Wastewater Tracer Study Utilizing
Carbamazepine, Triclocarban and Triclosan
in the Philadelphia Waterway.
A Thesis
Submitted to the Faculty
of
Drexel University
by
Michele M. Alshouli
in partial fulfillment of the
requirements for the degree
of
Master of Science
In
Analytical Chemistry
June 2012
ii
Acknowledgements
This Thesis is possible due to the Philadelphia Water Department for providing me with a laboratory and necessary instruments that allowed me to fulfill my laboratory experiments toward this project. Thank you to the Philadelphia Water
Department, for the financial and academic support towards my master’s degree in
Analytical Chemistry.
I would like to thank my supervisor Earl Peterkin, management, particularly Gary
Burlingame, my advisor from Drexel University, Dr. Joe P. Foley and my co- workers Dr. Xianhao Cheng, Dr. Luisa Lassová and Tyler Croteau for their help and guidance. Thanks also to Lerone Luster and Tyler Croteau again for their help in sample collection. Thank you to the Northeast Wastewater treatment Plant for sampling the wastewater samples for this project.
A special thanks to my family, especially my husband, for their constant support throughout the years.
iii
Table of Contents
LIST OF TABLES...... vi
LIST OF FIGURES ...... vii
ABSTRACT...... ix
1. Introduction...... 1
1.1 Pharmaceuticals and Personal Care Products (PPCPs) ...... 1
1.2 Objectives...... 6
2.0 Emerging Concern for PPCPs...... 7
2.1 Carbamazepine...... 7
2.2 Triclocarban & Triclosan...... 8
3. Fate of Chemical Tracers through Wastewater Treatment ...... 10
3.1 Carbamazepine...... 10
3.2 Triclocarban & Triclosan...... 12
4. Water Treatment ...... 14
4.1 Wastewater treatment...... 14
4.2 Distribution System Infrastructure...... 16
5.0 Combined Sewer Overflow (CSO) ...... 17
5.1 The Importance of Combined Sewer Overflow ...... 17
5.2 Green City Clean Waters ...... 18
6.0 Monitoring Program...... 20
6.1 Distinguishing between CSO and Wastewater ...... 20
6.2. Established Mandates for Controlling Pollution...... 22
7. 0 Sampling Considerations for the Water Samples ...... 23 iv
7.1 Importance of Sampling...... 23
7.2 Sample Collection...... 24
7.2.1 Sample bottles...... 24
7.2.2 Sample Volume...... 25
7.2.3 Location ...... 25
7.2.4 Head Space...... 25
7.2.5 Preservative...... 26
7.2.6. Filtration...... 26
7.3 Sample Frequency...... 26
7.4 Sample Storage ...... 28
7.5 Sampling Locations in the Philadelphia Watershed ...... 29
8.0 Analytical Methodology ...... 35
8.1 Equipment Used...... 35
8.2 Method Parameters ...... 36
8.3 Method Efficiency ...... 38
8.4 Method Capabilities & Validation...... 42
8.5 Sample Extraction ...... 44
9. Results...... 46
9.1 Wastewater...... 46
9.2 Source Water ...... 49
10. Discussion of the results ...... 52
10.1 Source Water and Wastewater...... 52
10.2 Mixing Ratio of Analytes...... 53
11. Troubleshooting...... 55
v
12. Conclusion ...... 58
13. Future Proposals...... 59
13. Bibliography ...... 64
vi
List of Tables
1. Physical Properties for Carbamazepine, Triclocarban, and Triclosan...... 4
2. Occurrence of Carbamazepine and other analytess in six watersheds sampled in 2006 in ng/L ...... 8
3. HPLC gradient program. Carbamazepine and Bispenol A D-16 elute isocratically at 50:50 Water:ACN, then the gradient changes to 30:70 Water:ACN where Triclocarban and Triclosan elute isocratically ...... 38
4. Repeatability Study; injecting QC sample of 25 ug/L same day for Intra day Precision ...... 43
5. Intermediate Precision study by injecting QC sample of 25 ug/L over 5 days...... 44
6. Method Procedural RSD: Prepared QC sample 7 times to observe RSD...... 44
7. Analyte concentration ranges for river and wastewater samples...... 48
8. Table showing the concentrations for Carbamazepine, Triclocarban, and Tricosan measured in source water samples. (nd= no detection)...... 51
vii
List of Figures
1. Pathways for PPCPs adapted from EPA 2008...... 5
2. Process flow diagram for a wastewater treatment plant ...... 15
3. Pollutants that were detected and not detected in CSOs...... 21
4. Comparison of the Fecal Indicator Bacteria loads discharged into the Seine River downstream from the City of Paris by the studied CSO and the three WWTPs of the area...... 22
5. Map showing Frankford Arsenal, Northeast Wastewater Treatment Plant and Penn Treaty Park. The Northeast Wastewater Treatment Plant is located at 3900 Richmond Street Philadelphia , Pennsylvania , 19137...... 30
6. Frankford Arsenal in Philadelphia, Pennsylvania at the intersection of Tacony and Bridge Streets ...... 31
7. Penn Treaty Park at 1195 North Delaware Ave in Philadelphia, Pennsylvania...... 32
8. Sample IDs and locations are coordinated with the map on Figure 9 ...... 33
9. Map of source water locations along the Wissahickon Creek and Schuylkill River...... 34
10. Restek Test Mix to test system suitability on the HPLC DAD...... 39
11. Thermo Test Mix to test system suitability on the HPLC DAD...... 40
12. Chromatogram at 231 nm showing the four tracers retention time, theoretical plates, and resolution. The method obtained analyte resolution above 2.2, and efficiency from 4805 to 28199 from the first to last eluting peak ...... 42
13. Wastewater influent and effluent of Carbamazepine...... 47
14. Wastewater influent and effluent of Triclocarban. 09/26/12 influent sample had interference, so no data available for this data point ...... 47
15. Wastewater influent and effluent of Triclosan...... 48
16. Carbamazepine river values before and after treated wastewater discharge. ..49
viii
17. Graph of source water values for Carbamazepine, Triclocarban, and Triclosan. The sample locations are organized by locations upstream to downstream and by date for each location...... 50
18. Scatter Plot of Triclocarban versus Triclosan in wastewater. The plot shows a positive correlation and linear regression r 2 value of 0.871...... 54
19. Scatter plot of Triclocarban versus Triclosan in source water. The plot shows a positive correlation with a linear regression r 2 of 0.574...... 55
20. Partial Inventory of Infrastructure Locations in Wissahickon Creek within Montgomery County, 2005. The figure shows bridges, dams, and outfalls. This will be a good guide to know where to sample near outfalls...... 61
21. Map of Philadelphia showing areas of combined sewer overflow and the River or Creek that are being affected by the outfall...... 62
22. Map of locations which the “Green City, Clean Water” program has or intends to build green space...... 63
ix
Abstract Wastewater Tracer Study Utilizing Carbamazepine, Triclocarban, and Triclosan in the Philadelphia Waterway. Michele Alshouli Joe P. Foley, PhD
Pharmaceuticals and personal care products (PPCPs) are chemicals that are manufactured and used extensively throughout the world. PPCPs end up in the wastewater system due to disposal or human waste. When treated wastewater is released back to the river, trace amounts of these chemicals are found in source water, which contaminate drinking water and pose a concern of unknown potential harm to the aquatic environment. Recent studies show PPCPs are an environmental hazard to aquatic organisms and humans as well. Since their detection in clean water in the late 1990s, many methods are being developed for analysis of PPCPs in the aquatic environment.1 The present study establishes a useful analytical method for PPCPs and uses selected PPCPs as tracers to investigate the impact of wastewater discharge on the waterways and to estimate the occurrence of PPCPs.
