The Effect of Increased Flows on the Treatability of Emerging Contaminants at
a Wastewater Treatment Plant during Rain Events
Kenya L. Goodson, Dr. Robert Pitt, Dr. Sam Subramaniam, and Dr. Shirley Clark
Objectives
• Introduction/Purpose of research• Background of emerging contaminants• Description of the treatment plant• Procedures• Results/Discussion• Conclusions• Acknowledgements
Emerging Contaminants
• “Emerging contaminants" can be broadly defined as any synthetic or naturally occurring chemical or any microorganism that is not commonly monitored in the environment but has the potential to enter the environment and cause known or suspected adverse ecological and (or) human health effects. USGS
History of Emerging Contaminants Research
• Pharmaceuticals were first reported in U.S. surface waters during investigations in the 1970s, although they were not regulated as legacy pollutants such as PCBs and DDTs (Snyder 2006).
• There have been many publications documenting the presence of antibiotics in groundwaters, surface waters, wastewaters and landfill leachates, including the National Reconnaissance study sponsored by the U.S. EPA and the U.S Geological Survey (Xu 2007; Kolpin 2003).
The Purpose of This Research
• To evaluate the effects of stormwater on wastewater treatability for each unit process.
• To understand other factors that affect the treatability of emerging contaminants and compare them to the effects of wet weather flows.
• To determine the concentrations of emerging contaminants that enter and leave the treatment plant.
• To compare wet weather emerging contaminant loadings at the treatment plant with stormwater sheetflow emerging contaminant characteristics.
Types of Emerging Contaminants• Pharmaceuticals and Personal Care Products (PPCPs)• Estrogens• Pesticides• Microorganisms• Heavy metals• Polycyclic aromatic hydrocarbons (PAHs)
Widely varying chemical characteristics of these compounds results in their varying fates and treatabilities (mostly relating to their associations with organic solids and their water solubilities).
Chemical Name (Pharmaceutical)
MW (g/mol)
Log kow Solubility (mg/L)
Half-life(hours)
Carbamazepine
236.1 2.45 17.7 10-20
Fluoxetine
309.3 4.05 38.4 24-72
Gemfibrozil
250.12 4.78 5.0 1.5
Ibuprofen
206 3.5-4.0 41.5 2
Sulfamethoxazole
253 0.9 600 10
Triclosan
289.5 4.8-5.4 2-4.6 125
Trimethoprim
290.32 0.79 400 8-10
Reported Characteristics of Pharmaceuticals that Affect their Treatability and Fate
Chemical Name MW(g/mol)
log kow Solubility (mg/L) Half Life(days)
naphthalene
128.2 3.37 31.5 3
acenaphthylene
152.2 3.89 3.80 21-121
acenaphthene
154.2 4.02 16.1 10-60 (soils)1-25 (surface waters)
fluorene
166.2 4.12 1.90 2-64
anthracene
178.2 4.53 0.045 108-139
phenanthrene
178.2 4.48 1.12 5.1
pyrene
202.2 5.12
0.132
16-200
fluoranthene
202.2 5.14 0.260 880
Reported Characteristics of PAHs that Affect their Treatability and Fate
Chemical Name (Pesticides)
MW (g/mol) Solubility in water (mg/L)
log kow Half-life
Methoxychlor
345.65 0.1 4.68-5.08 >100 days
Aldrin
364.91 0.027 6.5 20-100 days
Dieldrin
380.91 0.1 6.2 5 years
Chlordane
409.76 insoluble ~5.54 4 years
Arochlor Σ
257.9-453 insoluble 5.6-6.8 various
Lindane
290.83 17 3.8 15 months
Heptachlor
373.32 0.056 6.10 6 months-3.5 years
Heptachlor-epoxide
389.40 0.35 5.40 na
Reported Characteristics of Pesticides that Affect their Treatability and Fate
• Hilliard Fletcher Wastewater Treatment Plant– A secondary treatment system with a pretreatment phase, a primary
clarifier, an aeration tank, a secondary clarifier and UV disinfection system.
