Frida Book

Degree project for Master of Science 45 hec

Department of Biological and Environmental Sciences University of Gothenburg 2014

Risk assessment of mining effluents in surface water downstream the sulphide ore mine Aitik, northern Sweden

Risk assessment of mining effluents in surface water downstream the sulphide ore mine Aitik, northern Sweden Master thesis in Ecotoxicology, Master’s Program, 120 hec. Department of Biology and Environmental Science. University of Gothenburg

FRIDA BOOK Cover page: The Aitik open pit mine. Photo: Frida Book

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Preface This document comprises the master thesis of Frida Book in the field of ecotoxicology at Department of Biology and Environmental Sciences, University of Gothenburg. The project constitutes 45 credits. Supervision has been provided by Thomas Backhaus, Department of Biology and Environmental Science, University of Gothenburg. I would like to thank my supervisor and the staff working at the Swedish Agency for Marine and Water Management and the Norrbotten County Administration Board for providing me with valuable information and documents, which have been fundamental in order to conduct the study. Göteborg, 2014-11-05 Frida Book

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Abstract Mining industry in Sweden is growing and the Sweden Association of mines predicts a threefold increase in mining activities until the year of 2025. The main aim of this investigation was to evaluate current chemical and biological monitoring, controlled by the Water Framework Directive, on its ability to detect ecotoxicological impacts in mine adjacent recipients, with Aitik Europe’s largest copper mine as a basis. The present study also assessed the risk for mixture toxicity effects, which is not taken into account in today’s chemical safety limits. In order to evaluate current chemical- and biological monitoring the present report performed a status report on how the monitoring is carried out today. To conduct a status report, a literature research of directives, authority documents and regulations was performed together with a continuous communication with water authorities involved in the work with water management. Biological and chemical monitore data was collected from the Norrbotten County Administration Board. Potential risk from chemical mixtures was evaluated based on the addition of individual substances potential risk quotients. Results showed that current cocktail of substances in mine effluents has a potential risk to cause significant impacts far down in the receiving watercourses. There is also a lack of standardized biological methods specifically designed to detect effects of metals, which often are highlighted as main pollutants from mines. More knowledge on ecotoxicological effects of xanthates (collectors in flotation) in receiving waters is also required. The results emphasize the importance of additional research in the field, in order to ensure a sustainable mining development. Keywords – Mining, Chemical- and biological monitoring, Metals, Water Framework Directive, Mixture risk assessment, Xanthates

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Sammanfattning Gruvindustrin I Sverige expanderar och SveMin, branschorganisationen för gruvor, mineral och metallproducenter i Sverige förutspår en trefaldig ökning av industrin fram till 2025. Gruvutvecklingen inger hopp om tillväxt och ökade jobbtillfällen men skapar samtidigt en ökad oro för vilka miljöeffekter som kan uppstå på omgivningen. Studiens huvudsakliga mål var att utvärdera den nuvarande kemiska- och ekologiska övervakningens (som styrs av EU:s vattendirektiv) förmåga att upptäcka ekotoxikologika effekter i gruvnära vattendrag, med Aitik, Europas största koppargruva, som utgångspunkt. För att kunna utvärdera den nuvarande övervakningen genomfördes en nulägesrapport om hur övervakningen fullföljs idag. Nulägesrapporten utfördes baserat på en litteraturstudie av direktiv, myndighetsdokument och lagtexter i kombination med en kontinuerlig kommunikation med personer som på myndighetsnivå arbetar med vattenförvaltning i Sverige. Dessutom genomfördes en ekotoxikologisk riskbedömning av blandningar av ämnen i recipienter nedströms Aitikgruvan. För detta inhämtades biologisk och kemisk övervakningsdata från Länsstyrelsen i Norrbotten. Riskbedömningen av blandningar utgick ifrån att addera individuella ämnens potentiella risk-kvoter. Resultatet visade att nuvarande blandning utgör en risk för signifikanta effekter långt ner i mottagande recipienter. Det finns också en brist på biologiska standardmetoder för att detektera påverkan av metaller, som oftast framhävs som de vanligaste föroreningarna i utsläpp från gruvor. Det finns även en bristande kunskap om vilka ekotoxikologiska effekter xantater (samlarreagens i flotationsprocesser) kan medföra i närliggande vattendrag. Resultaten i studien betonar behovet av ytterligare forskning inom området, för att kunna säkerhetsställa en hållbar gruvutveckling. Nyckelord – Gruvor, Kemisk- och biologisk övervakning, Metaller, EU:s Vattendirektiv, Riskbedömning av blandingar, Xantater

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Abbreviations WFD Water Framework Directive EQSD Environmental Quality Standard Directive EQS Environemntal Quality Standard TOC Total Organic Carbon PPS Particular Pollutant Substance SEPA Swedish Environmental Protection Agency WISS Water Information System Sweden AA Annual Average MAC Maximum Accepted Concentration PAX Potassium Amyl Xanthate MB Miljöbalken (Swedish Environmental Law) NCAB Norrbotten County Administration Board PEC Predicted Environmnetal Concentration PNEC Predicted No Effect Concentration SRQ Summed Risk Quotient ECHA European Chemicals Agency ASPT Average Score Per Taxon MISA Multimetric Index for Stream Acidification ACID Acidity Index for Diatoms %PT Pollution Tolerant Valves TDI Trophic Diatom Index PICT Pollution Induced Community Tolerance

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Table of content 1 Introduction ........................................................................................................................... 7

1.1 An increasing mining industry .................................................................................................... 7 1.1.2 Environmental impacts on surface water ....................................................................... 7 1.1.3 European union protection of water ................................................................................ 7 1.1.4 Classification of chemical and ecological status ........................................................... 8 1.1.4.1 Biological quality elements ............................................................................................... 8 1.1.4.2 Physical-chemical quality elements .............................................................................. 9

1.2 Sustainable use of surface water .............................................................................................. 10 I. 1.3 Aim and objectives ........................................................................................................... 10

1.4 Scope and delineations ................................................................................................................. 10 1.5 Aitik ...................................................................................................................................................... 11

1.5.1. Short description of the production process .............................................................. 11 1.5.1.2 Water in the flotation process ....................................................................................... 12 1.5.2 Sulphide ore .............................................................................................................................. 13 1.5.3 Surrounding water area ....................................................................................................... 13 1.5.5 Protection for surface water .............................................................................................. 14

1.6 Mixture effects ................................................................................................................................. 15 1.6.1. Mixture effects of metals .................................................................................................... 15

2. Methods .............................................................................................................................. 16 2.1 Literature research and personal communication ............................................................ 16 2.2 Status report of chemical and ecological status .................................................................. 16 2.3 Mixture Risk Assessment ............................................................................................................. 16

2.3.1 Risk characterization ............................................................................................................ 16 2.3.2 Refinement in data ................................................................................................................. 17

2.4. Mapping ............................................................................................................................................. 17 6. Results ................................................................................................................................. 17

6.1 Status report of the current monitoring of chemical and ecological status in surface waters near Aitik .................................................................................................................... 17

6.1.2 Chemical monitoring ............................................................................................................. 17 6.1.3 Biological monitoring ........................................................................................................... 22

6.2 Mixture risk assessment .............................................................................................................. 25 6.2.1 Risk characterization ............................................................................................................ 25

7. Discussion ............................................................................................................................ 29 7.1 Chemical monitoring for determining good ecological- and chemical status .... 29 7.1.2 Ammonia- and nitrate nitrogen ........................................................................................ 29 7.1.3 Metals .......................................................................................................................................... 29

7.1.4 Suggestion for substances to be included in chemical monitoring .......................... 30 7.2 Risk assessment of metal mixtures .......................................................................................... 31 7.3 Biological methods for detecting metal effects ................................................................... 32

7.3.1 Suggestions for methods of improved biological monitoring on algae and benthic fauna ....................................................................................................................................... 33

7.4 Does an increasing mining industry in Sweden endanger a sustainable use of our waters? ....................................................................................................................................................... 34 7.5 Summative assessment and recommendations .................................................................. 35

8. Conclusions ......................................................................................................................... 36 References .............................................................................................................................. 37 Appendix A. Mining projects, 2013 ......................................................................................... 42

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1 Introduction

1.1 An increasing mining industry Mining industry in Sweden is growing and the driver is primarily the fast growing industry in China, India and other new industrialized countries. Deposits that earlier were not profitable to extract are today highly coveted and the Swedish Association of mines, SveMin, predicts a threefold increase in mining production until the year of 2025 (SveMin, 2012a). Large profits in combination with low taxes make Sweden an attractive country for mining. Sweden has globally one of the lowest taxes when it comes to extracting minerals. Mining companies, operating in Sweden, pay 0,05 percent of the revenues, in a mineral fee, to the state (Regeringskansliet, 2013). In 2013, Frasier Institute, ranked Sweden as the world’s number one most attractive country to conduct mining activities in, due to mining-related public policy factors such as taxation and regulation (Frasier Institute, 2013).