This thesis entails three main objectives; first, to develop a sensitive and robust method for three chemical tracers; second, to quantitate these tracers in the
Philadelphia watershed; and third, to develop a monitoring program in the
Philadelphia watershed to survey the impact that wastewater has on source water.
A method was developed for the simultaneous analysis of Carbamazepine (CBZ),
Triclocaban (TCS), and Triclosan (TCS) by solid-phase extraction (SPE) followed by high performance liquid chromatography (HPLC) with diode array detection x
(DAD). The calibration range was from 1-100 ug/L. All compounds had a coefficient of determination (r 2) > 0.9951, based on a minimum of 7 data points used in the regression of the calibration curve. Procedural recoveries with this method were 90%, 85%, and 80% for Carbamazepine, Triclocarban and Triclosan, respectively. Precision of the method was assessed by comparing repeatability and intermediate precision results with pre-determined criteria. For repeatability for intra-day precision, an RSD less than %16 was achieved. For intermediate precision, an RSD less than 9% was obtained. Procedural RSD was also determined to be less than 12%.
The fate of the chemical tracers was quantitated after the treatment process to assess their use as tracers. All three tracers were detected before and after wastewater treatment. Detections in wastewater effluent were in the ranges of 0.4 -
5.0 ug/L for Carbamazepine, 0.05-0.09 for Triclocarban, and 0.29-0.47 ug/L for
Triclosan. It was shown that Carbamazepine, Triclocarban, and Triclosan are removed through the wastewater treatment by 43% to 93%, 86 to 89%, and 71 to
83%, respectively. Concentrations found in source water are in the ranges of 0.006-
1.1 ug/L for Carbamazepine, 0.004 - 0.48 ug/L for Triclocarban, and 0.02-0.058 ug/L for Triclosan.
1
1. Introduction
1.1 Pharmaceutical & Personal Care Products (PPCPs)
Pharmaceuticals and personal care products (PPCPs) are chemicals that are discharged from household usage, airport and industrial manufacturing waste. This large group of
PPCPs consists of non-prescription drugs, prescription drugs, veterinary medicines, growth promoters, diagnostic agents, cosmetics, fragrances, sun screen agents and disinfectants used in industry, households and agricultural practices.2 Pharmaceuticals can also be excreted via feces and urine as well as the disposal of expired medicine via toilets. 3 Figure 1 demonstrates the pathways for PPCPs; including where they originate to how they enter into drinking water.
Trace amounts of PPCPs have been detected within the environment, leading PPCPs to be emerging contaminants due to their negative effects on aquatic organisms. 4 At the wastewater plant, high loads of PPCPs enter the wastewater influent for the treatment process, but many PPCPs will not be completely removed and will continue to contaminate source water. It has been shown that pharmaceutical discharges contribute to the contamination of rivers and creeks.5 Infiltration of source water containing PPCPs can contaminate groundwater as well due to leaks in landfills sites and sewer drains.3
Untreated wastewater can also contaminate waterways through leakages and combined sewer overflows, causing more of a hazardous threat to the environment.
There is now a consensus that the primary and constant sources of PPCPs to the aquatic environment are sewage treatment plant (STP) discharges, while combined sewer overflows (CSOs) can also lead to temporal PPCP discharges.6 The presence of PPCPs 2 cannot be eliminated completely due to influence from wastewater effluent and unintentional combined sewer overflows. However, the amount of PPCPs in source water varies seasonally due to weather conditions as well as being affected by environmental use and population. In the wastewater treatment process, it would be ideal for wastewater treatment to disinfect all pathogens and remove all hazardous chemicals effectively before introduction to source water, but unfortunately the wastewater treatment process was not designed to do so when the treatment plant was first developed.7, 8 After wastewater treatment, treated effluent, along with the undestroyed
PPCPs, enter the environment through seepage from treatment facilities or direct discharge of treated water. 9 Even though there is a consensus among scientists that acute toxicity is unlikely at environmentally relevant concentrations,10, 11 there have been studies that report adverse effects to aquatic organisms due to chronic exposure to pharmaceuticals or mixtures of pharmaceuticals.12-14 However, amounts found of PPCPs in drinking water are so low, that to achieve therapeutic doses, one would have to consume 1000x10 3 liters of water per day. Amounts of PPCPs found in source water are trace amounts ranging in the part-per-trillion levels, or ng/L, whereas therapeutic doses range near 61 milligrams/kg based on the average body weight.15, 16
Contamination of untreated wastewater poses a threat to aquatic life and to drinking water. Providing a sensitive method for detection of tracers to quantify magnitude of wastewater or CSOs is vital to ensure safety in drinking water. Developing a monitoring program will allow quantification for the amount of wastewater intrusion to
Philadelphia’s source water. Chemical tracers were chosen which are anthropogenic, stable, abundant, and enter from waste sources. It is important to see the fate of these 3 tracers through the wastewater treatment, to allow these chemicals to be suitable as tracers. Three stable and conservative tracers that are persistent in the environment and possess refractory behavior were used for this study: Carbamazepine, Triclocarban, and
Triclosan.
4
Table 1: Physical properties for Carbamazepine, Tricocarban, and Triclosan.
