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Mercury and mercury compounds: background data and predicted future emissions
September 2015
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We are the Environment Agency. We protect and improve the environment and make it a better place for people and wildlife.
We operate at the place where environmental change has its greatest impact on people’s lives. We reduce the risks to people and properties from flooding; make sure there is enough water for people and wildlife; protect and improve air, land and water quality and apply the environmental standards within which industry can operate.
Acting to reduce climate change and helping people and wildlife adapt to its consequences are at the heart of all that we do.
We cannot do this alone. We work closely with a wide range of partners including government, business, local authorities, other agencies, civil society groups and the communities we serve.
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© Environment Agency 2015
All rights reserved. This document may be reproduced with prior permission of the Environment Agency.
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Executive summary Mercury is a naturally occurring metallic element, but much of the mercury found in the environment today arises from past industrial activity.
Mercury can occur in various chemical forms which differ in their degree of toxicity and bioavailability. The change from one form to another occurs in water and sediment through biological processes. Methylmercury is the most toxic and bioavailable form.
Mercury and its compounds are classed as Water Framework Directive priority hazardous substances (PHS) under the Environmental Quality Standards Directive (EQSD; Directive 2008/105/EC amended by Directive 2013/39/EU) because they readily bioaccumulate, are highly toxic and persistent. They have been identified as ubiquitous, persistent, bioaccumulative, toxic (uPBT) substances.
Historically, mercury has had many industrial and domestic uses which are now banned or severely restricted in favour of safer alternatives. It has been used in electrical equipment such as thermostats and batteries, cosmetics, wood preservatives, textile treatment agents and as an antifouling agent on boat hulls. A major use of mercury has been in mercury amalgam dental fillings, although this is now declining. Liquid mercury has been used for many years in measuring devices such as thermometers, barometers and blood pressure monitors.
Direct mercury emissions to water are lower than atmospheric emissions. Industrial discharges contribute the largest proportion of the mercury load released to water, followed closely by background/ambient sources.
A range of actions are being taken to reduce mercury levels in products or phase out emissions. Many of these are co-ordinated under the EU Mercury Strategy (European Commission, 2015b).
The vast majority of water bodies meet the water column based environmental quality standard (EQS) for 'good status' as set in the EQSD 2008 (2008/105/EU).
The revised EQSD (2013/39/EU) has withdrawn the annual average water column standard for mercury and moves to a biota-based standard. This is a new approach which we and other member states are starting to implement.
Biota monitoring data have been gathered in an exploratory programme across a limited number of sampling sites. A 'face-value' assessment of compliance has been undertaken by comparing the measured biota concentrations with the EQS to indicate risks to local predators consuming biota. Results suggested a high incidence of failure of the biota EQS. This could have significant implications for achieving good chemical status. This does not infer increased risks to people from consuming shellfish and fish since the EQS is more stringent than standards for human consumption of fish and shellfish; being set to protect risks to wildlife via secondary poisoning, a more sensitive end point.
Whilst the reductions in use and emissions of mercury are clearly positive developments, the effect that this will have on the levels found in the water environment is less certain. Mercury cannot be degraded over time and local concentrations may even apparently increase due to remobilisation from land or sediment. As such, any speculation about predicted trends in the environment should be treated with caution.
Ensuring compliance with existing measures to reduce further emissions is important in managing the issue of environmental mercury, but the success of this strategy is likely to become apparent only over an extended period of time.
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Contents Executive summary ...................................................................................................................... 3
1. Introduction ............................................................................................................................... 5
2. Use pattern ................................................................................................................................ 6
3. Sources and pathways ............................................................................................................. 7
4. Emissions .................................................................................................................................. 9
5. Risk Assessment .................................................................................................................... 11
5.1. Water quality status ............................................................................................................ 11
5.2. Trends in freshwaters ......................................................................................................... 15
5.3. Trends in transitional and coastal waters ............................................................................ 15
6. Control measures ................................................................................................................... 18
6.1. Restrictions ......................................................................................................................... 18
7. Discussion ............................................................................................................................... 20
Appendix ..................................................................................................................................... 21
References .................................................................................................................................. 23
8. List of abbreviations and acronyms ...................................................................................... 29
9. Glossary .................................................................................................................................. 30
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1. Introduction Mercury is a volatile, metallic element occurring naturally in the environment as elemental mercury, inorganic mercury or methylmercury compounds. These forms differ in their degree of toxicity and natural processes can change one form to another (UNEP, 2002).
Historically, mercury has had many uses. In recent years many of these uses have been phased out, banned or restricted in favour of safer alternatives.
Mercury is released from both industrial processes and from consumer products. Releases to the environment will continue for years to come as products reach their end-of-life and are disposed of.
The risk to both humans and wildlife from mercury and its compounds, is determined by the likelihood of exposure and the form of mercury present. Methylmercury is the most toxic and bioavailable mercury compound. It is formed primarily by microorganisms in soil, sediment and water converting elemental mercury into methylmercury (RPA, 2002).
Methylmercury can be released from sediments back into the water column, where it readily bioaccumulates and biomagnifies through the food chain (WHO, 2003). Low levels of mercury in surface waters can lead to high concentrations in insects, fish and birds, resulting in very toxic contamination in parts of the ecosystem; especially in higher levels in the food chain (Environment Agency, 2010).
