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Contaminants of Emerging Concern in the Tidal Delaware River A Pilot Monitoring Survey y Science and Environmental Summit Delaware Estuary January 13, 2009 Ron MacGillivray, Ph.D.
• Goal Goal:: collect ambient water data on contaminants of •
emerging concern Participants:: DRBC, Axys Analytical Laboratories, Participants American Aquatic Testing Laboratory
Delaware River Basin
Sampling Locations
2007 Parameters
# of analytes
PBDE - polybrominated
46
diphenyl ethers
PFC - perfluorinated
compounds
PPCP - pharmaceuticals and
personal care products
Hormones and sterols
HR GC/MS EPA Method 1614
13 LC/MSMS
54 LC/MSMS
24 GC/LRMS
C b Carbamate t pesticides ti id
21 LC/MSMS
NP and NPE – nonylphenol l h l and NP ethoxylates
3 GC/MS
PPCP in Tidal Delaware River
Caffeine Triclocarban
400
Diphenhydramine Naproxen
350
OTC
Ibuprofen Fluoxitine
300
Codeine Carbamazapine
ng/L
250
prescription
Dilti Diltiazem Dehydronifedipine
200
Gemfibrozil
codeine
Trimethoprim p
150
Sulfanilamide Sulfamethoxazole
100
Sulfadimethoxine Sulfadiazine
50
Ofloxacin Norfloxacin
0 50 mouth of bay
68
80
90 RM
105
131
Erythromycin-H2O Clarithromycin
head of tide
Azithromycin
antibiotics
• Aquatic ecotoxicity data, primarily based on individual compounds d and d single i l species i tests, t t are readily dil available for only 16 out of the 21 PPCP analytes detected limiting assessment of risk to aquatic life. life
• Risk Index = PEC/PNEC – Risk Index > 1.0 (clarithromycin effect on algal growth) – Risk Index > 0.1 ((carbamazapine p effect on Ceriodaphnia p dubia, ibuprofen effect on Hydra, erythromycin and fluoxitine effect on Pseudokirchneriella subcapitata, sulfamethoxazole effect on cyanobacteria) – First Tier screening for prioritization of future assessment and characterization
• Concurrent, short short--term chronic toxicity tests in the ambient water samples p with endpoints p of survival,, growth g and reproduction did not indicate toxicity.
• In salinities from 0 to 10 ppt using six species: – – – – – –
fathead minnow, Pimephales promelas in a 77-day test mysid, Americamysis bahia in a 77-day test i l d silverside, inland il id Menidia M idi beryllina b lli in i a 77-day d test t t water flea, Ceriodaphnia dubia maximum of 88-days duration green alga, Pseudokirchneriella subcapitata in a 9696-hour test amphipod, h d Hyalella l ll azteca in a 1010 0-day d waterwater-only l test
• Assessment of ecotoxicity from PPCP in the tidal Delaware
River would be further informed by estrogenicity screening, biomarker measurements and population (sex ratio) surveys.
Hormones and Sterols In Ambient Waters Of The Tidal Delaware River 250
200
n ng/L
150
100
50
50
0 80 90
River Miles
105
head of tide
ne tro Es
131
N
mouth of bay
l ro te os m es ol D an st le ol ho an C st ro op ic Ep ol an st ro op ne C ro nd hi et or
68
PFC In Ambient Waters Of TheTidal Delaware River
1,000 900 800
ng/L
700 600 500 400 300 200 100 0
50
68
80
River Miles
90 105 131
PFOSA PFOS PFHxS PFBS PFDoA PFUnA PFDA PFNA PFOA PFHpA PFHxA PFPeA PFBA
PFOA In Ambient Water Of TheTidal Delaware River
80
@ S. Del. Mem. Br.
70 @ Liston Point
60
Minnesota Pollution Control Agency (MPCA) - fish consumption criteria (fcc) = 1,620 ng/L g water and fcc = 610 ng/L g - drinking
PFOA ng/L
50
40 @ Marcus Hook
30
20 @ Schuylkill R. @ Pennsauken R.
10
@ Biles Channel
0 50 0
68
80
90
River Miles
10 105
131
PFOS In Ambient Waters Of TheTidal Delaware River 9 @ Schuylkill R. @ Pennsauken R.