Analyte Structure Molecular Monoisotop Log Kow Formula ic mass: (Da)
Carbamazepine C15 H12N2O 236.094 2.45
Bisphenol A-d16 C15 H16 O2 244.38 3.32
Triclocarban C13 H9Cl 3N2O 315.58 4.2
Triclosan C12 H7Cl 3O2 289.54 4.8
Carbamazepine is a pharmaceutical compound while Triclocarban and Triclosan are personal care products. Carbamazepine is an anti-epileptic drug used to treat seizures and for patients with epilepsy while Triclocarban and Triclosan are used as disinfectants in 5 soaps and other products due to their antibacterial and antifungal properties. Due to copious amounts of these three chemicals being used, these three chemicals are suitable tracers that can be detected simultaneously in the Philadelphia waterway.
Figure 1 : Pathways for PPCPs 17 adapted from EPA 2008.9 6
1.2 Objectives
In this study, the fate of chemical tracers is observed before and after wastewater treatment. The tracers are then monitored after wastewater discharge and while being diluted in the source water. This developed tracer study quantitates the impact of treated wastewater on source water. It can also identify unintentional and indirect wastewater influences to source water. This is important because treated wastewater may contain significant amounts of PPCPs, while untreated wastewater may also contain PPCPs along with bacterial contamination.
The tracers are conservative and stable as well as abundant and detectable, even after dilution downstream. Samples from wastewater discharge and samples diluted along the waterway were measured and data was investigated for interpretation. The results obtained allow for a better quantitative analysis of PPCPs in the water system, showing how much wastewater contributes PPCPs to source water.
The goals of this work are to do the following:
1) Develop a sensitive and robust analytical technique for the detection of three
PPCPs as tracers
2) Understand the fate of these tracers and degradation
3) Evaluate the tracers’ efficiencies through the wastewater treatment process
4) Observe changes in detection based on seasonal and environmental conditions 7
5) Study the occurrence of these tracers in the Philadelphia water system
6) Develop a monitoring program for the tracers diluting into source water
7) Distinguish between treated WW contamination and untreated wastewater
2.0 Emerging concern for Pharmaceuticals and Personal Care Products (PPCPs) 2.1 Carbamazepine
Persistent Carbamazepine has been identified recently as a top priority pharmaceutical residue by the Global Water Research Coalition. 18 A human health risk assessment by
Virginia Cunningham was done to evaluate exposure of Carbamazepine and the metabolites Carbamazepine diol and Carbamazepine N-glucuronide. Carbamazepine has been detected in sewage treatment plant influents and effluents, surface water, drinking water and ground water in Europe, United States, and Canada since 1998. 19-23
Carbamazepine is a pharmaceutically active compound along with its metabolite
Carbamazepine N-glucuronide while Carbamazepine-diol is not. Carbamazepine levels in finished drinking water ranged from <0.8 to 258 ng/L. According to Cunningham,
Carbamazepine and its metabolites have a high margin of safety and have no appreciable risk to human health through the given environmental exposure based on available human data. 24 However, at high enough levels, Carbamazepine is a FDA Pregnancy Category D chemical substance, which shows there is positive evidence of human fetal risks.24 The highest concentrations of Carbamazepine are most likely to occur from samples directly from wastewater treatment plant effluents while the lowest concentrations would occur from a drinking water or source water that does not contain any effluent. 8
In 2006, Carbamazepine was measured from different watersheds from different states as shown in Table 2. The minimum, maximum, and median values found were 2, 188, and 2 ng/L, respectively. In Seville, Spain, concentrations found for Carbamazepine in wastewater influent and effluent were found to be 700 and 550 ng/L, respectively.
Concentrations in Israel measured for Carbamazepine from secondary and tertiary effluents in Israel ranged from 1012 to 1700 ng/L. 25
Table 2: Occurrence of Carbamazepine and other analytess in six watersheds sampled in 2006 in ng/L.26
2.2 Triclocarban and Triclosan
Current, combined inputs of biocides Triclocarban and Triclosan in the U.S. environment are known to exceed 600,000 kg/yr and may be as high as 10,000,000 kg/yr.27 A study from Conosa analyzed Triclosan by SPME-GCMS in Spain. Composite samples on two different days were collected from a hospital sewer, WW influent and WW effluent; 9 results found were 4148 and 13944 ng/L, 433 and 966 ng/L, 209 and 321 ng/L, respectively. Triclosan concentrations found in the inlet were much lower than those found in the USA (4 to 17 ng/mL)28 while the concentrations found in the effluent were close to the values found in Switzerland. 29
Margaretha et al. analyzed the amount of Triclosan found in fish that were exposed to municipal wastewater as well as fish living in receiving waters of three wastewater treatment plants (WWTPs) in Sweden. Rainbow trout fish were analyzed 1 and 2 km downstream of each of the three WWTPs. WWTP #1 concentration in bile (mg/kg fresh weight) at 1 and 2 km downstream were 25 and 17, at WWTP #2, 34-53 were found at 1 km downstream, and WWTP #3 was found to have 83-120 and 59-94, respectively.
WWTP #1 does not use anaerobic digestion and is not connected to large industries,
WWTP #2 treats sewage water and performs both anaerobic and aerobic digestion,
WWTP #3 is similar to WWTP #2, but uses slow sand filtration as an additional step.30 In addition, Margaretha et al. also analyzed 5 different sources of mother’s milk; the first 2 samples had no detects, while samples 3-5 had values of 60, 130, 300 µg/kg lipid weight.
Due to Triclosan’s high exposure and absorbance to human and aquatic life, Sweden abandoned Triclosan use in hospitals. 30
In Guangzhou, China, Triclosan was tested for in tap water and in twenty-one brands of bottled water. Concentrations of Triclosan from bottled water ranged from 0.6 - 9.7 ng/L.
Tap water from six drinking water plants were collected in June and December; June had results for Triclosan from 0.5 - 14.5 ng/L, while June had no detects.31 10
In South China, Triclocarban and Triclosan were investigated in the Pearl River system
(Liuxi, Zhujiang, and Shijing Rivers) and at four sewage effluents during dry and wet seasons. Liuxi, Zhujiang, and Shijing Rivers had mean values for Triclosan of 13.7, 16.8,
242 ng/L in water, while in sediments 56.5, 72.6, and 739 ng/L, respectively.