Mercury is highly toxic to humans. Exposure, even to small amounts, may have toxic effects on the nervous, digestive and immune systems, and on the lungs, kidneys, skin and eyes (WHO, 2013). Methylmercury is particularly damaging to developing embryos (USGS, 2000; WHO, 2013; EFSA 2012).
Human exposure to methylmercury is almost exclusively through consumption of contaminated fish and shellfish. Commission Regulation 466/2001 on setting maximum levels for certain contaminants in foodstuffs sets a threshold for the level of mercury in fish intended for human health consumption. The maximum level is 0.5 milligrams per kilogram (mg/kg; wet weight) with a higher threshold of 1mg/kg being set for specified larger fish such as tuna, pike and eel.
Current advice on the safe consumption of fish and shellfish from the Food Standards Agency with regards to mercury can be found on NHS choices here.
Predators like otters and large fish are more sensitive to mercury via the food chain than humans eating contaminated fish. For this reason, the biota EQS for mercury (20 microgram per kilogram (µg/kg)) is determined by risks to wildlife rather than risks to human health and is more stringent than standards for the human consumption of fish and shellfish.
The Shellfish Waters Directive (2006/113/EC) which previously included standards for mercury in water was repealed at the end of 2013 as the Water Framework Directive (WFD; 2000/60/EC) together with new domestic shellfish waters legislation, which has yet to be published, will provide at least equivalent protection.
Mercury and its compounds are classed as WFD priority hazardous substances (PHS) under the Environmental Quality Standards Directive (EQSD; Directive 2008/105/EC amended by Directive 2013/39/EU1) because they readily bioaccumulate and are highly toxic and persistent.
The UK is a signatory to the Minimata Convention on mercury. This is a global treaty, ratified October 2013, which aims to protect human health and the environment from the adverse effects of mercury.
1 The requirements of the EQSD 2008 are implemented into legislation in England through the River Basin
Districts Typology, Standards and Groundwater Threshold Values (Water Framework Directive) (England and Wales) Directions 2010. These directions have been replaced by The Water Framework Directive (Standards and Classification) Directions (England and Wales) 2015 incorporating the requirements of the revised EQSD (2013/39/EU).
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2. Use pattern The single largest industrial use of mercury in England is the production of sodium hydroxide, chlorine and hydrogen by electrolysis. There is only one chlor-alkali plant remaining in England; located in Runcorn in the northwest of England.
European data reported under the Mercury Export Ban (Regulation EC/1102/2008) show a downward trend in the use of mercury by the chlor-alkali industry. Quantities of metallic mercury used, as reported by the Euro Chlor plant in Runcorn, decreased from 947 tonnes in 2009 to 418 tonnes in 2014 (European Commission, 2015a).
As a consequence of an absolute life time limit on mercury emissions placed on the installation by the Environment Agency and a voluntary agreement with Euro Chlor, the remaining mercury cells at this site are expected to cease operation by 2020.
Trace quantities of mercury are found in coal and oil, used as fuel within a number of processes such as coal fired power stations, oil refineries, cement manufacture, metal (zinc, lead, iron and steel) production and waste incineration. Mercury is released, primarily to the atmosphere as a by product of these industrial processes (Pacyna, 2006; Defra, 2013).
The industries involved in the cleaning of natural gas, non-ferrous mining and smelting operations also report a downward trend in the use of mercury from 6.4 tonnes in 2011 to 0.03 tonnes 2013 (European Commission, 2015a).
In addition to its industrial uses, mercury has had many product applications. A major use of metallic mercury has been in dental amalgam fillings. Demand for mercury amalgam in dental fillings has decreased in recent years because of improvements in oral health, use of alternative materials, and the adoption of minimally invasive dentistry practices. These trends are expected to continue to reduce the demand for mercury amalgam over the next few years (BDIA, 2015). Waste mercury-based amalgam is classified as hazardous waste and dental practices must comply with the Hazardous Waste (England and Wales) Regulations (2011) under which there is a duty of care to dispose of mercury contaminated waste via licensed carriers and brokers.
Liquid mercury was used for many years in measuring devices such as thermometers, barometers and blood pressure monitors, although these uses are now restricted.
Mercury has been used in electrical control and switching equipment such as thermostats and tilt switches, and electrical and electronic equipment such as fluorescent lamps, although use is now prohibited, with a few exemptions.
Other uses have included batteries, cosmetics, wood preservatives, textile treatment agents and anti-fouling agents for boat hulls, although the EU now prohibits or restricts these.
Restrictions on the use of mercury are described fully in section 6.
Mercury has also been found as a trace contaminant in pesticides and biocides (European Commission, 2013).
A range of actions, are being taken to reduce mercury levels in products or to phase out mercury-containing products (WHO, 2013; European Commission, 2013, 2015a). These are mostly co-ordinated under the EU Mercury Strategy (European Commission, 2015b) and are described in more detail later in this report (Section 6).
Compliance with the existing restrictions and controls is thought to be good in the UK.
