CONTENTSImproved 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

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CONTENTS

INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY: REDESIGN AND FUTURE TRENDS 3Antero Aitio

CHEMICAL POLICY IN THE EUROPEAN UNION 7Kyriakoula Ziegler-Skylakakis

OECD AND CHEMICAL SAFETY 8Rolf F. Hertel

NATIONAL AUTOMATED SYSTEM FOR ENVIRONMENTAL MONITORING /NASEM/ 11Dimitar Vergiev

REGULATIONS RELATED TO CHEMICAL RISK ASSESSMENT IN HUNGARY 17Gyula Dura

CHEMICAL RISK ASSESSMENT IN THE USA 25Herman Gibb

PRIORITY TOXIC SUBSTANCES IN BULGARIA 29Nikolai Rizov, Fina Kaloyanova, Yordan Simeonov, Ivan I. Benchev

HEAVY METALS POLLUTION AROUND THE METALLURGY PLANTS IN SOME REGIONSIN BULGARIA 38Ivan Grancharov, Siyka Popova

CHEMICAL ACCIDENTS – ORGANIZATION OF THE PROTECTION, MEANS AND METHODSFOR MITIGATION OF THE CONSEQUENCES 48Svetoslav Andonov

BULGARIAN LEGISLATIVE FRAME FOR PREVENTING WATER POLLUTION BY CHEMICALS 53Veska Kambourova

THE CONTRIBUTION OF THE SMALL ENTERPRISE “HYGITEST” LTD. – SOFIA TO THEASSESSMENT OF CHEMICAL POLLUTION IN THE AMBIENT AND WORKPLACE AIR 59Petko Vardev, Dimitar Dimitrov

LIST OF PARTICIPANTS 64

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INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY:REDESIGN AND FUTURE TRENDS

ANTERO AITIOInternational Programme on Chemical Safety, Geneva, Zwitzerland

Environment and health are at the centre of strategies to promote sustainable development andan integrated approach is required whenever possible. IPCS is a collaborative body of threeintergovernmental 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 isbeing redesigned. This redesign process is in progress, and below are presented some aspects ofthe new IPCS, noting especially that changes are likely to occure when the plan is finalised andbefore it is fully implemented. IPCS work can be devided to four elements; they are brieflydiscussed below.

The long-term goal of IPCS is to reduce adverse effects of chemicals on human healthand the environment.

Element 1 Risk assessment and establishment of guidance values, as well as developmentand global harmonization of risk assessment methods

Goals Identify health and environment problems arising from exposure to chemicals throughfood, 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 identifyand promote appropriate preventive measures.Refine risk assessment methods, integrate procedures for the assessment of health andenvironmental effects of chemicals.Address emerging scientific issues, for example toxicogenomics, so that risk assessmenttools can be continually improved.

Assessments of the risk of chemicals to human health and the environment (includingConcise International Assessment Documents (CICADs) and International ChemicalSafety 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 ofChemicals in IPCS risk assessment products.Guidance for improving use and awareness of human toxicology data.

Outputs

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Countries are better able to identify and characterize exposure, hazards and risksand to identify and implement preventive and response activities.Improved communication on chemical risks is enabled by IPCS risk assessmentproducts.Development of country-specific activities to eliminate/minimize exposure tohazardous chemicals.Countries are better able to set priorities and measure progress towards chemicalmanagement goals.Improved priority-setting for research related to chemical safety and selection ofchemicals for assessment.

Impact atCountryLevel

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 theprevention 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-qualityinformation 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.

Awareness raising through presentations and publications on the role of poisonscentres 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 andmanagement and health care.Establishment of one or more poisons centres in countries where none exist andstrengthening of existing poisons centres.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 chemicalassessment and management processes.Risk assessment priorities more closely aligned with identified public healthpriorities.

Outputs


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Element 3 Chemical incidents and emergencies: prevention, preparedness, surveillance,alert and response

Strengthen national public health response plans for chemical incidents andemergencies occurring naturally, accidentally or deliberately.Establish and maintain a global mechanism for the timely detection of, and therapid response to, chemical incidents and emergencies of international concern.Improve the knowledge base for the sound management of chemicals, andenvironmental health policy and decision-making.Strengthen information exchange through global networks of partners.Strengthen collaboration and coordination of chemical incident and emergencyactivities.Ensure engagement in the process of review and implementation of the Interna-tional Health Regulations (IHR) to cover public health events of internationalimportance, including those of chemical aetiology.

Guidance and training material for countries.Global capacity building activities.A surveillance system for identifying chemical incidents and emergencies ofinternational importance.A mechanism for mobilising WHO experts, international organizations andother resources to provide technical assistance where requested by countries.A roster of experts available to respond to chemical incidents or emergencies atshort notice.An inventory of internationally-accessible resources for responding to chemicalincidents and emergencies.Regular outbreak reports, a quarterly newsletter to network members, annualreports and presentations.Improved public health capabilities and capacities to respond to chemicalincidents and emergencies of natural, accidental or deliberate origin.

Improved surveillance and investigation of incidents of chemical aetiology.Improved national chemical safety and environmental health policy anddecision-making.Improved access to internationally-available resources to respond to chemicalincidents and emergencies.

Goals


Outputs

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Element 4 Capacity-building support, for the above activities

To provide advice and tools for the development of infrastructure and qualifiedlocal individuals in all countries/regions to implement elements 1-3.To promote and facilitate international collaborative research.To transfer knowledge and facilitate technology transfer.

Expert Groups and teams for IPCS activities including experts from developingcountries and countries with economies in transition, e.g. in expert groupsdeveloping risk assessment methodologies and chemical-specific riskassessments 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, pesticideepidemiology.Local training courses, e.g. in pesticide handling.Technical support to enable countries to fulfil obligations under internationalconventions such as those relating to Prior Informed Consent and PersistentOrganic Pollutants.Technical support to enable implementation of the Globally HarmonizedSystem for Classification and Labelling.Improved indicators of performance.

National experts and agencies have information and skills for the assessmentand safe management of chemicals, and for the prevention and management ofpoisoning.Improved public health capabilities and capacities to investigate chemicalincidents 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 insupport of international obligations.

Goals

Outputs


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CHEMICAL POLICY IN THE EUROPEAN UNION

ZIEGLER-SKYLAKAKIS KYRIAKOULAEuropean Commission, Employment and Social Affairs, Luxembourg

About 100 00 different substances are registered in the EU market of which 10 000 are marketedin volumes of more than 10 tonnes and a further 20 000 are marketed at 1-10 tonnes. The worldchemical production in 1998 was estimated at � 1 244 billion, with 31 % for the EU chemicalindustry. In 1998, EU chemical industry was the world’s largest chemical industry, followed bythat of the US with 28% of production value. The chemical industry is also Europe’s third largestmanufacturing 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 ofresponding adequately to public concern in Europe about impact of chemicals on health andenvironment led the Commission to propose a new policy for chemicals. In the White Paper onthe Strategy for a Future Chemicals Policy the Commission outlined in 2001 the strategy toensure a high level of chemicals safety through a system for Registration, Evaluation andAuthorisation of Chemicals to be known as the REACH system. The White Paper is based onseven 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, permanufacturer/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 REACHsystem. 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, Authorisationand Restriction of Chemicals (REACH-Regulation).

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OECD AND CHEMICAL SAFETY

ROLF F. HERTELFederal Institute of Risk Assessment, Berlin / Germany

The Organisation for European Economic Co-operation (OEEC) was established in 1948 withthe aim to support implement the Marshall Plan in Europe. This organisation was succeeded in1961 by the Organisation for Economic Co-operation and Developement (OECD) with the aimof promoting economic growth and employment and track liberalisation thus improving thestandard of living within all 30 member countries.Since 1971 the OECD has established work on environment, health and safety in the so-calledEnvironmental 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 shareinformation about the risk of this chemicals by performing risk assessments and developing riskmanagement 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 detailedexposure information gathering is carried out at the national/regional level and is no longer partof 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 „sharethe 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 andmakes the information it has collected or generated available to other Member countries. Chemicalindustries 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 tobe conducted are undertaken in a timely manner. The work is carried out in collaboration withthe 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 productionvolume (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 informationnecessary to undertake a first evaluation of potential hazards associated with HPV chemicals iseither 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 andmake recommendations related to the need for further work. Finally, when complete data setsand 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 prioritylist from which chemicals are selected for testing and/or assessment. In consultation with theirchemical industries, Member countries identify chemicals for which, on a voluntary basis, theywill act as a Sponsor country in the HPV programme. The overall number of chemicals whichany Member country or group of Member countries (through, for example, the EU programme)

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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 elementsof exposure information. The SIDS is regarded as the minimum information needed to assess anHPV chemical and to determine whether any further work should be carried out or not. EachMember country is responsible for generating and making available SIDS data for the selectedchemicals. In return, it will benefit from receiving similar data on the chemicals from otherMember countries. All SIDS elements are listed in the OECD Manual for investigation of HPVChemicals.For any SIDS element on effects or characterisation for which no data are available or the dataare not considered adequate, testing will in principle be carried out. Any testing to complete theSIDS 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 andSIDS Testing Plans are forwarded by the Sponsor country to all SIDS Contact Points, so thateach country and the experts nominated by IPCS can study the proposals made by the Sponsorcountry.When a SIDS Testing Plan for a chemical is agreed by the other Member countries, the Sponsorcountry carries out the test(s) and/or the collection of information on exposure and effects. Whenall 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 timelymanner prior to the SIDS (prior to SIAM EDG) Initial Assessment Meeting (SIAM). At theSIAM 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 fromother Member countries and the Commission of the European Union, experts from non-Membercountries 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 thatpart 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 informationis 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 thework rests with industry.Finally during the OECD Joint Meeting, which is a policy body of OECD, Member countriesdiscuss 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 SIDSprogramme.