Triclocarban mean values in the water were 7.4, 19.9, and 158 ng/L and 173, 327, and
1305 ng/L in sediments. Effluents have a mean value of 71 ng/L in water samples while no detects in sediments for Triclosan, while 104 ng/L in water samples and no detects in sludge. 32
3. Fate of Chemical Tracers through Wastewater Treatment 3.1 Carbamazepine
There are four major processes that can cause removal of compounds from the liquid phase; volatilization, photolysis, sorption to wastewater sludge and biodegradation. The three proposed tracers are not volatile and photolysis would occur above their pK a; most
WWTP work at pH ranges of 6.5 to 8.5. Photolysis can be eliminated for Triclosan due to its pK a value of 8, while for Triclocarban and carbamazepine, photolysis is possible.
Table 1 shows selected chemical properties of the tracers.
Carbamazepine is an epileptic anticonvulsant drug used widely and found to be highly persistent within the environment. The carbamazepine molecule is uncharged and polar, but has been found to create weak, non-specific interactions with soils and minerals.33-35
Due to Carbamazepine’s physicochemical properties, it is weakly adsorbed to mineral soils and is resistant to biodegradation, suggesting Carbamzepine as an anthropogenic marker to track the fate of wastewater in aquatic systems.36 It is administered chronically 11 and usually in high doses (100-200 mg daily) and thus its annual consumption is high; the drug is excreted with <3% remaining in its unaltered form.36 Oral administration of
14 C- Carbamazepine indicates that 72% was found in urine while 28% was found in feces. Urinary radioactivity was composed of metabolites while 3% was unchanged and the feces contained a little over half as many metabolites and the rest as the unchanged drug that was not absorbed by the body. 37 Studies were done on the fate of
Carbamazepine in wastewater treatment systems and surface waters, suggesting its resistant behavior for removal; this recalcitrance and high usage is due to its high detection frequency. 24 The removal efficiency of Carbamazepine from treatment in sewage treatment plants had an efficiency of only 9%. 33, 38, 39 Kosjek compared the following three methods’ effect on the fate of Carbamazepine: (i) UV-radiation, (ii) oxidation with chlorine dioxide (ClO 2) and (iii) biological treatment with activated sludge. The most successful method for the removal of Carbamezepine was UV treatment. Based on the enhanced biodegradability of Carbamazepine residues achieved by UV radiation, two treatments in series were proposed: UV treatment followed by biological treatment.35 Under UV experimental conditions, Carbamazepine shows a steady decrease following first order kinetics.
Ternes examined the elimination of Carbamazepine during drinking water treatment at lab and pilot scales and in real waterworks. Processes such as bank filtration and artificial groundwater recharge and widely used techniques for surface water treatment such as activated carbon filtration, ozonation, and flocculation were investigated. Lab scale experiments showed that Carbamazepine is effectively removed by ozonation; 0.5 mg/L ozone was shown to reduce Carbamazepine by more than 90%. 3 Carbamazepine is 12 persistent to biodegradation and shows almost no elimination during wastewater treatment.39, 40 No significant amount of Carbamazepine was removed with sand under aerobic and anaerobic conditions, showing Carbamazepine’s low adsorption properties and high persistence with non-adapted organisms.3 Studies were also done with iron (III) chloride used for flocculation in lab scale experiments showing no significant removal. 3
3.2 Triclocarban & Triclosan
Triclocarban (3-(4-chlorophenyl)-1-(3, 4-dichlorophenyl) urea) is slightly water soluble and possesses antibacterial and antifungal properties.41 Triclocarban has been used in industries as early as the 1960s, with continual and increased usage due to the popularity of the compound. In the United States alone, 84% of antimicrobial bar soaps contain
Triclocarban 41 and its usage could reach an upper range as high as 750 metric tonnes/year.42, 43
Triclocarban is an active ingredient used in antibacterial soaps and detergents.
Triclocarban is commonly detected at ppm concentrations in biosolids and most of the biosolids are land applied, releasing Triclocarban to soils.44, 45 Up to 98% of Triclocarban present in wastewater influent is removed by activated sludge treatment 43 and around
75% accumulates in the solid fraction as sludge.46 14 C-Triclocarban was used to study anaerobically digested biosolids to measure degradation and changes in bioavailability
−1 with time. Noting Triclocarban’s limited solubility (0.045 mg L ) and moderate log K ow
(3.5),44, 45, 47 Triclocarban will preferentially partition to the biosolids matrix, potentially limiting bioavailability. 45 Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol) possesses antimicrobial agents used in many consumer goods. Triclosan has been detected 13 repeatedly in wastewater effluents 28 and source water 29 at 7ng/L.48 Triclosan was first registered as a pesticide in 1969.49 Triclosan is not water soluble, in fact, can easily enter inside the cell and poison a specific enzyme that many bacteria and fungi need for survival.50, 51 Triclocarban, which has many common properties to Triclosan, can possibly mimic this behavior as well.
Triclocarban and Triclosan enter the environment primarily through discharge of effluent from wastewater treatment plants and disposal of sludge on land. 52 Due to incomplete removal during wastewater treatment, their presence has been detected in sewage effluents and sludge.53 Fate modeling shows that neither compound degrades fast. rimary biodegradation in aerobic soils gave a half-life for Triclocarban and Triclosan of 108 and
18 days, respectively. In anaerobic soil, the compounds persist within 70 days and are resistant to biodegradation in anaerobic conditions.52 Triclosan, in the presence of hypochlorite or due to photochemical reactions, can be converted to a more toxic and persistent polar compound such as chlorinated phenols,30 polychlorinated biphenyl ethers 54 as well as Methyl-Triclosan, a nonpolar bio-accumulating compound that has been detected already in aquatic organisms tissues.54
Triclosan was measured at three points within wastewater treatment with the amounts removed as follows: rotating biological contactors, trickling filters, and activated sludge with removal efficiencies from 58-96%, 86-97%, and 95 to 98%, respectively.48
Wastewater treatment plants with long hydraulic retention times (<15 hours), such as with activated sludge, have shown removal greater than 95%, while with shorter retention times such as 1-4 hours, as with tickling filter, removal is only 58-86%. 48 14
4. Water Treatment 4.1 Wastewater Treatment
The wastewater treatment plant receives used water from household sinks, showers, bathtubs, toilets, washing machines, and dishwashers; these include human waste, food scraps, oil, soaps, and chemicals. 55 Business and industrial manufactures also dispose chemicals and other byproducts. The role of wastewater treatment is to remove suspended solids and disinfect pathogens before being discharged to the environment.
