsted Ptess, J. Wileys Sons, NY. 2. Ministry of Environment. List of contaminated agricultural land from industrial activity. Regulation N 3. Bul- garian State Journal, N 24, 1979a. 3. Ministry of Environment. Maximum permissible levels of toxic substances in soil. Regulation N 3. Bulgarian State Journal N 36, 1979b. 4. Ministry of Environment. Maximum permissible levels of toxic substances in soil. Regulation for addition of Regulation N 3 of Ministry of Environment, State Journal N 54, 1997. 5. Salt, D., M. Blaylock, P.B.A.Nanda, V.Duchenkov, B.D.Ensley, I.Chet and I.Raskin (1995).Phytoremediation: A novel strategy for the removal of toxic metals from the environment using plants. Biotechnology, v. 13, 468 – 471. 6. Simeonov L. (1997), Perspectives of Remediation of Agricultural Lands Polluted with Heavy Metals in the Kremikovtzi Region, Bulgaria. In Strategies to improve Occupational and Environmental Health in Central and Eastern Europe. Ed. R. Ungar and C. Slatin, University of Massachusetts, Lowell, 67-69. 7. Simeonov L., B. Simeonova and J. Nikolova (1999). Phytoremediation of Industrially Polluted with Heavy Metals Lands in Bulgaria (First trials). In Proceedings of Contaminated Site Remediation Conference, ed. I. D.Jonston, 21 – 25 March 1999 Premantle, Western Australia. Centre for Groundwater Studies, 551-557. 8. Simeonova B. and L. Simeonov (1997). Phytoremediation of polluted with heavy metals agricultural lands In Sc. Works, vol. XLII, book 2; Higher School of Agriculture, Plovdiv, Agroeco 97; 253-258. 9. Koulikov, A., H. Chulgjian, I. Iliev et al. (1997).Environmental Assessment of the Impact of Emissions from the Pirdop Copper Smelter on soils in the Pirdop-Zlatitsa Region. Project N BG 9310-03-05-02. Final Report. 10. Simeonov L.(1999). Express semi-quantitative multielement analysis of water solutions with the laser mass analyser LASMA in Contemporary problems of Solar-Terrestrial Influences, Sofia, November. Publ. CLSTI, BAS, 195-198. 11. Simeonov L. and G. Managadze (1999). Laser mass analysis of environmental samples with LASMA in Con- temporary problems of Solar-Terrestrial Influences, Sofia, November. Publ. CLSTI, BAS 191-194. 12. Simeonov L., Scheurmann and C. Schmidt (1996) Schnelle semiquantitative Multielement-analyse wabriger Losungen mit dem Laser-Massenanalysator LASMA. In Teratech Nov. Dez., 6, 29-31. 13. Simeonov L., G. Managadze, C. Schmidt and K. Scheuermann (1998) Ecology screening of heavy metal pollu- tion of the soil with Laser mass spectrometry. Comptes rendus de l’Academie bulgare des Sciences, Tome 51, No 5-6, 29-32.

47 CHEMICAL ACCIDENTS – ORGANIZATION OF THE PROTECTION, MEANS AND METHODS FOR MITIGATION OF THE CONSEQUENCES

SVETOSLAV ANDONOV Civil Protection Agency of the Republic of Bulgaria

Chemical accidents in our industry are not a rare phenomenon in present days, but it is necessary to pay attention that in this report will be emphasized on accidents with dangerous materials, classified in United Nation’s (UN) documentations. The chemical accidents in their origin can be divided as follows: - according to the place of the accident – in the plants, at the place of using or in their transportation and stockpiling - according to the type of the dangerous materials – toxic, flammable, corrosive, ex- plosive with contamination effects to environmental parameters - according to the type of their consequences – short time, middle time (from a couple of days to a couple of months) and durable (from a couple of months to a couple of years) - according to the type of the effects from the accident – Is there or not influence on other systems and activities (is there a multiple effects of the accident) - according to the range of the accident – at the working place, in the frames of the plant, outside of the plant (in that case – are affected the population, environment, transport network and plants located near the accident) - according to the capabilities for mitigation – if it is possible to mitigate (overcome) the accident or the consequences The count of the accidents in our chemical industry was reduced and big incidents for the last 10 years are not registered. Typical are accidents inside the plants with one or two victims due to the non-observance of the safety measures, inability in use of individual protective equipment (Himko-Vratza), non-obser- vance of the instructions for acting in probable incidents and non-compliance with specific situ- ation (entering of emergency teams with ambulance car in an atmosphere of flammable, explo- sive gases and provoke an explosion with serious hard consequences to the emergency teams). The analysis of the facts (in our country) shows, that the preventive measures have been under- taken for our national industry – objects and the activities of the Preventive Commission (which includes experts from regional commissions for protection of the population in natural disasters and accidents) in that range have contributed to a great extent such tragically accidents in our industry to be avoided. Undivided attention was paid to the plants which were stopped their manufacture for a short period or a long time and there could have happened strong accidents due to the reducing of the necessary safety measures. In defined conditions (thermo-electric power-station – Plovdiv north) were happened and could have been happened (Plama - Pleven) chemical accidents with strong effects to the environment. From thermo-electric power-station – Plovdiv north was spilled unknown volume of mazut

48 from the worker who was made redundant and the executives from Plama-Pleven were threaten- ing to release big quantities of waste oils in environment. With high percentage of risk are road transport and railway transport incidents with dangerous goods.

