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Boreal Environment Research L66 I 9 0 N HdV1DONOV1 BOREAL ENVIRONMENT RESEARCH The Boreal Environment Research is a new journal EDITORIAL BOARD published by seven Finnish organisations: the Finnish Environment Institute, the Finnish Game and Fisheries Dr. Sylvain Joffre, Finnish Meteorological Institute Research Institute, the Finnish Institute of Marine Re Dr. Juha Kamäri (Chairmain in 1996), search, the Finnish Meteorological Institute, the Air Finnish Environment Institute Pollution Prevention Association, the Finnish Limno Dr. Harri Kuosa, Finnish Institute of Marine logical Society and the Finnish Water Association. Research The journal is published quarterly, and in addition, Dr. Kari Larjava, Technical Research Centre, monographs can be published quarterly, and in addi Finland tion, monographs can be published irregularly in a Prof. Hannu Lehtonen, University of Helsinki subsidiary series Monographs of the Boreal Environ Dr. Goran Nordlund, Finnish Meteorological ment Research. Institute Dr. Martti Rask (Chairman in 1997), Finnish Game SCOPE OF THE JOURNAL and Fisheries Research Institute Dr. Kari Ruohonen, Finnish Game and Fisheries Boreal Environment Research is an international Research Institute interdisciplinary journal publishing original articles, Dr. Perth Seuna, Finnish Environment Institute reviews and short commentaries devoted to studies of various aspects of the boreal environment and its natu ral resources in particular on environmental problems, EDITORIAL OFFICE their assessment, understanding and management, as well as on the sustainable use of natural resources in Finnish Zoological and Botanical the fields of atmospheric, terrestrial, aquatic, marine Publishing Board, and fisheries sciences. P.O. Box 17 Borealis interpreted in a wide sense, i.a. including FIN-00014 Helsinki, Finland polar, subpolar and northern temperate conditions, biomes or ecosystems. The journal is a forum for em phasizing a holistic approach to environmental sci SUBMISSION OF MANUSCRIPTS ences, linking pressures via sources of pollution to the occurring in the various media. Articles dealing with Four copies of the manuscript are to be sent directly to monitoring, experimental, theoretical and modelling the appropriate Editor-in-Chief. Manuscripts related studies as well as their combination are all welcome. to aquatic, marine and fisheries sciences to Prof. Han nu Lehtonen, and those related to atmospheric and ter EDITORS-IN-CHIEF restrial sciences to Dr. Sylvain Joffre. Indicate clearly to whom the correspondence should be sent, and in Prof. Hannu Lehtonen clude the telefax number and, when available, the e Department of Limnology mail address. On a separate sheet, submit a list of four P.O. Box 27 qualified and unbiased referees with complete names FIN-00014 University of Helsinki, Finland and addresses. Dr. Sylvain Joffre SUBSCRIPTIONS Finnish Meteorological Institute P.O. Box 503 The journal is issued to form an annual volume of four FIN-00101 Helsinki, Finland numbers. The subscription fee is FIM 200 for indivi dual persons and FIM 500 for institutions. MONOGRAPHS OF THE BOREAL ENVIRONMENT RESEARCH 6 Harri Kankaanpaa Sedimentation, distribution, sources and properties of organic halogen material in the Gulf of Finland FINNISH INSTITUTE OF MARINE RESEARCH, FINLAND Helsinki 1997 ISSN 1239-1875 ISBN 952-11-0152-0 Hakapaino Oy, Helsinki 1997 Sedimentation, distribution, sources and properties of organic halogen material in the Gulf of Finland Harri Kankaanpaa Academic dissertation in Organic Chemistry, to be presented, with the permission of the Faculty of Science of the University of Helsinki, for public criticism in the Auditorium AllO of the Department of Chemistry, A. I. Virtasen aukio 1, Helsinki, on October 25th 1997 at 12 o’clock noon. As clear as mud Contents List of original publications .7 List of abbreviations 8 Introduction 13 2 Review of the literature 14 2.1 Characteristics of the study area 14 2.1.1 Characteristics of sedimentation 16 2.2 Pollution in the Gulf of Finland 18 2.2.1 Anthropogenic organochlorines 19 2.2.1.1 Chemical character of BKME 20 2.2.2 Natural organohalogens in the marine environment 21 2.3 Use of sum parameters in the Baltic Sea 22 2.4 Harmful effects of pulp mill effluents to marine organisms 24 3 Aimsofthestudy 25 4 Materials and methods 25 4.1 Collection of material 25 4.1.1 Positioning accuracy, ship stability and co-ordinates 25 4.1.2 Baltic sediment and marine fauna 26 4.1.3 Settling material 26 4.1.4 Antarctic sediments, plankton and fauna 26 4.1.5 Collection of water samples and BKME 26 4.1.6 Other material used for chemical analyses 27 4.2 Pre-treatment of sediments 27 4.2.1 Determination of <63 lIm fraction 27 4.2.2 Drying and homogenisation 27 4.3 Aquarium system for investigating effects of BKME on M. affinis 27 4.4 Chemical analyses 27 4.4.1 The AOX sediment procedure and its validation 27 