The amount of biochemical oxygen demand (BOD 5) is a measurement of the amount of oxygen microorganisms require to break down sewage in five days. Each treatment plant has a National Pollutant Discharge Elimination System (NPDES) permit listing allowable levels of BOD 5, suspended solids, coliform bacteria, and other pollutants that can be discharged to the environment.
The steps of wastewater treatment mainly consist of 6 steps. The first step is pre- treatment, which consists of screening, grit removal, flow equalization, and fate and grease removal. The second step involves primary treatment, followed by secondary and tertiary treatment, disinfection, and odor control. In the primary step, the wastewater is held in a basin where materials get separated by density; heavy solids settle on the bottom and lighter solids or grease float. The settled and floating materials get removed and the remainder is subjected to secondary treatment. Secondary treatment consists of activated sludge, surface-aerated basins, filter beds, constructed wetlands, soil bio-technology, biological aerated filters, rotating biological contractors, membrane bioreactors, and secondary sedimentation. Secondary treatment mainly removes dissolved and suspended 15 matter. Tertiary treatment consists of filtration, lagooning, and nutrient removal.
Treated water is disinfected by chemicals or is physically disinfected by lagoons or microfiltration, then is discharged into a stream, river, or waterway. After tertiary treatment, it can also be used for irrigation or groundwater recharge if sufficiently clean.
The sludge that is acquired goes through anaerobic digestion, aerobic digestion, composting, incineration, and sludge disposal. 56 Figure 2 shows a typical process for wastewater treatment.
Figure 2 : Process flow diagram for a wastewater treatment plant. 56
16
4.2 Distribution System Infrastructures
The Philadelphia Water Department (PWD) has 3,000 miles of sewers and water mains,
79,000 stormwater inlets, over 25 pump stations, 175 CSO regulating chambers, 164
CSO outfalls, 18 reservoirs, and more than 450 stormwater outfalls.57 ,58 Eighty-seven percent of the water mains in Philadelphia are made of cast iron; in the mid-1960’s ductile iron pipe began to be used due to better strength and flexibility.57 There are three drinking water plants and three wastewater plants. Two drinking water plants (Belmont and Queen Lane) take water from the Schuylkill River and one (Baxter) from the
Delaware River, distributing to 1.5 million Philadelphia residents. The Baxter Water
Treatment Plant treats an average of 200 million gallons a day, the most out of all three drinking water plants. Belmont Water treatment plant treats an average of 40 million gallons a day, while Queen Lane Water treatment plant treats an average of 70 million gallons a day. The wastewater treatment plants are divided into three drainage districts:
Northeast, Southeast, and Southwest. Each plant receives wastewater from household and other business waste through branch sewers and conveys it to a regulating chamber in the treatment plant. Combined sewer interceptors convey flow from regulating chamber and separate sanitary interceptors to the wastewater treatment plants. Storm relief sewers convey flow from storm relief chambers when there is high flow.
17
5. Combined Sewer Overflow 5.1 The Importance of Combined Sewer Overflow
In the United States, 772 communities have combined sewer systems, serving 40 million people. 59 In the 1960’s, it became apparent that CSOs impact water bodies, but it was not until the 1990’s that reducing CSOs became a concern.60 Combined sewer systems encompass a single pipe that collects sanitary sewage from people’s usage and stormwater runoff. When there are large variations in flow between dry and wet weather or during instances where there is too much flow, the combined sewer overflows, causing untreated water to discharge to nearby source water. When there is heavy rainfall, stormwater exceeds the sanitary flow, causing sanitary flow to be diluted to the rainfall events. There are two main factors that enhance the impact of CSO; the first is the presence of large amounts of particulate organic matter in the wastewater that is discharged during rain events and settles rapidly, and second is CSOs’ diffused character due to the large number of outlets causing geographical dispersion. 61
Combined sewer overflows pollute the source water with possible bacteria, pathogens, and toxic chemicals. Storm effects can vary; storms in the late summer during long periods of dry weather have the most pollutants containing oil, grease, fecal coliform, and pesticides. 62 In cold weather, pollutants from cars, people and animals accumulate on land during winter and are flushed into sewers during heavy spring rains.62
Reducing CSO involves sewer separation which entails building a second piping system, but only portions of some systems are able to be separated due to limitations from high cost or physical limitations. Building a CSO storage facility to store water during heavy 18 rain periods can help reduce sewer overflows by only being pumped out and conveyed to the wastewater treatment plant when the storms are over so there are no overflows occurring. Alternatively, a CSO flow-through facility can be constructed that will reduce pollution by screening and disinfecting CSO using sodium hypochlorite before discharging to source water. Other means that can be done to reduce the effects of CSO include the expansion of sewage treatment capacity and the reduction of stormwater flows.
5.2 Green City Clean Waters
In collaboration with the EPA, Philadelphia signed a 25-year plan to improve stormwater management with innovative green infrastructure. The program developed by the
Philadelphia Water Department is called “Green City, Clean Waters”. This sustainability program increases green space and manages rainfall. The older approach of managing pipes and underground pipes is costly whereas this new program embraces green technology rain gardens, green roofs, southwest trenches, decentralized infrastructure which will transform the city overtime. Green City, Clean Waters was established primarily as a response to a regulatory mandate to reduce CSO over 25 years and increasing greenery in neighborhoods by restoring waterfronts and improving recreation
“The process is daunting”, according to Glen Abrams, PWD's Manager of Policy and
Strategic Initiatives, “but computerized mapping helps with street design, constructing pervious surfaces to help manage rainfall, and collaborates including school districts and other entities help pursue this green program”. 58 19
Green2015 is another program that has a goal of building 500 acres of green city by
2015. Trust Republic Land and the William Penn Foundation have helped fund this program. Green2015 would like to unite city government and neighborhood residents to transform empty or underused land in Philadelphia into parks for neighborhoods.63 This program addresses wet weather inflow and infiltration in areas of combined sewer systems by implementing green stormwater infrastructure.
Green stormwater infrastructe is a way to maintain healthy waters by an approach other than using pipes to dispose of rainwater. Instead, this program uses vegetation and soil to manage rainwater. Other assets this program provides besides stormwater management is flood mitigation and air quality management. The City of Philadelphia possesses an old infrastructure system which needs replacement or repair, but this also possesses a lot of expenses and funding that may not be available at the time. This approach will help with stormwater management in an affordable means that can help reduce the issues of CSOs.