A) ROAD – TRANSPORT INCIDENTS

The first such a serious incident happened on 12 October 1992 at approximately 5 km from the town of Slivnitza on the highway. Where in a collision with a car, a truck with a trailer – Greek registration plates had an accident. The truck was transporting cyanides and a little quantity of barium chloride and after the collision the freight was spilled out on both sides of the road at approximately 15 000 sq.m. This incident happened near the drinkable water sources located on this territory and it was a danger of contamination of the water to Slivnitza, nearby settlements and an army corpus. Therefore immediate steps were undertaken, as a first step manual collec- tion of the cyanides and the barium chloride, and as a next step on both sides of the road the surface ground layer of land was taken out (approximately 10-15 sm deep) and was stored under a shelter at the nearby airdrome of the agricultural aviation until their processing into non-toxic substances. After inactivation of the cyanides the soil was transported and stored in Kremikovtzi factory – village Musachevo. After the accident near Slivnitsa there were other road-transport incidents such as – with tanks transporting sulphuric acid – village Bulgarski Izvor and town Iablanitsa, Lovech district; with diluents for oil-base paints – ring-road Sofia; with car fuels; with by-products from the coke- plant of Kremikovtzi. There was an incident with tank transporting hydrogen chloride to Kremikovtzi. It happened at Karlovo railway station. Another incident was with tank transport- ing propan-butan at the center of the Plovdiv city (the tank was turned over) and an accident with tank transporting akril-nythril to Macedonia, but in this case any negative consequences were avoided. All of this described above made necessary to held a workshop on the problem which to include representatives from all legally involved authorities. Unfortunately, there were not deputies from the factories owners of the tanks transporting dangerous materials, from the authorities perform- ing the technical choice of the tanks, and from the Carrier’s Community. Independently that workshop achieved its aim to build up an organization and to organize a cooperation between the authorities for mitigation of chemical emergencies of road-transport accidents. Only for the last two months were happened two accidents with tanks (Sofia, Sindel) transport- ing hydrogen chloride. Obviously, it is indispensably to have new regulations for the terms of applicability and a new license of the tanks transporting dangerous freights. It does not make any sense, time for checking up of a new tanks (at 10 years) and the old once (at 25 years) to be in 4 years. Independently from the guaranties, inside layers of the tanks getting old and with the years that checking up have to be done as frequently as the tank gets older. The last such an incident in Sofia shows that the tank was checked up two years ago and had a license of transport for 4 years. Similar accident is the incident with tank-spilling at Sindel railway station. The practical experience presents the following decisions: 1. Immediately pouring of a liquid from a broken tank into a new one where as the level of the liquid is under the place of a puncher or pouring the whole quantity. Deacidify of spilled acid with calcium carbonate or hydrated lime. 2. Sealing the tank puncher with a wooden or a rubber keys or with a special pillows and after that pouring into another vessel or emergency transportation back to the producer or to the customer.

49 3. When the leakage is on the bottom part of the tank, on a big area, and it is not possible to seal it, it is necessary to pour over the tank with a water to reduce the emissions of dangerous gases in the air and deacidify of spilled quantity of acid on the ground. If the leakage allows to be caught with another devices such as rubber gloves and so on, the liquid is being poured into vessels and then being transported into tanks allowing its stocking and transportation. Another big accident was the incident in Thermo-electric power-station – Sofia where due to a failure in bank supplying system, with volume of the banks – 100 000 t, in a transport channel, pump department, through forgotten drainage became a leakage of the biggest part of bank – 1 as about 100 t was realized out side of the area of the Station and during the night passed by the Purifying – Station in the area of Benkovski quarter. This leakage was noticed in the next morn- ing when it was already reached to Iskar defile in the area of Reburkovo. As a result Iskar river was contaminated with mazut from Kurilo to Mezdra, where a floating boom was built to catch the spilled under surface mazut. At that time due to the weather conditions ( it was raining) a part of mazut spots was broken to a small pieces and one part of the pieces stuck durable on a plastic garbage floating in the river and the other part left on a bottom of the river as only 5-10 % of the spilled mazut was caught from the floating boom. It was also established that partially charged fragments were floating in the middle of the river and can’t have caught by floating boom. Particularly dangerous were accidents connected with uncontrolled stockpiling of pesticides. After closing down the former cooperative communities and agricultural and industrial societies a part of their funds was robbed by person knowing what was kept in the storehouses as it price. In these storehouses big quantities of forbidden or with expired term of use pesticides were left (about 3500 tons). One part of them was stolen, repacked and sold “cheap” to naïve citizens. As a result levels of concentration of DDT at about 0.0005 mg/l were established in Maritza river. It should be noted that DDT was out of use since 1969 as insecticide. Planting material from several greenhouses was destroyed (the biggest one was about 40 decares) due to the spraying of a plant with “cheap” herbicides instead insecticides. Some of the stockhouses were ignited to cover up robberies (Zlati Voivoda village, Nikola Kozlevo village in Hisaria municipality of the Plovdid district). Some measures were undertaken with delay. In that activities took part Ministry of Environment and Waters, State Agency for Civil Protection, Ministry of Internal affairs and local authorities which gathered and put the pesticides into bigger stocks and later used BB-cubes for stockpil- ing of the pesticides (these cubes are used for stockpiling of radioactive materials). Towards this moment about 1200 tons of pesticides are stockpiled in BB cubes, 1000 tons in repaired and guarded stockhouses. About 1300 tons are still waiting for some measures to be taken for their stockpiling and restriction. For prevention of failures with pesticides till the moment we could notice the next: 1. There is not a methodology for their inactivation by chemical way due to the fact that these pesticides which have to be inactivated are mixtures consisting of differ- ent substances and the biggest part of these substances is very stable against any influence of burning, which could lead to evaporation of much more toxic sub- stances and gases and in that way to increase the negative effects. 2. The furnace devices (incinerators) in our country are not suitable for this purpose – burning up pesticides. 3. Due to the irregular approach of the Ministry of Environment and Waters munici- pality authorities refused the building up of incinerators which could be paid by means of the European Community projects. 50 4. At the moment the departmental commission inspects and proposes based on ap- proved regulations the funding of projects for stockpiling of pesticides. The resources for improving the stockpiling are subject of the funds of the Ministry of agriculture and forests. 5. The way of stockpiling the pesticides in BB cubes creates favorable conditions for the safety for many years. A problem is arising for their further inactivation as pesticides are mixed with inert substances – zeolites and the inactivation may be difficult. 6. There are trials of different firms and organizations to present to the authorities of the Ministry of Environment and Waters and Ministry of Agriculture and Forests incompetent and dangerous projects for burning of the pesticides (such a project was burning pesticides in coke-chemical department of the Kremikovtzi steel pro- ducing plant). 7. Under a joint project with the kingdom of the Netherlands 40 tons of chlorine containing pesticides (DDT and hexochlorone) were exported for destruction. These were probably purified and redirected for use in a country where they are not forbidden. 8. After clearing the small stocks and these containing pesticides before their recharg- ing into BB cubes, municipality authorities offer these buildings for use under leasing or destroy them and send all usable material, but without good cleaning (decontamination) of the buildings. In both cases a direct risk for the population is created when in contact with the building or its materials, impregnated with pesti- cides. Extremely dangerous is the use of wood materials from such buildings as fir.