8
@ S. Del. Mem. Br. @ Marcus a cus Hook oo C Creek ee
PFOS ng P g/L
7
MPCA human health based surface water criteria 6 ng/L Mississippi River
@ Liston Point
6 5 4 @ Biles Channel
3 2 1 0 50
68
80
90
River Miles
105
131
PBDE In Ambient Waters Of TheTidal Delaware River
8000 7000 6000
4000 3000 2000 1000 0 D E
BD
BD
N
xB
E
E
BD
D pB
H
E
D
E
E
D
E
E
D
D iB Tr
iB
131
D E
head of tide
105
BD Te
90
River Miles
B Pe
80
H
68
O
50 mouth of bay
pg/L
5000
Summary PPCP
– Detected 21 compounds out of 54 compounds – Concentrations in the ng/L range – Availability of ecotoxicity data limiting assessment of risk to aquatic life
Hormones
– Primarily detected fecal sterols – New analytical method with few surrogates available and numerous QA/QC notes
PBDE
– DBDE and other homologs detected at pg/L levels – PBDE monitoring continuing in fish tissue
PFC – PFNA highest PFC concentrations at ng/L levels – PFOS levels exceed some safety benchmarks – Additional information needed for assessment especially on longer p chain and sulfonated compounds
Next Steps – Survey: 2008 sampled; 2009 planned – Information I f ti exchange h – Investigate additional assessment methodologies
• e.g., Species sensitive distribution – Characterize effects • e.g., estrogenicity bioassays, aquatic life Contact Information: [email protected] http://www.state.nj.us/drbc/emc.htm
• Goal Goal:: collect ambient water data on contaminants of •
emerging concern Participants:: DRBC, Axys Analytical Laboratories, Participants American Aquatic Testing Laboratory
Delaware River Basin
Sampling Locations
2007 Parameters
# of analytes
PBDE - polybrominated
46
diphenyl ethers
PFC - perfluorinated
compounds
PPCP - pharmaceuticals and
personal care products
Hormones and sterols
HR GC/MS EPA Method 1614
13 LC/MSMS
54 LC/MSMS
24 GC/LRMS
C b Carbamate t pesticides ti id
21 LC/MSMS
NP and NPE – nonylphenol l h l and NP ethoxylates
3 GC/MS
PPCP in Tidal Delaware River
Caffeine Triclocarban
400
Diphenhydramine Naproxen
350
OTC
Ibuprofen Fluoxitine
300
Codeine Carbamazapine
ng/L
250
prescription
Dilti Diltiazem Dehydronifedipine
200
Gemfibrozil
codeine
Trimethoprim p
150
Sulfanilamide Sulfamethoxazole
100
Sulfadimethoxine Sulfadiazine
50
Ofloxacin Norfloxacin
0 50 mouth of bay
68
80
90 RM
105
131
Erythromycin-H2O Clarithromycin
head of tide
Azithromycin
antibiotics
• Aquatic ecotoxicity data, primarily based on individual compounds d and d single i l species i tests, t t are readily dil available for only 16 out of the 21 PPCP analytes detected limiting assessment of risk to aquatic life. life
• Risk Index = PEC/PNEC – Risk Index > 1.0 (clarithromycin effect on algal growth) – Risk Index > 0.1 ((carbamazapine p effect on Ceriodaphnia p dubia, ibuprofen effect on Hydra, erythromycin and fluoxitine effect on Pseudokirchneriella subcapitata, sulfamethoxazole effect on cyanobacteria) – First Tier screening for prioritization of future assessment and characterization
• Concurrent, short short--term chronic toxicity tests in the ambient water samples p with endpoints p of survival,, growth g and reproduction did not indicate toxicity.
• In salinities from 0 to 10 ppt using six species: – – – – – –
fathead minnow, Pimephales promelas in a 77-day test mysid, Americamysis bahia in a 77-day test i l d silverside, inland il id Menidia M idi beryllina b lli in i a 77-day d test t t water flea, Ceriodaphnia dubia maximum of 88-days duration green alga, Pseudokirchneriella subcapitata in a 9696-hour test amphipod, h d Hyalella l ll azteca in a 1010 0-day d waterwater-only l test
• Assessment of ecotoxicity from PPCP in the tidal Delaware
River would be further informed by estrogenicity screening, biomarker measurements and population (sex ratio) surveys.
Hormones and Sterols In Ambient Waters Of The Tidal Delaware River 250
200
n ng/L
150
100
50
50
0 80 90
River Miles
105
head of tide
ne tro Es
131
N
mouth of bay
l ro te os m es ol D an st le ol ho an C st ro op ic Ep ol an st ro op ne C ro nd hi et or
68
PFC In Ambient Waters Of TheTidal Delaware River
1,000 900 800
ng/L
700 600 500 400 300 200 100 0
50
68
80
River Miles
90 105 131
PFOSA PFOS PFHxS PFBS PFDoA PFUnA PFDA PFNA PFOA PFHpA PFHxA PFPeA PFBA
PFOA In Ambient Water Of TheTidal Delaware River
80
@ S. Del. Mem. Br.
70 @ Liston Point
60
Minnesota Pollution Control Agency (MPCA) - fish consumption criteria (fcc) = 1,620 ng/L g water and fcc = 610 ng/L g - drinking
PFOA ng/L
50
40 @ Marcus Hook
30
20 @ Schuylkill R. @ Pennsauken R.
10
@ Biles Channel
0 50 0
68
80
90
River Miles
10 105
131
PFOS In Ambient Waters Of TheTidal Delaware River 9 @ Schuylkill R. @ Pennsauken R.
8
@ S. Del. Mem. Br. @ Marcus a cus Hook oo C Creek ee
PFOS ng P g/L
7
MPCA human health based surface water criteria 6 ng/L Mississippi River
@ Liston Point
6 5 4 @ Biles Channel
3 2 1 0 50
68
80
90
River Miles
105
131
PBDE In Ambient Waters Of TheTidal Delaware River
8000 7000 6000
4000 3000 2000 1000 0 D E
BD
BD
N
xB
E
E
BD
D pB
H
E
D
E
E
D
E
E
D
D iB Tr
iB
131
D E
head of tide
105
BD Te
90
River Miles
B Pe
80
H
68
O
50 mouth of bay
pg/L
5000
Summary PPCP
– Detected 21 compounds out of 54 compounds – Concentrations in the ng/L range – Availability of ecotoxicity data limiting assessment of risk to aquatic life
Hormones
– Primarily detected fecal sterols – New analytical method with few surrogates available and numerous QA/QC notes
PBDE
– DBDE and other homologs detected at pg/L levels – PBDE monitoring continuing in fish tissue
PFC – PFNA highest PFC concentrations at ng/L levels – PFOS levels exceed some safety benchmarks – Additional information needed for assessment especially on longer p chain and sulfonated compounds
Next Steps – Survey: 2008 sampled; 2009 planned – Information I f ti exchange h – Investigate additional assessment methodologies
• e.g., Species sensitive distribution – Characterize effects • e.g., estrogenicity bioassays, aquatic life Contact Information: [email protected] http://www.state.nj.us/drbc/emc.htm