1.1.2 Environmental impacts on surface water A growing mining industry leads to more jobs and hopes for development in remote local areas where the population growth long has waned, but it also leads to an increased concern regarding impacts on the environment and not least on the aquatic environment. Mining entail large amounts of mine waste (Naturvårdsverket, 2010a) both waste rock from blasting and tailings from the enrichment processes. Water in contact with mine deposits often contains large amounts of pollutants such as heavy metals (Länsstyrelsen i Västerbotten, 2012). This can have devastating impacts on surrounding aquatic environments. One can find several examples of dead lakes and urgent need of remediation methods in mine adjacent recipients without having to go far back in history. Hornträsket in Västerbotten is one example of a lake, which has been strongly affected by mining industries (Länsstyrelsen i Västerbotten, 2012). Surrounding mines were closed during the 1990s but the lake has not yet recovered from the damages. Leachate with large amounts of toxic metals have continuously reached Hornträsket during the 2000s despite remediation actions (Länsstyrelsen i Västerbotten, 2012). Blaiken is another example of a mine with large effects on the water quality, due to high zinc concentrations(Naturvårdsverket, 2014). Mining and enrichment started in 2006, but because of environmental problems and inability to achieve profitability the mine was shut down in 2012. Only three million Swedish crones were left behind for after-treatment. The bill for remediation may end up on 200 million Swedish crones expected to be paid by the Swedish taxpayers(Västerbottennytt 2012-12-09). Besides from metals, mining can also emit elevated concentrations of water-soluble nitrogen compounds, e.g NO3-N and NH4-N, which originates from nitrogen-rich blasting agents (SveMin, 2012b).

1.1.3 European union protection of water Together with an expanding mineral industry Sweden is committed to follow several European Union legal acts, which control the management of water. The water framework directive (WFD) 2000/60/EG (European parliament and council, 2000) was established in 2000 and aims to establish a framework for the protection of inland surface waters. WFD

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stipulates that surface water shall achieve at least good status until the year of 2015. If that is not the case then actions must be taken. Good surface water status is classified by the ecological and chemical status, depending on which is worse (see description of classification in section 1.1.4). Good surface water status means the status achieved by a surface water body when both its ecological status and its chemical status are at least good. European water bodies can also be protected by the Habitats directive 92/43/EEC (COUNCIL, 1992) under the name Natura 2000 because of its importance to preserve and promote the biological diversity.

1.1.4 Classification of chemical and ecological status Chemical surface status can be classified with either non-good- or good status and is regulated by the WFD daughter directive on environmental quality standards 2008/105/EC (European parliament and council, 2008) (EQSD).The EQSD sets environmental quality standards for 33 priority hazardous substances plus 8 other substances. The surface water is classified as good if the measured concentration is below the EQS and bad if the concentration exceeds the EQS. Ecological status is classified into five categories; high, good, moderate, unsatisfying and bad. Ecological status is classified by different quality elements; biological, physical-chemical and hydro-morphological. Biological elements are ranked higher than the other quality factors according to the WFD. Physical-chemical quality factors only need to be taken into consideration if the biological factors show good or high status. Hydro-morphological quality factors only need to be classified if both the biological- and the physical-chemical quality factors show high or maximum potential. Chemical-physical and hydro-morphological chemical quality factors are all supporting factors for the biological status. The overall management is controlled by the concept that the worst classification determines the final status of the water body.

1.1.4.1 Biological quality elements Biological status is determined based on tests from three different trophic levels; periphyton (primary producers), benthic fauna (herbivores) and fish (predators). Biological studies have many advantages in order to reflect the ecological status in rivers in comparison to chemical monitoring. Different environmental factors can result in large fluctuations, which affect the concentration and dilution of various substances in the water. This could be due to natural fluctuations or caused by repeated emissions from e.g industries, water power stations or agriculture. Such environmental changes can make it difficult to achieve an accurate picture of the ecological condition in the watercourse, based on only physical- and chemical factors. Biological factors, in comparison with chemical- and physical factors have the advantage to reflect the condition in the water over a longer period of time, instead of an overview of a specific moment. Periphyton communities (biofilms) grow on solid substrates under the river surface and are characterized by the slippery film, which makes the cover of i.e stones, sand and leaves. Biological tests included in the ecological assessment of ecological status focus on the diatoms, which often are the dominant algae specie within the biofilm. Other organism groups except from algae are bacteria, fungus and microscopic animals (Wetzel, 1983). Periphyton communities play an important role as primary producers, especially in rivers, (Naturvårdsverket, 2009a) and posses various properties which make them suitable in

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monitoring (Stevenson et al., 1996). Biofilm communities constitute a key position in the aquatic ecosystem and have both direct and indirect affect on other species in the food web. These adherent organisms cannot escape environmental changes such as pollutants and have to adapt in order to remain. This makes them good representatives of the water, which they are situated in. Benthic fauna are small animals living on the bottom of the sea, lakes, watercourses and wetlands. These small animals are representing many different life forms and life cycles. A rich and miscellaneous benthic fauna assumes that the life cycle have not encountered any major hazards. Examples of freshwater benthic faunal groups are mayflies, caddisflies, shells, amphipods and beetles. Many of these species living at the bottom of watercourses are important nourishment for species higher up in the food chain such as fish and birds (Naturvårdsverket, 2009b). A divergence in species composition where species are totally or partially disappeared or where a few species suddenly are dominating could be an evident indicator of an impaired ecosystem, caused directly or indirectly by e.g pollution, acidification, hypoxia or turbidity. Fish has a high protection value. If effects appear on fish, this is a sign that the watercourse is severely affected. Preferably, effects should be detected at a lower trophic level. In this way, measures can be taken at an earlier stage before effects occur on fish population.

1.1.4.2 Physical-chemical quality elements Physical-chemical quality factors reflect general conditions such as nutrients, total organic carbon (TOC), Secchi depth and acidification and particular pollutant substances (PPS), which are compounds released in significant amounts.

1.1.4.3 Particular pollutant substances (PPS) Particular pollutant substances are compounds released in significant amounts. Significant amounts are by SEPA interpreted as such a quantity of a substance that may prevent that the biological status/potential are met by 2015. PPS can vary between water bodies and are derived from impact assessments based on information such as emission sources, use of pollution substances and environmental monitoring data. Water authorities have the responsibility to classify the PPS for each watercourse. Water authorities also have the responsibility to set class limits for PPS(Naturvårdsverket, 2007b). Suggested PPS limit values are given by the ITM report (ITM, 2013) written by the Institution for applied environmental science at the Stockholm university on behalf of the Swedish Environmental Protection Agency and the five national water authorities. These limit values are based on the methods and principles of the European Union Technical Guidance Document (TGD) no 27(ITM, 2013), which is a guidance document developed in order to support the derivation of EQSs for priority substances(TGD no. 27, 2011). These limit values are based upon results from laboratory toxicity tests performed with individual species exposed to single substances (ITM, 2013). Suggestions for PPS limit values can also be found in SEPA’s report 5799 (Naturvårdsverket, 2008). These limit values do not take additive or synergistic effects into account. These effects should, however, be captured by the biological quality elements (Naturvårdsverket, 2007a). Sweden is divided in five different water districts where one administrative county in each district has been designated as a water authority, responsible for the management of the surface water (Naturvårdsverket, 2007a).

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1.2 Sustainable use of surface water An overall goal with the WFD is to establish a European framework for protection of surface waters, in order to prevent deterioration and to improve the status of aquatic ecosystems. The WFD also serves the purpose to promote a sustainable use of water based on a long-term protection of available water resources. Monitoring of water chemistry and abundance and diversity of aquatic organisms is a part of the strategy to meet these objectives. Safety concentration limits for pollutants is a way of preventing key species from harmful effects. Species are a part of ecological networks, which means that if one species is significantly affected this would lead to changes for other species. Concentration limits such as for PPS and Priority substances safeguard against toxic-driven changes in species composition. The present study interprets sustainable use of surface water as a concept, with the aim to not change species composition.