B) ACCIDENTS INVOLVING RAILWAY TANKS

Accidents involving railway tanks are especially difficult for relief, if happen in the road-bed between railway stations. In that case the access to the place of accident is very difficult. Other complicated situation is on the stock stations sites, where a lot of railways are present and thus the access to the accident place with other machinery and technique is impeded. For instant - the accident near the Vlado Trichkov railway station in 1999 involving 5 railway tanks with propane-butane. What we have done by now to improve the protection of the population and all activities for mitigation of accidents involving dangerous chemical substances? 1. With the update of the National Emergency Plan an organization for the population notification in case of emergency is created. Individual protective equipment is dis- tributed to the population living in the vicinity of the potentially dangerous sites. 2. The Civil Protection State Agency rescue teams are equipped with some technical means, but it is insufficient and not enough effective to mitigate large scale acci- dents. 3. Specialists foreseen to deal with chemical accidents need some more training. There is not a system established for training, retraining and qualification of specialists in that matter. 4. The legislative basis regulating precisely all relationships between bodies acting in case of chemical accidents is missing. Legislative process in that matter is very slow. Responsibilities are not clearly distributed . No warehouses for dangerous waste are designated. No methodologies for destruction of dangerous substances

51 are developed. Ministry of environment and waters has no clear position on that subject, which is bad for the resolving of the problem. 5. Still unresolved is the problem with recovery of the damages in mitigation an accident and following regressive demands. 6. Two months ago the Government provided 2.5 millions of levs in order to improve the response possibilities in case of any chemical accident related to the Iraqi crisis. It is a sip of fresh air taking into account that more than 10 years no instrumenta- tion or other technical equipment was bought to support the adequate response of the rescue teams. 7. Indicating tubes sets were distributed to all the Civil Protection Directorates in the country, in order to be able to identify and determine concentrations of industrial poisonous substances. Still unresolved are the problems of escorting dangerous goods and the implementation of an automated system for survey of their movement. Concerning prevention of the transport risk by now only one decision of high level is taken – the road-bed and the order of transportation of acrylonitril is determined from the town of Bourgas to Macedonia. Railway transport is foreseen for the road from Bourgas to Radomir and automo- bile transport from Radomir to Guyeshevo. By this transportation scheme the risk was avoided of any large scale accident with irremediable consequences from road accident in the city of Sofia. Another problem is that customs and road police officers are not enough aware about dangerous goods characteristics and first measures to intervene in case of road accidents followed by spill or spread of dangerous goods over the road or the ditch where it is important to take into account if the accident is close to water flow (river, channels), in case of rain or snow. Private transport companies don’t regularly mark the transportation vehicle in case of dangerous goods transpor- tation. Up to now none of the vehicles is observed to have the mark “transporting pesticides, pints with high concentration of acetone” or other dangerous goods.

Conclusion

Republic of Bulgaria disposes enough potential to fight chemical accidents. Attention has to paid to the training of specialists, training for response, preventive work, implementation of the technical requirements on the safe work with dangerous goods, compulsory licensing of the people dealing with dangerous substances, as the technical equipment used to deal with them. Unfortunately in the higher schools, training specialist in that matter low attention is taken on protection from dangerous substances. And one has to take into account that these specialist may become heads of chemical industrial companies, companies for dangerous substances trans- portation and one of their tasks will be organization of preventive activities and mitigation of the consequences from chemical accidents with protection of the personnel and the population.

52 BULGARIAN LEGISLATIVE FRAME FOR PREVENTING WATER POLLUTION BY CHEMICALS

VESKA KAMBOUROVA National Center of Hygiene Medical Ecology and Nutrition, Sofia, Bulgaria

Introduction and approach

As one of the basic elements supporting the life and the natural environment as well as media for transmission of pollution the water is an important component for sustainable development. Chemical releases have a significant impact on the water quality and affect the water environ- ment not only at the point of discharge and not for a limited time span. During the recent years due to the pre-accession obligations of Bulgaria first attention was given to the transposition of the EU water directives into the national legislation. The comparative assessment performed in 1999 concluded that principal differences exist to the logical frame, scope and targets of the existed national regulations and the EU policy in the water field (NCHMEN, 1999). The harmonization of the main documents was completed in 2002. The current paper presents a short summary of the Bulgarian legislative frame in the water field adopted during the last three years, with particular attention on the provisions associated with the regulation of chemical substances in different types of water. It is aimed to outline priority actions for managing chemical issues in the water environment.

Overview of the water related regulations

Protection of the environment for the present and future generations, and public health preven- tion are general objectives of the Bulgarian environmental policy (Environmental Protection Act, 2002). The policy on water protection has to be based on a rationale water management at national and river basin level with a main goal achievement of a good status of all ground and surface waters in order to ensure the necessary quantity and quality of water for: – drinking water and domestic purposes; – favorable status and development of the ecosystems and wetlands; – economic and social activities. It is an obligation of the users of water or water bodies to maintain the water quality in compli- ance with the legislative requirements and with the particular conditions set in the use permits (Water Act, 1999). The combined approach to emission related and imission related measures to reduce pollution, as a key point in the EU policy, has been introduced by the developed regulations. The waters and water bodies are protected against pollution and deterioration by prohibiting and/or limiting of discharges of dangerous substances, establishment of Sanitary Protection Zones (SPZ) around the sources for drinking water supply, building of Waste Water Treatment Plants (WWTP), etc.

53 A categorization of the waters has to be performed based on quality objectives taking into ac- count: the intended water use; conditions for safeguarding of the surface water ecosystems; the vulnerability of the ground waters. The permits for discharging have to ensure achievement of the categorization accepted.