This program also will allow people to be able to live near more green space and parks, since many neighborhoods do not have close access to nearby parks. This is one of the
21 st century greatest challenges to the health of our nation’s rivers and streams but will give a result of greener, healthier cities by reducing CSO and wastewater contamination.
20
6. Monitoring Program
6.1 Distinguishing between CSO and Wastewater
Wastewater, stormwater, and CSO demonstrate differences in both the quality and quantity of contaminants as well as differences in their pollutant patterns. Riechel showed that a reliable sign of CSO influence can be determined by drops in conductivity; however there are natural seasonal and daily variations that may positive direct identification of CSO not possible. 64 Another study by Passerat et al. also used conductivity as a conservative tracer to help determine the proportion of the average river water as an estimate of the dilution rate of the CSO in the water. 65 A more thorough study of Paris’ watershed evaluated water quality of CSOs, wastewater, and stormwater.
Gasperi et al. have shown that CSOs have more hydrophobic organic pollutants and particulate bound materials than wastewater and stormwater, due to the contribution of in sewer deposit erosion. 66, 67 For pesticides and zinc, however, values seem to be close for all three water matrices, suggesting runoff as the major contributor, while wastewater appears to be the main source of volatile organic compounds. Monitoring CSO impact is essential since studies show CSO discharges pose a risk for polycyclic aromatic hydrocarbons (PAHs), tributyltin compounds, and chloroalkanes. 66
A study evaluated in an urban watershed in Paris by Johnny Gasperi wanted to observe the difference in water quality parameters that can help discern water contamination’s origin, such as from stormwater, CSO, or wastewater. Eighty-eight substances were monitored and data trends observed to characterize each matrix. Detection in wastewater and runoff include nine analytes: chloromethylphenol, benzene, chloroform, 21 dicloromethane, chlorpyrifos, simazine, metaldehyde, Polychlorinated Biphenyl 52
(PCB), and pentachlorophenol. Compounds that were detected in CSOs include forty- nine compounds: 4 metals (Pb, Cr, Cu, Zn), 5 volatile Organic Carbons (VOCs)
(ethylbenzene, toluene, xylenes, tetrachloroethylene, trichloroethylene), 9 pesticides
(aldrin, dieldrin, atrazine, desethylatrazine, diuron, isoproturon, aminotriazole, glycophosphate, AMPA), 3 organotoxins, 3 alkylphenones, 16 Polycyclic Aromatic
Hydrocarbons (PAHs), and 7 (PCBs), which can be found in Figure 2.66 Heavy metals, particularly, cadmium, copper, chromium, lead, nickel, and zinc, are indicative of industrial and transportation landuses. 68
Figure 3 : Pollutants that were detected and not detected in CSOs. 66
A method by Weyrauch in Berlin, Germany assessed the ratio of CSO to wastewater treatment plant effluents. This study indicated that annual loads are dominated by CSO 22 for substances with removal in wastewater treatment plants above 95%, while substances poorly removable decreased in CSO influenced samples due to dilution effects. Overall, the results are essential indicating the potential importance of the CSO pathway of well removable sewage based trace contaminants to rivers. 18 A study by
Passerat et al estimated that CSO discharged 79 more times more E. coli and 1000 more times more intestinal enterococci than the wastewater treatment plants as shown in Figure
3.65
Figure 4 : Comparison of the Fecal Indicator Bacteria loads discharged into the Seine River downstream from the City of Paris by the studied CSO and the three WWTPs of the area. 65
6.2. Established Mandates for Controlling Pollution
In 1989, the EPA published its National Combined Sewer Overflow Control Strategy to help control discharge through CSOs of domestic sewage and toxic substances. 6, 9, 55, 69-71
This would help minimize impacts of CSO on water quality by combining all wet weather CSO into compliance of the Clean Water Act. To further assist in insuring minimal impact of CSO, the Clean Water Act set a new policy in 1994 amended by
Congress to require municipalities to reduce or eliminate CSO-related pollution 23 problems.70 Prior to 1990, Michigan, for example, had an estimate of more than 30 billion US gallons per year of untreated combined sewage discharge. 62 In 2005, $1 Billion dollars has been spent to reduce untreated discharge by more than 20 billion US gallons per year, yielding a 67% reduction in CSO.62
The Clean Water Act mandated wastewater treatment plants to reduce pollution to the waters of the United States; however, non-point source pollution, such as stormwater runoff is a major contributor to pollution of receiving waters. 68 In response to non-point source pollution, regulatory agencies are requiring stormwater monitoring programs through NPDES to quantify and identify high risk discharges and reduce stormwater pollution.68
7. Sampling Considerations for the Water Samples 7.1 Importance of Sampling
The sampling step in an analysis is just as important, if not more, than the measurement step. Sampling can have a significant impact on the quality of environmental data, since any minuscule mistake can give significant errors in result and interpretation. The combined sampling errors typically amount to 10-100, or even as much as 100-1000 times the specific analytical errors associated with the chemical analytical step itself.72
Since sampling and analysis are two crucial factors, both must be done with the same care, accuracy and reproducibility.73 Christopher Ort et al. demonstrates that sampling imprecision can lead to over-interpretation of measured data and wrong conclusions. Ort discusses two factors, namely concentration and flow variations generating the fluctuations of PPCP loads in sewers. Concentration and flow variations can be affected 24 by rainfall events and dry weather conditions. Rain can impact the occurrence and fate of pollutants, especially in combined and separate sewers; other ‘events’ that may occur rely on household waste discharges.74 Environmental conditions, population density and usage are all contributing factors to pharmaceutical and personal care products concentration and occurrence.
According to Peterson et al., other important factors to consider for sampling are: the type of sample bottle (clear glass or amber), size of container, head space, preservative, filtration, and frequency. Developing a systematic approach in sample collection, frequency, and procedure helps guide approaches for representative samples and reproducible sample location.72
7.2 Sample Collection
The procedure for sample collection is crucial so there is no variability in sample collection, which can lead to sample analysis bias. Below is a description of some important factors of sample collection to be considered.
7.2.1 Sample bottles
The tracers used in this study are reasonably stable, with the exception of Triclosan being photosensitive. Therefore the samples were collected in amber glass bottles. Another reason to use amber glass bottles was to help reduce formation of algae, which may affect analysis by analyte degradation or increased acidity of the samples. Since amber glass vials contain a high content of transition metals (0.7-1.4% Fe 2O3 and 0.7 TiO 2), amber glass should not be used for analytes possessing a high oxidation potential, causing 25 analyte decomposition. 75 The tracers used for this study do not have a high oxidation potential and should not be affected using amber glass.