– Current capacity is 30 MGD; being upgraded to 45 MGD by 2013.– Separate sanitary sewer system
11City of Tuscaloosa photo
Treatability of Tuscaloosa WWTP
Wastewater Treatment Flows and Rains during Wet Weather Sampling
Rainfall (in)
Flow rate (MGD)
01/16/10 0.55 18.2
03/02/10 0.68 23.3
04/24/10 1.01 16.5
06/25/10 trace 20.7
10/24/10 trace 15.7
11/02/10 trace 20.5
03/09/11 2.7 42.2
09/20/11 2.2 26.5
13
0 0.5 1 1.5 2 2.5 30
5
10
15
20
25
30
35
40
45
Treatment Plant Flow and Observed Rainfall
Rainfall (inches)
Daily
Flo
w (M
GD)
Increased daily flows at wastewater treatment plant associated with rains greater than about 1.5 or 2 inches
Comparison of pH and pka
Wet weather date
Influent pH
Effluent pH
01/16/10 7.23 6.80
03/02/10 7.42 6.79
04/24/10 6.94 6.61
06/25/10 6.93 6.62
10/24/10 7.02 6.72
11/02/10 6.92 6.48
03/09/11 7.24 6.64
09/20/11 7.09 7.04
Pharmaceutical pka
Carbamazepine 13.9
Fluoxetine 9.5
Gemfibrozil 4.5
Ibuprofen 4.91
Sulfamethoxazole pka1=1.7, pka2=5.6
Triclosan 8.0
Trimethoprim 6.6
Sample Collection
• Four composite one liter samples collected during each event:– At the inlet right before the screen and grit chamber– After wastewater leaves the primary clarifier– After biological treatment and wastewater leaves the secondary clarifier– After final effluent is treated by UV
• Seven wet weather samples and seven dry weather samples collected during a range of treatment flow conditions and analyzed for:– pharmaceuticals– PAHs– Pesticides
• Wet weather sheetflow samples also being collected in area• This presentation presents a preliminary evaluation of the available
data15
Analyses• Acidic and basic pharmaceuticals
– EPA standard method 1268 (modified)– Solid phase extraction – High performance liquid chromatography (HPLC) analysis with UV detector
• PAHs– EPA standard method 8270 SIM targeted ions– Separation flask with Kuderna-Danish (KD) concentration– Gas chromatography with mass spectrophotometer detector (GC-MSD)
analysis• Pesticides
– EPA standard method 508– Separation flask with Kuderna-Danish (KD) concentration– Gas chromatography with electron capture detector (GC-ECD) analysis
16
Preliminary PAH results
4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
(x10,000)
TICTICTICTICTICTICTICTIC
20/
19/B
enzo
(a)p
yren
e
15/F
lour
anth
ene
16/
17/
18/P
yren
e
6/ 7/8/ 9/
10/A
nthr
acen
e11
/12
/13
/14
/
5/Fl
uore
ne
2/3/
Acen
apht
hyle
ne4/
Acen
apht
hene
1/N
apht
hale
ne
4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.00.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
(x10,000)
TICTICTICTICTICTICTICTIC
2/
1/N
apht
hale
ne
Preliminary Pharmaceutical Data
Minutes
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
mA
u
0
250
500
750
1000
1250
1500
1750
mA
u
0
250
500
750
1000
1250
1500
1750
1
333
4427
6 1
.928
45.
294
2
543
6345 2
.652
7.3
85
3
108
1828
2 6
.512
14.
695
4
232
075 7
.056
0.3
15
5 6
8201
73 7.4
60 9
.264
6
242
2533 7
.988
3.2
91
7 5
7127
33 8.2
52 7
.760
8 1
3212
46 9.0
76 1
.795
9
218
2001 9
.408
2.9
64
10
546
341 1
0.48
4 0.7
42
11 1
0771
20 10.
928 1
.463
12
138
044 1
2.14
4 0.1
88
13 4
7580
9 12.
620 0
.646
14
318
647 1
3.40
4 0.4
33
15
1793
21 14.
208 0
.244
16
4700
2 14.
356 0
.064
17
1818
71 14.
520 0
.247
18
9768
5 15.
108 0
.133
19
2655
17 15.
420 0
.361
20
1363
38 15.
820 0
.185
21
9074
6 16.
404 0
.123
22
2142
1 16.
868 0
.029
23
3402
6 16.
992 0
.046
24
6117
3 17.
360 0
.083
25
165
2915 1
8.36
0 2.2
45
26
315
7 23.
016 0
.004
27
341
23.