I. REGULATIONS DIRECTED TO PREVENT AND ELIMINATE WATER POLLUTION Emission related standards or limit values are intended to reduce the load of pollutants most harmful to the aquatic environment that might be affected by discharges of these substances. Several regulatory acts are aimed to protect waters against pollution by point and diffuse inputs.

I.1. Industrial effluents and urban waste waters The Regulation on emission limits for harmful and hazardous compounds in waste waters dis- charged into water bodies lays down admissible concentrations for 17 substances according to the type of emission source (Regulation 6, 2000). Programs have to be developed and completed until 2010 in order to avoid and/or discontinue the pollution with substances as Hg, Cd, tetrachloromethane, pentachlorophenol, HCH, DDT, aldrin, dieldrin, endrin, isodrin, HCB, hexachlorobutadiene, chloroform, 1,2-dichloroethane, trichloroethilene, perchlorethilene, trichlorobenzene. Additionally for 37 industrial activities emission limits are set for 41 param- eters, including 20 metals and metalloids, cyanides and some organics – pesticides, benzene, benzo(a)pyrene, etc. The relevant competent authority is responsible to specify limit values for substances or indus- trial sectors not included in the regulation when issuing permits for discharge. The Regulation on waste water discharges in the urban sewage systems regulates the conditions of industrial discharges into the sewage systems of the settlements with or without municipal WWTPs (Regulation 7, 2000). Except the requirements for normal operation of the construc- tions, limit values are set for some chemical substances dangerous for the water environment (petroleum products, oil, anionic detergents, phenols, Fe, Hg, Cd, Pb, As, Cu, Cr3+, Cr6+, Ni, Zn, CN). They concern both the effluents before their discharge into the sewage system or into the WWTP. The Regulation on issuing permits for waste water discharge and setting up individual emission limit values for industrial installations imposes prior authorization of discharges into surface waters from point sources of pollution (Regulation 10, 2001). The goal is to safeguard the project category of the receiving water bodies, predefined according to their designated use. Discharges are prohibited in area I of the WPZs around the sources for abstraction of drinking water. Per- mits for discharges are issued only on the basis of permission for water use. The individual emission limit values should not be less stringent to the emission limits set by regulation 6, but might be more restrictive in order to ensure the project category of the receiving body. They should not be more stringent to the quality objectives of the project category. Regulation 1 addresses the rules for assessment, use and protection of ground waters including the measures necessary to avoid and/or limit groundwater pollution by hazardous and harmful substances (Regulation 1, 2000). For 106 advisable parameters (including metals, metalloids, PAHs, pesticides, chlorinated hydrocarbons, etc.) limits are set for two levels - ecological threshold and pollution threshold, aimed to serve as indicators for the severity of contamination and taken into consideration by issuing permits for waste water discharges into groundwater.

54 I.2. Discharges from agricultural activities The Regulation on protection of waters against pollution caused by nitrates from agricultural sources is directed to all ground, surface, mineral and coastal waters (Regulation 2, 2000). Re- strictions for use of fertilizers are introduced for area II of the WPZ if the nitrate content in the concerned water source exceeds 35 mg/l. Specific requirement is the necessity to determine vulnerable areas with respect to groundwater pollution by nitrates. Manuals for good agricul- tural practice should be elaborated. Closely linked to the activities aiming to protect the water environment against pollution by chemicals is the recently adopted Regulation concerning the authorization of plant protection products (PPP), 2002. Obligatory requirement for placing on the marked and agricultural use of PPP is that the application according to the labeling instructions should not lead to pollution of water environment, including ground and drinking waters.

I.3. Other linked regulations The Regulation on the Water Protection Zones (WPZs) around the sources used for abstraction of drinking water is directed to ensure protection of the drinking water against pollution (Regu- lation 3, 2000). Depending on the type of water source (ground or surface) safeguarding regimes have to be established in the WPZs according which certain activities that in long term aspect may lead to deterioration of the water quality and quantity should be prohibited or restricted. WPZ consists of three areas: I - for strong protection around the water source; II - for protection against pollution by easily dissipating, readily degradable and strongly sorbtive substances, and III - for protection against pollution by substances with properties opposite to the before men- tioned. Well operating monitoring networks are essentially to determine the state of and trends in chemical quality of waters. The Regulation on establishment and operation of the National water monitor- ing system aims to create a basis for assessment and prediction of the status of ground and surface waters, to collect information concerning the waste water discharges into water bodies (Regulation 5, 2000). It imposes the concept for monitoring conducted by all users of water/ water bodies and control monitoring. One of the tasks of the system is to provide information for human health and environmental risk assessment. The surveillance of hazardous and harmful substances has to be performed according to the relevant Regulation 6 or Regulation 1 if surface or ground waters are concerned, taking into account the site specific hydrological/hydrogeological and/or ecological/hydroecological conditions.

II. REGULATIONS DIRECTED TO WATER QUALITY OBJECTIVES

The general intention is for establishing rules pertaining to consumer/user protection and safe- guarding the bio-diversity. The Regulation on the quality of surface waters intended for the abstraction of drinking water defines the quality of the fresh waters, suitable to be used for drinking water supply after ad- equate treatment (Regulation 12, 2002). Three categories are distinguished depending on the water quality and the complexity of the treatment methods applied. Water with quality param- eters exceeding those set for the third category should not be used for drinking water supply. After assessing the health risk the competent authority issue use permits in all cases when no alternative water supply exists, as well as lays down additional parameters for monitoring if permanent or potential pollution sources are available. Chemical parameters indicating pollu- tion (heavy metals, pesticides, PAHs, etc.) have to be determined only in waters where their presence is likely to exist.