1.3 Aim and objectives According to the future growing mining industry and the mines’ potential environmental effects on waters, the aim of the present investigation was to examine the environmental monitoring (controlled by the WFD) in surface waters near mines, with Aitik, Europe’s largest copper mine (Regeringskansliet, 2013), as a basis. Impacts from mines on surface water were assessed from an ecotoxicological perspective. Current biological and chemical monitoring, was evaluated with respect to their ability to describe the ecological status in recipients near mines. Uncertainties regarding the environmental impacts on surrounding recipients were highlighted followed by suggestions on how the water monitoring in these concerned waters could be improved, in order to covet at least good water status. It is important to critically review current approaches and address weaknesses so that the use of our waters does not stand in conflict with national and international agreements that Sweden is adopted to follow. It is crucial that these uncertainties are identified as early as possible in order to prevent significant adverse environmental effects from mining. In recent years there has been an increased debate regarding combination effects of chemicals. This has caught the attention of both U.S Environmental Protection Agency (EPA) and the European Commission(COM 2012-252, EPA, 2007). This has led to debates regarding if current chemical safety limits are underestimating the real effects. Studies have also shown that this could be the case (Carvalho et al., 2014, Backhaus et al., 2000, Kortenkamp et al., 2009). Based on this background, the present report performed an environmental risk assessment of chemical mixtures in streams downstream Aitik. The present study had the following aims:

• Evaluate current chemical and biological monitoring on its ability to detect ecotoxicological impacts in mine adjacent recipients

• Assess the risk for mixture toxicity effects in adjacent recipients • Suggest improvements in environmental monitoring and risk assessment approaches • Discuss the possibility of a sustainable use of surface water a long with a growing

mining industry

1.4 Scope and delineations Within the timeframe of the project the present study has restricted the chemical risk assessment to water courses near the mine Aitik, which is Sweden’s largest copper open pit

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mine. Although water management in Sweden is based on the same general manuals and regulations water management could in detail vary between mines. The current report does not include effects on groundwater. Monitoring sites, which are not registered in Water Information System Sweden (WISS), are presented with local descriptions but not illustrated in the maps, due to lack of coordinates. Addition of individual substances potential risk quotients was based on calculation of annual average (AA) concentrations except for Hg, which is represented with a maximum annual concentration (MAC) limit value, according to the EQSD directive. Fluctuations of various substances are however discussed further during data refinement. The reports focus is on ecological effects and not effects on human health.

1.5 Aitik Aitik mine, Figure 1, is situated within the County of Norrbotten, which is a center for mining activities. It is located around 15 km south east of the town Gällivare. The land area affected by the activity is estimated to approximately 38 km2. Mining of minerals in Aitik started in 1968 and is today the largest open pit mine in Sweden. The deposit contains extensive mineral resources classified as low-grade copper sulphide ore. On average the ore contains 0,24 % copper. A smaller amount of gold and silver is also extracted. The mine today has the permission to mine up to 36 billion ton ore per year. Aitik is currently applying for a permission to mine up to 45 billion ton ore per year (Boliden, 2012).

1.5.1. Short description of the production process Explosives are used in the pit in order to separate waste rock from the ore (Figure 2). Waste rock is transported to waste rock storages and the ore to a crushing plant. Crushed ore is then transported via an intermediate storage to the dressing plant. When the ore reaches the dressing plant it is grinded before entering the flotation process where it is enriched into a copper concentrate (CuFeS2). The copper concentrate is then dewatered and stored before transport to the smelter in Rönnskär, Skelleftehamn. Excess water from the enrichment process is pumped together with the finely ground waste (tailings) to the tailings pond. This sand sediments in the pond while excess water continuously flows onto the clarifications pond. Water from the clarification pond is recirculated to the enrichment process. Excess water from the clarification pond is periodically released to the recipient Leipojoki.

Figure 1. Aitik mine is situated 15 km south east of town Gällivare, County of Norrbotten. Map was created in GoogleEarth.

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1.5.1.2 Water in the flotation process Water is necessary for the enrichment process and is used in several steps. In the beginning of the enrichment process water is used to increase the efficiency of the ore grinding process. This produces finely ground sand, which automatically flows to the unit where the flotation takes place. Water is continuously used in the flotation process where the valuable mineral is separated from waste particles and formed into a mineral concentrate. Valuable mineral is separated due to differences in surface chemical properties of host mineral particles compared to other grinded particles. Surfaces of host mineral particles are naturally more hydrophobic that the non-host mineral particles. This difference in properties is utilized in order to separate valuable mineral particles from waste particles. This difference is being amplified by changing the water chemistry such as pH and addition of flotation reagents that affects the surface properties (Boliden, 2012) These hydrophobic surfaces enables adsorption to air bubbles. By blowing air into the water, valuable mineral particles are transported together with air bubbles to the surface, while waste rock settle on the bottom (Nationalencyklopedin, 2014).

1.5.1.2.1 Flotation reagents - xanthates Flotations reagents, such as xanthates, are used in the enrichment process, because of their property to form hydrophobic complexes with heavy metals (Sasaki, 1983). Xanthates are

Figure 2. Aitik production process from blasting to transportation to Rönnskär smelter.

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selectively picked depending on the ore type (European comission, 2009). The Aitik mine use potassium amyl xanthate (PAX) as a reagent in the flotation process, in order to separate valuable minerals from waste rock (Boliden, 2012). PAX (C6H11OS2K), Figure 3, also called the collector in mineral processing terms, consists of one hydrophobic (hydrocarbon group) side and one hydrophilic (ionized) side. The collector binds to the mineral particle with the hydrophobic side facing out, which makes the bubble adhesion possible (European comission, 2009). Remaining amounts of xanthate is hydrolyzed into ethanol and carbon disulfide. This reaction is slow in neutral and basic conditions and is a reaction that can extend over several months. Xanthates could therefore be released to the sand- and clarification ponds (Boliden, 2012).

Figure 3. Chemical structure of potassium amyl xanhtate. The structure was created at www.chemspider.com

1.5.2 Sulphide ore The ore in Aitik is a sulphide ore. Sulfide ions in contact with air and water produce sulfuric acid, which acidifies the leachate. An acidification of the leachate releases metals, which pollutes the water. The most common sulfide mineral is the pyrite FeS2. Pyrite in contact with water follows the chemical reaction: 2FeS2 +O2(g) + 2H2O(aq) 2Fe2+ (aq) + 𝟒𝟒𝟒𝟒𝟐−(aq) 4H

+ (aq)

This chemical reaction occurs for all types of sulfide minerals in combination with water and air. The water content in the air is usually sufficient to start the reaction (Länsstyrelsen i Västerbotten, 2012). The current dressing plant in Aitik is equipped with an ability to reduce the amount of sulfides in the tailings. If necessary, lime is added to the process at times with high sulfur levels. Lime increases the buffering capacity and prevents release of toxic metals. Although, the dressing plant has an ability to reduce the amount of sulfides in the tailings it cannot always reduce it to desired low levels (Boliden, 2012).

1.5.3 Surrounding water area As mentioned earlier, water emissions from the clarification pond is emitted into the river Leipojokki, which - via the Vassara river, which empties into the Lina river, north of the mine area. Water is, in exceptional cases, also emitted from the recovery water system to the Sakajoki river, which also empties in Lina river. The stream Myllyjoki meanders through the southeast part of the mine and ends in lake Sakajärvi. Some leachate from the waste rock is assumed to emerge towards Myllyjoki. Overflowing water is normally released during the

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period May-September. Lina river is also a recipient for the iron ore mine Malmberget, located north of Gällivare (Boliden, 2012). The Leipojokki-, Vassara-, Lina, Myllyjoki- and Sakajoki rivers are all tributaries to the Kalix River, which represent the main flow in the Kalix river basin. The Kalix River has its headwater in Kebnekaise (west of town Kiruna) and empties into Bottenviken at Kalix, Figure 4. The basin covers an area of 23 846 km2 and is, together with Torne river basin, the largest river system in western Europe that is not exploited by waterpower installations. The basin is characterized by a low population density surrounded by large areas of wooded land from which only a small part is used by agriculture.(Hushållningssälskapet Rådgivning Nord AB, 2010b)

Figure 4. Position of the Kalix River (Kalixälven) represented with a bold blue line. Map retrived from Wikimedia Commons 2014-10-05.