192 0
.000
28
337 2
6.16
4 0.0
00
SPD-M20A-263 nm0518Inf0309
NamePk #AreaRetention TimeArea Percent
Minutes
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
mA
u
0
100
200
300
400
mA
u
0
100
200
300
400
1 4
6926
2.25
6 0.3
13
2 1
0270
601
3.2
12 6
8.44
9
3 7
0296
7 4.0
88 4
.685
4 2
1158
54 7.3
68 1
4.10
1
5 8
63 1
1.68
4 0.0
06
6 4
2759
18.8
60 0.2
85 7
601
43 19
.356 0
.401
8 4
8967
2 20.
152 3
.263
9 9
7946
9 21.
500 6
.528
10
0 2
2.40
8 0.0
00 1
1 17
8614 2
2.95
6 1.1
90
12
6738
3 25.
464 0
.449
13
7048
27.
408 0
.047
14
1318
1 28.
252 0
.088
15 1
0213
28.9
76 0.0
68
16
1628
4 29.
616 0
.109
17
2866
29.
860 0
.019
SPD-M20A-263 nmFIN 030911 Acid
NamePk #AreaRetention TimeArea Percent
Preliminary Pharmaceutical Data
Minutes
12 14 16 18 20 22 24 26 28
mA
u
20
40
60
80
100
120
mA
u
20
40
60
80
100
120
1 2
0339
12.
776
2 1
3977
0 13
.108
3 3
386
13.3
684
157
806
13.6
68
5 4
1064
14.
340
6 6
2425
14.
648
7 9
2586
15.
260
8 4
6396
4 15
.616
9 1
4430
08 1
6.40
0
10 3
0141
9 17
.232
11 7
7673
8 17
.532
12 1
3663
33 1
7.77
213
136
4187
18.
092
14 2
6980
9 18
.536
15 4
1159
5 18
.916
16 9
7265
4 19
.480
17 1
5731
78 1
9.98
418
452
432 2
0.27
619
753
36 2
0.57
620
136
02 2
0.78
421
231
731 2
1.13
6
22 4
4516
3 21
.532
23 4
0603
0 21
.860
24 2
0604
6 22
.248
25 1
575
22.7
36
26 1
6733
0 23.
160
27 6
1777
23.
520
28 7
0325
24.
072
29 3
3146
24.
468
30 1
2720
25.
468
31 7
483
25.8
00
32 5
0261
26.
652
33 7
967
27.0
9634
149
4 27
.432
35 6
5616
27.
820
36 6
1154
28.
708
37 5
4432
28.
984
38 2
6871
29.
508
SPD-M20A-263 nm0510Influ010116Acid
Pk #AreaRetention Time
Minutes
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
mA
u
0
20
40
60
mA
u
0
20
40
60
1 1
6480
12.
500
2 1
4389
13.
068
3 1
9796
13.
444
4 1
612
13.
772
5 8
327
14.
232
6 6
87 1
4.50
87
223
66 1
4.95
28
487
71 1
5.55
29
1 1
5.76
410
195
960
16.3
0811
138
021
16.7
7212
167
221
17.1
7213
209
190
17.5
8414
406
059
18.0
6815
191
337
18.5
0816
300
781
18.9
0817
285
845
19.1
9218
974
25 1
9.52
419
896
1 1
9.92
8
20 3
1880
20.
724
21 1
8119
5 21
.904
22 6
3438
23.
088
23 1
5697
23.
492
24 2
2686
23.
960
25 1
4424
24.
448
26 1
4368
25.
420
27 7
117
25.
728
28 1
641
26.
328
29 4
639
26.
532
30 1
806
27.
000
31 2
638
27.
368
32 4
721
27.
744
33 2
6622
28.
704
34 1
0723
28.
972
35 5
268
29.
300
36 1
0458
29.
592
SPD-M20A-263 nm0510Final010116Acid
Pk #AreaRetention Time
Preliminary Conclusions• Stormwater only affects the flow rate at the treatment facility
during large rainfall events (>1.5 inches). However, the preliminary data shows stormwater infiltration into the separate sanitary system does contribute to the mass load of ECs to the wastewater treatment plant: there were increases in masses for both PAHs and pharmaceuticals during some of the rain events.
• Some inconsistencies in rain and flow. For example, the flow rate was low for April 2010, the rainfall was over one inch and most of the PAHs during this weather event had the highest concentrations and lowest treatability.
• Final conclusions will be based on the complete data set, but these preliminary data indicate performance as expected, with minimal wet weather effects, although wet weather is shown to be a significant source of some of the ECs.