55 The Regulation on the quality of water intended for drinking and domestic purposes sets mini- mum requirements and should lead to a reduction of risk and improvement of the quality of tap water (Regulation 9, 2001). Maximum admissible concentrations are laid down for 26 chemical parameters (e.g. As, Hg, Cd, Pb, Cr, benzene, benz(a)pyrene, pesticides, PAHs, THM, etc.) potentially dangerous for the human health via exposure to drinking water. All public water supplies have to be periodically tested for a specified list of chemicals, depending on the re- gional characteristics. 17 of the substances (mostly organics) have never been tested in the Bul- garian drinking waters or the data available are very limited. In case of derogation of the water quality decisions should be taken on the basis of health risk assessment. The Regulation on the quality of fish and shellfish water defines the quality requirements for the fresh surface waters and coastal marine waters that are natural living environment for fishes and shellfishes (Regulation 4, 2000). The regulation does not apply to the fish breeding farms. A number of chemical parameters (metals and organics) have to be controlled in order to protect aquatic life and ensure consumer’s safety. The Regulation on the quality of coastal marine water defines parameters and quality objectives aimed at protection against pollution by dangerous and harmful substances, maintaining favor- able conditions for their use and normal development of the marine and coastal ecosystems (Regulation 8, 2001). Except the parameters indicating the integral pollution load requirements are set for specific substances as anionactive detergents, phenols, pesticides, oil and petroleum products. In the areas of existing and perspective water use the discharge of untreated waste waters, including these from vessels are prohibited. For treated waste waters individual emis- sion limits equal to the quality objectives have to be established on case by case basis. The Regulation on the quality of bathing water sets requirements on the quality of the natural running/still fresh waters and sea water with the main goal public health protection (Regulation 11, 2002). A number of chemical parameters (pesticides, heavy metals, cyanides, phosphates, nitrates, etc) indicating pollution are listed, and have to be measured in all cases when contami- nation is suspected. If necessary the competent authorities may include requirements for other relevant parameters. The Regulation on the categorization of water in water bodies is under development. At present the project category is determined by ordinance of the Ministry of Environment and Waters (MoEW) based on the national Regulation 7 on the parameters and norms for the quality of surface running waters (Regulation 7, 1986). Table 1 includes chemical substances for which provisions are set by two or more documents. Some of the pollutants presented in the list of priority substances in the field of water policy are also noted (EC Decision 2455, 2001). For 27 out of 33 substances or group of substances, which are shown to be of major concern for European waters certain legal provisions already exist. It is matter of further assessment to clarify in which extent the recently identified water pollutants: pentabromobiphenylether, C10-13 chloroalkanes, nonylphenols, tributhyltin compounds (classi- fied as priority hazardous substances), di(2-ethylhexyl)phtalate and octylphenols (possible pri- ority hazardous substances, requiring additional review) would constitute practical interest for the Bulgarian water environment.

56 Table 1. Selected list of the chemical substances targeted in the water regulations

Regulation No Parameter 6 7 10 1 12 9 4 8 11 EC IE 1 UWW2 IEP3 GW4 SW5 DW6 FW7 SeW8 BW9 PS10 Antimony xxx Arsenic x x xxxx x x x Berilium xxx Cadmium x x xxxx x x xh Chromium x x xxxx x x x Copper x x xxxx x x Cyanides x x xxxx x Fluorides x xxx Lead x x xxxx x x xr Mercury x x xxxx x x xh Nickel x x xxxx x x n Nitrates xxx x Selenium x xxxx Zink x x xxx x x Vanadium xxx Phenols x x xxx x x x Petroleum products xxxx xxx Benzene xxxn PAH xxx h Antrazene xr Naphtalene xr Vinilchloride xxx 1,2-dichloroethane xxxxn Dichloromethane xn Pentachlorobenzene xh Pentachlorophenol xxxr Tetrachloroethane xx Tetrachloromethane xxx Trichlorobenzene xxxr Perchlorethilene xx Trichloroethilene xxx Hexachlorobenzene * xxxh Hexachlorobutadiene xxh Chloroform xxxn Pesticides (sum/a.i.) x xxx x x Aldrin * xxxx Atrazine xr DDT * xxx Dieldrin * xxxx Endrin * xxx Endosulfan xr Isodrin xxx HCH xxxh Simazine xr Heptachlor * xx 1 IE - industrial effluents 2 UWW - urban waste waters 3 IEP - industrial effluents 4 GW - groundwater 5 SW - surface water 6 DW - drinking water 7 FW -fish and shellfish water 8 SeW - sea water 9 BW -bathing water 10 PS - priority substances identified under Decision No 2455/2001/EC (h - identified as hazardous, r - under review, n - does not meet the criteria for hazardous substances (toxic, persistent, liable to bio-accumulate) * substances regulated under POP’s Convention

57 Conclusions Converting into the national law principles that have been operating in the EU countries for about 30 years it is a priority task of the Bulgarian competent authorities to ensure in relatively short terms adequate implementation of the whole set of new water regulations. The obligations are divided among diverse institutions with a leading role of the MoEW and the MoH as con- cerns drinking and bathing waters. The respective authorities have different level of readiness for fulfilling their specific tasks. In order to comply with the requirements a preparatory work have to be continued and directed: – to strengthen the co-ordination among the responsible institutions; – to elaborate site specific, rationale and flexible monitoring schemes; – to improve the existing monitoring capabilities; – to introduce quality assurance systems; – to give much more stress on pollutants identified as requiring priority actions on international level (e.g. Decision 2455/2001/EC, POP’s convention, etc.); – to strengthen the control and inspection mechanisms; – to involve research institutions in investigative surveys that might facilitate the identification of polluted sites and priority substances; – to improve the methodological basis for human health and environmental risk assessment in water field; – to ensure easily accessible information concerning water chemical pollutants in order to support decision making on regional level; – to provide public awareness and training programs for the user of water/water bodies.

