The EU Water Framework Directive (WFD) (2000/60/EC) was transposed into Irish law in 2003 as the European Communities (Water Policy) The level of priority substances present in water bodies is most commonly judged against set environmental quality standards (EQSs) . These standards dictate the maximum allowable concentrations (MAC EQS) or range of concentrations (Annual Average or AA EQS) of specific pollutants allowed to ensure compliance with the EC guidelines. The EU WFD was transposed into Irish Law in 2003 and as such these EQS values now form the basis of priority substance water monitoring in Ireland

Cahill, Michael

Forde, Ken

Furey, Ambrose

Jones, Lisa

Kinsella, Brian

Lawlor, Antoin

Regan, Fiona

DCU Online Research Access Service

Lisa Jones*1, Antoin Lawlor1, Michael Cahill2, Brian Kinsella2, Ken Forde2, Ambrose Furey2, Fiona Regan1.  1NCSR, Dublin City University, Ireland. 2 Cork Institute of Technology, Ireland. Polycyclic Aromatic Hydrocarbons (PAHs)   This project is funded by the EPA as part of the Science, Technology, Research and Innovation for the Environment (STRIVE) Programme 2007–2013. This programme is financed by the Irish Government under the National Development Plan 2007–2013.   Pesticides The EU Water Framework Directive (WFD) (2000/60/EC) was transposed into Irish law in 2003 as the European Communities (Water Policy) The level of priority substances present in water bodies is most commonly judged against set environmental quality standards (EQSs) . These standards dictate the maximum allowable concentrations (MAC EQS) or range of concentrations (Annual Average or AA EQS) of specific pollutants allowed to ensure compliance with the EC guidelines. The EU WFD was transposed into Irish Law in 2003 and as such these EQS values now form the basis of priority substance water monitoring in Ireland.   Priority Pollutants Priority and Hazardous Substances Volatile Organic Compounds (VOCs) Metals/Trace Elements Pesticide Mol. Wgt (g) AA EQS (µg L-1) Pesticide Mol. Wgt (g) AA EQS (µg L-1) Alachlor 269.77 0.3 Simazine 201.66 1 Atrazine 215.68 0.6 para-para-DDT 354.49 0.01 Chlorfenvinhos 359.57 0.1 Aldrin 364.91 ∑=0.005 Brominated Diphenylethers 564.70 0.0002 Dieldrin 380.91 Chlorpyrifos 350.59 0.03 Endrin 380.91 Maneb 265.30 0.1 Isodrin 364.91 Diuron 390.54 0.2 Trifluralin 335.28 Di(2-ethylhexyl) phthalate (DEHP) 233.09 1.3 Epichlorohydrin 92.53 0.1 Zineb 275.74 0.1 Mecoprop 214.65 0.02 Hexachlorobenzene 284.80 0.01 Pirimiphos Methyl 305.30 0.05 Hexachlorobutadiene 260.76 0.1 Fenitrothion 277.20 0.01 Thiram 240.43 0.1 Malathion 330.36 0.01 Isoproturon 206.28 0.3 Epoxiconazole 329.76 0.1 (4-(para)-nonylphenol) 220.35 0.3 Glyphosate 169.08 0.1 Para-tert-octylphenol 206.32 0.01 α -Endosulfan 406.93 0.0005 Pentachlorobenzene 250.34 0.0007 Hexachlorocyclohexane (Lindane) 290.83 0.002 Pentachlorophenol 266.34 0.4 Mancozeb 266.31 0.1 VOCs Mol. Wgt (g)  AA EQS (µg L-1) Benzene 78.11 8 1,2-Dichloroethane 98.96 10 Dichloromethane 84.93 20 Trichlorobenzenes 181.45 0.4 Trichloromethane 119.38 2.5 Carbontetrachloride 153.82 12 Tetrachloroethylene 165.83 10 Trichloroethylene 131.39 10 PAH Mol. Wgt (g)  AA EQS (µg L-1) Anthracene 178.23 0.1 Fluoranthene  202.25 0.1 Naphthalene 128.17 1.2 Benzo(a)pyrene 252.31 0.05 Benzo(b)fluoranthene 252.31 ∑=0.03 Benzo(k)fluoranthene 252.31 Benzo(g,h,i)perylene 276.33 ∑=0.002  Indeno(1,2,3-cd)pyrene 276.33 Mol. Wgt (g) AA EQS ( µg L-1) Mol. Wgt (g) AA EQS (µg L-1) Lead cmpds 207.20 7.2 Mercury cmpds 200.59 0.05 Nickel cmpds 58.69 20 Antimony 121.75 0.4 Fluoride 18.90 1000 Molybdenum 95.94 4.3 TBT cmpds 291.06 0.0002 Tin 118.69 0.2 Arsenic 74.92 1 Barium 137.34 1 Zinc 65.39 2.3 Boron 10.81 6.5 Copper 63.54 0.5 Vanadium 50.94 0.9 Chromium 52 0.3 Cobalt 58.93 0.2 Selenium 78.96 5.3 Cadmium 112.41 0.2 Note: The AA EQS values listed above apply to freshwater systems. MAC EQS values were not  available for all compounds listed.  Anthracene Fluoranthene  Naphthalene Benzo(a)pyrene Benzo(b)fluoranthene Indeno(1,2,3cd)pyrene Benzo(k)fluoranthene Benzo(g,h,i)perylene   This project is funded by the EPA as part of the Science, Technology, Research and Innovation for the Environment (STRIVE) Programme 2007–2013. This programme is financed by the Irish Government under the National Development Plan 2007–2013.   