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OECD decided that Member countries shall make information obtained from the co-operativeinvestigation of chemicals publicly available via IRPTC. Therefore all information, includingtest reports, SIDS dossiers and SIDS Initial Assessment Reports, are transmitted to IRPTC andthe information is entered in the IRPTC database, thus being available to users throughout theworld.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 thePesticide Programme focussing on pesticides used in agriculture and on a group of productscalled „non-agricultural pesticides“ and biocides.The Programme on Harmonization of Classification and Labelling Systems was successful inharmonizing the many different chemicals classification systems and is implemented throughthe United Nations in both OECD and non-member countries.Another activity of OECD is the Chemical Accidents Programme, which helps to prevent chemicalaccidents and to respond appropiately if one does occur. A further highlight in the EHS-programmeare 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/).

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NATIONAL AUTOMATED SYSTEM FOR ENVIRONMENTALMONITORING /NASEM/

DIMITAR VERGIEVExecutive Environment Agency, Ministry of Environment and Water, Bulgaria

The Executive Environment Agency /ExEA/ is a structure under the Minister of Environmentand 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 andwater.Bulgaria has a long tradition of environmental monitoring, particularly monitoring of ambientair 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. TheClean Air Act, adopted in 1996 and amended in 2000, establishes the monitoring obligations ofoperators of stationary sources, as well as their reporting obligations. It provides the frameworkfor an air quality monitoring management structure, with national and municipal networks. Theoperator of an installation can be required to monitor local air quality at source.

a) Ambient air quality monitoringThe network for ambient air quality monitoring, set up in 1972, has improved significantly overthe past ten years. The network now consists of 66 stationary stations, operated by the ExEA andthe Ministry of Health. There are 16 automated online stations, and 50 stations with manualsampling 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 outare for TSP, Pb, aerosols, SO

2, NO

2 and H

2S. In industrial areas NH

3, phenols, THC, As aer.,

HCl, Cl2, CO, NO, O

3, Cd and Mn are also measured. Tropospheric ozone is monitored at most

(i.e. 15) automatic stations and PM10

is measured at most stations.

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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 qualitymonitoring, 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 NIHMcarry 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 lowerDanube. Seven automated stations for air quality control and two meteorological stations wereinstalled 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 monitoringEmissions monitoring has improved considerably since 1996, following adoption of the CleanAir Act, which provides for mandatory regular reporting of emissions by large enterprises andsupports enforcement of regulations. Bulgaria’s 150 largest enterprises produce around 80% ofair pollutant emissions. As part of their emissions control efforts, these enterprises must carryout self-monitoring on a periodic or continuous basis. Continuous emissions monitoring will bemandatory for large industrial plants as of the beginning of 2004. A list of enterprises obliged toundertake this type of self-monitoring according to the decision for Reporting on EnvironmentalImpact Assessment is held by the Ministry of environment and water /MOEW/. Monitoringprogrammes for self monitoring of the emissions are approved by the ExEA. Self-monitoringactivities 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, SO

2, NO

2 and other specific pollutants are directly measured in order to

assess compliance with national emissions standards. This takes place twice a year, using fourmobile automatic stations and eight mobile analysers. A list of enterprises to be monitored isapproved every year by the MOEW.In the case of mobile sources, responsibility for emissions control lies with the State AutomobileInspectorate (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 isidling), which report back to the MOEW. The ExEA on the basis of motor fuel consumption dataand 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 motorvehicles, including exhaust emission data.

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The MOEW provides the UN-ECE Convention on Long-range Transboundary Air Pollutionwith early emissions data on SO

2, NO

2, CH

4, NMVOC, CO, NH

3, Cd, Pb, Hg, PAH, PCBs,

HCB, PCP and dioxins from 11 activity sector groups. Included are emissions from differenttypes 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, aswell as from agriculture and nature. Data on SO

2, NO

2, CH

4, NMVOC, CO and NH

3 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 ClimateChange (UNFCCC). Data on ozone depleting substances are reported annually to the UNEPOzone Secretariat.

Water monitoring

Water quality monitoring is carried out through a number of programmes co-ordinated under theNASEM. 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 ofcoastal waters. The health administration is mainly responsible for monitoring water quality insources supplying drinking water and for overseeing bathing waters (physical, chemical andmicrobiological analysis).According to the Water Act, the biggest water polluting enterprises are required to self-monitorthe quantity and quality of their sewage water.

a) Surface water monitoringThe main purposes of the national surface water monitoring network are to:

– obtain quantitative and qualitative data on the state of surface waters and assesstrends 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 qualitycomprises 253 stations covering all major river basins. Three of these stations, located on therivers 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,NH

4, NO

2, NO

3, total N, PO

4, 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 ofsensitive 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 threeareas (Sofia, Stara Zagora, Smolyan) at the same sampling sites as those used for physical andchemical monitoring.Monitoring of the Black Sea takes place in connection with the Black Sea Convention

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(Bucharest, 1992), which was signed by six bordering countries. Due to its hydrophysical andecological 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 thecontent of oil products in sea water, sediments and the bottom bio-indicators. According to theConvention on the Protection and Sustainable Use of the River Danube, five of Bulgaria’s waterquality stations on the Danube and three on its Bulgarian tributaries belong to a transfrontiermonitoring network. Data are regularly submitted to the Commission on the Protection of theRiver Danube in Vienna and to the data base of the ExEA in Bratislava..Bulgaria reports monitoring results from 111 surface water stations to the EUROWATERNETsystem.

b) Ground water monitoringThe 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 groundwater;

– 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 aresampled two or four times a year for about 30 parameters. Bulgaria reports monitoring resultsfrom 74 ground water stations to the EUROWATERNET system.

c) Water resources and useThe national network for monitoring water resources comprises 373 rainfall measuring stations,236 hydrological stations and 595 hydrogeological stations. The headquarters for this network isbased within the National Institute of Hydrology and Meteorology (NIHM) in Sofia. Meteoro-logical information is collected and received via satellite from 18 hydrological stations, whichalso serve to give warning in case of flood danger. Water quantity is monitored via the networksof other specialised administrations, such as the “Reservoirs and Cascades” administration, whichoperates 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 andAgroecology. Soil contamination of industrial sites is also monitored using EIA procedures andan environmental auditing system. This monitoring is associated with the liability issues ad-dressed as part of the privatisation process.

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b) Biodiversity monitoringIn 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 iscarried out by the National Parks Directorate of the MOEW, established in 1999. Monitoring offorest damage is carried out in the framework of the Convention on Long Range TransboundaryAir Pollution (LRTAP) and the International Co-operation Programme on Forests led by the EUand UN-ECE. The ExEA acts as a focal point; field studies are carried out by University ofForestry and the Forest Research Institutes.

Waste monitoring

Data on municipal waste are directly obtained from the municipalities responsible for wastemanagement. The NSI collects data on non-hazardous industrial waste from enterprises throughannual statistical surveys.Data on hazardous waste compiled by the ExEA are transmitted to the Secretariat of the BaselConvention. Database on hazardous waste is currently functionning at the ExEA.The waste reporting system covers some 620 landfills; almost 2 000 other waste dumps operatewithout proper reporting on the quality and quantity of wastes deposited. It is expected that thesedumps will be closed by 2007 and will be replaced by regional landfills. The National WasteManagement Programme foresees the construction of 37 new landfills that would meet EUcriteria 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 meetinternational 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 entirecountry. The nuclear power plant “Kozlodouy” benefits from special monitoring through a higherdensity of monitoring stations around the plant. All LMS are supplied with measurement andcommunication 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 foremergency situations and civil protection (i.e. the Civil Defence Department and the Committeeon the use of Atomic Energy for Peaceful Purposes).The measurements taken are collected, processed and stored in the data base of the ExEA. Theyare 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 requestthrough public information centres at the MOEW and the ExEA, via Green Phone lines withinthe MOEW and the RIEWs, and at regular press conferences. Certain types of environmental

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

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

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

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REGULATIONS RELATED TO CHEMICAL RISK ASSESSMENT INHUNGARY

GYULA DURAFodor József National Public Health Centre, National Institute of EnvironmentalHealth, 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 ofthe firms belong to the group of SME. Small farms which are using chemicals enlarged to somehundred 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 tothe 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 thedifferent 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 EU2. Commitments to OECD3. Chapter 19 of Agenda 214. 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 ScopeChapter 2 Determination of Hazards of Dangerous Substances and Preparations to Man and

the Environment; Hazard IdentificationChapter 3 Classification of Substances and Preparations; Reporting and Notification of New

SubstancesChapter 4 Packaging, Labelling, Stockpiling, Transport and Advertisement of Dangerous

Substances and PreparationsChapter 5 Risk Assessment, Risk ReductionChapter 6 Risk ManagementChapter 7 Risk Communication, Information Exchange

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Chapter 8 Conditions of Activity with Dangerous Substances and Preparations; Supervision ofChemical 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

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 healthconsequencies 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 shouldprovide authority control. Some elements of inspection:

– employee (manufacturer, importer, trader) is allowed to conduct any kind of activityonly with registered or notified chemicals. Components of preparates aslo should beregistered 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 widercontext the scientific findings according to the regulation of chemicals.

covers Function Institutions

new

and

existingchemicals

data collection

risk assessment

risk magement

risk communication

inspection/controll

penalitites

Government

minister of health

intersectorial committee

National Public Health and Medical Officers Service

National Public Health Centre Institute of Chemical Safety Toxicological Information Centre Poison Centre

County Public Health Institutes (21)

Municipal Publ Health Institutes (136)

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Legislation related to environmental and human health risks in aspects of environmentalsafety

1) Law on emergency preparednes and protection against major accidents involvingdangerous substances (LXXIV/1999)

2) Governmental Decree on protection against major accidents involving dangeroussubstances (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

- preventionw recognition and identification of hazards arising from possible major chemical ac-

cidentsw analysis of the different kinds of risks coming from contaminated environmental

mediaw proactive protection of human health and of the environmentw reduction of risks of chemicals to human health and the environment

- intersectorial co-operationw involvement of all stakeholders

- improvement of risk communicationw 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 riskassessment to evaluate serious environmental and public health hazard situation arising from thepolluted environment (hot spots). This resulted establishment of site specific soil and groundwater higienic limit values, remediation (clean-up) concentrations for hot spots (see table ofHungarian 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 healthauthority expertise, resolution, licensing) by efficient use of risk assessment.

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Case studies on Human Health Risk Assessment in Hungary

RQ Risk QuatientRA Risk Assisstant softwareHESP Human Exposure to Soil Pollutant software

PBPK model Physiologically-Based-Pharmaco-kinetic ModelUS EPA IEUBK Integrated Exposure Uptake Biokinetic Model for LeadUSES Unified System for Evaluation of Substances

CalDTSC Lead Risk Assessment software CALIFORNIA DEPART-MENT OF TOXIC SUBSTANCES CONTROLRBCA Risk Based Corrective Action, ASTM Standard, USA

Environmental Contaminants Area/Site Population Method/model Results media (No of exposed

people)

Soil Pb, Cd, Zn, Cu Budapest-Nagytétény Children and adult HESP RQ > 1 validated (Pb-blood)Lead processing plant (some hundreds) Ministerial order on site

specific values

Ground and As S-E Hungary (natural occurence) General population Quality assessment Improvement of d.w.drinking water (over 300 thousands) management/treatment

Deep thermal BTEX S-E Hungary (natural occurence) General population RA Advice for using thermal waterwater in swimming pools

Soil, Sediment Pb, Cd, As, Zn Gyöngyösoroszi Children HESP RQ....?flooded area of home-gardens Adults RA RQ < 1

(few)

Soil Pb Heves (illegal demolition of batteries) Children PBPK model, Investigation of lethal and heavy(few) CalDTSC intoxication of children

EPA IEUBK

Soil Chlorobenzenes Gare, hazardous waste disposal site Workers Potential risk on site(Tetra-, penta-, (few)hexachlorobenzene),

Dioxin Population living near the site RA Joint ministerial order on site(5 thousand) specific limit values for soil and

and ground water on site andoff site of the dump

Soil and TPH, BTEX, PAH Oil mining, refinery, pipe-line, Workers on site, RBCA Clean-up valuesgroundwater underground tank inhabitants off site

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Legislation of environmental and human health risks arising from major chemicalaccidents (Seveso II.)

Emergency preparednes and protection against major accidents involving dangeroussubstancesw 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 facilityw characterization of the environment surrounding the site (inhabitants; natural

values; economic values; public institutions; public utilities)w other hazardous sites or activities near the facilityw characterization of the health consequences and impacts on the natural environment

due to an industrial accidentw detailed description of the site by the meaning of manufacturing; production; use,

quantity of dangerous substance; description of technologies; circumstances of safeoperation;

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 anperformed/implemented in Bulgaria, Hungary, Romania. Flowchart of the REHRA procedure isshown 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 conditionsfor work which make possible the prevention of occupational accidents/injuries andoccupational 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

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QUESTIONAIRE

1. Identification of facility,activity,

2. Technology data,3. Hazardous substances,4. Environmental data,5. Health data.

DATACOLLECTION

DATABASES

1. Industrial code,SIC code2. "SEVESO II." lists:

threshold quantities,3. EU classification list of

hazardous substances(67/548/EEC),

4. Other lists: water pollutants,5. Toxicological databases.

INPUT

SCORINGin accordance with questionary

SITE INDEXaccording to questioner 2.

• type of activity• organization/automatization

DANGEROUS SUBSTANCEINDEX

according to questioner 3.• Seveso II. lists• EU classification list of hazardous

substances (67/548/EEC)

ENVIRONMENT ANDSURROUNDINGS:

• sourface and ground water,• soil,• meteorology,• ecology

(according to questioner 4.)

HEALTH DATA,demografic characteristics

(according to questioner 5.)

SUMMING-UP SCORES

FINAL SITE HAZARD INDEX

CHEMICAL ACCIDENT RISK( M A R S )

POPULATION RISK ( PEC / PNEC )

DATA PROCESSING

Figure 1. RAPID ENVIRONMENTAL AND HEALTH RISK ASSESSMENTin tributaries of the lower Danube basin.

Ranking hazardous facilites

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implementing collective and individual protection and by using the best availabletechnology;

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 alsoexecute regular medical examinations.

Implementation of workplace legislation:

Chemical safety of workplacesw 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 substancesw 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-

stancesw regulations for working with asbestosw regulations for working with vinyl-chloride monomer

Accentuated tasks in chemical risk assessment in Hungary

Chemicals as public health challenge – problems & actions

Problems Actionsinsufficient knowledge on chemicals improve dissemination and exchange of information, tox.

information centresafety of the unborn/new-born child focus on reproductive health, pre-, peri- and postnatal

effectsneurodevelopmental disorders

lack of data on human exposure strengthening biomonitoringhealth risk of hazardous waste special attention to obsolete pesticidespost marketing surveillance of chemicals biocides, pesticides, household chemicalssite specific risk assessment offormer/abandoned industrial facilities

land/groundwater remediation, derivation of environmentaland human health risk-based clean up values

multi-exposure, multi-factorial, multi-outcomeapproach in risk assessment procedureuncertainties in risk assessment

Good Modelling Practiceacceptability of risks (precautionary principle)

health, environment and safety in enterprises integrated risk assessmentenvironmental health impact assessment populational risk assessment

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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.

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CHEMICAL RISK ASSESSMENT IN THE USA *

HERMAN GIBB, PH.D.National Center for Environmental AssessmentU.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)

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• 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 beexposed 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-producinganimals if no residue will be found in edible tissues OR if lifetime dietary risks willbe less than one in a million

• EPA and other agencies uses “de minimus risk” of one in a million as the point ofdeparture 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 toosmall 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) increasedrisk of an adverse effect (e.g., cancer, death) occurring over a lifetime in a largepopulation

• Exposure to a substance associated with a risk of 1 x 10-6 would increase chances ofdeveloping cancer from all causes (1 in 3) by 0.0003%

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Risk Comparisons for Involuntary Risks

Activities That Increase Risk of Death by One in a Million

Evolution of Risk Assessment at EPA

1 in 100 billionMeteorite

Source: JAMA, 244, 1126, 1980

1 in 10 millionNuclear power plant

1 in 588,000Earthquakes (California)

1 in 455,000Tornados (Midwest)

1 in 455,000Floods

1 in 20,000Struck by automobile

1 in 12,500Leukemia

1 in 5000Influenza

RISK OF DEATH/PERSON/YEARRISK

Source: Technology Review, 81 (1979)

Cancer from radiationRisk of accident by living

within 5 miles of a nuclear

reactor for 50 years

Cancer from radiationOne chest X-ray

Cancer from radiationFlying 1000 miles by jet

AccidentTraveling 300 miles by car

AccidentTraveling 10 miles by bicycle

Cancer, heart diseaseSmoking 1.4 cigarettes

Cause of DeathActivity

� complex mixtures

� susceptible subpopulations

� uncertainty evaluations

� new tools/approaches

2000s

� peer review

� dermal and inhalation routes

� understanding mechanisms

� cumulative risks

1990s

� guidelines

� basic methods

� dosimetry

� data bases (IRIS)

1980s

� beginnings of the field (tools, approaches)

� emphasis on oral route per FDA precedent1970s

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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 ofadverse 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 mgchemical 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 toexposure 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 RiskInformation System (IRIS) at www.epa.gov/iris.

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PRIORITY TOXIC SUBSTANCES IN BULGARIA

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

Introduction

During the last several decades the international organizations increased their concern to protecthuman health and environment from chemical pollution. This is associated with the increaseduse 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, immunesystem 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 forchemical safety. Their principal goal was “to achieve that chemicals are used and produced inways that lead to minimization of significant adverse effect on human health and environment,using transparent science-based risk assessment procedures and science-based risk managementprocedures, taking into account the precautionary approach, as set out the principle of the RioDeclaration on Environment and Development” (Rapport de la Conference 1992).In Bulgaria chemical safety had high priority in the preventive activity of the Ministry of Healthstarting in 1966 with the special regulations. At present the Ministry of Environment and othergovernmental, independent research and training institutions and NGO’s play a considerablerole in chemical regulation and safety.