References 1. NCHMEN, Report “Analysis of the basic European documents in the water field and their correspondence to the Bulgarian regulations”, 1999. 2. Environmental Protection Act, St. G. 91, 2002. 3. Water Act, St. G. 67, 1999. 4. Regulation 6 on emission limits for the admissible concentration of harmful and hazardous compounds in waste waters discharged into water bodies, St.G. 97, 2000. 5. Regulation 7 on waste water discharges in the urban sewage systems, St.G. 98, 2000. 6. Regulation 10 on issuing permits for waste water discharge and setting up individual emission limit values for industrial installations St.G. 66, 2001. 7. Regulation 1 on the assessment, use and protection of ground waters, St.G. 57, 2000. 8. Regulation 2 on protection of waters against pollution caused by nitrates from agricultural sources, St.G. 87, 2000. 9. Regulation concerning the authorization of plant protection products, St.G.93, 2002. 10. Regulation 3 on the conditions and rules for assessment, project preparation, approval and exploitation of the sanitary protection zones around the sources and equipment for drinking water supply and mineral waters, St.G., 88, 2000. 11. Regulation 5 on establishment and operation of the National water monitoring system, St.G. 95, 2000. 12. Regulation 12 on quality of surface water intended for the abstraction of drinking water, St.G. 63, 2002. 13. Regulation 9 on the quality of water intended for drinking and domestic purposes, St.G. 30, 2001. 14. Regulation 4 on the quality of fish and shellfish water, St. G. 88, 2000. 15. Regulation 8 on the quality of coastal marine water, St.G. 10, 2001. 16. Regulation 11on the quality of bathing waters, St.G. 25, 2002. 17. Regulation 7 on the parameters and norms for the quality of surface running waters, St.G. 96, 1986. 18. Decision No 2455/2001/EC establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC, O.J. L 331, 15.12.2001.

58 THE CONTRIBUTION OF THE SMALL ENTERPRISE “HYGITEST” LTD. – SOFIA TO THE ASSESSMENT OF CHEMICAL POLLUTION IN THE AMBIENT AND WORKPLACE AIR

PETKO VARDEV, DIMITAR DIMITROV HYGITEST Ltd. – Sofia, Bulgaria

HYGITEST Ltd. is a small enterprise with about 40 years history in the production of appliances for express analysis of toxic gases and vapours in the air. In far 1965 in the Research Institute of Work Safety and Occupational Diseases was organized a small workshop for experimental pro- duction of colorimetric detector tubes. There were produced about 10 types of detector tubes. Their design was product of research and development work and most of the chemical reagents in the detector tubes were patented in Bulgaria. On this basis the firm “HYGITEST” was registered in 1983 as joint enterprise with the partici- pants the National Center of Hygiene, Medical Ecology and Nutrition in Sofia and the Center for Implementation of New Technologies “Progress”. Twenty years after the HYGITEST Ltd. is a small independent enterprise with stable place on the Bulgarian market and export activities in many other countries. The manufacturing range of HYGITEST covers colorimetric indicator tubes (detector tubes) for express analysis of toxic gases and vapours in the ambient and workplace air, adsorbent sampling tubes for instrumental analysis, instrumentation for air sampling, special express tests for hygienic control, glassware, plastic disposable articles etc. The production of HYGITEST Ltd. is targeted to Bulgarian market, but the quality and the variety of types of the produced sorbent sampling tubes and colorimetric detector tubes is com- parable with the production of leading firms in the world: Draeger and Auer in Germany and Gastec and Kitagawa in Japan. Other big producers are in Czech Republic, Poland and Russia. The development of the production of colorimetric detector tubes in Bulgaria follows the world tendency of rapid increase of variety of types. After a certain fall in the production during the period 1970 – 1979 due to the organizational problems, a rapid increase in volume and variety of types of the produced indicator tubes took place after the establishment of the HYGITEST Ltd. in 1984.

“HYGITEST” DETECTOR TUBES

The HYGITEST detector tubes (colorimetric indicator tubes) are used for express determination of the concentrations of toxic gases and vapours in the industrial environment. The analyses are quick, easy to perform and inexpensive. No special training is required for the operating staff. For this reason the detector tubes are widely used in all branches of industry, agriculture, transport, etc. They are used for seeking of leakages, control of technological pro- cesses and determination of toxic substances in the environmental air, for hygienic evaluation, testing the presence of toxic and inflammable substances in confined spaces, determination of workers personal exposure, determination of gas components in liquids, etc. A feature worth mentioning is that the data on the substance is determined instantly on the spot.

59 The HYGITEST indicator tubes are glass tubes, filled with solid granular material-carrier, im- pregnated with an appropriate chemical reagent. The tips of the tube are sealed, thus its content is isolated from the environment. Before analysis, the tips of the tube are broken and the tube is inserted in the special sampling pump. In the presence of the substance to-be-analysed, the reagent system in the tube changes its colour and the length of the discoloration is directly proportional to the concentration of the substance determined. The concentration is read directly on the scale, printed on the outside surface of the indicator tube. This method for determination is very quick, easy and cheap. Before use the glass tube has to be broken off on both sides and placed in the sampling pump. In the presence of the analysed substance the tube colour changes and the length of discoloration is directly dependent on the respective concentration of the substance.

60 Various kinds of colorimetric indicator tubes are produced: AT short term colorimetric indicator tubes for express analysis and determination of the compliance with the STEL concentrations; LTlong term colorimetric indicator tubes for up to 8-hours sampling and determination of compliance with the TWA limits of exposure; PM passive (diffusion) indicator tubes for determination of up to 8-hours exposure to toxic substances in the workplace area. HST indicator tubes for special testing of contaminants in the environmental samples – waste waters, sludge, soils, plastics etc.

“ALCONAL” DETECTOR TUBES

The “Alconal” detector tubes are used for detecting the presence of alcohol vapours in the ex- haled air, e.g. of drivers. As result of research work is established that the alcohol content in exhaled air is in direct dependence to the alcohol content in blood. The “Alconal” tubes contain yellow coloured reagent, which turns up to bluish-green in contact with alcohol vapours. The tube is opened in both welded ends using the file and then breaking off. The mouthpiece has to be put in the measuring bag closely to the tube. The examined person blows, if possible, by only one single exhalation through the tube into the measuring bag, until the latter is completely full. The duration of blowing has to be between 30 and 40 seconds.

61 When the discoloration stain doesn’t reach the scale mark 0.5 ‰, it is reckoned that the exam- ined person has allowable alcohol content in the exhaled air. Colouring of the indicator layer beyond the blue line, signals that the examined person has alcohol content above 0.5 ‰. Ac- cording to Bulgarian legislation on the scale of the ALCONAL detector tubes are two marks – at 0.5 ‰ and at 1.2 ‰. The result from the sample shows the alcohol content in the exhaled air at the moment and is valid only at the moment of sampling. The packing contains 10 pieces hermetically welded test tubes, 10 mouthpieces, file for cutting both ends of the tube and measuring bag.