1.5.5 Protection for surface water The Kalix- and Torne river systems together constitutes a Natura 2000 area, area code SE0820430, and this area is protected by the Habitats directive 92/43/EEC. The area consists of Torne- Tärendö- och Kalix river water systems with mainstream, lakes and tributaries. This means that several tributaries adjacent to the Aitik mine are under protection by the Habitats directive such as Leipojoki, Vassara and Myllyjoki. All Natura 2000 areas are included as national interests according to the 4 chapter. 8 § Swedish environmental law, Miljöbalken (MB). Kalix river system is also a national interest accordning to 3 chapter. 6 § and 4 chapter. 6 § of MB. In addition, all watercourses are protected by the WFD, which stipulates that all water courses should have at least good status. The Kalix river has therefore, based on this background, a high protection value.

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1.6 Mixture effects Agreed and suggested safe limits for priority substances (EQS values) and PPS are based on the assumption that the given compound is present as the sole toxicant. This not the case in the real world where species are frequently exposed to mixtures of chemicals. Mixtures are of different complexity depending on e.g number of substances, type of substances, how they are transported and interacting, both with each other and with the surrounding environment. Current chemical risk assessments based on single substances tend to underestimate the real effects that occur in the environment. In order to achieve a more realistic scenario it is important to include mixtures in the risk assessment (Dyer et al., 2011). Recently, studies with mixtures, all present at AA-EQS, elicited quantifiable toxic effects on various organisms. Mixtures of 14 or 19 substances including heavy metals, pharmaceuticals, pesticides, polyaromatic hydrocarbons, a plasticizer and a surfactant caused changes in microbial compositions, microalgae toxicity, Daphnia magna immobilization, fish embryo toxicity, impaired frog embryo development and increased expression on oxidative stress-linked reporter genes (Carvalho et al., 2014). This shows that current concentrations believed to be safe actually underestimate the real impact.

1.6.1. Mixture effects of metals Predicting effects of metal mixtures has proven to be complex in comparison to mixtures of other substances. This complexity depends on metals interactions and reversible processes both in the uptake- and target phase. It has long been known that the metals may compete for the same ligand. For example less toxic calcium ions can prevent toxic metals from interact with the ligand (Paquin et al., 2002) but if the metal concentration increases it will be the opposite with metals binding to the ligand instead. Besides from an interaction between the organism and the outer environment there are also interaction mechanisms within the organism at for example detoxifying. The relationship between cause and effect for a mixture with metals is therefore anything but simple. There are different methods suggested for predicting the effects of metal mixtures. One of the methods is based on the assumption that the compounds have the same mode of action. This means that the total effect corresponds to the sum of the individual toxicity of the substances. Another method is based on the concept that different substances have different mode of action and are therefore interacting independently without presence of others, but can still give the same effect, i.e lethality. There are situations deviating from these two scenarios and that is synergism and antagonism, which are not predictable. In 2011 a meta-analysis was performed in order to evaluate trends of ecotoxicology effects of metal mixtures in aquatic environments. This was a first step in order to develop a model for predictions of metal mixture effects. The meta-analysis was based on articles published during the period of 1981-2009 studying effects of Cd, Cu and Zn on organisms living in aquatic environments. Conclusions of the study showed a low frequency of additive effects in comparison with synergistic- and antagonistic effects. However, if looking from a precautionary perspective, the additive method would accurately predict or over-estimate 75 percent of the cases (Vijver et al., 2011).

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2. Methods

2.1 Literature research and personal communication In order to evaluate current chemical- and biological monitoring the present report performed a status report on how the monitoring is carried out today and if current concentrations exceed EQS or PPS class limits or causes visible biological effects (see more detailed methodology description in section 2.2). A regular communication has occurred with water authorities that are involved in the work with water management, both on a national level (Swedish Agency for Marine and Water Management) and within the Norrbotten region (NCAB). This was combined with reviews of authority documents, directives and regulations within the topic. Knowledge, which forms the base of present monitoring, was hence compared with the recent research within the ecotoxicological scientific field. A chemical risk assessment of mixtures was conducted based on established and proposed methods presented within research of chemical risk assessment. Ecotoxicity data of mining related contaminants were also collected via literature search, through databases provided by the university library.

2.2 Status report of chemical and ecological status Data on monitored (measured) chemical concentrations was collected from the Norrbotten County Administrative Board (NCAB). Measured concentrations during the years 2009-2012 were risked assessed and evaluated individually, in accordance with existing EQS and PPS class limits. The latest biological monitoring report conducted in 2010 was reviewed and summarized.

2.3 Mixture Risk Assessment

2.3.1 Risk characterization The present environmental risk assessment of chemical mixtures was based on a conceptual framework (Backhaus and Faust, 2012). Potential risks from chemical mixtures were assessed based on the addition of individual substances potential risk quotients (RQ), which can be expressed as RQPEC/PNEC:

𝑅𝑅 𝑃𝑃𝑃𝑃𝑃𝑃𝑃=∑

𝑃𝑃𝑃𝑖𝑃𝑃𝑃𝑃𝑖

=∑ 𝑃𝑃𝑃𝑖𝑚𝑚𝑚 (𝑃𝑃50𝑎𝑎𝑎𝑎𝑎,𝑃𝑃50𝑑𝑎𝑑ℎ𝑛𝑖𝑑,𝑃𝑃50𝑓𝑖𝑓ℎ)𝑖 𝑥 1/𝐴𝐴𝑛𝑖=1

𝑛𝑖=1

Predicted Environmental Concentration (PEC) is the measured environmental concentration for compound i. Predicted No Effect concentration (PNEC) is the corresponding concentration for substance i, which is considered to be the safe concentration causing no significant adverse effects on the environment. PNEC values are based on toxicity data from the most sensitive trophic level of algae, crustacean (Daphnid) or fish divided with a safety factor (assessment factor: AF). A chemical mixture has the potential to cause significant adverse effects if the RQPEC/PNEC ratio>=1 and no significant adverse effects are assumed if the RQPEC/PNEC ratio

17

2.3.1.1 Selection of substances Substances included in the chemical risk assessment of mixtures were retrieved from actual monitoring data from the NCAB. Selected substances were PPS, priority substances and other compounds frequently measured, and which were found in notably elevated concentrations compared to reference sites upstream.

2.3.1.2 Selection of PEC and PNEC values PNEC values used in the risk characterization were in accordance with limit values used in water management of chemical- and ecological status, namely EQS and PPS class limits. PNECs for substances not defined as EQS or PPS were retrieved from ECHA’s website on registered substances, based on ecotoxicological data on freshwater organisms. PEC values were represented as the annual mean concentrations of measured data.

2.3.2 Refinement in data Individual substances were evaluated on their contribution for the common risk, which are the prominent drivers for the SRQ and how they are interacting with other chemicals present in the mixture. Measured data were also examined on the nature of exposure. Exposure was reviewed regarding how often exposure occurred over time and if concentrations were constant or fluctuating. Risk characterization in section 2.3.1 assume that exposure to all substances occurs at the same time. Further refinement in data investigates if this really is the case or if substances may be released subsequently one after another. Exposure patterns we compared between a reference site and an affected site.

2.4. Mapping An overview map of the Aitik mine area with vicinity was downloaded from Lantmäteriet distribution service Geographic Extraction Tool. Coordinates for different sampling points, included in chemical and biological monitoring, were compiled in ESRI ArcMap and in GoogleEarth. Coordinates for sites included in chemical monitoring were conducted through the Swedish Water Information System (VISS). Coordinates for sites included in the biological monitoring were conducted from the latest biological survey performed by (Hushållningssälskapet Rådgivning Nord AB, 2010a).