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3. Sources and pathways Mercury is released from natural reservoirs in the earth’s crust to the atmosphere through volcanic and geological activity. There is a natural biogeochemical cycle of atmospheric transport, deposition to land and water, and volatilization to the atmosphere. Emitted to the atmosphere in its elemental form, atmospheric mercury travels worldwide before deposition to land and water. Mercury continues to circulate between the atmosphere, oceans and terrestrial system for centuries to millennia before it returns to deep-ocean sediments (Selin, 2009).
Human activity has significantly increased the amount of mercury in the global cycle (Lambert et al, 2012). Figure 1 shows the main anthropogenic sources and pathways of release of mercury and its compounds to surface waters.
Figure 1. Anthropogenic sources and pathways of mercury into the environment
Atmospheric releases of mercury are significantly greater than direct emissions to water (Defra, 2013). The UK Pollutant Release and Transfer Register (UK-PRTR) identifies thermal power plants and combustion installations as the largest emitters of mercury to the atmosphere. Other industrial processes that release mercury to the atmosphere include cement production, nonferrous metal production, pig iron and steel production, the chlor-alkali industry, and waste disposal. Mercury released directly to the atmosphere from these sources is subsequently deposited on land and in water (RPA, 2002).
Mercury has an atmospheric lifetime of between 6 months and 2 years (Strode et al., 2008; Lin et al., 2006; Schroeder and Munthe, 1998), and so has the potential for global, long range transport. Mercury has been detected in remote regions including the Arctic (Durnford et al., 2010).
Lee et al. (2001) modelled a flux budget for mercury in the UK. Their modelling suggested that 68% of the UK’s mercury emissions are exported and 32% deposited within the UK. Further breakdown of the modelled data for mercury deposited in the UK indicated approximately 25% originates from the Northern Hemisphere/global background, 41% from the UK itself and 33% from
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other European sources (Lee et al., 2001). Emissions, transport and deposition of mercury are therefore a global environmental issue.
Figure 2 shows a modelled source apportionment of mercury emissions to water using SAGIS (Source Apportionment Geographic Information System, v2010); a GIS based source apportionment tool and surface water model (Comber et al., 2012).
Figure 2. Sectoral analysis of mercury emissions (kg/yr) as modelled by SAGIS v2010
Of the total mercury load released to water, the modelled results suggest industrial discharges contribute the largest proportion of the load, closely followed by background/ambient discharges, and then urban run-off and waste water treatment works (WwTWs).
WwTWs are a direct pathway but not the primary source of mercury to the aqueous environment. In addition to localized industrial releases of mercury to WwTWs, we anticipate that the gradual abrasion of dental amalgam and the fraction of waste amalgam that escapes recovery at dental surgeries may contribute to the diffuse mercury load in waste water received by WwTWs (WRC, 2009).
Monitoring of WwTW influent and final treated effluent as part of the Chemical Investigations Programme (CIP) (UKWIR, 2014a, 2014b) suggests that mercury is not readily removed during waste water treatment processes. Removal was less than 50% (Gardener et al., 2013).
Monitoring of WwTW final treated effluent as part of the CIP demonstrated that mercury is generally found at low levels. At two sites, higher concentrations of mercury were detected in the WwTW effluent although in these instances the source was considered to be associated with a specific local point source (UKWIR, 2014a, 2014b).
Most analyses performed under the CIP used an earlier, less sensitive analytical method than is now available. Many of the earlier WwTW influent sample results were less than the limit of detection so cannot be used for estimating removal rates. The second phase of the CIP, commencing in 2015 will provide evidence on removal in waste water treatment; using an improved and more sensitive analytical method. The first results from this programme are anticipated in 2017 with further results reported through to 2020.
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Although mercury is not readily removed during waste water treatment, some mercury will be present in sewage sludge. Loss of mercury from sludge applied to agricultural land is thought to be a relatively minor source (Nicholson and Chambers, 2008). Land-spreading of sewage sludge is regulated by the Sludge (Use in Agriculture) Regulations (Amendment) Regulations 1990 (SI 1990/880) which set limits for the amounts of certain trace metals, including mercury.
Mercury is also present in trace amounts in livestock manures, fertilisers and lime applied to land (WRC, 2009).
Storm water runoff contributes to the mercury load to water, since trace concentrations of mercury from motor fuel may be deposited onto urban surfaces such as roads and subsequently washed off during rainfall (Fulkerson et al., 2007). The CIP (UKWIR, 2014a; 2014b) reported low levels of dissolved mercury in urban run-off although the significance of this source appears to vary geographically.
At a local scale, the significance of different sources as contributors to the total mercury load will vary according to land use, local industry, population density and degree of historical contamination. For example, in contrast to the source apportionment described above (Figure 2), which identified natural background and industrial inputs as the most significant sources at a national scale, Chon et al. (2012a) identified urban run-off as the most significant source of mercury runoff (47% of total load) in a study to assess the relative contribution of WwTWs to levels of metals in receiving waters in the Yorkshire Aire-Calder catchment.
Further work to evaluate SAGIS (v2010) estimates of load, using CIP monitoring data is ongoing and will be used to refine future emission estimates for the next river basin management plan (RBMP) reporting cycle.