1. APPROACHES USED

The Intergovernmental Forum on Chemical Safety (IFCS) has requested the Inter-organizationProgramme for the Sound Management of Chemicals (IOMS) member organizations, to identifycriteria for setting priorities for various types of risk assessments and to elaborate, on the basis ofthese criteria a list of priority chemicals for risk assessment. The global criteria for selection ofchemicals for international assessment have been developed but additional criteria have beenapplied in selecting for IPCS EHC and CICAD programmes. It was noted that priority setting bycountries was carried out within a national legal framework, which might involve additionalcriteria for selection of chemicals (IFCS/ISG3/98.08w, 8 June 1998).There are also international targeted risk assessments. Some of them may provide informationon given endpoint like the International Agency for Cancer Research (IARC) evaluations ofchemicals for their potential carcinogenicity, others provide assessment of chemicals present ingiven 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 thecombined criteria with national significance. Of all CICAD criteria the most important ones forour country are:

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– there is a probability of exposure, and/or significant toxicity/ecotoxicity, and/orsignificant 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 andscoring.Emphasis was given to the long-term effects, especially carcinogenicity. In this respect it wasimportant but not easy and possible to take into account the recently defined new phenomenonknown as a multiple chemical sensitivity (MCS). We took into consideration the necessity toevaluate 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 dueto 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 amongwomen, 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 mimichuman hormones or affect their metabolism, may be carcinogenic. (Forum 1997). Taking intoaccount the big group of chemicals with endocrine disruption effects, we may see the magnitudeof the problem and the pressing need of research in this field.

1. 1. Industrial chemicalsChemical production plants are the principal sources of environmental pollution. The chemicalindustry 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 seriousproblem 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 andthermoelectric power stations are responsible for air pollution by lead, sulfur dioxide, dust andother contaminants.Metal pollution is one of the most important and to some extent well known problemsLead is the principle pollutant arising from non-ferrous metallurgy.A correlation exists between some pollutants and morbidity from certain diseases, especiallyrespiratory system disorders, allergic reactions and anemia. Lead exposed individuals very oftenhave 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 Plovdivhas shown unusually high levels (242 ± 78 mg/l) of lead in blood samples from a representativegroup 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 fromair. This pollution contributes considerably to the exposure of the general population. The mostserious problem with a global significance is presented by the metallurgical plants producinglead and zinc near Plovdiv and Kurdjaly and the plant producing copper and rare metals inSrednogorie. An important and long lasting problem is the decontamination of soils pollutedwith 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

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metallurgical plants. Chromium is not well studied. There is no organized waste disposal ofchromium 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 luminescentlamps 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 seaand river ports.The measures undertaken for risk reduction should take into account cost/benefit analyses. Inorder to achieve effective results it will be necessary to identify and deal with the worst and themost easily controllable risk factors of global significance.Sources and emissions of hexachlorobenzene and polychlorinated biphenyls (PCBs) included inthe POPs list need additional national inventory and monitoring.According to the data published in the Annual Bulletin of MOEW for 2000, 6 PCBs have beenmonitored in soil samples. The conclusion is that the concentrations measured are below thebackground values and there is no potential risk for soil contamination by PCBs).Polyaromatic hydrocarbons (PAHs) are widely dispersed and poorly investigated. Some PAHshave been found in soil samples in the vicinity of a plant producing carbamide, formaldehyderesins, 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 onsoils, also in regions of high potential impact.1,1-Dichlorethane presents a local problem for waters in the region of Varna due to the chemicalindustry in Devnja. Nitrobenzene is a regional problem associated with waste waters from thechemical 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 withsome 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.

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Table 1. Different industrial chemicals

Name Scores Media of concern

PCBs 5 No dataPAHs 5 Water, working environment, soilCyanides 5 Working environment; waterPhenol 5 Water, working environmentMusk xylene 4 Working environmentNitrobenzene 4 Water, working environmentShort chain chlorinated paraffins 3 Working environment2,4,6-tris-(1,1-Dimethylethyl) phenol 1 Working environmentHexachlorobenzene 1 Water, working environment

Table 2. Chorinated organic chemicals


Solvent Chloroform 5 Water, working environmentOthers Hexachlorobutadiene 3 Working environmentBenzenes 1,2-Dichlorobenzene 2 Working environment

1,3-Dichlorobenzene 2 Working environmentSolvent 1,1- Dichloroethane 2 Working environmentBenzene 1,4-Dichlorobenzene 2 Working environmentSolvent 1,1,1-Trichloroethane 1 Working environmentBenzene 1,2,4-Trichlorobenzene 1 Working environment

1,2,4,5-Tetrachlorobenzene 1 Working environmentPentachlorobenzene 1 Working environment

Others Octachlorostyrene 1 Working environment

Table 3. Metals and organometals


Arsenic 5 Total environmentCadmium 5 Total environmentChromium 5 Working environment; waterLead 5 Total environmentOrganic lead 5 Working environment; foodMercury 5 Working environment; water; foodOrganic mercury 5 Water; foodAntimony 4 Water; working environmentBeryllium 4 Water; working environmentZinc 4 Working environment; waterOrganic tin 4 Working environmentNickel 4 Working environment; waterCopper 3 Working environment; water; foodSelenium 3 Working environment; water

Table 4. Phthalate esters


Dibutyl phthalate 4 Working environmentButylbenzyl phthalate 4 Working environmentDiethylhexylphthalate 2 Working environmentBis-(2-ethylhexyl)phthalate 1 Working environment

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1. 2. PesticidesIn Bulgaria only registered pesticides are applied for agricultural or public health use. The mostused 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 growthregulators - 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 registeredin 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 thisreason it was not necessary to look for alternatives for malaria control. It was very easy toexclude agricultural use of DDT due to the large number of alternative pesticides. The mostimportant 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 quantitiesand on small areas. Toxaphene was banned in 1985 and heptachlor in 1991. Mirex, HCB andchlordane have never been registered.Nevertheless, despite the limited use of persistent pesticides, the pollution problem is presentdue to different reasons. DDT was detected in the Danube River at concentrations of up to 0.002µg/l in the Bulgarian section but up to 21.8 µg/l in some other Danube basin countries. Up to8.13 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 from0.04 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 forlindane with maximum values of 0.2 µmg/l. Hexachlorobenzene and heptachlor were detectedin water samples in a few cases in amount of 0.05 µmg/l. Residues of 15 pesticides have beenfound in 19% of the examined 176 water samples. The most positive findings were related tolindane (10%), and atrazzine (13%). The contamination levels ranged from 0.01 to 0.1 µmg/l foratrazine and from 0.01 to 0.06 µmg/l for lindane (Bratanova and Vassilev, 2001). Because of thepermanent presence of triazines in the water environment, especially in ground water, it mightbe proposed to include triazines in the list of priority chemicals (Bratanova and Vassilev, 2001).

Table 5. Persistent Pesticides


DDT 4 Water, soilBHC, including lindane 4 Water, foodHeptachlor 1 Water

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1. 3. Unintended by-productsDioxinsDioxins 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. Anational 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.FuransFurans 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 mainsources may be waste incineration and transport. Contaminated animal products may representthe major source of human exposure.According to the MOEW data (2000) the greatest part of the estimated emissions of dioxins andfurans 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 samplesfrom three Bulgarian regions) were analyzed in Germany for presence of PCBs, dioxins andfurans. The results obtained rank Bulgaria among the first four countries with the lowest concen-trations of those chemicals.

Table 6. Unintended by-products


Dioxins 5 Total environmentFurans 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; andContamination 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 chemicalswith 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,

35

as well as compounds containing arsenic, chromium, cadmium and cyanide presenthealth 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 andlong 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 asthey are formed by burning processes and constitute health problems.

Other industrial chemicals: phenol, cyanide, chloroform

2.3. Long term adverse health and environmental effectsCarcinogenicityChemical carcinogens have first priority due to the character of the effect they may producedirectly 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 potassiumchromate), lead, nickel (nickel trioxide, nickel dioxide, nickel monoxide (II) nickeldisulfide, 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 substancesDuring the last 10 years considerable efforts have been made by the Ministry of Health, Ministryof 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 Conventionsand related national plansDevelopment and implementation of regulatory controlEnforcement of regulatory controlTechnology transfer activitiesSupporting and introducing alternativesImplementation of outreach and information programmesImplementation of remedial action plans for stockpiles and contaminated sitesResearch and monitoring programmes on sources and movementResearch and monitoring programmes on human and environmental impacts of chemi-

cals

36

Table 7. Implementation of existing documents

Implementation Evaluation score

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

3. 2. Research programmes for solving the main problemsSome topics for research and development are proposed below.

A) Precise exposure and health risk assessment by means of biomonitoring surveyswith stress to long term effects (cancer, reproductive and developmental toxicity).

B) In-depth and long-term assessment of the consequences of incidents and accidentsrelated 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 systemsfor chemical analyses in environmental media.

F) Projects for decontamination of polluted sites by phytoremediation, bioremediationand other effective technologies should be encouraged. The existing data from labo-ratory experimental modeling (Simeonova and Simeonov, 1997) and field studiesin Kremikovtzi metallurgic plant region, demonstrated that phytoremediation is aperspective approach in the land clean-up (Simeonov, 1997; Simeonov et al., 1999).

International coordination and financial support are necessary, especially for analyses requiringexpensive 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.

37

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 IGIFCS. Yokohama, Japan, 1-4 December 1998.