6. Results

6.1 Status report of the current monitoring of chemical and ecological status in surface waters near Aitik

6.1.2 Chemical monitoring Norrbotten’s county administrative (NCAB) board collect recipient data from the mine’s recipient monitoring, which is a part of the mine’s control program. NCAB compiles the data and compares the measured concentrations with EQS and PPS class limits (Table 1) in order to evaluate the surface water status. Measured priority substances in the recipients are Pb, Ni, Cd and Hg. EQS are either AA values or MAC values. The AA value is the annual average accepted concentration and MAC is the maximal accepted concentration. The chemical

18

status is considered as good if the measured concentration is below EQS. PPS class limits are based on the limit values suggested by the Swedish Agency for Marine and Water Management, letter dnr: 3383-13 (Personal communication with Sara Elfvendahl, NACB) which are based on limit values from the ITM report and EPAs report 5799 (Havs och vattenmyndigheten, 2013 ) Physical-chemical quality factors such as nutrients, TOC, pH and other elements such as micronutrients; Fe, Ca, S and Mn, are also measured in order to study the general condition of the surface water. Table 1. EQS(European parliament and council, 2008) and PPS class limits(Havs och vattenmyndigheten, 2013 ) included for classification of ecological- and chemical status. AA μg/L is the annual average accepted concentration and MAC µg/L is the maximum accepted concentration. Limit values for cadmium and zinc are controlled by the hardness of the water measured as CaCO3 mg/L.

Compound EQS/PPS AA µg/L MAC µg/L Pb EQS 1,2 14 Hg EQS - 0,07 Ni EQS 4 34

Cd EQS

19

Table 2. Compiled monitoring sites included in Aitik monitoring program. Sites are represented with recipient and local description. Site Recipient Local description Aitik recipient monitoring River 521 Sakajoki Upstream the screen trench 522 Myllyjoki Before the lake Sakajärvi 523 (reference) Leipojoki Upstream the clarification pond 524 Leipojoki Upstream Vassara river 525 (reference) Vassara Reference site 526 Vassara At the stone bridge 527 Lina At Kiruna road 529 Sakajoki By the road E10 530 Lina Bridge in Dokkas 531 Myllyjoki Upstream exploration, eastern Liikavaara 532 Lina Downstream Sakajoki river 533* Myllyjoki Upstream the new road 534* Myllyjoki Downstream the new road *Not registered in WISS

Figure 5. Compiled monitoring sites included in Aitik monitoring program. Scale 1:100 000. Lantmäteriet: Permission i2012:995

6.1.2.1 Assessment of metals included in the ecological status classification Several documents have been written by Sweden’s five water authorities in order to support the county administrations to classify the ecological status in the water courses (Vattenmyndigheterna, 2013a, Vattenmyndigheterna, 2013b) before it is reported in WISS. It is important to point out that these help documents do not replace any other regulations or manuals. According to this help document metal concentrations should, if the measured

523

524

525

526

527

530

532

522

531

529 + 521

20

concentration exceeds limits for PPS, be related to the background concentration. The background concentration should be withdrawn from the measured concentration if it exceeds the PPS limit value before it is compared with the limit value. If the measured value still is higher than the PPS class limit then it is classified with moderate status. Local background concentrations are to prefer but in the absence of this there are general regions background concentrations (Vattenmyndigheterna, 2013a).

6.1.2.2 Exceedance of metal limit values Exceedance of metal limits values occur at 4 stations during the period 2009-2012 according to recipient data, Figure 6-10. Exceedance has occurred for Zn and Cu.

Figure 6. Site 529. To the left: annual average PEC/PNEC for Cu between 2009-2012. Red line represents the risk quotient of 1. Red points represent an annual risk quotient>=1. To the right: Annual distribution of PEC/PNEC ratios 2009(n=12), 2010(n=12), 2011(n=16), 2012(n=14). Unfilled points should be multiplied with 4 for actual PEC/PNEC ratios.

Figure 7. Site 529. To the left: annual average PEC/PNEC for Zn between 2009-2012. Red line represents the risk limit of 1. Red points represent an annual risk quotient>=1. To the right: Annual distribution of PEC/PNEC ratios 2009(n=12), 2010(n=12), 2011(n=16), 2012(n=14). Unfilled points should be multiplied with 3 for actual PEC/PNEC ratios.

0

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30

2009 2010 2011 2012

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PNEC

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Site 529 Annual average PEC/PNEC ratio for Cu

05

1015202530

2009 2010 2011 2012

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Site 529 Annual PEC/PNEC ratio for Cu

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101520

2009 2010 2011 2012

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Site 529 Annual average PEC/PNEC ratio for Zn

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2009 2010 2011 2012

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Site 529 Annual PEC/PNEC ratios for Zn

21

Figure 8. Site 522. To the left: annual average PEC/PNEC for Zn between 2009-2012 at site 522. Red line represents the risk limit of 1. Red points represent an annual risk quotient>=1. To the right: Annual distribution of PEC/PNEC ratios 2009(n=12), 2010(n=22), 2011(n=18), 2012(n=11).

Figure 9. Site 531. To the left: annual average PEC/PNEC for Zn between 2009-2012 at site 531. Red line represents the risk limit of 1. Red points represent an annual risk quotient>=1. To the right: Annual distribution of PEC/PNEC ratios 2009(n=11), 2010(n=24), 2011(n=13), 2012(n=11).

Figure 10. Site 534. To the left: annual average PEC/PNEC for Zn between 2009-2012 for site 534. Red line represents the risk limit of 1. Red points represent an annual average risk quotient>=1. To the right: annual distribution of PEC/PNEC for 2010(n=8), 2011(n=2), 2012(n=11).

0

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Station 522 Annual average PEC/PNEC ratio for Zn

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Site 522 Annual PEC/PNEC ratios for Zn

0

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Station 531 Annual average Zn PEC/PNEC

02468

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2009 2010 2011 2012

PEC/

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Site 531 Annual PEC/PNEC ratios for Zn

0

4

8

2009 2010 2011 2012

PEC/

PNEC

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Site 534 Annual PEC/PNEC ratios for Zn

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8

2009 2010 2011 2012

PEC/

PNEC

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Station 534 Annual average Zn PEC/PNEC

22

6.1.2.3 Exceedance of ammonia- and nitrate nitrogen limit values Nitrate (NO3-N) concentrations were measured during 2009 and 2012 for the sites 523, 524, 525, 526, 527, 530 and 532. Concentrations are frequently presented as a limit value, i.e. “160 μg/L

Table 4. Exceedance of MAC limit (2000 μg/L) at station 524 during 2009(n=14) and 2012(n=16).

Site Year > 2000 μg/L

524 2009 2500 2200 3100 2300

2012 2070 2290 2130 2190 2160

6.1.3 Biological monitoring Biological monitoring is performed every five years and Hushållningssällskapet AB, on behalf of Boliden AB, conducted the latest biological investigation in 2010. This survey in 2010 included sampling of fish (quantitative electrofishing), benthic organisms and diatoms. Sampling sites for biological monitoring are illustrated in Figure 11. Biological monitoring was performed in accordance with instructions from SEPA, which are based on the standards SS EN 14011:2006 for electrofishing), SS EN 27 828 for benthic organisms and SS EN 13946:2003 for benthic diatoms (Naturvårdsverket, 2010b, Naturvårdsverket, 2009a, Naturvårdsverket, 2010c). An overall description of what the various methods measure, used in 2010 biological monitoring, is presented in section 6.1.3.1-3. In section 6.1.3.4 is a summary of the result.

6.1.3.1 Quantitative electrofishing A quantitative electrofishing include mandatory species identification and fish length measurements. A density assessment is based on the total amount of fish/100 m2. (Naturvårdsverket, 2010b)

6.1.3.2 Benthic organisms A status evaluation of the benthic organisms was performed based on the indexes ASPT (Average Score Per Taxon), MISA (Multimetric Index for Stream Acidification) and DJ (Dahl and Johnsson), which together are supposed to give an overall picture of the status in the recipients. ASPT, MISA and DJ indexes are evaluated based on species composition according to SEPA assessment criteria (2007:4). ASPT is an index, which describes the general ecological quality in the water and integrates effects from eutrophication, oxygen-consuming pollution and effects on habitats due to straightening/cleaning within the

23

watercourse. DJ is an index specialized for eutrophication effects and MISA is an acidification index, Table 5. Mayflies and shells (Gastropoda) are for example sensitive to acidification and some chironomid larvae are tolerant to low oxygen conditions often caused by eutrophication. The ecological status is classified as high, good, moderate, unsatisfactory or bad (Naturvårdsverket, 2007b).