The wide use of mercury in industrial processes and products means that historical uses could still be a significant source of pollution. Products containing mercury will continue to enter the waste stream as they reach their end of life. Mercury in waste that is not recovered may be disposed of to landfill and there is evidence that this can evaporate into the air to re-enter the mercury cycle through movement of the waste as its deposited and also through flaring of landfill gas (Southworth et al., 2005).
Historically contaminated sediments release mercury back into the water column (Randall and Chattopadhyay, 2013; Chon et al., 2012b; Vane et al., 2009). This may be a particularly significant source of mercury in areas of localized high contamination from historic industrial sources, such as the Mersey estuary, where elevated levels of mercury have been attributed to the high density of chemical factories in the Widnes-Runcorn area (Vane et al., 2009).
4. Emissions The inventory of emissions, discharges and losses of priority and priority hazardous substances is a formal requirement of the WFD under the 2008 EQSD (2008/105/EC). The inventory for England can be found at https://ea.sharefile.com/d-sab675d1e4d74e5e8. It provides an estimate of emissions of mercury from both point and diffuse sources by river basin district for the baseline reporting year (2010). Total emissions per river basin district are shown in Figure 3. Results for the Solway Tweed river basin district are reported by the Scottish Environmental Protection Agency and the Dee river basin district by Natural Resources Wales.
Estimates have been determined using SAGIS (v2010), a GIS based source apportionment tool and surface water model (Comber et al., 2012) combined with estimates of releases to sea from long sewer outfalls from the Pollution Inventory. We estimate that approximately 385.5kg of mercury was released to surface waters in England in 2010; 184.3kg from point sources2 and 201.1kg from diffuse sources3.
2 WwTWs, storm tanks, combined sewer overflows, mines and industry
3 Arable and livestock farming, natural background, highways and septic tanks
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Figure 3. Baseline year total emissions, discharges and losses to water for mercury for each river basin district. Results for Solway Tweed are reported by the Scottish Environmental Protection Agency and the Dee by Natural Resources Wales
Estimates of emissions of mercury to water vary across river basin districts, ranging from 11kg/yr in Northumbria to 156kg/yr in the North West river basin district.
Point source and diffuse emissions within each RBD also vary. Point source emissions range from approximately 5kg/yr in Northumbria to 176kg/yr in the North West. Diffuse inputs range from 7 mg/kg (Northumbria) to 50kg/yr (Severn).
With only one year of data in the inventory of emissions we cannot yet describe any temporal trends in emissions. Data collected by OSPAR on chemical loads released to sea between 1998 to 2006 reports a significant decrease in the riverine inputs of mercury in the Greater North Sea (75%) and Celtic Seas (85%). Direct discharges were much smaller and showed a similar scale of decrease (OSPAR, 2006).
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5. Risk Assessment 5.1. Water quality status Where a priority or priority hazardous substance fails to meet the EQS, the water body is classified as ‘failing to meet good chemical status’. A water body needs to meet both good ecological status and good chemical status to be classified as 'good status'. We classify water bodies as good unless the EQS has been failed.
The 2008 EQSD (2008/105/EU) introduced a biota standard of 20µg/kg wet weight for mercury along with water column standards for the protection of wildlife. The revised EQSD (2013/39/EU) retains the biota standard but where this could be monitored in any biota before, this has now been clarified as applicable only in fish. The annual average water column standard is omitted from the new Directive. Because of uncertainties in implementing the biota standard, explained below, the current water body classification is based on the 2008 water column standard (0.05µg/l).
5.1.1 Compliance with water column standards
Figure 4 shows the results of classification based on water column monitoring and comparison of the results with the annual average water column EQS (2008/105/EU). Of 322 water bodies in England monitored for mercury, 308 of these were compliant with the EQS.
Figure 4. Classification results (2015) for mercury
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5.1.2 Initial findings from biota monitoring
As part of the exploratory programme of work to develop a biota monitoring strategy in England (see text box below for fuller explanation), we have gathered data on mercury residues in freshwater and marine biota from a limited number of locations around England.
Mean measured concentrations in whole fish sampled from 25 freshwater sites in England in 2014 ranged from 11.5 to 106µg/kg wet weight.
Biota monitoring
Environmental quality standards are threshold concentrations in the environment intended to protect humans and wildlife from direct exposure to chemicals (eg drinking water) or indirect exposure (eg eating contaminated prey). Most EQSs are expressed as a water concentration but some chemicals do not remain in the water column and are taken up by plants and animals where they accumulate. To reflect the potential risks posed by such substances, in 2008, the EU published EQSs for 3 substances that are expressed both as water concentrations and as concentrations in aquatic animals (usually fish). This was followed by biota EQSs for a further 8 substances in the revised EQSD (2013/39/EU).
Compliance with these biota EQSs would indicate good chemical status of water bodies. However, this is a new approach and the implementation of these EQSs has been complicated by a lack of knowledge and the need for inter-comparability across Europe. To address this, the EU published guidance on the implementation of biota standards in 2014, focussing on their use for classifying chemical status. The UK, like other member states is beginning to implement this and in 2014 to 2015 we undertook a programme to pilot the new EQSs and the EU guidance under conditions in England.