Kaloyanova F. (1998) Pesticides in Danube River and Tributaries. In Proceedings of Subregional warness raisingworkshop 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 pesticidesranking by hazard. In: Modelling of Environmental Chemical Exposure and Risk, J.Linders ed. NATO ScienceSeries 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 ofpesticides 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 HazardAssessment for Aquatic Environment, in J.B.H.J.Linders (ed.) Modelling of Environmental Chemical Exposureand 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 Bulgariafor 1998. 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 theKremikovtzi Region, Bulgaria. In Strategies to improve Occupational and Environmental Health in Central andEastern 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 analyserLASMA 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 wabrigerLosungen 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 pollutionof 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 MetalsLands 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 theiroffspring. 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 EasternEurope. Annual Report 2002 (abstract), http://www.uni-giessen.de/~ghi5/incocop01.htm

38

HEAVY METALS POLLUTION AROUND THE METALLURGYPLANTS IN SOME REGIONS IN BULGARIA

IVAN GRANCHAROV, SIYKA POPOVADepartment of Inorgnic Chemical Technology, University of Chemical Technologyand Metalurgy, Sofia, Bulgaria

1. Introduction

The soil is a key component of terrestrial ecosystems, both natural and agricultural, beingessential for the growth of plants and the degradation and recycling of dead biomass. It is acomplex heterogeneous medium comprising mineral and organic solids, aqueous and gaseouscomponents.

The soil is a dynamic system, subject to short-term fluctuations, such as variations inmoisture status, pH and redox conditions and also undergoing gradual alterations in response tochanges in management and environmental factors. These changes in soil properties could affectthe form and bioavailability of metals and need to be considered in decisions on the managementof polluted soils.

“Heavy metals” is a general collective term applying of metals and metalloids with anatomic density greater than 6 g/cm3. Although it is only a loosely defined term it is widelyrecognized and usually applied to the elements such as Cd, Cr, Cu, Hg, Ni, Pb and Zn which arecommonly associated with pollution and toxicity problems. An alternative and theoretically moreacceptable name for this group of elements is “trace metals” but it is not as widely used. Unlikemost organic pollutants, such as organohalides, heavy metals occur naturally in rock-formingand ore minerals and so there is a range of normal background concentrations of these elementsin 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 sourcesof 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 highconcentrations of Cu or As fed to improve food conversion efficiency. Sewage sludge

39

usually contain relatively high concentrations of several metals, especially thosefrom 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 theair 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 andthe plant are shown in Figure 1. The soil-plant system is an open system subject to inputs, suchas contaminants, fertilizers and pesticides, and to losses, such as the removal of metals in har-vested plant material, leaching, erosion and volatilisation.

Whatever their sources, toxic elements can and do reach the soil, where they become part of thelife cycle of soil ® plant, animal ® human (Figure 2). Unfortunately, once the elements becomepart 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

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

40

– Eliseina; Kremikovtzi company; Mining company “Asarel – Medet” (Table 1) (Ministry ofEnvironment,1979a). The data presented in Table 1 show that heavy metal contaminated soilsare quite a common and widespread in industrialized regions of Bulgaria, especially around themetallurgy plants. More than 35 years of unrestricted environmental pollution with heavy metalsfrom mining and metallurgical activity have resulted in a contamination of approximately 200000 decares with Cu, Pb, Zn, Cd and As.

Industrialproducts,burned fuel,fertilizers,pesticides

Air

Soil

Water

Rocks inearth crust

Birds

Domesticanimals

Fish

Plants Humans

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

Region Living place Conta-Minatedareas,

DecaresElementcontaminatedsoils

Source ofcontamination

Total Including over 2times 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 Zincplant

Shiroko pole 2700 1000 “ “

Vishegrad 1000 500 “ “

Tcherna skala 1000 500 “ “

Sedlovina 2000 1000 “ “

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

41

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

OstrovitzaAnd another14 villages

3500 2000 “ “

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 andanother 4villages

14977 7306 “ “

Sofia town Total 11689 3314 - -

Buhovo 2690 2217 Pb Kremikovtzicompany

Jelava 1090 - “ “

Kremikovzi 963 870 “ “

Seslavtzi 1944 - “ “

GorniBogrov 1564 202 “ “

Dolni Bogrov 357 - “ “

Jana 2893 25 “ “

Botunez 119 - Pb “

Chelopechene 69 - “ “

Sofia-district

Total 47400 11000 - -

Pirdop 15000 5000 Cu, As UMPC –Pirdop

Zlatiza 12000 4000 “ “

Anton 6000 2000 “ “

Chelopech 5000 - “ “

Dushantzi andanother 4villages

1500 -

- Cu, As Pb

Kremikovtzicompany

Total forthe country

193581 64542 - -

42

Having established that an area of soils is contaminated, it is necessary to make a decision aboutthe action that needs to be taken in order to avoid unnecessary risk of health effects or of damageto 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 interpretationof contaminated land are given in Tables 2 and 3 (Ministry of Environment, 1979; 1997).

3. Remediation of contaminated land

Once an area of land has been identified as been contaminated, it becomes necessary to decidewhat action ought to be taken with regard to restrictions on its use and, or, requirements for theamelioration or “clean-up” of the soil. There are several options available for the remediation ofcontaminated 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 ofthe appropriate options and the regulations which apply in the country or region where the site islocated. The remediation options can vary from the minimum of reducing the bioavailability ofthe contaminants, to the maximum of either complete clean-up of the soil or its removal from thesite. 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 casesof low and medium pollution of agricultural lands with heavy metals, a wide spread situation inBulgaria around the heavy industry plants, the only possible remediation technology seems to bephytoremediation. Phytoremediation is a new emerging technology, which uses the ability ofspecially selected higher terrestrial plants, called hyperaccumulators to extract and accumulateconsiderable amounts of heavy metals from polluted soil and water sites (Salt et al., 1995;

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

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Simeonov,1997; Simeonov et al., 1999; Simeonova and Simeonov, 1997;, The hyperaccumulatorsextract with their root system toxic elements from the soil and translocated them to the shoottissues 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 soilfor further processing (ex-citu), or the application of in-citu technologies, which are mainlychemical, 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 ordersof magnitude less, than the cost, related to physicochemical technologies), aesthetic (soil nonde-structive and public accepted) and technical (a relatively low-tech method) advantages overtraditional 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 dryweight for Cd, > 1000 mg/kg for Ni, Cu, Co and Pb,> 10000 mg/kg for Zn and Mn. The numberof plants, reported in the literature and classified as hyperaccumulators is nearly 400 species. Niis 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 metalscontaminated soil: it is a time-consuming process, which makes it economically suitable forsoils, contaminated at medium and low concentrations; - the process is strongly dependent onthe 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 growthrequirements and characteristics in respect to European climate; - the process of phytoremediationdepends greatly on the metal availability in soil. Only free metal ions and partially the solublemetal complexes are readily subjected to phytoremediation. Some increase of the bioavailablepart of the metal content could be achieved by changing the pH level, by the application ofspecial chelation agents and changing the fertilizers to exploit the metal competition in asolutionor 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 connectionwith 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 – Plovdivand information about current contamination with heavy metals of the soil around this plantsand it remediation are presented and discussed.

UMPC – PirdopThe company is situated in the Zlatitsa – Pirdop valley. It is the biggest non-ferrous productionplant in Bulgaria.The environmental problems, which are a result of the plant activity up to the privatization, canbe summarized in the following order:

– An influence over the atmospheric air in the region caused by organized sources ofSO

2 and production dust;

44

– An influence over the surface waters in the region caused by the copper producingactivity;

– An influence over the soils and underground waters as a result of the uncoordinatedstorage of production and harmful waste materials.

After the problems had been considered and analysed Compliance program for their solutionwere 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 ofheavy 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 theindustrial contamination of the soils is due to several main sources. There is also a hypothesisfor pedogenic (lithogenic) reasons for the increased concentration of heavy metals and arsenic inZlatitsa – Pirdop hollow. A new field and analytical investigations on the soils and interpretationof 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 isin 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 ofspies, 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 whenthose 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 characterof 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), phitotoxicitycaused 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 designof a melioration activity, related to immobilization of the contaminators and neutralization of theharmful acidity.

Kremikovtzi Corp.Kremikovtzi Corp. is the greatest industrial enterprise in Bulgaria, situated at about 17 kms fromSofia with over 35 years of production activities. Kremikovtzi Corp. is an enterprise with com-

45

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, KremikovtziCorp. presents a serious contamination of environment as a whole. From the productive activityof Kremikovtzi Corp., significant quantities of dust, SO

2, NO

x, CO, CO

2, H

2S, HCN, heavy

metal etc. are emitted. The general quantity of the dust emission in the atmosphere for 1997 is 38054 tons. The serious environmental problem, that cannot be easily solved, is the heavy-metalcontamination of the soil. More, than three decades of unrestricted environmental pollution withheavy metals have resulted in a contamination of hundreds of hectares of originally very rich soilto 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 ofPb, Mn, As and Cd. Higher concentration is observed in Jana and another areas, depending ondistribution of dust, aerosols, water and wastes emission. Heavy metals in Sofia-field are reachedsignificant 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.

