AQUATIC TOXICITY TESTING IN IRELAND 2012 SHANNON AQUATIC TOXICITY LABORATORY

Transcription

1 AQUATIC TOXICITY TESTING IN IRELAND 2012 SHANNON AQUATIC TOXICITY LABORATORY

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3 AQUATIC TOXICITY TESTING IN IRELAND 2012 Shannon Aquatic Toxicity Laboratory Contact: Robert Hernan / Kathleen O Rourke Shannon Aquatic Toxicity Laboratory Shannon Town Centre Shannon Co Clare T: F: HUURobert.hernan@enterprise-ireland.comU HUUKathleen.orourke@enterprise-ireland.comU 3

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5 Summary...7 Introduction...8 Toxicity Testing of Industry...10 Sample Type...12 Receiving Waters Effluents...13 Aquatic Toxicity Tests...16 Effluent Results...17 Test Species Results...21 Solid Waste...23 Other SATL Activities in Quality Control...28 Appendix

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7 Summary 2012 Shannon Aquatic Toxicity Laboratory (SATL) tested 185 samples. o 70% effluents o 18% solid wastes and o 12% others. The Chemical Sector (Category 5) accounted for 45% of the effluents tested. 43% of the effluents discharged to Waste Water Treatment Plants (WWTP), 31% to freshwaters and 26% to coastal waters. 312 toxicity tests were carried out on all samples. 228 tests carried out on 129 effluent samples. The most commonly used species for testing effluent samples were Vibrio fischeri (43%), Tisbe battagliai (17%) and Daphnia magna (16%). 88% of effluent samples tested were within the EPA emission limit value of 10 toxic units. The marine algae Skeletonema costatum was the most sensitive test species with 26% of the tests carried out >10 toxic units. 34 solid waste samples were tested. o 58% of these were <10 toxic units, however after ph neutralisation this increased to 85%. SATL also carried out tests on a range of other samples pilot plant influents and effluents, pharmaceuticals, process lines. All reference chemical quality control requirements were achieved for each species. Inter-laboratory testing was carried out for D.magna, T.battagliai and V.fischeri and was within satisfactory range. 7

8 Introduction Enterprise Ireland s Shannon Aquatic Toxicity Laboratory (SATL) provides an independent nation-wide service to industry and local authorities for investigating the hazards posed by substances discharged to the aquatic environment. The laboratory has over 30 years of experience and is the only toxicity testing laboratory in Ireland. The toxicity (hazard) of a substance is measured by carrying out toxicity tests on a battery of test species ranging from fish, crustaceans and algae. The tests are usually short term (acute) exposures and can be used to assess the potential hazard of a broad range of substances such as effluents, solid wastes, sediments, landfill leachates and chemicals. Substances are deemed harmful to the aquatic environment if they persist, bio-accumulate and are toxic (PBT criteria). Traditionally effluents have been controlled on a substance by substance (chemical specific) basis. The lack of detailed chemical characterisation of some effluents and the potential for combined (synergistic) effects means that the risk to the environment posed by many complex discharges may not be accurately estimated by the chemical specific means alone. Some may remain acutely toxic despite complying with traditional chemical specific discharge conditions. Toxicity tests offer the advantage of measuring the whole effect of the effluent. They measure the effects of both known and unknown substances and the synergistic (combined) effects of constituent chemicals. This is particularly important in the case of complex (non simple) discharges with unknown substances, that will not have environmental quality standards, or for which analytical methods may not exist. A simple discharge is one where all the components have been identified and where the toxicity is explained by the chemical properties of the components, including any potential for combined effects. The toxicity tests are not used to 8

9 assess the degree of actual harm but to provide a robust prediction of the hazard posed by the effluent, which can then be used within a risk assessment process. An integrated (holistic) approach combining chemical, toxicological and biological assessment, especially of complex discharges, is recommended by many environmental regulators. This integrated approach is applied in many countries: US EPA (Whole Effluent Tests, WETs), Canada, England and Wales (Direct Toxicity Assessment) and in many EU countries. The OSPAR Commission also advocate the use of Whole Effluent Assessment (WEA) to allow greater protection of aquatic life. In Ireland the EPA have used toxicity tests as part of their IPPC licences since