Until 2014 there was no experience of regulatory biota monitoring for chemicals in English freshwaters. An exploratory programme was set up to address a number of issues that were new to us. For most substances, the recommended species for sampling are fish but for some, like PAHs, invertebrates (molluscs or crustaceans) are recommended. For these substances we have used signal crayfish. Sampling sites were strongly dictated by the availability of fish, leading to most sampling toward the lower end of catchments where sufficient fish of a suitable size could be found. For crayfish sampling, sites were selected where this species was abundant.
There are animal welfare and analytical issues to consider, logistical issues in the rapid transfer of biological material to laboratories for analysis and selection of appropriate tissue for analysis. The variability between individuals also needs to be understood before we can use biota data to determine chemical status with confidence. Finally, to present a consistent view of chemical status across Europe, we need to allow for biomagnification of chemicals in the food chain (‘trophic magnification’). For fish data, this means we should estimate concentrations in fish toward the top of the food chain based on measurements in fish at a lower point in the food chain. Our exploratory work also highlighted the lack of reliable information about trophic magnification for all but a few of the substances with a biota EQS.
In the marine environment, there has been a long-term programme of biota monitoring under OSPAR. This has moved away from fish monitoring because of problems with securing sufficient samples within a spatially defined area and has instead relied on sampling shellfish (mussels). We have considered the practicalities of using the existing monitoring strategy as a basis for classifying the chemical status of TraC waters. As in freshwaters, there are few reliable data about trophic magnification for most substances, so it is difficult to estimate compliance with the biota EQS in animals higher up the food chain.
Whilst some of these issues have been resolved, others have not, and future biota monitoring programmes may need a different approach, eg when selecting species. Before reliable decisions can be made using biota standards, further work on trophic status and trophic magnification is needed, as is work on harmonised reporting and attributing status failures to sources.
Owing to these uncertainties, our current assessment of biota monitoring data is therefore preliminary and so we have currently retained the previous water column standards to classify water bodies for these substances.
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Biota standards for mercury in transitional and coastal (TraC) waters are specified for fish in the revised EQSD (2013/39/EU). For the reasons outlined in the text box above, we have data for TraC waters for mussels. Although there are currently uncertainties about the trophic magnification factors that would be needed to account for this difference, the application of the standard in mussels is likely to be the only practicable option for monitoring biota in TraC waters.
As part of the OSPAR Clean Seas Environmental Monitoring Programme (CSEMP) mussels (Mytilus edulis) from 31 TraC water bodies (34 sites) were sampled in England between 2009 and 2014. Mean measured concentrations in the flesh of mussels ranged from 8 to 93µg/kg wet weight.
The water body locations of our biota monitoring strategy and results for freshwater water bodies and for TraC waters using a face value assessment (no adjustment for biomagnification in the food chain) are shown in Figure 5.
At 17 out of 25 freshwater bodies sampled, mercury concentrations were greater than the biota EQS. At 8 sites, the mercury concentration was below the EQS when using a face value assessment. We can adjust the freshwater concentrations for biomagnification as described in the text box above, to allow for comparison of EQS compliance across Europe. When correction factors are applied the adjusted concentrations all exceed the biota EQS, since mercury biomagnifies in the food chain.
At 25 of the 31 sites in TraC water bodies, the concentration of mercury in mussels exceeds the EQS and in 6 sites the concentration was below the EQS. We do not currently have appropriate factors to allow for biomagnifications for the TraC water samples. Based on the outcomes for the freshwater samples, we expect the incidence of mercury EQS failures in TraC waters to be higher if we could adjust for biomagnification in the food chain.
There is no obvious association between the location of current emissions (Figure 3) and the results from our biota monitoring strategy (Figure 5), supporting the view that historical mercury contamination is a major influence on environmental trends and concentrations.
Another option for assessing the risks of a substance with a biota standard is to set an equivalent water column standard that corresponds to the biota EQS. This is known as the 'back-calculated water concentration'. The critical concentration in water would be one that would lead to a concentration of 20µg/kg (wet weight); the biota EQS, in the flesh of biota after biomagnification in the food chain.
Recent research in the Netherlands (RIVM, 2015), published after our classification for 2015 was complete, has proposed an equivalent water concentration of 0.07 nanogram per litre (ng/l) which may open up the possibility of conducting a risk assessment using predicted water column concentrations in future risk assessments. Measurement of mercury in water samples at levels at and below 0.07ng/l is beyond current analytical capabilities, so whilst this could potentially be used to model the extent of failure, it could not be confirmed in the water column.
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Figure 5. Results of our biota monitoring for mercury 2014 to 2015
To gain greater insight into the likely picture of risks posed by mercury at the national scale we have reviewed the scientific literature for measured mercury concentrations in fish in UK fresh and saline waters. The comparison between measured concentrations and the biota EQS in the studies below is again, only a face value assessment with no adjustment for biomagnification or trophic level.