7.2.2 Sample Volume
The developed method requires 500 mL of sample to be extracted through a SPE cartridge. Sample analysis involves replicates and duplicates. Replicates here means analyzing two samples from the same bottle to observe sample precision, while duplicates require two separate sample bottles to assess sample collection reproducibility.
Collecting the samples in 1L sample bottles is sufficient for this method.
7.2.3 Location
After the sample locations are determined, the exact location should be noted in as much detail as possible; this can be noted by miles upstream and by nearby landmarks to describe the location.
7.2.4 Head Space
The analysis of these three tracers does not require an absence of head space since these compounds are not volatile. If these compounds were semi-volatile, having head space would cause analyte loss and incorrect quantification. Samples were collected without head space to ensure that there is enough sample volume available.
26
7.2.5 Preservative
A preservative should be used to prevent the decomposition for the analyte of interest.
For the beginning of the method, samples will not have a preservative; instead they were analyzed within a week time. Few papers mention that Triclosan sticks to glass, which can be prevented by adding methanol. For the beginning stages of this method, 5mL of methanol were added to the 1L sample bottles before collection to help Triclosan to stay in solution. No other preservatives were used.
7.2.6. Filtration
Filtration is recommended immediately after sample collection to prevent bacterial growth. However, since filtration does reduce analyte recovery and the sample matrix does not have high turbidity, sample filtration was not used. Instead, samples were analyzed within seven days, and samples were left to settle any particles (if any) for one hour before sample extraction.
7.3 Sample Frequency
The frequencies of the samples were determined based on weather and flow conditions.
The concentration of the various determinants in a stream varies due to random and systematic changes.61, 6 Sampling intervals should be chosen on expected frequency of changes, which may vary from as little as 5 min to as long as 1 hr or more.6 This will help determine how the water quality changes with time for a specific location. Unfortunately, for this study, no such equipment was available and sample times were chosen once daily under different weather conditions. The frequency of samples from one location to the 27 next should be based on detention time and flow, to ensure the same matrix has moved downstream. The detention time is the time that it takes for the ‘same’ water to move downstream.
The concentrations of the collected samples can fluctuate due to random and systematic changes. To understand when and how the variations occur, it would be ideal to use an on-line real time measurement, but such instruments are not yet available and portable. A good approximation of the variation can be accomplished by collecting grab samples at high frequency over a period of time and environmental conditions. Another approach commonly used is to have a 24-hour composite sample, representative of the 24-hour period. One drawback, however, is that short term variations will not be determined.
River flows can also determine the sampling mode. Oto et al. claim, “If the wastewater varies in quantity or quality with time, a continuous flow discharge record is necessary to obtain a reliable estimate of the load”. 1 This approach would be advantageous since it would show short term variation frequency. Weather conditions have an effect on sample concentration, so samples should be collected in dry and wet weather, since wet weather will dilute the sample and change the water quality. Seasonal variability also has an impact on water quality; during the summer the flows are low and temperatures are high, while in winter there are high flows due to rain and snow and the temperatures are cold.
Cold weather may also prevent soil leaching to water. When there is too much rain, wastewater can contaminate source water by combined sewer overflows (which give short term inconsistent contamination). Also, rain dilutes the rivers and results in the underestimation of the analytes found in the rivers. Rainstorms wash runoffs to the river, 28 wastewater discharge year round, and industries discharge with permits, and other incidental contamination all will cause variations in water quality. However, even during consistent weather patterns, there may be short-term variations from the wastewater plant. Rain also has an influence on the quality of the runoff in relative to the time of sampling. When collecting grab samples for a stormwater monitoring program, for example, the timing of the sample is important since the first flush creates a higher concentration at the beginning of the runoff. 68 The plant can have varying amounts of wastewater discharge from households, different amount of flushes per day, different times of the day that can give peak heights of contaminants (6am, 9pm time when people shower and times when people get ready for sleep). Each STP (sewage treatment plant) and sewer system is unique due to different topology and drainage layout, which includes retention tanks and actuators (pumping stations, flow regulators, etc.). To ensure safety in the environment, there should be knowledge of what chemicals go into the water and to what impact the water quality is affected. It would be ideal for a continuous monitoring of changes in water quality and what precautions should be enforced to prevent harsh environmental conditions.
7.4 Sample Storage
Samples were stored at 4 oC. The water samples should not be frozen during storage however should be cold enough to deter any algae formation or bacterial growth. Samples should also be away from excessive sunlight.
29
7.5 Sampling Locations in the Philadelphia Watershed
The impact of wastewater into source water was evaluated by collecting samples upstream of the wastewater treatment plant and continuing downstream to pass the tributary for the WWTP and for miles down the river. The locations before the outfall of the WWTP gives an idea of the background water quality before local immediate known wastewater influences.
Based on the stability of the tracers, we expected them to be detectable in wastewater effluent after treatment. Samples were collected from the Northeast Wastewater
Treatment Plant, which is located at 3900 Richmond Street Philadelphia , Pennsylvania ,
19137. Locations sampled were at the influent and from the effluent (after 12 hours) before being discharged to the river. Wastewater influent samples were collected after grit removal, while wastewater effluent was collected after chlorination, with a 12-hour detention time. The 12-hour detention time is the time the water is estimated to spend in the plant. Since we would like to sample the “same” water before and after treatment, we waited 12-hours to collect the wastewater effluent. The tracers were monitored through wastewater treatment to determine their fate in the wastewater treatment process. These samples are collected to see the impact of the wastewater treatment discharge to the
Delaware River. All analytes were detected at the influent and effluent (see section 9.2).
Two locations were also chosen upstream and downstream of the wastewater plant to assess the quality of the river water before and after discharge. The locations can be seen in Figure 5. Frankford Arsenal used to be a United States Army ammunition plant in
Northeast Philadelphia. It is upstream of the Frankford Creek, a minor tributary of the 30
Delaware River that originated as Tookany Creek. Frankford Arsenal is about two miles north of the Northeast Wastewater Treatment Plant, and was analyzed to observe the water quality before the wastewater is discharged. Frankford Arsenal is at the intersection of Tacony and Bridge Streets. Two miles south of the Northeast Wastewater
Treatment Plant is Penn Treaty Park. Penn Treaty Park is a small park on the western bank of the Delaware River in the Fishtown section of Philadelphia at the intersection of
Delaware Avenue and Beach Street. The actual locations for sample collections can be seen in Figures 6 and 7.