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. Soilsamples were collected at the depths 0 – 10 and 10 – 25 cm before and after the harvest ofdecorative low-height sunflower possessing big and rich root system. The process of extractionof the metals was monitored by AAS and semi-quantitatively by a mass analyses of accumulatordepots by laser mass-spectrometry Simeonov (1999), Simeonov and Managadze (1999), Simeonovet al. (1996).The experimental materials show that the phytoremediation process could be completed in a fewdays. This outlines the rate of amendment application and the chemical manipulation of the soilfor 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 – PlovdivThe 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 stronglycontaminated with heavy metals – mainly Zn, Pb, Cd in less extent – Cu. The contaminationwith Cu is mainly due to the situated nearby plant “Agria” for pesticides production.

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 -

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

46

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 aroundthe plant is divided in three zones: I – up to 1000 m, II – from 1000 to 3000 m, III – from 3 to 15km. In table 5 are presented average heavy metal content in soil.

There are suggestions of what kind of plants may be grown in each of these zones in order to usethe 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 improvementson the impact and pollution of the environment, a project is developed which realization isexpected to become reality in the end of 2003. In this project, there are proposed two trends formodernization, 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 harmfulsubstances in the waste gases from the “N.F.M.Works” Co., and an essential improvement of thequality of the air in the region will be reached. From this, it should be expected a positiveinfluence of the realization of the project, on the whole chain of anthropogenic influence on theway of the air upon the rest compounds of the environment – soils, plantation, livestock, healthstatus of the population in the region.

5. Conclusion

The biggest areas for heavy metals pollution of agricultural land in Bulgaria are in connectionwith industrial activities and are situated around the metallurgy plants. Some environmentalproblems 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 heavymetals have resulted in a contamination of hundreds of hectares of very rich soil to values overpermissible levels for Cd, Pb, Mn, Zn, As.There are suggestions of what kind of plants may be grown in different contaminated regions inorder to use the land properly and ecologically sound agricultural production. A new method forphytoextraction of heavy metal from soil are presented and discussed.

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

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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 theKremikovtzi Region, Bulgaria. In Strategies to improve Occupational and Environmental Health in Central andEastern 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 HeavyMetals 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 InSc. 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 thePirdop 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 massanalyser 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 wabrigerLosungen 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.

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CHEMICAL ACCIDENTS – ORGANIZATION OF THEPROTECTION, MEANS AND METHODS FORMITIGATION OF THE CONSEQUENCES

SVETOSLAV ANDONOVCivil Protection Agency of the Republic of Bulgaria

Chemical accidents in our industry are not a rare phenomenon in present days, but it is necessaryto 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 theirtransportation 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 coupleof days to a couple of months) and durable (from a couple of months to a couple ofyears)

- according to the type of the effects from the accident – Is there or not influence onother 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 theplant, 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 10years are not registered.Typical are accidents inside the plants with one or two victims due to the non-observance of thesafety 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 (whichincludes experts from regional commissions for protection of the population in natural disastersand accidents) in that range have contributed to a great extent such tragically accidents in ourindustry to be avoided.Undivided attention was paid to the plants which were stopped their manufacture for a shortperiod or a long time and there could have happened strong accidents due to the reducing of thenecessary safety measures.In defined conditions (thermo-electric power-station – Plovdiv north) were happened and couldhave 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

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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 dangerousgoods.

A) ROAD – TRANSPORT INCIDENTS

The first such a serious incident happened on 12 October 1992 at approximately 5 km from thetown of Slivnitza on the highway. Where in a collision with a car, a truck with a trailer – Greekregistration plates had an accident. The truck was transporting cyanides and a little quantity ofbarium chloride and after the collision the freight was spilled out on both sides of the road atapproximately 15 000 sq.m. This incident happened near the drinkable water sources located onthis territory and it was a danger of contamination of the water to Slivnitza, nearby settlementsand 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 thesurface ground layer of land was taken out (approximately 10-15 sm deep) and was stored undera shelter at the nearby airdrome of the agricultural aviation until their processing into non-toxicsubstances. After inactivation of the cyanides the soil was transported and stored in Kremikovtzifactory – village Musachevo.After the accident near Slivnitsa there were other road-transport incidents such as – with tankstransporting sulphuric acid – village Bulgarski Izvor and town Iablanitsa, Lovech district; withdiluents 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 toKremikovtzi. 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 withtank transporting akril-nythril to Macedonia, but in this case any negative consequences wereavoided.All of this described above made necessary to held a workshop on the problem which to includerepresentatives from all legally involved authorities. Unfortunately, there were not deputies fromthe 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 thatworkshop achieved its aim to build up an organization and to organize a cooperation betweenthe 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 ofapplicability and a new license of the tanks transporting dangerous freights. It does not make anysense, time for checking up of a new tanks (at 10 years) and the old once (at 25 years) to be in 4years. Independently from the guaranties, inside layers of the tanks getting old and with theyears that checking up have to be done as frequently as the tank gets older. The last such anincident in Sofia shows that the tank was checked up two years ago and had a license of transportfor 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 thelevel 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 pillowsand after that pouring into another vessel or emergency transportation back to theproducer or to the customer.

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3. When the leakage is on the bottom part of the tank, on a big area, and it is notpossible to seal it, it is necessary to pour over the tank with a water to reduce theemissions of dangerous gases in the air and deacidify of spilled quantity of acid onthe ground. If the leakage allows to be caught with another devices such as rubbergloves and so on, the liquid is being poured into vessels and then being transportedinto tanks allowing its stocking and transportation.

Another big accident was the incident in Thermo-electric power-station – Sofia where due to afailure 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 asabout 100 t was realized out side of the area of the Station and during the night passed by thePurifying – 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 riverwas contaminated with mazut from Kurilo to Mezdra, where a floating boom was built to catchthe spilled under surface mazut. At that time due to the weather conditions ( it was raining) a partof mazut spots was broken to a small pieces and one part of the pieces stuck durable on a plasticgarbage floating in the river and the other part left on a bottom of the river as only 5-10 % of thespilled mazut was caught from the floating boom.It was also established that partially charged fragments were floating in the middle of the riverand 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 societiesa 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 Maritzariver. 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 40decares) 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, NikolaKozlevo village in Hisaria municipality of the Plovdid district).Some measures were undertaken with delay. In that activities took part Ministry of Environmentand Waters, State Agency for Civil Protection, Ministry of Internal affairs and local authoritieswhich 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 inrepaired and guarded stockhouses. About 1300 tons are still waiting for some measures to betaken 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 factthat 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 anyinfluence 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 bymeans of the European Community projects.

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4. At the moment the departmental commission inspects and proposes based on ap-proved regulations the funding of projects for stockpiling of pesticides. The resourcesfor improving the stockpiling are subject of the funds of the Ministry of agricultureand forests.

5. The way of stockpiling the pesticides in BB cubes creates favorable conditions forthe safety for many years. A problem is arising for their further inactivation aspesticides are mixed with inert substances – zeolites and the inactivation may bedifficult.

6. There are trials of different firms and organizations to present to the authorities ofthe Ministry of Environment and Waters and Ministry of Agriculture and Forestsincompetent and dangerous projects for burning of the pesticides (such a projectwas 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 chlorinecontaining pesticides (DDT and hexochlorone) were exported for destruction.These were probably purified and redirected for use in a country where they arenot 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 underleasing 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 iscreated 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-bedbetween railway stations. In that case the access to the place of accident is very difficult. Othercomplicated situation is on the stock stations sites, where a lot of railways are present and thusthe 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 withpropane-butane.What we have done by now to improve the protection of the population and all activities formitigation of accidents involving dangerous chemical substances?

1. With the update of the National Emergency Plan an organization for the populationnotification 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 technicalmeans, 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. Thereis not a system established for training, retraining and qualification of specialistsin that matter.

4. The legislative basis regulating precisely all relationships between bodies acting incase of chemical accidents is missing. Legislative process in that matter is veryslow. Responsibilities are not clearly distributed . No warehouses for dangerouswaste are designated. No methodologies for destruction of dangerous substances

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are developed. Ministry of environment and waters has no clear position on thatsubject, which is bad for the resolving of the problem.

5. Still unresolved is the problem with recovery of the damages in mitigation anaccident and following regressive demands.

6. Two months ago the Government provided 2.5 millions of levs in order to improvethe 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 ofthe rescue teams.

7. Indicating tubes sets were distributed to all the Civil Protection Directorates in thecountry, in order to be able to identify and determine concentrations of industrialpoisonous substances.

Still unresolved are the problems of escorting dangerous goods and the implementation of anautomated system for survey of their movement.Concerning prevention of the transport risk by now only one decision of high level is taken – theroad-bed and the order of transportation of acrylonitril is determined from the town of Bourgasto 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 avoidedof any large scale accident with irremediable consequences from road accident in the city ofSofia.Another problem is that customs and road police officers are not enough aware about dangerousgoods characteristics and first measures to intervene in case of road accidents followed by spillor spread of dangerous goods over the road or the ditch where it is important to take into accountif the accident is close to water flow (river, channels), in case of rain or snow. Private transportcompanies 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 topaid to the training of specialists, training for response, preventive work, implementation of thetechnical requirements on the safe work with dangerous goods, compulsory licensing of thepeople 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 onprotection from dangerous substances. And one has to take into account that these specialistmay 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 theconsequences from chemical accidents with protection of the personnel and the population.