A study of monitoring data (Jürgens et al., 2013) for 2007 to 2011 for fish, mainly roach (Rutilus rutilius) but also bleak (Alburnus alburnus) and eels (Anguilla anguilla), from the rivers Thames, Kennet, Nene and Glen reported concentrations of mercury exceeding the EQS of 20µg/kg wet weight in most (79%) samples. Concentrations ranged from 6 to 68µg/kg wet weight. Concentrations were found to increase with increasing fish weight, reflecting a further complication when interpreting biota residue data. There was no trend assessment, with only one site having reported data for two consecutive years for the same fish, but the authors noted that mercury concentrations were much lower than they had been 20 or 30 years ago in England (Jürgens et al., 2013).
Rose et al. (2014) reported a similar concentration range for mercury in whole fish of 27 to 402µg/kg; exceeding the EQS at all sites.
CEFAS (2012) reported mercury concentrations in dab (Limanda limanda) muscle between 2006 and 2010 in coastal areas of England and Wales. Values were in the range of 52 to 305µg/kg wet weight. For England, elevated concentrations were recorded in the Tyne and Humber areas and
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slightly less elevated values were given for the Eastern and Western Channel. Concentrations were found to be more elevated in some waters adjacent to industrialised estuaries.
In summary, water column monitoring indicates little evidence of EQS failure when data are compared to the water column standards in the 2008 EQSD (2008/105/EU). However, preliminary results of an investigation in English rivers by the Environment Agency and others indicate a high incidence of failure of the biota EQS and this situation would be exacerbated when biomagnification is taken into account as part of the intercalibration required before using this in classification. We plan to undertake further work to better understand the risks posed by mercury over the next RBMP cycle.
5.2. Trends in freshwaters We are able to comment on trends for some TraC waters because of well established monitoring programmes but it is too early yet to draw any conclusions for freshwaters.
We have monitoring data on mercury concentrations in water (as opposed to biota) for a large number of water bodies. This has been used to report compliance since 2009, in the first cycle of the WFD. Because the numbers of water bodies and the method used to assess values reported below the limit of detection has changed over time, it is difficult to assess true temporal trends.
We have reviewed the scientific literature to look for reported trends in environmental concentrations of mercury in the UK to help us understand whether mercury concentrations are declining.
We have analysed our historic freshwater sediment data for mercury for the period 1991 to 2012 collected under the Dangerous Substances Directive to identify any trends in concentrations. Unfortunately the degree of uncertainty associated with the sampling is so high that it is not possible to discern any statistically significant trends (Environment Agency, 2015).
Monitoring at nine lakes across England over the period 2008 to 2012 was conducted by the OPAL Water Centre (Turner et al., 2013). No long-term patterns could be reported for concentrations of mercury in water. The highest mercury concentrations were reported for a pike (Esocidae sp.), a species at the top of the food chain in that lake and greater than 10 years old.
The same report (Turner et al., 2013) associates increases in mercury concentrations in lake sediment cores with industrialisation, particularly fossil fuel combustion; with higher concentrations found in sediments deposited around the mid-20th century. At sites in the Midlands and East Anglia, possible historical increases owing to metal processing, production or manufacture are reported. While a decline in concentration was observed at some sites, other sites showed very little decrease. It was unclear from the study why mercury concentrations were not declining. Remobilisation of mercury from contaminated sediment could be a possibility.
Yang and Smyntek (2014) studied sediment cores from Red Tarn in the Lake District which showed that the sediment record responded well to the decline in UK mercury emissions following the Clean Air Act of 1968 up to the 1990s. There was an increase in the concentration of mercury since 2000; possibly resulting from increased inputs of legacy mercury. These authors suggested that observed and prospective increases in extreme weather events, as predicted by climate change models could result in enhanced erosion, leading to greater inputs of legacy mercury into the environment.
5.3. Trends in transitional and coastal waters The Clean Seas Environment Monitoring Programme (CSEMP) has collected data on concentrations of mercury in fish, sediment and mussel (Mytilus sp.) in marine waters since 1999. Data collected under this programme can be viewed in the UK MERMAN database, hosted by the British Oceanographic Data Centre, using the data assessment tool.
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An overview of monitoring data for mercury collected through CSEMP is given in Figure 5. Data are very variable with only a few sites exhibiting a statistically significant trend.
Under the CSEMP, fish muscle has also been analysed for mercury from 29 sites around England. At four of these sites, concentrations of mercury in fish tissue show a downward trend in concentrations over the reported period (1999 to 2012). There is an upward trend in mercury concentrations in fish sampled from two sites by 2011 (Figure 5). More recent data are not available. Future investigations on trends will focus on mussel tissue because of difficulties in obtaining geographically representative samples in fish, as described previously in the text box in section 5.1.2.
Data for mercury in sediment are also available under the same programme (1999 to 2012). Of 36 sites, three have declining mercury concentrations whilst one site shows an upward trend (Figure 5).
The strongest evidence base for a declining trend in mercury concentrations comes from sampled mussels (Mytilus edulis). Of the 33 sites monitored by the CSEMP, four sites in the North West, Northumbria and Anglian river basin districts show a downward trend (Figure 6).