Acknowledgements
• U.S. Environmental Protection Agency• NSF EPSCOR• The University of Alabama• Penn State-Harrisburg• Miles College
References(1) Kolpin, D. W.; Furlong, E. T.; Meyer, M. T.; Thurman, M. E.; Zaugg, S. D.; Barber, L. B.; Buxton, H. T. Pharmaceuticals, Hormones, and other Organic Wastewater Contaminants in U.S. streams, 1999-2000: A National Reconnaissance. Environ Sci Technol 2002, 36, 1202-1211. (2) Miao, X. S.; Yang, J. J.; Metcalfe, C. D. Carbamazepine and its metabolites in wastewater and in biosolids in a municipal wastewater treatment plant. Environ. Sci. Technol. 2005, 39, 7469-7475. (3) Nentwig, G. Effects of pharmaceuticals on aquatic invertebrates. Part II: The antidepressant drug fluoxetine. Arch. Environ. Contam. Toxicol. 2007, 52, 163-170. (4) PubMed Molecular Biology Database http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~23N7w0:1:fate. (5) Chem Spider-Ibuprofen http://www.chemspider.com/Chemical-Structure.36498.html. (6) Nghiem, L. D.; Schäfer, A. I.; Elimelech, M. Pharmaceutical retention mechanisms by nanofiltration membranes. Environ. Sci. Technol. 2005, 39, 7698-7705. (7) Singer, H.; Müller, S.; Tixier, C.; Pillonel, L. Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment plants, surface waters, and lake sediments. Environ. Sci. Technol. 2002, 36, 4998-5004. (8) Mikes, O.; Trapp, S. Acute toxicity of the dissociating veterinary antibiotics trimethoprim to willow trees at varying pH. Bull. Environ. Contam. Toxicol. 2010, 1-6.
References(9) de Maagd, P. G.; ten Hulscher, D. T. E. M.; van den Heuvel, H.; Opperhuizen, A.; Sijm, D. T. H. M. Physicochemical properties of polycyclic aromatic hydrocarbons: Aqueous solubilities, n-octanol/water partition coefficients, and Henry's law constants. Environmental Toxicology and Chemistry 1998, 17, 251-257. (10) Dabestani, R.; Ivanov, I. N. A Compilation of Physical, Spectroscopic and Photophysical Properties of Polycyclic Aromatic Hydrocarbons. Photochem. Photobiol. 1999, 70, 10-34. (11) Crunkilton, R. L.; DeVita, W. M. Determination of aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs) in an urban stream. Chemosphere 1997, 35, 1447-1463. (12) de Maagd, P. G.; ten Hulscher, D. T. E. M.; van den Heuvel, H.; Opperhuizen, A.; Sijm, D. T. H. M. Physicochemical properties of polycyclic aromatic hydrocarbons: Aqueous solubilities, n-octanol/water partition coefficients, and Henry's law constants. Environmental Toxicology and Chemistry 1998, 17, 251-257. (13) Monteith, H. D.; Parker, W. J.; Bell, J. P.; Melcer, H. Modeling the Fate of Pesticides in Municipal Wastewater Treatment. Water Environ. Res. 1995, 67, pp. 964-970. (14) Katsoyiannis, A.; Samara, C. Persistent organic pollutants (POPs) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal. Water Res. 2004, 38, 2685-2698. (15) ATSDR 2011 Profile for Methoxychlor. http://www.atsdr.cdc.gov/. (16) IPCS INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY ALDRIN AND DIELDRIN; Health and Safety Guide No. 21; UNITED NATIONS ENVIRONMENT PROGRAMME; INTERNATIONAL LABOUR ORGANISATION; WORLD HEALTH ORGANIZATION(17) Williams, J. Endocrine Disruptors in Wastewater. (18) ATSDR 2011 Profile for Arochlor. (19) ATSDR 2011 Profile for Lindane. http://www.atsdr.cdc.gov. (20) ATSDR 2011 Profile for Heptachlor. http://www.atsdr.cdc.gov/. (21) Wikipedia-Tuscaloosa, A. http://en.wikipedia.org/wiki/Tuscaloosa,_Alabama. (22) Information for Tuscaloosa, A. http://www.tuscaloosacountyalabama.com/local/cityinfo.html. (23) City of Tuscaloosa; Wastewater Management http://www.ci.tuscaloosa.al.us/index.asp?NID=229