Occurrences of priority substances in selected catchments
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Occurrences of Priority Substances in Selected
Catchments
L. Jones, B. Kinsella, A. Furey, F. Regan
Outline • Project aim • Sampling plan and catchments • Rainfall data • PAH levels • Total Suspended Solids
Project Outline • Monitor priority pollutant levels in wastewater treatment plant ef4luents • SPE, GC-‐MS, LC-‐FLD/MS, ICPAES
• Relate levels detected to emission factors • Population equivalents, rainfall, traf4ic, etc.
• Create model/index of priority substance emissions from wastewater treatment plants
Priority Substances in Wastewater • Wastewater major point-‐source • Responsible for localised EQS exceedances • Often upstream of drinking water abstraction • Can be controlled • Few data on wastewater PS discharges • Will complement storm water studies, and inform targeted PS monitoring
Sampling Site Overview
WWTPs • Cork
• Ballincollig • Bandon • Charleville • Clonakilty • Fermoy • Mallow • Ringaskiddy
• Dublin • Ringsend • Swords
Site Overview WWTP Level of
Treatment Type of Treatment Agglomeration
PE Plant PE
Receiving Waters
Ballincollig Secondary Activated sludge (Aeration Basin)
16,339 15,000 Freshwater (R)
Bandon Secondary
Activated sludge (Oxidation Ditch)
8178 20,000 Freshwater (R)
Charleville Secondary 2,984 6,415 Freshwater (R)
Clonakilty Secondary 7,500-15,000 15,000 Estuarine Fermoy Secondary,
NR Activated sludge
(Oxidation ditches; anaerobic-, anoxic- and
aeration tanks) Phosphorous Removal
5,800 12,960 Freshwater (R)
Site Overview WWTP Level of
Treatment Type of Treatment Agglomeration
PE Plant PE Receiving
Waters Mallow Secondary,
NR Activated sludge
(Anaerobic-, anoxic- and aeration tanks)
Phosphorous Removal
7,091 12,000 Freshwater (R)
Ringaskiddy None None 14,864 0 Estuarine
Ringsend Tertiary Activated sludge (Sequencing Batch
Reactors) U.V Disinfection
2,870,333 1,640,000 Estuarine
Swords Secondary Activated sludge (Anaerobic-, anoxic- and aeration tanks)
50,000 60,000 Estuarine
SAMPLING PLAN
• Populate model • Temporal and seasonal variability • Flexible
– DWF / WWF • Monthly samples • Intensive sampling
Rationale
Site Sample Type Timeframe (months)
Volume (L) Sample Breakdown
Ballincollig Grab 14 6.5
6 x 500 mL PAH analysis (3 filtered) 6 x 500 mL Pesticide analysis
(3 filtered) 500 mL Metals analysis
Bandon Grab 13 6.5
Charleville Grab 12 6.5
Clonakilty Grab 4 6.5
Fermoy Grab 13 6.5
Mallow Grab 13 6.5
Ringaskiddy Grab/Comp. 12 6.5
Ringsend Grab 25 12.5 6 x 1 L PAH analysis (3 filtered) 6 x 1 L Pesticide analysis (3 filt.)
500 mL Metals analysis Swords Composite 20 12.5
SAMPLING PLAN
Typical Sampling Campaign 2009 2010 2011
Month J A S O N D J F M A M J J A S O N D J F M A M J J
Ballincollig X
Bandon
Charleville
Clonakilty
Fermoy
Mallow
Ringaskiddy
Ringsend X X X X X X
Swords X X X X X X
RAINFALL DATA
Rainfall Stations
Dublin (Ringsend) Dublin
(Simmonscourt) Dublin
(Merrion Square)
Dublin (Ringsend) 1 Dublin (Simmonscourt) 0.66615 1 Dublin (Merrion Square) 0.89307 0.68413 1
Rainfall Data
Mallow (Sewage Treatment Works) Mallow (Spa House)
Mallow (Sewage Treatment Works) 1 Mallow (Spa House) 0.37697 1
PAH OCCURRENCE
Anthracene
Fluoranthene
4.63
4.7 – 5.33
Naphthalene
3.3
Benzo(a)pyrene
5.97– 6.15
Benzo(b)fluoranthene
5.78 – 6.57
Indeno(1,2,3cd)pyrene
6.4 – 7.1
Benzo(k)fluoranthene
6.00 – 6.84 6.18 – 7.23
Benzo(g,h,i)perylene
PAHs and Log Kow Values
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=33
Range
min max Naphthalene 1.2 0.0001 33 5.44 x 10-‐4 1.69 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 33 <LOD 2.33 x 10-‐2 Fluoranthene 1 x 10-‐1 0.0001 33 <LOD 1.89 x 10-‐2 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001
15 <LOD 4.02 x 10-‐2
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 12 <LOD 3.03 x 10-‐2 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005
21 <LOD 4.21 x 10-‐2
Ballincollig June 2010 – May 2011
Bandon July 2010 – May 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=24
Range