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BULGARIAN LEGISLATIVE FRAME FOR PREVENTING WATERPOLLUTION BY CHEMICALS

VESKA KAMBOUROVANational 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 fortransmission 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 givento the transposition of the EU water directives into the national legislation. The comparativeassessment 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 fieldadopted during the last three years, with particular attention on the provisions associated withthe regulation of chemical substances in different types of water. It is aimed to outline priorityactions 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 ProtectionAct, 2002). The policy on water protection has to be based on a rationale water management atnational and river basin level with a main goal achievement of a good status of all ground andsurface 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 prohibitingand/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.

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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; thevulnerability of the ground waters. The permits for discharging have to ensure achievement ofthe 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 mostharmful 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 watersThe 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 tothe type of emission source (Regulation 6, 2000). Programs have to be developed and completeduntil 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 conditionsof industrial discharges into the sewage systems of the settlements with or without municipalWWTPs (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 theWWTP.The Regulation on issuing permits for waste water discharge and setting up individual emissionlimit values for industrial installations imposes prior authorization of discharges into surfacewaters from point sources of pollution (Regulation 10, 2001). The goal is to safeguard the projectcategory of the receiving water bodies, predefined according to their designated use. Dischargesare 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 individualemission limit values should not be less stringent to the emission limits set by regulation 6, butmight be more restrictive in order to ensure the project category of the receiving body. Theyshould 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 includingthe measures necessary to avoid and/or limit groundwater pollution by hazardous and harmfulsubstances (Regulation 1, 2000). For 106 advisable parameters (including metals, metalloids,PAHs, pesticides, chlorinated hydrocarbons, etc.) limits are set for two levels - ecological thresholdand pollution threshold, aimed to serve as indicators for the severity of contamination and takeninto consideration by issuing permits for waste water discharges into groundwater.

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I.2. Discharges from agricultural activitiesThe Regulation on protection of waters against pollution caused by nitrates from agriculturalsources 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 theconcerned water source exceeds 35 mg/l. Specific requirement is the necessity to determinevulnerable 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 bychemicals is the recently adopted Regulation concerning the authorization of plant protectionproducts (PPP), 2002. Obligatory requirement for placing on the marked and agricultural use ofPPP is that the application according to the labeling instructions should not lead to pollution ofwater environment, including ground and drinking waters.

I.3. Other linked regulationsThe Regulation on the Water Protection Zones (WPZs) around the sources used for abstractionof 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 regimeshave to be established in the WPZs according which certain activities that in long term aspectmay 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 protectionagainst pollution by easily dissipating, readily degradable and strongly sorbtive substances, andIII - 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 chemicalquality 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 andsurface 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 forhuman health and environmental risk assessment. The surveillance of hazardous and harmfulsubstances has to be performed according to the relevant Regulation 6 or Regulation 1 if surfaceor ground waters are concerned, taking into account the site specific hydrological/hydrogeologicaland/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 waterdefines 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 thewater 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 noalternative water supply exists, as well as lays down additional parameters for monitoring ifpermanent or potential pollution sources are available. Chemical parameters indicating pollu-tion (heavy metals, pesticides, PAHs, etc.) have to be determined only in waters where theirpresence is likely to exist.

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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 tapwater (Regulation 9, 2001). Maximum admissible concentrations are laid down for 26 chemicalparameters (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 watersupplies 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 waterquality 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 thefresh surface waters and coastal marine waters that are natural living environment for fishes andshellfishes (Regulation 4, 2000). The regulation does not apply to the fish breeding farms. Anumber of chemical parameters (metals and organics) have to be controlled in order to protectaquatic life and ensure consumer’s safety.The Regulation on the quality of coastal marine water defines parameters and quality objectivesaimed 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 requirementsare set for specific substances as anionactive detergents, phenols, pesticides, oil and petroleumproducts. In the areas of existing and perspective water use the discharge of untreated wastewaters, 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 naturalrunning/still fresh waters and sea water with the main goal public health protection (Regulation11, 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 otherrelevant parameters.The Regulation on the categorization of water in water bodies is under development. At presentthe 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 ofsurface 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 arealso noted (EC Decision 2455, 2001). For 27 out of 33 substances or group of substances, whichare shown to be of major concern for European waters certain legal provisions already exist. It ismatter of further assessment to clarify in which extent the recently identified water pollutants:pentabromobiphenylether, C

10-13 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 forthe Bulgarian water environment.

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

Regulation NoParameter 6 7 10 1 12 9 4 8 11 EC

IE 1 UWW2 IEP3 GW4 SW5 DW6 FW7 SeW8 BW9 PS10

Antimony x x xArsenic x x x x x x x x xBerilium x x xCadmium x x x x x x x x x hChromium x x x x x x x x xCopper x x x x x x x xCyanides x x x x x x xFluorides x x x xLead x x x x x x x x x rMercury x x x x x x x x x hNickel x x x x x x x x nNitrates x x x xSelenium x x x x xZink x x x x x x xVanadium x x xPhenols x x x x x x x xPetroleum products x x x x x x xBenzene x x x nPAH x x x hAntrazene x rNaphtalene x rVinilchloride x x x1,2-dichloroethane x x x x nDichloromethane x nPentachlorobenzene x hPentachlorophenol x x x rTetrachloroethane x xTetrachloromethane x x xTrichlorobenzene x x x rPerchlorethilene x xTrichloroethilene x x xHexachlorobenzene * x x x hHexachlorobutadiene x x hChloroform x x x nPesticides (sum/a.i.) x x x x x xAldrin * x x x xAtrazine x rDDT * x x xDieldrin * x x x xEndrin * x x xEndosulfan x rIsodrin x x xHCH x x x hSimazine x rHeptachlor * x x1 IE - industrial effluents 2 UWW - urban waste waters 3 IEP - industrial effluents 4 GW - groundwater5 SW - surface water 6 DW - drinking water 7 FW -fish and shellfish water 8 SeW - sea water9 BW -bathing water10 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

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Conclusions

Converting into the national law principles that have been operating in the EU countries forabout 30 years it is a priority task of the Bulgarian competent authorities to ensure in relativelyshort terms adequate implementation of the whole set of new water regulations. The obligationsare 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 readinessfor fulfilling their specific tasks. In order to comply with the requirements a preparatory workhave 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 theBulgarian 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.

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

PETKO VARDEV, DIMITAR DIMITROVHYGITEST Ltd. – Sofia, Bulgaria

HYGITEST Ltd. is a small enterprise with about 40 years history in the production of appliancesfor express analysis of toxic gases and vapours in the air. In far 1965 in the Research Institute ofWork 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 reagentsin 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 forImplementation of New Technologies “Progress”.Twenty years after the HYGITEST Ltd. is a small independent enterprise with stable place onthe Bulgarian market and export activities in many other countries. The manufacturing range ofHYGITEST covers colorimetric indicator tubes (detector tubes) for express analysis of toxicgases and vapours in the ambient and workplace air, adsorbent sampling tubes for instrumentalanalysis, 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 thevariety 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 andGastec 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 worldtendency of rapid increase of variety of types. After a certain fall in the production during theperiod 1970 – 1979 due to the organizational problems, a rapid increase in volume and variety oftypes 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 determinationof 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 theoperating 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 ofworkers personal exposure, determination of gas components in liquids, etc. A feature worthmentioning is that the data on the substance is determined instantly on the spot.

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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 contentis isolated from the environment. Before analysis, the tips of the tube are broken and the tube isinserted in the special sampling pump.In the presence of the substance to-be-analysed, the reagent system in the tube changes its colourand the length of the discoloration is directly proportional to the concentration of the substancedetermined. The concentration is read directly on the scale, printed on the outside surface of theindicator tube.This method for determination is very quick, easy and cheap. Before use the glass tube has to bebroken off on both sides and placed in the sampling pump. In the presence of the analysedsubstance the tube colour changes and the length of discoloration is directly dependent on therespective concentration of the substance.

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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 inexhaled 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 contactwith alcohol vapours.The tube is opened in both welded ends using the file and then breaking off. The mouthpiece hasto 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 themeasuring bag, until the latter is completely full. The duration of blowing has to be between 30and 40 seconds.

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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 layerbeyond 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 – at0.5 ‰ and at 1.2 ‰.The result from the sample shows the alcohol content in the exhaled air at the moment and isvalid only at the moment of sampling.The packing contains 10 pieces hermetically welded test tubes, 10 mouthpieces, file for cuttingboth 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 lowflow 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 systemsand common tube holding systems.The tubes are delivered in plastic or paper boxes. The boxes contain 10 tubes each and arepacked five boxes per carton (sold in 50-tube quantities). Each tube comes with a pair of endcaps for sealing after sampling. The figures below show typical shapes of HYGITEST sorbenttubes.

CHARCOAL (COCONUT BASED) 70 x 6 mm100/50 mg sorbent, 2 sections

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Typically each tube is divided into two adsorbent sections. The first section is twice the size ofthe back section and will collect the compounds of interest. The second section is a backupsection 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 resistbreakage. These boxes secure tubes during transport, storage and day-to-day handling, alloweasy labeling and organizing of test samples, protect against damaging light and U.V. rays. Eachsingle box snaps shut to protect any sampled and unused tubes. Boxes contain 10 tubes each andare packed five boxes per carton (sold in 50-tube quantities). Each box of 10 tubes comes with10 pairs of end caps for sealing after sampling.The production of HYGITEST Ltd. includes also low flow rate and high flow rate air samplingpumps for particulate matter and gases, accessories for sampling, production of spot tests fortoxic aerosols, precise flow meter (electronic bubble meters) etc.