Figure 11. Sample sites included in Aitik biological monitoring. Scale: 1:100 000. Lantmäteriet: Permission i2012/995. Table 5. Indices for benthic fauna and what they mesure.

Index Measures effects from: ASPT Eutrophication Oxygen-consuming compunds Straightening/cleaning

DJ Eutrophication

MISA Acidification

6.1.3.3 Periphyton communities- diatom analysis Diatoms are used in order to evaluate effects on periphyton communities caused by eutrophication, organic pollution or acidification. This method aims to describe the state and detect changes with respect to species composition, number of species and the relative presence of species, especially indicator species. The evaluation covers four index; IPS (Indice de Polluo-sensibillité Spésifique) index which is a measurement of the amount of nutrients and easily degradable organic material, ACID (Acidity Index for Diatoms) gives a measurement of the acidity in the recipient an the supporting parameters %PT (Pollution Tolerant valves) indicates easily degradable organic material and TDI (Trophic Diatom Index) measure eutrophication, Table 6. The latter two are used in uncertain cases when the IPS-index is close to a classification limit. Reference values and class limits are the same for

Le 1

Le 2

Va 1

Va 2

Li 3

My 1

My 2

Sa 1 + Sa 2

Li 5

Li 4 Sa 3

24

the whole Sweden. IPS is determined based on the total amount of detected diatoms (Naturvårdsverket, 2009a). Table 6. Index for diatiom analysis and what they measure. Index Measure effects from:

IPS Nutrients Easily degradable organic material ACID Acidification %PT Easily degradable organic material TDI Eutrophication

6.1.3.4 Summary of the biological assessment in 2010

Electrofishing Fish was caught at all sites except from Li 3, Lina älv, and the numbers of species were high. The density of trout was low, but it was positive that one-season trout was caught in both Vassara älv and Leipojoki. One-season salmon was also caught in Lina älv. In comparison with previous surveys it was still a low fish density in general, but this applies to the whole area with no difference between impacted and reference sites.

Benthic fauna The result showed a difference in MISA index between the reference site upstream, Le 1, with the site downstream the clarification pond. The reference site was classified as moderate acid and the downstream site as very acid. This difference is due to the characterization of the species found and the distribution of different species. Shells that are sensitive to acidic environments were found at the reference station but not at the impacted site. Also the distribution of mayflies and stoneflies were different between the two sites. Mayflies were the dominating specie upstream compare to downstream where the distribution of mayflies and stoneflies were more even.

Diatoms Results from the diatom investigation showed small differences in index values between sites. In comparison with the benthic fauna investigation these results did not indicate any impacts from acidification, which implies a clear difference in the methods. Small differences in the index values in reference- and impact sites for the watercourses Sakajoki and Myllyjoki indicate some impacts from nutrients and readily biodegradable organic materials. Future investigations will show if this impact is temporary or consistent. Impacts in Myllyjoki is due to surface runoff and lake emptying (Hushållningssälskapet Rådgivning Nord AB, 2010a).

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6.2 Mixture risk assessment

6.2.1 Risk characterization SRQ are decreasing with increasing distance/dilution from emission point, Figure 12. SRQ were calculated for the substances Hg, As, Cd, Co (PNEC=0,51 μg/L), Cr, Cu, Ni, Pb, Zn and NH3-N. SRQPEC/PNEC ratio>=1occurs for all sites except for reference site 523, during the period 2009-2012. PNECs for cadmium and zinc have been adjusted to the water hardness, Table 7. Water hardness (CaCO3 mg/L) was higher at downstream sites in comparison with upstream sites for the corresponding time period (2009-2012). Highest water hardness was found at site 524 and 526, Table 7.

Figure 12. SRQ values for selected sites. SRQ are decreasing with increasing distance/dilution from emission point(see Figure 4). PNEC values for cadmium and zinc are adjusted to the water hardness. Table 7. Water hardness average 2009-2012 measured as CaCO3 mg/L. Site Hardness* 529 12,19 524 122,33 522 10,43 521 10,94 532 33,94 526 49,15 530 25,32 527 17,78 525 (ref) 10,10 523 (ref) 6,21

* (CaCO3 mg/L)

0

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529 524 522 521 532 526 530 527 525 (ref) 523 (ref)

Sum

of a

vera

ge ri

sk q

uotie

nt

Sum of the average risk quoient 2009-2012 Hg As Cd Co Cr Cu Ni Pb Zn NH3-N

Average SRQ

Risk limit

26

6.2.2 Refinement in data Individual substances contribution for the SRQ (Figure 12) for the period 2009-2012 varied between sites, Figure 13.

2,2 0

1

RQ

Average Risk Quotient (RQ) 2009-2012, site 524

4,9 3,0 2,2 0

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RQ

Average Risk Quotient (RQ) 2009-2012, site 529

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Average Risk Quotient 2009-2012, site 521

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Average Risk Quotient (RQ) 2009-2012, site 532

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Average Risk Quotient (RQ) 2009-2012, site 526

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Average Risk Quotient (RQ) 2009-2012, site 522

27

Figure 13. Individual RQ for Hg, As, Cd, Ni, Cr, Pb, Co, Cu, Zn and NH3 during the period 2009-2012. Background concentrations has not been withdrawn for essential metals. At site 529, RQ for Cu, Co and Zn are exceeding the risk limit of 1. Actual RQ are presented as labels at the base of the bar. This also applies for Co at site 524.

Exposure of Co, Ca, Cu, Zn and N-tot during 2012 (May-October) at site 524 are following the same concentration pattern, Figure 14. Exposure of Co, Ca, Cu, Zn and N-tot during 2012 (May-October) at site 523(ref) are not following the same concentration pattern, Figure 15.

Figure 14. Fluctuation of Co, Ca, Cu, pH, Zn and N-tot at site 524. Co, Ca, Cu, Zn and N-tot are following the same concentration pattern. pH stays around 7. For actual Ca concentration measured values should be multiplied with 15. Measured values are between May and October, 2012. Each point represent one measurement.

0

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Site 524 (2012) Fluctuation of Co, Ca, Cu, pH, Zn and N-tot

Co µg/l

(Ca mg/l)*15

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TOC mg/L

0

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Risk Quotient (RQ) 2009-2012, site 530

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Average Risk Quotient (RQ) 2009-2012, site 527

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Average Risk quotient (RQ) 2009-2012, site 525 (ref)

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Average Risk Quotient (RQ) 2009-2012, site 523 (ref)

28

Figure 15. Fluctuation of Co, Ca, Cu, pH and N-tot at reference site 523. Ca, pH and Zn should be multiplied with 10 for actual measured concentration. Measured values are between May and October, 2012. Each point represents one measurement.

0

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Conc

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May-October 2012

Station 523 (2012) Fluctuation of Cu, Co, Zn, P-tot, N-tot, Ca, pH

N-tot mg/l

Co µg/l

Ca*10 mg/l

Zn*10 µg/l

pH*10

Cu µg/l

29

7. Discussion Both chemical and biological monitoring methods in water management are used in order to detect deviations in water status between impacted and less impacted sites. If they indicate a deviation and thus a status, which is less than good actions must be taken (according to the WFD). In this way, these methods can be perceived as protectors of the surface waters. Biological methods report direct effects on organisms, while chemical limit values indirectly aims to protect from significant adverse effects on aquatic biota. However, these methods can also hide effects if they are not adjusted to local conditions. The present study evaluated current biological and chemical monitoring methods ability to describe the ecological status in mine adjacent recipients. Possible adverse effects caused by mine effluents were put against what effects these methods actually can measure/protect. This is essential in order to be able to evaluate what effects a future increase in metal mining could have on water surface status. I the case with Aitik, it should not be forgotten what large conservation values adjacent rivers possess. Many of the rivers are not only protected by the WFD but also by the Habitats directive 92/43/EEC as the constitution of a Natura 2000 area. An increasing mining activity in Sweden is therefore not only a national issue but also something that concerns the European agenda.

7.1 Chemical monitoring for determining good ecological- and chemical status Regarding chemical status, only four priority substances are included in the monitoring program. Little is therefore known regarding the possibility for other priority substances to be present in the waters. This might substantially underestimate the actual ecotoxicological pressure in the recipient streams.