10 Toxicity Testing of Industry The EPA, as part of their IPPC programme, has categorised various industrial activities (Table 1) and require toxicity testing of discharges that are deemed non-simple (complex). Non-simple (complex) discharges are those whose effects cannot easily be accounted for by the traditional substance by substance approach. In 2012, SATL carried out 228 tests on effluent samples from companies in 11 of the 13 EPA categories, the exceptions being categories 6 and 13 (Fig 1 and Table 2). Most samples came from companies in the Chemical sector (Category 5, 54%) followed by Consultants (Cat. 14, 15%) and Minerals and other materials (Cat. 1), Food and Drink (Cat. 7) and WWDA (Cat. 15) all on 5%. Table 1: EPA Category of Industry Category of Industry Activity 1 Minerals and other materials 2 Energy 3 Metals 4 Mineral fibres and glass 5 Chemicals 6 Intensive Agriculture 7 Food and Drink 8 Wood, Paper, Textiles and Leather 9 Fossil Fuels 10 Cement 11 Waste 12 Surface Coatings 13 Other Activities (e.g. testing of engines, lime kilns, ceramics) 14* Other (Consultants, Local Authorities, EPA) 15* Wastewater Discharge Authorisation (WWDA) * SATL designation 10

11 Figure 1: Origin of Effluent Samples, 2012 M inerals & other materials Energy No. of Companies M etals M ineral fibres & glass Chemicals Intensive Agriculture Food and Drink Wood, Paper, Textiles and Leather Fossil Fuels Cement Waste 0 Category of Industry Surface Coatings Other Activities Other WWDA Table 2: Origin of Effluent samples, 2012 Category of Industry No. of Companies % No. of Samples Total % 11

12 Sample Type SATL receives a variety of samples each year including effluents, solid wastes and others. Others can be anything from chemicals, process lines, and landfill leachates to marine sediments. The main driver for aquatic toxicity testing is the EPA IPPC licensing Framework. Some landfill sites require toxicity testing to compliment the chemical analysis to assess suitability of the solid waste for land-filling. In 2012 SATL received 185 samples, 70% of which were effluents, 18% solid wastes and 12% others (Figure 2). Figure 2: Sample Type, No. of Samples Effluent Solid Waste Other Sample Type 12

13 Receiving Waters Effluents The main purpose of IPPC Licences is to protect aquatic life in the receiving environments, be they surface waters (marine, estuarine, freshwater) or Waste Water Treatment Plants (WWTP). The salinity of the receiving waters dictates the appropriate battery of aquatic test species to be used (Table 3). Table 3: Receiving Waters and Appropriate Test Species Trophic Level Marine /Estuarine Receiving Water Freshwater Fish Psetta maxima (turbot) Oncorhynchus mykiss (rainbow trout) Crustacean Tisbe battagliai Daphnia magna Plant/Alga Skeletonema costatum Pseudokirchneriella subcapitata Bacterium Vibrio fischeri Vibrio fischeri If a discharge goes to a WWTP, the most appropriate test is respirometry along with the fish/crustacean/algal tests appropriate to the receiving waters downstream of the WWTP. In 2012, 43% of effluent samples tested by SATL discharged to Waste Water Treatment Plants (WWTP), 31% to freshwaters and 26% to coastal waters, (see Figure 3). Effluents from Category 5 (Chemical) discharge predominantly to WWTPs (63%) or to coastal waters (26%) and freshwaters (11%) (See Figure 4 and Table 4). 75% of Categories 1 (Minerals and other materials) and 7 (Food and drink) discharge to freshwaters. 13

14 In recent years increasing numbers of discharges are going to WWTPs such as Ringsend (Dublin), Carrigrennan (Cork), Bunlicky (Limerick) and Mutton Island (Galway). This enhanced waste treatment reduces the risk to the receiving waters. Table 4: Effluent Receiving Waters, 2012 Category of Industry Freshwater Marine Estuary WWTP Number Total %

15 Figure 3: Effluent Receiving Waters, % Freshwater Marine Estuary WWTP Receiving Waters Figure 4: Category 5 Effluent Receiving Waters, % Effluents Freshwater Marine Estuary WWTP Receiving Waters 15

16 Aquatic Toxicity Tests The test species used are selected and validated based on a number of criteria including: Practicality of method; Sensitivity to a wide range of compounds; Standardisation; Demonstration of acceptable inter-test variability (through ring testing); Ecologically appropriate. Toxicity is chemical specific and organism specific i.e. different chemicals act in different ways and different organisms respond in different ways. No one species is always the most sensitive for all chemicals or effluents. Thus, it is important to test a battery of organisms from different trophic levels, generally a fish, crustacean and alga. Tests organisms are exposed to a concentration series of the effluent for a designated time, generally short term (acute), but can also be long term (chronic). At the end of the exposure time the effects (e.g. lethality, immobilisation) are measured. This allows for the drawing of a concentration-effect graph and calculation of an LC 50 (Median Lethal Concentration) or EC 50 (Median Effective Concentration). Toxic units are calculated by dividing 100 by the LC 50 or EC 50. The EPA requires that initial screening is carried out on a final effluent sample to at least four aquatic species from different trophic levels. Subsequent compliance monitoring is carried out on the two most sensitive species. The EPA has assigned a toxicity emission limit value of no more than 10 toxic units to most effluent discharges. This means that after 10 dilutions the effluent should cause no more than 50% effect. 16