CHARCOAL (COCONUT BASED) 110 x 8 mm400/200 mg sorbent, 2 sections

CHARCOAL (COCONUT BASED) 110x10 mm800/200 mg sorbent, 2 sections

SILICA GEL 70x6 mm150/75 mg sorbent, 2 sections

SILICA GEL 110x8 mm520/260 mg sorbent, 2 sections

TENAX 70x6 mm30/15 mg sorbent, 2 sections

TENAX 110x8 mm100/50 mg sorbent, 2 sectio

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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 marketstill for about 25 years. The products are well received, useful, at accessible prices, comparablewith the competitive products from other producers.The HYGITEST Ltd. is in the procedure for becoming a Certificate of quality according to ISO9001:2000. The evidence for the quality of production are also the stable relations to the clientsin USA, Italy, Spain, Israel, Russia, Hungary, Romania, Macedonia, Czech republic etc.In conclusion HYGITEST Ltd. with his experience, good working tradition and well-organizeddistribution 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 morecomplicated and expensive instrumentation and methods. Both possibilities make for more flex-ible and effective assessment and management of the chemical risk in working and ambientarea.

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Eng Svetoslav AndonovDeputy Director, Civil Protection Agencyof the Republic of Bulgaria30, N. Gabrovski Str.Sofia 1172BulgariaTel.: +359 2 96010328E-mail: [email protected]

Dr Ivan BenchevComplex Lulin 5Block 508 vhodA, Apart.31SofiaBulgariaTel.+359 2 5812 525Fax: +359 2 954 1277

Dr Raj ChhabraNational Institute ofEnvironmental Health SciencesPO Box 12233Research Triangle ParkNorth Carolina 27709USATel.: +1 919 541 3386Fax: +1 919-541 4704E-mail: [email protected]

Dr Christopher De RosaAgency for Toxic Substance andDisease Registry (ATSDR)Centres for Disease ControlAtlanta, Georgia 30333USATel.: +1 404 498 0160Fax: +1 404 498 0094E-mail: [email protected]

Ms Ioana ChristovaExecutive Environment AgencyMinistry of Environment and WaterBul Tzar Boris III, 136Sofia 1618BulgariaTel.: +359 2 940 64 66Fax: +359 2 955 9011

LIST OF PARTICIPANTS

Eng Dimitar DimitrovDirector, SE HYGITEST LTD15 Dimitar Nestorov Blvd.Sofia 1431BulgariaTel.: +359 2 595026Fax: +359 2 594097E-mail: [email protected]

Dr Stuard DobsonCentre for Ecology and HydrologyMonks Wood, Abbots Ripton,Huntingdon, Cambridgeshire, PE28 2LSUnited KingdomTel.: +44 1487 772 494Fax: +44 1487 773 467E-mail: [email protected]

Dr Gyula DuraProfessor, Head, Environmental HealthNational Institute of Environmental Health ofJózsef FodorGyáli út 2-6, Budapest 1097HungaryTel.: +361 218 3158Fax: +361 215 0148E-mail: [email protected]

Dr Lawrence Fishbein4320 Ashford LaneFairfax, Virginia 22032USATel.: +703 764 5232Fax:+703 764 7281E-mail: [email protected]

Dr Herman GibbNational Center for Environmental AssessmentUS Environmental Protection Agency (8601D)Ariel Rios Building1200 Pennsylvania AvenueN.W., Washington, DC 20460USATel.: +1 202 564 3334Fax: +1 202 565 0059E-mail: [email protected]

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Dr Ivan GrancharovProfessor, Head,Department of Inorganic Chemical TechnologyUniversity of Chemical Technology andMetallurgy8, Kliment Ohridski Blvd.Sofia 1756BulgariaTel.: +359 2 76 53 13

Dr Rolf F. HertelFederal Institute of Risk AssessmentFG-82, BGVVThielallee 88-9214195 BerlinGermanyTel.: +49 30 8412 3931Fax: +49 30 8412 3003E-mail: [email protected]

Dr Paul HoweCentre for Ecology and HydrologyMonks Wood, Abbots Ripton,Huntingdon, Cambridgeshire, PE28 2LSUnited KingdomTel.: +44 1487 772 499Fax: +44 1487 773 467E-mail: [email protected]

Dr Susumu IshimitsuDivision of Safety Information on Drug,Food and ChemicalsNational Institute of Hygienic Sciences1-18-1 Kamiyoga, Setagaya-kuTokyo 158-8591JapanTel.: +813 3700 9548Fax: +813 5717 7180E-mail: [email protected]

Dr Veska KambourovaNational Center of Hygiene,Medical Ecology and Nutrition15, Dimitar Nestorov Blvd.Sofia 1431BulgariaTel.: +359 2 5812643Fax: +359 2 954 1277E-mail: [email protected]

Dr Debabrata KanungoCentral Insecticides BoardDirectorate of Plant Protection,Quarantine & StorageMinistry of AgricultureGovernment of IndiaNH IV, Faridabad-121 001HaryanaIndiaTel.: 91-129-241 2049(O)91-129-237 0094E-mail: [email protected]

Dr Janet KielhornFraunhofer InstituteNikolai-Fuchs-Strasse 1D-30625 HannoverGermanyTel.: +49 511 5350 329Fax: +49 511 5350 335E-mail: [email protected]

Dr Ivan KokalovTrade Union “KNSB” (NGO)SofiaBulgariaTel.: +359 2 9170445E-mail: [email protected]

Ms Ekaterina KrastevaNational Agency for Plant ProtectionMinistry of AgricultureSofiaBulgariaTel.: +3592 9533345E-mail: [email protected]

Mr Plamen LazarovDirector,National Agency for Plant ProtectionMinistry of AgricultureSofiaBulgariaTel.: +359 2 9533370E-mail: [email protected]

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Dr Takeshi MoritaSenior ResearcherDivision of Safety Information on Drug,Food and ChemicalsNational Institute of Hygienic Sciences1-18-1 Kamiyoga, Setagaya-kuTokyo 158-8591JapanTel.: +813 3700 9548Fax: +813 5717 7180E-mail: [email protected]

Mr Frank K. MuchiriDirectorate of OccupationalHealth and Safety ServicesP.O. Box 34120NairobiKenyaTel.: +254 3 511 138E-mail: [email protected]

Dr Bojidar NikiforovProf., PhD, DSc,National Centre of Hygiene,Medical Ecology and Nutrition (NCHMEN)15, Dimitar Nestorov Blvd.Sofia 1431BulgariaTel.: (+359 2) 9541123Fax: (+359 2) 9541277E-mail: [email protected]

Dr Larry OlsenResearch ChemistBiological Monitoring andHealth Assessment BranchDivision of Applied Research and TechnologyNIOSH Mailstop C264676 Columbia ParkwayCincinnati, OH 45226USATel.: 513-533-8594Fax: 513-533-8494E-mail: [email protected]

Dr Siyka PopovaAssoc ProfUniv. of Chemical Technology and Metallurgy8, Kliment Ohridski Blvd.Sofia 1756BulgariaTel.: +359 2 765313

Dr Nikolai RizovAssoc Prof, Director,National Center of Hygiene,Medical Ecology and Nutrition15, Dimitar Nestorov Blvd.Sofia 1431BulgariaTel.: +359 2 954 1300Fax: +359 2 954 1277E-mail: [email protected]

Dr Jun SekizawaProfessorFaculty of Integrated Arts and SciencesTokushima University1-1 Minami-josanjimaTokushima 770-8502JapanFax/Tel.: +8188 656 7263E-mail: [email protected]

Dr Fina SimeonovaProfessorBoul. Zarigradsko shosse 4a, block 2aSofia 1113BulgariaE-mail: [email protected]

Dr Salah SolimanAlexandria UniversityFaculty of AgricultureEl ShatbyAlexandria 21545EgyptTel.: +203 592 0067Fax: +203 481 7232E-mail: [email protected]

Dr Jennifer StauberCSIRO Energy TechnologyCentre for Advanced Analytical ChemistryPrivate Mail Bag 7Bangor, NSW 2234AustraliaTel.: +61 2 9710 6808Fax: +61 2 9710 6837E-mail: [email protected]

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Eng Petko VardevSE HYGITEST LTD.15, Dimitar Nestorov Blvd.Sofia 1431BulgariaTel.: +359 2 595026Fax: +359 2 594097E-mail: [email protected]

Dr Peter WattsToxicology Advice & Consulting Ltd.Westmead House, Westmead RoadSurrey SM1 4JHUKTel.: + 44 208 722 4701Fax: + 44 208 770 0544E-mail: [email protected]

Dr Deborah WillcocksGPO Box 58Sydney,NSW 2001AustraliaTel.: +61 2 8577 8890Fax: +61 2 8577 8888E-mail: [email protected]

Dr Kyriakoula Ziegler-SkylakakisEuropean CommissionDG Employment & Social AffairsRue Alcide de Gasperi2920 LuxembourgTel.: +352 4301 34424Fax: +352 4301 43259E-mail: [email protected]

Secretariat

Dr Antero AitioInternational Programme on Chemical SafetyWorld Health Organization20 Avenue Appia1211 Genève 27SwitzerlandTel.: + 41 22 791 3592Fax: +41 22 791 4848E-mail: [email protected]

Mr Teruyoshi EharaInternational Programme on Chemical SafetyWorld Health Organization20 Avenue Appia1211 Genève 27SwitzerlandTel.: + 41 22 791 4334Fax: +41 22 791 4848E-mail: [email protected]