Combining the CSEMP mussel data with additional monitoring data collected in 2015 suggests a downward trend in mercury concentrations in mussels at a number of specific sites in the Thames, Tyne and Tees (Appendix 1). These are sites where historically we have observed elevated concentrations because of legacy pressures. Interpretation of the data requires care as these site specific trends appear to be substantially influenced by local, short term conditions. For example, winter storms and floods appear to have triggered elevated concentrations in the Tyne and Tees in 2014, possibly because of resuspension of contaminated sediment. This is a complex picture that will require further assessment before we can confidently report a declining trend at these sites.
At some sites where we monitor the concentrations of mercury in mussels we would expect little historical contamination and at these sites we observe little change in concentration with time. The concentrations reported are close to the biota EQS (before it has been adjusted for biomagnification) and mercury concentrations at these sites may reflect coastal background values.
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Figure 6. Monitoring and trends in concentrations of mercury in biota and sediment in English coastal waters covering the period from 1999 to 2012
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6. Control measures 6.1. Restrictions There are numerous control measures for mercury emissions and restrictions for the use of mercury in products, many of which originate from the European mercury strategy (European Commission, 2015b). This was launched in 2005 and specifically addresses mercury emissions to air, an export ban for mercury and certain mercury compounds and restrictions on products containing mercury and industrial processes using mercury.
The Mercury Export Ban (Regulation EC/1102/20084) bans the export and ensures the safe storage of metallic mercury. This regulation does not apply to articles containing mercury.
The Battery Directive (2006/66/EC5) prohibits batteries and accumulators (rechargeable batteries) being placed on the market if they contain more than 0.0005% of mercury by weight. Military and space applications are exempt. The Directive also seeks to improve the environmental performance of batteries and accumulators and of the activities of all those involved in the life cycle of batteries and accumulators, including producers, distributors, end users and those involved in the treatment and recycling of waste batteries and accumulators.
Annex XVII of the REACH Regulation (EC/1907/20066) has several entries relating to mercury restrictions:
• Entry 18 – prohibits the placing on the market or use of mercury for antifouling of boats, as a wood preservative, impregnation of industrial textiles and treatment of industrial waters (EC/552/2009)
• Entry 18a – prohibits the placing on the market of measuring devices (eg thermometers, sphygmomanometers, barometers) containing mercury after 10 April 2014. From 2009 onwards, use of mercury in these items was restricted to professional use only (EC/847/2012)
• Entry 62 – prohibits the placing on the market or use of five phenylmercury compounds from 10 October 2017 (EC 848/2012).
The Restriction of the use of certain Hazardous Substances (RoHS) in Electrical and Electronic Equipment (EEE) Directive (2011/65/EU7) prohibits new electrical and electronic equipment containing mercury from being placed on the market with the exception of some fluorescent lamps.
The Industrial Emissions Directive (IED) (2010/75/EU8) aims to minimise emissions of mercury and other substances from major industrial sources and replaced a number of older directives. These sites require permits which place limits on emissions. Emissions to air are addressed by the specific inclusion of mercury in the IED as a substance requiring application of ‘best available techniques’ to minimise emissions.
There is only one chlor-alkali plant remaining in England; located in Runcorn in the northwest of England. Quantities of metallic mercury used, as reported by the Euro Chlor plant in Runcorn, decreased from 947 tonnes in 2009 to 418 tonnes in 2014 (European Commission, 2015a).
4 Implemented in the UK by The Mercury Export and Data (Enforcement) Regulations 2010 (SI 2010/265).
5 Implemented in the UK by The Batteries and Accumulators (Placing on the Market) Regulations 2008 (SI
2008/2164) and the Waste Batteries and Accumulators Regulations 2009 (SI 2009/890). 6 Implemented in the UK by The REACH Enforcement Regulations 2008 (SI 2008/2852).
7 Implemented in the UK by The Restriction of the Use of Certain Hazardous Substances in Electrical and
Electronic Equipment Regulations 2012 (SI 2012/3032). 8 Implemented in England by The Environmental Permitting (England and Wales) Regulations 2010 (SI
2010/675).
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As a consequence of an absolute lifetime limit on mercury emissions placed on the installation by the Environment Agency and a voluntary agreement with Euro Chlor, the remaining mercury cells at this site are expected to cease operation by 2020.
Since 2005 waste dental amalgam containing mercury has been classified as hazardous waste under the Hazardous Waste Regulations (2008/98/EC9) and requires disposal without endangering human health and the environment. This means that waste dental amalgam cannot be flushed down the drain and must be separated using an amalgam separator.
Mercury is not approved for use in biocidal products under the Biocides Regulations (EU/528/201210). Use of mercury in cosmetic products is also prohibited under the Cosmetics Regulations (EC/1223/200911) and for many years prior to this under the preceding legislation.
The UK is a signatory to the Minimata Convention on mercury. This is a global treaty, ratified October 2013 and aims to protect human health and the environment from the adverse effects of mercury. It bans a range of activities and products with the aim of phasing out emissions of mercury. This includes a ban on new mercury mines, phase out of existing mercury mines, control measures on air emissions Amongst other requirements the convention also requires that mercury emissions from industrial sources such as coal fired power stations are controlled, phasing out/reduction of mercury use in products such as batteries and measuring devices, phasing out/reduction in the use of mercury in manufacturing processes such as chlor-alkali manufacture, and controls over the supply and trade in mercury.