Dangerous Substances Directive 76/464/EEC and 2006/11/EC   The EU Water Framework Directive (2000/60/EC) Legislation Controlling the Emission of Priority Pollutants Although many efforts have been made in the area of environmental policy, a significant step towards a cleaner environment was taken in October 2000 as the European Parliament established the Water Framework Directive (WFD). This document acts as a single piece of legislation which covers rivers, lakes, groundwater and transitional (estuarine) and coastal waters. The main objective of this directive is to attain „good‟ status in water bodies that are below „good‟ status at present, as well as to retain „good‟ or better status where it currently exists, by 2015.The WFD was transposed into Irish law in 2003 as the European Communities (Water Policy) Regulations 2003 (S.I. 722 of 2003) and is the principal piece of legislation governing water quality in Ireland. Under this legislation water bodies in Ireland were divided into 7 River Basin Districts (RBD‟s), which are river catchments or groups of catchments, which must be monitored.   The WFD aims to „achieve the elimination of priority hazardous substances and contribute to achieving concentrations in the marine environment near background values for naturally occurring substances‟ with a list of priority hazardous substances being defined and established by an amendment to the WFD in 2001.  This Directive lays down rules for protection against, and prevention of, pollution resulting from the discharge of certain substances into the aquatic environment. It applies to inland surface water, territorial waters and internal coastal waters. Two lists of dangerous substances have been compiled to combat pollution: discharge of substances in list I must be eliminated; while discharge of substances in list II must be reduced. Pursuant to Annex IX of the WFD, quality objectives and emission limit values are established by the “daughter directives” of Directive 2006/11/EC. Moreover, emission limit values for pollutants must be based on the best available techniques in line with Article 10 of the WFD. All discharges of substances included in list I require prior authorisation by the competent authority in the Member State concerned. For the substances on list II, the Member States adopt and implement programmes to preserve and improve water quality. All discharges are subject to prior authorisation by the competent authority in the Member State concerned that lays down the emission standards.  The Member States draw up an inventory of the discharges into the waters covered by this Directive and may take more severe measures than those laid down by Community legislation to reduce or eliminate pollution caused by dangerous substances. Before 22 December 2012, Member States may carry out surveillance and notification pursuant to Articles 5, 8 and 15 of the Water Framework Directive. 1972  Federal Water Pollution Control Ammendments in the USA are introduced.  1976 Dangerous Substances Directive introduced. 1994 Integrated Pollution Control (IPC) Licensing introduced Water Framework Directive introduced.  EPER, predecessor of the E-PRTR, is established. 2000 WFD transcribed into Irish law. IPC licensing amended to IPPC licensing. 2003 Dangerous Substances Directive codified to include all amendments. E-PRTR issued. Groundwater Directive introduced. 2006 Water Information System for Europe (WISE) launched. 2007 IPPC Directive codified to include all amendments 2008 EU WFD Dangerous  Substances Dangerous Substances Directive codified QA/QC Commission Directive introduced.  S.I. 272 establishes EQS values for priority pollutants in surface waters. 2009 EQS values established for PPs in surface waters Lisa Jones*1, Antoin Lawlor1, Michael Cahill2, Brian Kinsella2, Ken Forde2, Ambrose Furey2, Fiona Regan1.  1NCSR, Dublin City University, Ireland. 2 Cork Institute of Technology, Ireland. Monitoring and Modelling the Occurrence of Priority Substances in Wastewater Lisa Jones*, Antoin Lawlor,Fiona Regan.  1NCSR, Dublin City University, Ireland. lisa.a.jones@gmail.com   Introduction In 2000 the Water Framework Directive (WFD), 2000/60/EC, was introduced and a group of 66 chemicals, including pesticides, polycyclic aromatic hydrocarbons, and metals were  listed as chosen priority pollutants. The levels of these priority pollutants in the environment are regulated by set environmental quality standards (EQSs) and are affected by a number of emission factors including anthropogenic activities, population equivalents, and weather. In order for these EQSs to be enforced, regular monitoring of all water bodies must be carried out, a process which is both costly and time consuming. We have developed a model defining emission levels relating to priority pollutants occurrence in the environment. This is based on information collected from local authorities, Met Eireann and pollutant levels in waste water treatment plant (WWTP) effluents.  