min max Naphthalene 1.2 0.0001 24 <LOD 2.92 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 24 <LOD 1.10 x 10-‐3 Fluoranthene 1 x 10-‐1 0.0001 21 <LOD 6.14 x 10-‐4 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 12 <LOD 1.84 x 10-‐4 Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 6 <LOD <LOD Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 6 <LOD <LOD
Charleville August 2010 – May 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=9
Range
min max Naphthalene 1.2 0.0001 9 <LOD 2.98 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 9 <LOD 2.87 x 10-‐3 Fluoranthene 1 x 10-‐1 0.0001 9 <LOD 1.44 x 10-‐3 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 3 <LOD 1.79 x 10-‐3
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 3 <LOD 1.57 x 10-‐3 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 9 <LOD 4.67 x 10-‐2
Clonakilty April – May 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=6
Range
min max Naphthalene 1.2 0.0001 6 <LOD 1.67 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 6 <LOD 7.60 x 10-‐4 Fluoranthene 1 x 10-‐1 0.0001 6 <LOD 2.34 x 10-‐4 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 0 nd nd
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 0 nd nd Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 0 nd nd
Fermoy July 2010 – May 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=27
Range
min max Naphthalene 1.2 0.0001 27 <LOD 2.76 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 21 <LOD 1.52 x 10-‐3 Fluoranthene 1 x 10-‐1 0.0001 24 <LOD 2.56 x 10-‐4 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 9 <LOD <LOD
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 6 <LOD 2.07 x 10-‐2 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 9 <LOD 4.36 x 10-‐3
Mallow July 2010 – May 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=30
Range
min max Naphthalene 1.2 0.0001 30 <LOD 3.00 x 10-‐3 Anthracene 1 x 10-‐1 0.0005 21 <LOD 6.53 x 10-‐4 Fluoranthene 1 x 10-‐1 0.0001 18 <LOD 7.36 x 10-‐4 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 12 <LOD 3.12 x 10-‐4
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 9 <LOD 1.24 x 10-‐3 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 15 <LOD 7.13 x 10-‐3
Ringaskiddy June 2010 – Nov. 2011
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=18
Range
min max Naphthalene 1.2 0.0001 18 <LOD 2.00 x 10-‐2 Anthracene 1 x 10-‐1 0.0005 18 <LOD 5.79 x 10-‐2 Fluoranthene 1 x 10-‐1 0.0001 18 <LOD 5.75 x 10-‐2 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 18 <LOD 5.48 x 10-‐3
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 15 <LOD 8.98 x 10-‐3 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 18 <LOD 4.91 x 10-‐2
Swords Nov. 2009 – Aug. 2010
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=72
Range
min max Naphthalene 1.2 0.0001 72 4.69 x 10-‐5 6.26 x 10-‐2 Anthracene 1 x 10-‐1 0.0005 72 <LOD 5.96 x 10-‐2 Fluoranthene 1 x 10-‐1 0.0001 72 <LOD 3.42 x 10-‐2 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 66 <LOD 2.55 x 10-‐4
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 63 <LOD 1.79 x 10-‐2 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 66 <LOD 9.20 x 10-‐4
Ringsend July 2009 – Aug. 2010
Parameter
Target EQS
(µg L-‐1) LOD
(µg L-‐1) Frequency
N=96
Range
min max Naphthalene 1.2 0.0001 96 5.82 x 10-‐7 5.37 x 10-‐2 Anthracene 1 x 10-‐1 0.0005 96 <LOD 4.10 x 10-‐2 Fluoranthene 1 x 10-‐1 0.0001 96 <LOD 2.49 x 10-‐2 Benzo-‐b/k-‐fluoranthene Σ 3 x 10-‐3 0.0001 90 <LOD 1.51 x 10-‐4
Benzo-‐a-‐pyrene 5 x 10-‐2 0.0005 87 <LOD 9.02 x 10-‐3 Indeno-‐1,2,3cd-‐pyrene /Benzo-‐ghi-‐perylene Σ 2 x 10-‐3
0.0001 0.0005 87 <LOD 5.74 x 10-‐2
Flow and Rainfall
Rainfall and Total Suspended Solids
TSS (mg L-‐1 ) and Rainfall (mm)
Flow and PAH Concentration
Sept.
Summary - PAHs Dublin Cork
2 Sites 7 Sites
N=168 N =147
PAHs detected in all samples PAHs detected in all samples Exceedances at 1 site: Indeno-1,2,3cd-pyrene/Benzo-ghi-perylene
Exceedances at 5 sites: Indeno-1,2,3cd-pyrene/Benzo-ghi-perylene, Benzo-b/k-fluoranthene
Acknowledgements 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. It is administered on behalf of the Department of the Environment, Heritage and Local Government by the Environmental Protection Agency, which has the statutory function of co-ordinating and promoting environmental research.
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