ADSORBENT TUBES FOR SAMPLING OF VAPOURS AND GASES

HYGITEST Ltd. offers a line of standard Charcoal, Silica gel and Tenax sorbent tubes for low flow adsorption sampling of toxic substances in the air. HYGITEST™ sorbent tubes comply with all US NIOSH specifications for tube dimensions, adsorbent quality and particle size, pore size and overall design, sorption/desorption characteris- tics etc. These tubes are designed for use in conjunction with all low flow air sampling systems and common tube holding systems. The tubes are delivered in plastic or paper boxes. The boxes contain 10 tubes each and are packed five boxes per carton (sold in 50-tube quantities). Each tube comes with a pair of end caps for sealing after sampling. The figures below show typical shapes of HYGITEST sorbent tubes.

CHARCOAL (COCONUT BASED) 70 x 6 mm 100/50 mg sorbent, 2 sections

62 CHARCOAL (COCONUT BASED) 110 x 8 mm 400/200 mg sorbent, 2 sections

CHARCOAL (COCONUT BASED) 110x10 mm 800/200 mg sorbent, 2 sections

SILICA GEL 70x6 mm 150/75 mg sorbent, 2 sections

SILICA GEL 110x8 mm 520/260 mg sorbent, 2 sections

TENAX 70x6 mm 30/15 mg sorbent, 2 sections

TENAX 110x8 mm 100/50 mg sorbent, 2 sectio

Typically each tube is divided into two adsorbent sections. The first section is twice the size of the back section and will collect the compounds of interest. The second section is a backup section to determine if airborne contaminants breakthrough occurred on the front section. HYGITEST™ sorbent tubes are manufactured under stringent quality control to provide: - Physical dimensions to assure proper fit in tube holder systems - Uniform pressure drop to assure repeatable sampling results - Accurate sorbent weight for uniform testing results - Highest sorbent material purity for contamination-free samples. HYGITEST™ sorbent tubes are packaged in sturdy, molded black polyethylene boxes to resist breakage. These boxes secure tubes during transport, storage and day-to-day handling, allow easy labeling and organizing of test samples, protect against damaging light and U.V. rays. Each single box snaps shut to protect any sampled and unused tubes. Boxes contain 10 tubes each and are packed five boxes per carton (sold in 50-tube quantities). Each box of 10 tubes comes with 10 pairs of end caps for sealing after sampling. The production of HYGITEST Ltd. includes also low flow rate and high flow rate air sampling pumps for particulate matter and gases, accessories for sampling, production of spot tests for toxic aerosols, precise flow meter (electronic bubble meters) etc.

63 The production of HYGITEST Ltd. is sealed in about 200 enterprises, plants, laboratories, hy- gienic stations, stations for environmental control etc. HYGITEST is on the Bulgarian market still for about 25 years. The products are well received, useful, at accessible prices, comparable with the competitive products from other producers. The HYGITEST Ltd. is in the procedure for becoming a Certificate of quality according to ISO 9001:2000. The evidence for the quality of production are also the stable relations to the clients in USA, Italy, Spain, Israel, Russia, Hungary, Romania, Macedonia, Czech republic etc. In conclusion HYGITEST Ltd. with his experience, good working tradition and well-organized distribution net contributes for real estimation of the chemical risk on the site and in real time. The mreceived inforation is very useful and in addition to the information collected with more complicated and expensive instrumentation and methods. Both possibilities make for more flex- ible and effective assessment and management of the chemical risk in working and ambient area.

64 LIST OF PARTICIPANTS

Eng Svetoslav Andonov Eng Dimitar Dimitrov Deputy Director, Civil Protection Agency Director, SE HYGITEST LTD of the Republic of Bulgaria 15 Dimitar Nestorov Blvd. 30, N. Gabrovski Str. Sofia 1431 Sofia 1172 Bulgaria Bulgaria Tel.: +359 2 595026 Tel.: +359 2 96010328 Fax: +359 2 594097 E-mail: [email protected] E-mail: [email protected]

Dr Ivan Benchev Dr Stuard Dobson Complex Lulin 5 Centre for Ecology and Hydrology Block 508 vhodA, Apart.31 Monks Wood, Abbots Ripton, Sofia Huntingdon, Cambridgeshire, PE28 2LS Bulgaria United Kingdom Tel.+359 2 5812 525 Tel.: +44 1487 772 494 Fax: +359 2 954 1277 Fax: +44 1487 773 467 E-mail: [email protected] Dr Raj Chhabra Dr Gyula Dura National Institute of Environmental Health Sciences Professor, Head, Environmental Health PO Box 12233 National Institute of Environmental Health of Research Triangle Park József Fodor Gyáli út 2-6, Budapest 1097 North Carolina 27709 Hungary USA Tel.: +361 218 3158 Tel.: +1 919 541 3386 Fax: +361 215 0148 Fax: +1 919-541 4704 E-mail: [email protected] E-mail: [email protected] Dr Lawrence Fishbein Dr Christopher De Rosa 4320 Ashford Lane Agency for Toxic Substance and Fairfax, Virginia 22032 Disease Registry (ATSDR) USA Centres for Disease Control Tel.: +703 764 5232 Atlanta, Georgia 30333 Fax:+703 764 7281 USA E-mail: [email protected] Tel.: +1 404 498 0160 Fax: +1 404 498 0094 Dr Herman Gibb E-mail: [email protected] National Center for Environmental Assessment US Environmental Protection Agency (8601D) Ms Ioana Christova Ariel Rios Building Executive Environment Agency 1200 Pennsylvania Avenue Ministry of Environment and Water N.W., Washington, DC 20460 Bul Tzar Boris III, 136 Sofia 1618 USA Bulgaria Tel.: +1 202 564 3334 Fax: +1 202 565 0059 Tel.: +359 2 940 64 66 E-mail: [email protected] Fax: +359 2 955 9011 65 Dr Ivan Grancharov Dr Debabrata Kanungo Professor, Head, Central Insecticides Board Department of Inorganic Chemical Technology Directorate of Plant Protection, University of Chemical Technology and Quarantine & Storage Metallurgy Ministry of Agriculture 8, Kliment Ohridski Blvd. Government of India Sofia 1756 NH IV, Faridabad-121 001 Bulgaria Haryana Tel.: +359 2 76 53 13 India Dr Rolf F. Hertel Tel.: 91-129-241 2049(O) Federal Institute of Risk Assessment 91-129-237 0094 FG-82, BGVV E-mail: [email protected] Thielallee 88-92 14195 Berlin Dr Janet Kielhorn Germany Fraunhofer Institute Tel.: +49 30 8412 3931 Nikolai-Fuchs-Strasse 1 Fax: +49 30 8412 3003 D-30625 Hannover E-mail: [email protected] Germany Tel.: +49 511 5350 329 Dr Paul Howe Fax: +49 511 5350 335 Centre for Ecology and Hydrology Monks Wood, Abbots Ripton, E-mail: [email protected] Huntingdon, Cambridgeshire, PE28 2LS United Kingdom Dr Ivan Kokalov Tel.: +44 1487 772 499 Trade Union “KNSB” (NGO) Fax: +44 1487 773 467 Sofia E-mail: [email protected] Bulgaria Tel.: +359 2 9170445 Dr Susumu Ishimitsu E-mail: [email protected] Division of Safety Information on Drug, Food and Chemicals Ms Ekaterina Krasteva National Institute of Hygienic Sciences National Agency for Plant Protection 1-18-1 Kamiyoga, Setagaya-ku Tokyo 158-8591 Ministry of Agriculture Japan Sofia Tel.: +813 3700 9548 Bulgaria Fax: +813 5717 7180 Tel.: +3592 9533345 E-mail: [email protected] E-mail: [email protected]