WWTP: Ringsend Swords Ballincollig   Bandon Charleville Fermoy Mallow Ringaskiddy Population Equivalent 1,900,000 50,000 26,000 20,000 15,000 20,000 18,000 97,556 Main contributions Industrial and  domestic Domestic and agriculture Domestic and  Industrial Level of treatment Tertiary Secondary None Type of sample Grab Composite Grab Composite Over the sampling plan 71 samples were collected over an 18 month period with intensive sampling for several weeks of the summer and winter.  Wastewater effluent was the chosen medium for this study for a because it is:  A major point-source input to surface waters Responsible for localised EQS exceedances Often upstream of drinking water abstraction Controllable.  Data on emission factors was collected to populate our model and map the patterns between these emission factors and the occurrence of our priority pollutants.    This study involved the analysis of samples from 8 WWTPs in both Cork and Dublin, Ireland, for priority pollutants, Table 1. These sites were chosen for their varying population equivalents, geographic locations, and main contributions, in order to make the final model of emission factors as comprehensive as possible.  Table 1 – Comparison of WWTPs included in this study, with the largest sites; Ringsend and Swords, located in County Dublin, and the rest of the sites located in County Cork.  Figures 1, 2 - Relation of flow through a WWTP and local rainfall. Then relation of rainfall to TSS levels in WWTP effluent. 0200000400000600000800000100000012000000.00E+005.00E-051.00E-041.50E-042.00E-042.50E-0410/09/2009 10/01/2010 10/05/2010FLOW m3/day Anthracene FluorantheneBenzo-b/k-fluoranthene Benzo-a-pyrene Indeno-1,2,3cd-pyreneBenzo-ghi-peryleneConc. (µg/L) Flow m3/day Compared rainfall levels and TSS levels to PP levels in the WWTP effluent (Figures 3 and 4). Increased rainfall can bring forward stale sewage in a flushing effect. PPs in wastewater greatly increase, sometimes 10 – 100 fold when compared to dry weather levels. This specifically affects PAHs with regard to road-runoff, with PAHs being released from motor vehicles as particulates which settle on the roads and are washed into the sewers during periods of rainfall.   Increased rainfall and thus increased TSS content increased the PAH levels, but we can see that the more water soluble PAHs (e.g. anthracene) increased more than the less water soluble PAHs (e.g. benzo-ghi-perylene) as they were likely adsorbed onto the solid material.   Figures 3,4 -  Relation of flow through a WWTP and PAH concentration, with the insert highlighting the value of intensive sampling data. Relation of PAH concentration to total suspended solids levels in WWTP effluent.  Parameter AA EQS (µg L-1) LOD  SPE-GCMS  (µg L-1) Frequency (N=71) Range         Min Max Naphthalene 1.2 0.0001 48 1.07 x 10-4 0.035 Anthracene 0.1 0.0005 27 6.30 x 10-4 0.013 Fluoranthene 0.1 0.0001 28 1.40 x 10-4 0.0086 Benzo-b/k-fluoranthene Σ=0.003 0.0001 29 1.20 x 10-4 0.0044 Benzo-a-pyrene 0.05 0.0005 19 5.50 x 10-4 0.0036 Indeno-1,2,3cd-pyrene Σ=0.002 0.0005 35 1.55 x 10-4 0.0025 Benzo-ghi-perylene 0.0005 20 5.90 x 10-4 0.0032 Conclusions Figures 1 and 2 show the relation between rainfall and flow through the WWTP, and then rainfall and total suspended solids (TSS) through the WWTP.   Table 2 summarises the results for one group of PPs over the sampling timeframe., compared to the Annual Average EQS (AA EQS) level. All samples tested positive for PAHs, but never exceeded these standard values. Table 2 – Summary of results for one group of the priority pollutants, the PAHs.  0510152025300.00E+005.00E-061.00E-051.50E-052.00E-052.50E-0515/10/2009 15/11/2009 15/12/2009 15/01/2010TSS mg/L Anthracene FluorantheneBenzo-b/k-fluoranthene Benzo-a-pyrene Indeno-1,2,3cd-pyreneBenzo-ghi-peryleneConc. (µg/L) TSS (mg L-1) This project is funded by the EPA as part of the Science, Technology, Research and Innovation for the Environment (STRIVE) Programme 2007–2013. This programme is financed by the Irish Government under the National Development Plan 2007–2013.   This study serves to inform targeted priority substance monitoring, highlighting the importance of high intensive sample collection, especially with regard to valuable temporal variation data, and the value of creating an index of emission factors relating to priority substance occurrence in the environment.   TSS (mg L-1) and Rainfall (mm) Results 

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