7.1.2 Ammonia- and nitrate nitrogen Ammonia nitrogen concentrations are well below the limit concentration (Figure 13). Risk for effects caused by ammonia concentrations therefore appears to be low. Measured nitrate nitrogen (NO3-N) concentrations are recurrently exceeding the MAC limit concentration during 2009 and 2012 at site 524, Table 4, and the AA limit during 2009 at all sites except from reference stations 525 and 523. Concentrations are presented with a reporting limit of 500 μg/L during 2009, although the class limit for chronic exposure is set to be 160 μg/L. This hampers the calculation of annual average concentrations of NO3-N for 2009. A reporting value of 500 μg/L is probably due to a former class limit value of 2400 μg/L (ITM, 2013). No measured concentrations of nitrate nitrogen were reported during 2010 and 2011, but based on the high concentrations during 2009 and 2012, it is likely that the concentrations were high also for these years, but this has not been confirmed. Reported values show that there is a large difference in nitrate nitrogen concentrations between upstream (reference sites) and downstream waters. High concentrations occur far down in the Lina River and it is unclear how far down a concentration above 160 μg/L ranges. Nitrate nitrogen, NO3-N, is known to cause direct negative effects on various organisms such as fish, molluscs, amphibians and insects (ITM, 2013).

7.1.3 Metals Metal concentrations exceeded AA limits at four stations during the period 2009-2012. Exceedance of AA limits occurs for Cu at site 529 and for Zn at the sites 534, 522 and 531. Limit values for Zn and Cu were assessed based upon annual average values giving no

30

attention to large fluctuations. Large concentrations can therefore be hidden behind the average value. For example Cu concentrations have varied between 2,6 μg/L up to 560,0 μg/L at site 529 during the years 2009-2012. Zn concentrations varied between

31

Xanthates (including transformation products) also appear to be relatively stable at low temperatures, which increase the retention time in recipients. Ecological effects can therefore not be excluded (Walterson, 1984) and rivers in northern Sweden should be especially vulnerable, due to the colder climate with long and cold winters. Important to emphasize is that these hydrophobic complexes with metals can increase the availability of heavy metals to aquatic animals (Block and Pärt, 1986, Block and Nilsson, 1990) and increases the risk for uptake in lipid rich tissue such as brain in fish. A PAX concentration of 1 mg/L has proven to cause altered brain catecholamine levels in rainbow trout. In fish catecholamines appears to be involved in the regulation of gonadotropin secretion (Block and Nilsson, 1990). In this way the presence of PAX in effluent water could cause effects on reproduction at concentrations of metals below their PNECs. Since PAX is an organic compound it might be expected that concentrations could be captured by the parameter TOC (included in measurement of general water condition), but TOC is not a sufficient measurement to indicate amounts of PAX. TOC concentrations varied from 2 to 9 mg/L at reference site 523 and between 3 and 9 mg/L at the impacted site 524, Figure 14 and 15. Potentially toxic amounts of PAX can therefore likely be hidden behind measured TOC concentrations. Boliden AB states that presence of xanthates in recirculating/excess water will be analysed during the winter 2013 (Boliden, 2012). Results from these measurements are presently unknown.

7.2 Risk assessment of metal mixtures Risk characterization indicates a potential risk for mixture effects of metals in the majority of sampling sites investigated, Figure 12. Average summed risk quotients are decreasing with increasing distance/dilution from emission point, which confirms the mine as the major pollution source. Individual analysing of RQ indicate Cu, Zn, Co and As as the main contributors to the SRQ at non-reference sites, Figure 13. RQ for As shows small variations between sites while RQ for Zn, Co and Cu can escalate closer to the mine. Increased refinement in exposure patterns for site 524 confirms an exposure of elevated Co, Zn, and Cu concentrations simultaneously, Figure 14. It is also important to note that reference sites in this report do not equal unaffected sites with natural background concentrations, e.g site 525 is situated downstream the town Gällivare, which potentially could be a diffuse source of pollutants. PNECs for cadmium and zinc have been adapted to the water hardness. Natural water hardness in this region appears to be low with an average CaCO3 concentration of 6, 2 mg/L at reference site 523, in comparison with 122 mg/L at site 524. Adapted PNECs for cadmium and zinc are therefore not chosen due to a natural hardness but based on an artificial. Adding lime for increased buffering capacity can however act as a protector against metals in two ways by; increasing the buffering capacity and preventing toxic metals from binding to ligands. Without the water hardness above 24 mg/L as CaCO3 at the sites 524, 532, 526 and 530, the risk of zinc would be significantly higher and also the risk of cadmium would be slightly higher. Without analysing only metals and looking at the general water condition between site 523 and 524, water chemistry is controlled by overflowing water from the mine. Peaks are representing the moment when the water sample is taken and sometimes weeks passes before the next sampling. It is therefore not possible to deduce for how long period peaks are ranging and if periods between sampling can be interpreted exclusively as recovery periods.

32

The risk assessment performed in the present study is suggested as a first tier level in risk assessment of mixtures and there are restrictions that need to be highlighted. The risk assessment is based on different kind of species as the PNECs are based on the most sensitive species of e.g algae, daphnia and fish. Therefore, the risk assessment cannot answer which species that has the highest risk to be negatively affected. The PNECs are also not derived from typical species from this particular area but this should however be captured by the assessment factor (AF), which is used in the extrapolation step in the development of the PNEC value. The help document for determining ecological status states that class limits for metals are reported without respect to background levels and if the measured concentration of the metal exceeds the limit value, background concentrations should be withdrawn and then re-compared with the limit value. If the value still exceeds the class limit, the status is being determined as moderate. From an ecotoxicological perspective this approach is not straight-forward and the present report has not withdrawn any background concentrations. It could be e.g be argued that background concentrations should be withdrawn for essential metals and not for non-essential metals such as lead and cadmium. Zinc, copper and cobalt, which can appear in significantly high concentrations in nearby recipients, belong to the group essential metals and especially zinc and copper are necessary for many biological processes. Copper e.g act like a co-factor for over 30 biological enzymes (Flemming and Trevors, 1989) and zinc has a important role for protein structure(Salgueiro et al., 2000). Despite their essential properties, they can become toxic at high concentrations. The present report assumes that the risk for potential significant effects is a result of the total amount of metals regardless of background concentrations. The help document lists background concentrations for the different Swedish ecoregions. In the region studied, there is e.g a background concentration of 1 μg/L for Zn, 0,3 g/L for Cu and 0,034 μg/L for Co (Vattenmyndigheterna, 2013a). This might have been crucial for a SRQ being under or over 1. Although, for some sites close to the mine such as 524 and 529 a withdrawn of background concentrations would not have been crucial for the final result. It is also important to highlight that the SRQ is an average of a four-year period so even if the SRQ would be under 1 it could still be a SRQ over one for single years. The causal link between exposure and effects of metals is complicated due to metals interactions and reversible processes both in uptake- and target phase. To develop a model for predictions of metal effects is a challenge due to high frequency of synergism and antagonism (Vijver et al., 2011). This is not captured by todays limit values, which are based on single substance exposure tests. Determining the ecological status of metals can therefore be perceived as extra dependant on the biological methods for detecting impatcs.

7.3 Biological methods for detecting metal effects Both EQS and PPS class limits are based on instructions given by the TGD, which is based on toxicity data from laboratory tests with individual substances (Kortenkamp et al., 2009). This is also confirmed in the SEPA manual on ecological status regarding PPS class limits. SEPA, however, states that this should be captured by the biological quality elements (Naturvårdsverket, 2007b), but when investigating what present biological indexes actually measure this is not linked in an obvious way. Current indexes for benthic fauna and diatoms are not developed for detecting effects caused by metals (Löfgren, 2010). This is also stated in the latest biological investigation conducted in 2010 (Hushållningssälskapet Rådgivning

33

Nord AB, 2010a). Standardised ecotoxicological methods detecting metal effects are therefore highly requested. An attempt to develop new methods in order to detect effects of metals on biota in rivers is in progress (Löfgren, 2010, Kahlert, 2012). Kahlert (2012) in a study on rivers in Sweden have however noticed the high capacity for diatom species to develop increased tolerance for heavy metals resulting in inseparable diatom communities in metal polluted sites compared to reference sites. It should be noted that reference values used for heavy metal gradient in the Kahlert study in 2012 were derived from the previous classification system of heavy metals and not in accordance with newer suggested class limits (Naturvårdsverket, 2008) or EQS. Low unaffected watercourses in the Kahlert study were equal to copper concentrations up to 9 μg/L, 60 μg/L for zinc, 0,3 μg/L for cadmium and 3 μg/L for lead. These values are significantly higher than today’s effect limits, Table 1. The chance for development of an altered diatom community towards a more metal tolerant one is therefore likely to occur already at what Kahlert refers to as unaffected sites. Account of regional variations in backgrounds levels of metals (Naturvårdsverket, 2008) were also not paid attention in Kahlert study, which further increases the uncertainty in that study.