17 SATL has classified the acute toxicity results into five different categories (Table 5). Table 5: Toxicity Classification Toxic Units Description < 3 Non Toxic 3-10 Slightly Toxic Toxic Very Toxic > 100 Extremely Toxic Effluent Results In 2012, SATL carried out 228 tests on 129 effluent samples from 75 different companies. The most tested species were V. fischeri (99), T.battagliai (39) and D.magna (37) (Table 6). 88% of the samples tested were within the 10 toxic unit emission limit value assigned by the EPA, which is comparable with results from recent years (Figures 5 and 6). 78% of these were <3 toxic units, 10% <10, 8% were between 10 and 50 toxic units, 1% between 50 and 100 and 3% >100, Table 7. Of the 34 Chemical sector companies tested, 9% (3) were outside the 10 toxic unit emission limit value (Table 8). All three discharged to WWTP. 17

18 Table 6: Effluent Toxicity Classification, 2012 Species < >100 Total Number Oncorhynchus mykiss Daphnia magna Pseudokirchneriella subcapitata Vibrio fischeri Psetta maxima Tisbe battagliai Skeletonema costatum Lemna minor Crangon crangon Tigriopus brevicornis Totals Table 7: Effluent Toxicity Classification, 2012 Toxic Units % Effluents < >

19 Figure 5: Effluent Compliance, Pass Fail % 2012 Year Figure 6: Effluent Toxicity Classification, < > % Year 19

20 Table 8: Effluent Compliance per Industrial Category, 2012 Category Effluents Fail > 10 Toxic Units In recent years the majority of effluents have been within the 10 toxic unit limit (Figure 5) and the 2012 data indicates that the steady improvement continues. In the period from 1983 to 1990 the reverse was the situation with most effluents greater than the 10 toxic unit limit. Indeed a number were extremely toxic at >100 toxic units. The improvement in the discharges may be due to improved treatment of effluents on site. Also the EPA came into being in 1992 and introduced toxicity requirements into its IPPC licences which may have acted as a driver for dischargers to identify (Toxicity Identification Evaluation) and reduce toxicity (Toxicity Reduction Evaluation). Prior to 1992 the Local Authorities issued licences and only a few of these, mainly Cork County Council, required toxicity testing of effluents. 20

21 Test Species Results In 2012 S. costatum was the most sensitive test species followed by T.battagliai and V.fischeri (Figure 7 and Table 9). Sensitivity is based on the percentage of effluent tests per species with a result greater than 10 toxic units. Historically we have found that the fish tests, rainbow trout and turbot, are the least sensitive test species. Other species including Lemna minor and Crangon crangon have also exhibited low sensitivity to effluents. In general the marine alga, S. costatum, is the most sensitive. Figure 7: Effluents, Tests Species Compliance, % Pass O.mykiss D.magna P.subcap V.fischeri P.maxima Tisbe S.costaum L.minor C.crangon Tigriopus Test Species 21

22 Table 9: Test Species, % Compliance, 2012 Species % Pass <10 Toxic Units % Fail > 10 Toxic Units O.mykiss D.magna 92 8 P.subcapitata V.fischeri P.maxima T.battagliai S.costatum L.minor C.crangon T.brevicornis

23 Solid Waste The type of solid waste samples tested include industrial/local authority wastewater treatment plant sludges, local authority drinking water treatment plant sludges and dried filter cakes from belt presses. An eluate is generated from the solid waste sample using a German DIN standard method. The toxicity of the eluate is assessed using aquatic organisms from three trophic levels (crustaceans, algae and bacteria). In 2012, SATL tested 34 waste samples with the majority of the samples coming from Category 14, Local Authorities/Consultants (22) and Category 5, Chemicals (6) (Figure 8 and Table 10). The number of waste samples tested per year over the last 15 years ranged from 20 to 73. Figure 8: Origin of Solid Waste Samples, No. of samples Chemicals Wood, paper, textiles and leather Waste Other(Consultants, Local Authorities, EPA) Category of Industry 23

24 Table 10: Origin of Solid Waste Samples, 2012 Category Number of Companies % Number of Samples % 1,2, 3, , , , Total In 2012, 58% of the samples tested were <10 toxic units before ph neutralisation and 85% were <10 toxic units after ph neutralisation. 15 eluates required ph neutralisation (ph outside 6-9), resulting in a reduction of toxicity in 13 of the eluates to < 10 toxic units. Two eluates had low dissolved oxygen and were aerated prior to testing and the toxicity results where within 10 toxic units. Figure 9 looks at the solid waste results for all wastes tested from Each year at least 69% or more of waste samples tested were <10 toxic units except in 1999 (54%). Table 11: Solid Wastes, Toxicity Classification, 2012 Toxic Units % Solid Wastes % Solid Wastes - after ph neutralisation < >