Dr Veska Kambourova Mr Plamen Lazarov National Center of Hygiene, Director, Medical Ecology and Nutrition National Agency for Plant Protection 15, Dimitar Nestorov Blvd. Ministry of Agriculture Sofia 1431 Sofia Bulgaria Bulgaria Tel.: +359 2 5812643 Fax: +359 2 954 1277 Tel.: +359 2 9533370 E-mail: [email protected] E-mail: [email protected]

66 Dr Takeshi Morita Dr Nikolai Rizov Senior Researcher Assoc Prof, Director, Division of Safety Information on Drug, National Center of Hygiene, Food and Chemicals Medical Ecology and Nutrition National Institute of Hygienic Sciences 15, Dimitar Nestorov Blvd. 1-18-1 Kamiyoga, Setagaya-ku Sofia 1431 Tokyo 158-8591 Bulgaria Japan Tel.: +359 2 954 1300 Tel.: +813 3700 9548 Fax: +359 2 954 1277 Fax: +813 5717 7180 E-mail: [email protected] E-mail: [email protected] Dr Jun Sekizawa Mr Frank K. Muchiri Professor Directorate of Occupational Faculty of Integrated Arts and Sciences Health and Safety Services Tokushima University P.O. Box 34120 Nairobi 1-1 Minami-josanjima Kenya Tokushima 770-8502 Tel.: +254 3 511 138 Japan E-mail: [email protected] Fax/Tel.: +8188 656 7263 E-mail: [email protected] Dr Bojidar Nikiforov Prof., PhD, DSc, Dr Fina Simeonova National Centre of Hygiene, Professor Medical Ecology and Nutrition (NCHMEN) Boul. Zarigradsko shosse 4a, block 2a 15, Dimitar Nestorov Blvd. Sofia 1431 Sofia 1113 Bulgaria Bulgaria Tel.: (+359 2) 9541123 E-mail: [email protected] Fax: (+359 2) 9541277 E-mail: [email protected] Dr Salah Soliman Alexandria University Dr Larry Olsen Research Chemist Faculty of Agriculture Biological Monitoring and El Shatby Health Assessment Branch Alexandria 21545 Division of Applied Research and Technology Egypt NIOSH Mailstop C26 Tel.: +203 592 0067 4676 Columbia Parkway Fax: +203 481 7232 Cincinnati, OH 45226 E-mail: [email protected] USA Tel.: 513-533-8594 Dr Jennifer Stauber Fax: 513-533-8494 CSIRO Energy Technology E-mail: [email protected] Centre for Advanced Analytical Chemistry Dr Siyka Popova Private Mail Bag 7 Bangor, NSW 2234 Assoc Prof Australia Univ. of Chemical Technology and Metallurgy 8, Kliment Ohridski Blvd. Tel.: +61 2 9710 6808 Sofia 1756 Fax: +61 2 9710 6837 Bulgaria E-mail: [email protected] Tel.: +359 2 765313

67 Eng Petko Vardev Secretariat SE HYGITEST LTD. 15, Dimitar Nestorov Blvd. Dr Antero Aitio Sofia 1431 International Programme on Chemical Safety Bulgaria World Health Organization Tel.: +359 2 595026 20 Avenue Appia Fax: +359 2 594097 1211 Genève 27 E-mail: [email protected] Switzerland Tel.: + 41 22 791 3592 Dr Peter Watts Fax: +41 22 791 4848 Toxicology Advice & Consulting Ltd. E-mail: [email protected] Westmead House, Westmead Road Surrey SM1 4JH Mr Teruyoshi Ehara UK International Programme on Chemical Safety Tel.: + 44 208 722 4701 World Health Organization Fax: + 44 208 770 0544 20 Avenue Appia E-mail: [email protected] 1211 Genève 27 Switzerland Dr Deborah Willcocks Tel.: + 41 22 791 4334 GPO Box 58 Fax: +41 22 791 4848 Sydney, E-mail: [email protected] NSW 2001 Australia Tel.: +61 2 8577 8890 Fax: +61 2 8577 8888 E-mail: [email protected]

Dr Kyriakoula Ziegler-Skylakakis European Commission DG Employment & Social Affairs Rue Alcide de Gasperi 2920 Luxembourg Tel.: +352 4301 34424 Fax: +352 4301 43259 E-mail: [email protected]

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