7.3.1 Suggestions for methods of improved biological monitoring on algae and benthic fauna

7.3.1.1 PICT Periphyton communities, which the diatoms is a part of, are known for their ability to develop increased tolerance due to various organic and metal pollutants (i.e Cu and Zn), in aquatic systems (Blanck and Wängberg, 1988, Wängberg et al., 1991, Molander et al., 1990, Gustavson and Wängberg, 1995, Dahl and Blanck, 1996, Gustavson et al., 1999, Nyström et al., 2000, Soldo and Behra, 2000, Petersen and Gustavson, 2000). This was also proven to consistent with an altered community structure. Experiments were based on the Pollution-Induced Community Tolerance (PICT) concept/methodology, which gives the opportunity to study effects from pollutants on a community level instead of only individual algal species such as diatoms. PICT has already been identified as a potential effect-based tool, which can be used in monitoring programs linking chemical and ecological status assessment under the WFD (Euroepan Comission, 2014). PICT has the advantage to link cause and effect of toxic substances, making it possible to exclude other stressors in the environment (Blanck, 2002). A PICT study is conducted on periphyton communities collected from the river, which is examined. PICT requires a gradient in toxic concentration, which can be found in the rivers near Aitik. The concept of PICT also offers the possibility to include additive and synergistic effects of compounds, because of the fact that the effect response will correspond to the actual chemical mixture in the river where the communities are grown. The present report therefore suggests PICT as a possible monitoring tool in mine adjacent recipients.

7.3.1.2 SPEAR-index A suggested tool for finding impacts on aquatic invertebrate is the Species At Risk (SPEAR) index(Liess and Von Der Ohe, 2005), which could be a potential tool for detecting effects from e.g xanthates or metals. The proposed method is based on the concept that species are classified and grouped according to their vulnerability to a certain substance. Groups defined as sensitive are based on ecological traits such as generation time, migration ability and

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presence of sensitive aquatic stages during periods of increased concentrations of contaminants. For example in the case with Aitik, certain species that are sensitive to metals and undergo a sensitive development stage during times of increased discharge of excess water and with low migration abilities would be classified at higher risk. A reduction of abundance and number of SPEAR is a result of an affected aquatic invertebrate community composition related to the substance of concern. The SPEAR index has been proven to work for pesticides (Liess and Von Der Ohe, 2005).

7.4 Does an increasing mining industry in Sweden endanger a sustainable use of our waters? The Swedish government highlights the importance of a sustainable future utilization of mineral resources in Sweden (Regeringskansliet, 2013), but with the background of this report, there are large knowledge gaps on what effects mining activities actually constitutes on surrounding waters. There is a lack of robust and reliable standardized biological monitoring methods that can link cause and effects of metals, which often is highlighted as main polluters in mine adjacent recipients. Very little is also known regarding ecotoxicological effects from xanthates, which are widely used as collectors in enrichment processes. From a precautionary perspective, today’s water management cannot secure a sustainable growing mining industry. There is a potential risk that profits from mining operations instead will be rendered for remediation actions or be borne by the society with present and future generations. Sulphide ore mines, such as Aitik, are inherently more problematic than other mines due to the production of sulphuric acid, which acidifies the leachate and releases unwanted metals. Sweden has a long history of sulphide ores, which usually contains valuable metals such as zinc, copper, lead, silver and gold (Länsstyrelsen i Västerbotten, 2012). Sweden has also become one of the leading countries in Europe for deposits of gold, copper, zinc, lead and silver (SGU, 2012). In 2013, SGU, listed current mining projects in Sweden, both active and planed objects, Appendix 1. The majority of these projects consist of activities with base metals such as those mentioned above. The present study has not gone into detail on how many sulphide ore mines that are planned in the nearest future and how close those objects, listed by SGU in 2013, are to open full-scale mining operations. No matter where these projects are in their permitting processes, it is clear that the number of mines will increase in the future and that an increased knowledge of environmental effects caused by mining is needed. Aitik is far from the only example of a sulphide ore in Sweden so it is likely that similar chemical risks presented in this study occur in other downstream recipients. Boliden AB for example wants to reopen a copper mine in Laver in the same size as Aitik (Nordnytt 2012-06-27)containing a deposit of similar character as the one found in Aitik. Looking back in history a lot has happened since the 60s and 70s when large amounts of untreated water from mines could be released directly into the environment. The technology has since then become more advanced and the authorities now have the opportunity to set higher demands on mining companies with help from the Swedish environmental law, which entered into force in 1998. Sweden has been highlighted as a country that could handle a sustainable growing mining industry due to a strong and working environmental law (Regeringskansliet, 2013). In comparison with other countries such as Papa New Guinea and Western Guinea(Earthworks and MiningWatch Canada, 2012), environmental problems in

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Sweden may be perceived as relatively small. Despite this, environmental problems caused by mining in Sweden are not negligible and especially not as in the case with Hornträsket and Blaiken (mentioned in the introduction). The majority of mines in Sweden are situated in places where there are no or small populations, often dependant on the mine as a survival of the countryside. This might attenuate residents’ ability to question and think critically, especially in times when jobs are on the top of the political agenda. Mine effluents has flowed through the Kalix River tributaries for many decades and it is difficult to assess if, as the biological survey imply, a low fish density in general is due to extensive chronic exposure or because of natural causes. Although, emissions do not cause acute visible toxic effects, emissions could have reduced different species ability to avoid predators or survive natural extreme variations of e.g temperature, salinity and pH. Differences in species composition further down in the food web may have impacted species higher up, also known as the “bottom up effect”. More knowledge regarding chronic effects in mine adjacent areas is also desirable.

7.5 Summative assessment and recommendations Effects from mines on surface water is assessed as an issue that need more attention especially since the mining industry is expected to increase threefold during the next decade. More research dedicated biological methods for detecting effects from e.g metals are not just something, which would contribute to monitoring near mines, but also monitoring throughout Sweden, as metals are a recurrent subject in the wider pollution context. This thesis question the belief that current biological quality elements in general (under the WFD) capture additive or synergistic effects. The monitoring needs new biological methods, which can link cause and effects of specific substances. Otherwise the situation could lead to economical impacts that easily could eat up the profits from the mining. Development of improved monitoring could show that effluents affect the water status more than what has previously been thought, but it can also proof the opposite. This could reduce the increased suspicion towards mining and it would also facilitate the agencies’ work in making demands on companies. Many companies want to be ahead when it comes to environmental efforts and with new technology they can often become leaders within their industry. The present study suggests further discussions between authorities, companies and researchers, in order to find solutions, which could be beneficial for all.

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8. Conclusions In relation to the Aitik mine only four priority pollutants are measured in the receiving water. No chemical monitoring occurs for xanthates or cobalt, which potentially could affect the water status. Xanthates are widely used as flotation agents meaning that similar risks could occur in rivers downstream many other mines. The risk for mixture effects occur at the majority of sites investigated as opposed to just studying the risks of individual substances. Background concentrations for metals have however not been withdrawn from the measured concentrations, which could have over-estimated the result. Metals are often highlighted as the main polluters from mines, but current biological methods are mainly designed to detect effects of eutrophication and not designed for detecting impacts from metals. Biological methods for detecting effect from metals are therefore highly requested, especially since metal mixtures can result in additive or more frequently synergistic effects. Suggestions on new monitoring methods to detect effects from metals on periphyton communities and benthic fauna are PICT (periphyton communities) and SPEAR (benthic fauna). The use of PICT could potentially also be used to examine causality between single substances and environmental effects. That contaminated water from mines can cause acute effects on aquatic systems is not something new. However, little seems to be known regarding the chronic effects. More research in this field is needed in order to disentangle the question how mine-adjacent recipients are affected. The possibility of a sustainable use of surface water along with a growing mining industry is therefore uncertain.

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