25 Figure 9: Solid Waste Results, Solid Waste Results < 10 Toxic units > 10 Toxic units % Year 25

26 Other SATL Activities in 2012 Toxicity testing was also carried out on a range of other test substances from pilot plant influents and effluents, in-process wastewaters, existing and newly introduced chemicals, e.g. surfactants, and waste samples for hazardous waste classification. Toxicity tests where used for both toxicity identification evaluation (TIE) to evaluate the toxicity of different waste streams and toxicity reduction evaluation (TRE) to determine best treatment options. TIE is a systemic investigation involving physicochemical manipulation, e.g. ph adjustment, activated carbon treatment, combined with toxicity tests to track the toxicity and attempt to ascertain the toxic agent. TRE is an examination of various remedial treatments to improve the quality of the effluent end of pipe approach. SATL collaborated with Dr Brian Quinn (GMIT) and Gillian McEneff (DCU) in assessing the bioaccumulation of pharmaceuticals in rainbow trout. Mussels were placed downstream of Ringsend WWTP and these exposed mussels were fed to O.mykiss in a 28 day exposure and the bioaccumulation of various pharmaceuticals was assessed. SATL also collaborated with Sligo IT, Dr Frances Lucy/Sara Meehan, in investigating the toxic effects of the natural pesticide Zequanox (MBI-401) to aquatic organisms. It is hoped that the pesticide will be used against the zebra mussel. SATL examined the toxic effect of the pesticide to Salmo trutta (brown trout) and Daphnia magna (acute and chronic). Technical advice was provided to a number of other research institutions, e.g. UCC, TCD, UCD, UL, IT Tralee and Cork IT. 26

27 SATL held ecotoxicological workshops for EPA licensing officers and for the Environmental Toxicology Unit of the Department of Agriculture Food and Marine s Pesticide Registration & Control Division. SATL presented a poster Effluent toxicity testing in Ireland ( ) at the Environmental Science Association Ireland s 2013 Irish Environmental Researcher s Colloquium in January in Galway. A platform presentation on Effluent toxicity testing in Ireland ( ) will be presented at the 23 rd Annual Meeting of the Society of Environmental Toxicology and Chemistry (SETAC Europe) in May in Glasgow. SATL has the capacity to use other test species including Crangon crangon (estuarine shrimp), Lemna minor (duckweed) Tigriopus brevicornis (marine copepod) and various terrestrial species. 27

28 Quality Control SATL maintains a quality assurance system to ensure accurate and precise results. Tests are carried out using internationally recognised procedures (e.g. ISO or OECD), as outlined in Appendix 1. SATL routinely carries out reference chemical testing and in 2012 all reference testing was compliant (Table 12). The reference chemicals used are zinc sulphate, potassium dichromate and dichlorophenol. The test methods assign upper and lower compliance limits for each chemical (generally based on ring tests) and a test is valid if it meets these limits. Table 12: Mean Reference Chemical Data, 2012 Species Reference Chemical ZnSO 4 mg/l Zn K 2 Cr mg/l 3,5 DCP mg/l O.mykiss * - D.magna P.subcapitata V. fischeri P.maxima * - T.battagliai S. costatum *Mean Result over a number of years. SATL also participate quarterly in an inter-laboratory proficiency scheme with Aquacheck for the D.magna, T.battagliai and V.fischeri tests and all were within satisfactory range for

29 Appendix 1 Toxicity Test Methods and Procedures 1. Freshwater Crustacean ISO 6341:1996/Cor.1:1998: Water quality Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) Acute toxicity test 1B1B1B2. Marine Bacterium ISO :2007: Water quality - Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) Part 3: Method using freeze-dried bacteria 3. Marine Copepod ISO 14669:1999: Water quality Determination of acute lethal toxicity to marine copepods (Copepoda, Crustacea) 4. Marine Algae ISO 10253:2006: Water quality - Marine algal growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum 5. Freshwater Algae ISO 8692:2004: Water quality Freshwater algal growth inhibition test with unicellular green algae [Pseudokirchneriella subcapitata] 6. Freshwater Plant ISO 20079:2005: Water quality Determination of the toxic effect of water constituents and waste water to duckweed (Lemna minor) Duckweed growth inhibition test 7. Marine Fish OECD 1992: Guideline 203: - Fish, acute toxicity test 8. Freshwater Fish OECD 1992: Guideline 203: - Fish, acute toxicity test 9. Estuarine Crustacean Method 6.9 based on MAFF SOP No. BEG/030:1996: Brown Shrimp (Crangon crangon) 96 h acute toxicity for liquid effluents and wastes 10. Marine Amphipod ICES, No. 28, 2001: Biological effects of contaminants: Corophium sp. sediment bioassay and toxicity test 11. Eluate Generation Eluate Generation based on DIN part 4, 1984: Sludge and Sediments (Group S) Determination of leachability by water (S4) 29