4.4.2 Preparation of water samples for AOX determination 28 4.4.3 BOX extraction and method validation 28 4.4.4 Microcoulometric detection of halogens 29 4.4.5 NAA detection of halogens 29 4.4.6 Determination of chiorophenolics, PCBs and OCPs 29 4.4.7 Determination of TC 30 4.4.8 Recording of UV-VIS spectra 30 4.4.9 RP-HPLC analysis 30 4.4.10 SEC-HPLC analysis 30 4.4.11 TLC separation 30 4.4.12 Mass spectrometric methods 30 4.4.13 NMR analyses 31 4.5 Estimation of rate of sedimentation 31 4.5.1 Detection of 37Cs and calculation of sedimentation rates 31 4.5.2 Sedimentation rates from sediment trap experiments 31 4.5.3 Calculation of total EOX for the Gulf of Finland 31 5 iVbUIL 5.1 Validity of results 32 5.2 EOX concentrations in different matrices 33 5.3 Areal distribution of AOX and EOX 34 5.4 Vertical distribution of EOX 37 5.5 Sedimentation according to sediment trap studies and the ‘37Cs method 39 5.6 Chemical characterizations 40 5.7 Aquarium experiments and effects of BKME on M. affinis 46 6 J,uatuaanunn 46 6.1 Applicability and reliability of the methods 46 6.2 Polluted areas and transport of pollutants 48 6.2.1 The Kotka-Kymi river area 48 6.2.1.1 Adverse effects of pulp mill effluents 49 6.3 Evidence of extensive natural organohalogen production 50 6.3.1 Presence of halogens in all matrices 50 6.3.2 Seasonal sedimentation of EOX 51 6.3.3 Sedimentation and total quantities of organic halogen in sediments 51 6.3.4 Possible causes of vertical EOX distribution in non-polluted sediments 52 6.3.5 The chemical character of EOX 53 6.3.6 Role of chlorophyll RC I 55 6.3.7 Other possible explanations’ 55 6.4 Monitoring and recommendations 56 7 Conclusions References., Appendix 1 Appendix 2 Sedimentation, distribution, sources and properties of organic ... 7 List of original publications This thesis is based on the following original papers, which are referred to in the text by their respective Roman numerals: I Kankaanpaa H. & Masuku C. P. 1992. Adsorbable organic halogen compounds (AOX): determination in sea sediments. Chemosphere 24: 1331-1345. II Kankaanpia H. & Tissari 3. 1 994a. Background levels of EOX and AOX in the sediments of the Gulf of Finland - molecular weight distribution of BOX in the sediments. Chemosphere 28 (1): 99-116. III Kankaanpäa H. & Tissari 3. l994b: Analysis for BOX and AOX in two industry influenced coastal areas in the Gulf of Finland. Levels of BOX and AOX in the Kotka region, Finland. Levels of BOX in the Neva Bay, Russia. Chemosphere 29 (2): 241-255. IV Kankaanpaa H., Lauren M., Mattson M. & Lindstrbm M. 1995. Effects of bleached kraft mill effluents on the swimming activity of Monoporcia affinis (Crustacea, Amphipoda) Lindstrom. Chemosphere 31(11/12): 4455-4473. V Kankaanpaa H., Lauren M., Saarcs R., Heitto L. & Suursaar U. 1997. Distribution of halogenated organic material from anthropogenic and natural sources in the Gulf of Finland catchment area. Environmental Science and Technology 31(1): 96-104. VI Kankaanpaa H., Vallius H., Sandman 0. & Nicmistö L. 1997. Determination of recent sedimentation in the Gulf of Finland using ‘37Cs in the Gulf of Finland. Oceanologica Acta 20, in press. VII Kankaanpaa H., Korhonen M., Suortti A. -M. & Heiskanen A. -S. Seasonal sedimentation of organic matter and contaminants in the Gulf of Finland. Accepted for publication in Boreal Environment Research. Papers Ito IV are reprinted with kind permission from Elsevicr Science Ltd, The Boulevard, Langford Lane, Kidlington, 0X5 1GB, UK. Paper V is reprinted, with permission, from Kankaanpaii, H., Lauren, M., Saares, R., Heitto, L. and Suursaar, U. 1997. Distribution of Halogenated Organic Material in Sediments from Anthropogenic and Natural Sources in the Gulf of Finland Catchmcnt Area. Environmental Science & Technology 31(1): 96-104. Copyright American Chemical Society. Paper VI is printed with permission from Gauthicr-Villars and paper VII with permission from the publisher of the Boreal Environment Research. Some unpublished results are also presented. Corrections to original publications Paper II, page 99, second row in abstract and page 112, third row in conclusions: 2.5 should be replaced by 6.0. Paper II, page 114: TOC % should be TOC mg g’. Paper V, page 102: dry matter sedimentation rate should be 0.51 kg m2 a1. Paper V, page 103: the annual sedimentation of BOX is 56 t. 8 Kankaanpäã Monographs of the Boreal Environment Research No. 6 The author’s contribution In paper I the author was responsible for planning and carrying out the research. Dr Christopher Masuku assisted with preparing the manuscript and correcting the English. In papers II and III the author planned the experimental set-up, made the data-processing and drafted the manuscripts. Chemical analyses were carried Out by Mr Jorma Tissari, who helped in developing new analytical methods, in interpreting the results obtained and in preparing the manuscripts.
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