9 Implemented in England by The Waste (England & Wales) Regulations 2011 (SI 2011/988).
10 Implemented in the UK by The Biocidal Products and Chemicals (Appointment of Authorities and
Enforcement) Regulations 2013 (SI 2013/1506). 11
Implemented in the UK by The Cosmetic Products Enforcement Regulations 2013 (SI 2013/1478).
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7. Discussion Mercury is a naturally occurring metallic element but concentrations in the environment have increased because of anthropogenic activity. Mercury has the potential for global, long range transport. Emissions, atmospheric transport and deposition of mercury are therefore a global environmental issue.
Whilst there is a high degree of compliance with the 2008 EQSD (2008/105/EC) in England, there have been significant technical difficulties in implementing the newer standards (revised EQSD; 2013/39/EC) based on the levels found in fish. Our initial work to overcome these issues has suggested that we are likely to be faced with a large number of exceedances of this biota-based EQS in water bodies across England in the future. This could have significant implications for achieving good chemical status. However, this does not indicate increased risks to people from consuming shellfish and fish.
Whilst the reductions in use and emissions of mercury are clearly positive developments, the effect that this will have on the levels found in the water environment is less certain. Mercury cannot be degraded over time and local concentrations may even apparently increase due to remobilisation from land or sediment. As such, any predicted trends in the environment should be treated with caution.
Ensuring compliance with existing measures to reduce further emissions are important elements in managing the issue of environmental mercury, but the success of this strategy is likely to become apparent only over an extended period of time.
Further work will take place over the next river basin management planning cycle in order to understand the extent of compliance with the biota standards, and we will continue to engage with stakeholders on the implications as our knowledge improves.
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Appendix The graphs below summarise monitoring data from selected locations in transitional and coastal (TraC) waters around England and have been used to illustrate possible trends in mercury concentrations in mussels (Mytilus edulis). The data have been collected under the Clean Seas Environmental Monitoring Programme (CSEMP) between 2001 and 2014 and additional EQSD monitoring data we have collected.
Data are plotted as mean ± standard deviation, (n = 3)
Figure 1. Concentration of mercury in mussel (Mytilus edulis) flesh sampled from saline Thames sites, 2001 to 2015. Data are plotted as mean ± standard deviation, (n = 3)
Figure 2. Concentration of mercury in mussel (Mytilus edulis) flesh sampled from saline Tees sites, 2001 to 2015. Data are plotted as mean ± standard deviation, (n = 3)
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Figure 3. Concentration of mercury in mussel (Mytilus edulis) flesh sampled from saline Tyne sites, 2001 to 2015. Data are plotted as mean ± standard deviation, (n = 3)
Figure 4. Concentration of mercury in mussel (Mytilus edulis) flesh sampled from Cleethorpes (Humber), 2001 to 2011. Data are plotted as mean ± standard deviation, (n = 3)
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8. List of abbreviations and acronyms CEFAS Centre for Environment, Fisheries and Aquaculture Science
CIP Chemical Investigations Programme
CSEMP Clean Seas Environment Monitoring Programme
EEE Electrical and Electronic Equipment
EQS Environmental Quality Standard
EQSD Environmental Quality Standards Directive
IED Industrial Emissions Directive
OSPAR OSPAR is the mechanism by which 15 Governments & the EU cooperate to protect the marine environment of the North-East Atlantic.
PBT persistent, bioaccumulative, toxic
PS priority substance
PHS priority hazardous substance
RBMP river basin management plan
REACH Registration, Evaluation, Authorisation and Restriction of Chemicals
SAGIS Source Apportionment Geographic Information Systems
TraC transitional and coastal
uPBT ubiquitous PBT
UK-PRTR UK Pollutant Release Transfer Register
WFD Water Framework Directive
WwTWs waste water treatment works
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9. Glossary Amalgam In dentistry, amalgam is an alloy of mercury with various metals used for
dental fillings. It commonly consists of mercury (50%), silver (~22–32%), tin (~14%), copper (~8%), and other trace metals.
Anthropogenic (chiefly of environmental pollution and pollutants) originating in human activity
Bioaccumulate the accumulation of a substance, such as a toxic chemical, in various tissues of a living organism
Biota The animal and plant life of a particular region, habitat, or geological period
Bioavailability the extent to which a substance can be absorbed by a living organism
Biomagnification the sequence of processes in an ecosystem by which higher concentrations of a particular chemical are reached in organisms higher up the food chain, generally through a series of prey-predator relationships
Chlor-alkali the chlor-alkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of sodium chloride. It is the technology used to produce chlorine and sodium hydroxide (caustic soda), which are commodity chemicals required by industry
Inorganic not consisting of or deriving from living matter
Microorganisms a microscopic organism, especially a bacterium, virus, or fungus
PBT
Persistent, bioaccumulative and toxic. These substances are a class of compounds that have high resistance to degradation from abiotic and biotic factors, high mobility in the environment and high toxicity.
Remobilisation the process of returning a substance to circulation within a particular system
uPBT Ubiquitous PBT. PBTs that are widespread and found everywhere
Volatile (of a substance) easily evaporated at normal temperatures liable to change rapidly and unpredictably, especially for the worse
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