Figure 5: Map showing Frankford Arsenal, Northeast Wastewater Treatment Plant and Penn Treaty Park. The Northeast Wastewater Treatment Plant is located at 3900 Richmond Street Philadelphia , Pennsylvania , 19137.
31
Figure 6: Frankford Arsenal in Philadelphia, Pennsylvania at the intersection of Tacony and Bridge Streets.
32
Figure 7: Penn Treaty Park at 1195 North Delaware Ave in Philadelphia, Pennsylvania.
The monitoring program includes tracing the pathway of pollutants upstream near an outfall of wastewater discharge and downstream of the discharge. A set of locations that were chosen for a screening for the monitoring program were along the Wissahickon
Creek. The Wissahickon Creek is a stream in southeastern Pennsylvania, running 23 miles (37 km) through Northwest Philadelphia before emptying into the Schuylkill River at Philadelphia.76 The map of sampling locations can be seen in Figure 9. These locations were chosen for screening since they are known to be polluted from wastewater effluent 33 and are already locations used for USGS gage stations. These locations are good entry points allowing for easy sampling access. The locations are sampled regularly by the watersheds staff, measuring parameters such as pH and dissolved oxygen. Figure 8 shows samples location IDs collected along the Wissahickon going downstream; ideally values would decrease going downstream, as a contribution of dilution, which is shown in the results.
Figure 8 : Sample IDs and locations are coordinated with the map on Figure 9. 34
Figure 9: Map of source water sample locations along the Wissahickon Creek and Schuylkill River.
35
8. Analytical Methodology
8.1 Equipment Used
Instruments: Hitachi LaChrom Elite Low Pressure System Hitachi Column Oven L2300 Hitachi Autosampler L-2200 Hitachi PumpL-2130 Hitachi Diode Array Detector L-2450 Hitachi Fluorescence Detector L-2480 Pickering Labs PCX 5200 Post-Column Derivatizer Dionex Autotrace 280 SPE Caliper Life Science TurboVap LV
Solvents : Purchased from Fisher Scientific Acros Water HPLC grade 4L Fisher Acetonitrile HPLC grade 4L Acros Methanol HPLC grade 4L
Glassware: Fisher Boro Glass bottles 1000 mL Disposable Pipettes (muffled 400 oC for 1 hour) Pyrex 1000 mL Graduated cylinders SUPELCO 2 mL vials, screw top, amber glass, 12x32 mm Thermo Scientific HyperSep C18 SPE Column - 6mL volume, 1g bed weight
Chemicals:
Bisphenol A- d16 98% atom D, neat- purchased from Sigma Aldrich Carbamazepine neat purchased from Sigma Aldrich Triclocarban 1000 ug/mL in Methanol purchased form Accustandard 36
Triclosan 1000 ug/mL in Methanol purchased from Accustandard
8.2 Method Parameters
Samples were analyzed by High Performance Liquid Chromatography (HPLC) with
Diode Array Detection (DAD). Since most pharmaceutical and personal care products are nonvolatile, thermally labile, and polar, liquid chromatography is usually the technique of choice. HPLC is a chromatographic technique utilized for separation of compounds in analytical chemistry. This technique uses columns that are composed with a particular stationary phase that has an affinity to certain classes of compounds. The column is often referred to as the heart of the separation. Nonpolar hydrocarbons, for example, would have an affinity for C-8 or C-18 stationary phase, while polar compounds have an affinity for polar stationary phases, such as silica. The analytes for this method range from medium polarity to nonpolar compounds. Reversed phase chromatography was used, which is the best method for neutral species. The column used for this method was a Thermo Hypersil Gold C-18 column with dimensions of 50 mm
(length) x 4.6 mm (inner diameter), with an average particle size of 5 µm. Particles of this size give a good compromise for efficiency, pressure drop, convenience, equipment requirements, and column lifetime. 77 The particle size and type of particle (spherical versus irregular) are primary factors for determining column efficiency, since they can influence the homogeneity of the packed bed.
The HPLC utilizes high pressure to push the mobile phase and dissolved sample components through the densely packed columns, which causes people to infer that
HPLC stands for High Pressure Liquid Chromatography. Unless sufficient selectivity is 37 not achieved, the preferred solvents that are combined into a mobile phase for this method are water and acetonitrile. Organic solvents that are preferred when performing reversed phase chromatography should be water miscible, relatively non-viscous, stable under the conditions of use, transparent at the lowest possible wavelength for UV detection, and available in high purity at a relatively moderate cost. 77 Acetonitrile has a
UV cutoff wavelength of 190 nm, a dielectric constant of 36.64 and the normal boiling point of 81.6 oC. Water has a UV cutoff of 191 nm, a dielectric constant of 80.10, and a normal boiling point of 100 oC. The HPLC is interfaced with a diode array detector
(DAD). The DAD has variable wavelength in the UV-VIS range (200-700 nm). While the analyte is passing through the flow cell, the detector performs spectroscopic scanning and absorbance readings at varying wavelengths. The DAD allows for detection at multiple wavelengths for increased sensitivity during quantitative analysis, as well as spectral identification for qualitative identification. The analytes Carbamazepine,
Triclocarban, and Triclosan have common absorbance at 231 nm. Detection at 231 nm allows for analysis of all three analytes as well as the internal standard, Bisphenol A d-
16. Detection at 260 nm allows for more sensitive analysis of Triclocarban, since there is a higher absorbance at 260 than 231 nm. The temperature of the analysis was controlled by the oven thermostat at 40 oC. Having a higher temperature than ambient allows for more reproducible analysis since ambient temperature variation can cause fluctuations in the viscosity and pressure of the solvent, causing a shift in retention times. An increase in column temperature by 1 oC can result in a decrease in the retention factor (k) by 1-2% for each peak in the chromatogram, so it’s important for the temperature to be constant. 77
The HPLC gradient method can be seen in Table 2. The flow rate is 1 mL/min and the 38 injection volume is 40 µL.
Table 3: HPLC gradient program. Carbamazepine and Bispenol A D-16 elute isocratically at 50:50 Water:ACN, then the gradient changes to 30:70 Water:ACN where Triclocarban and Triclosan elute isocratically.
Time (min) Water ACN Flow (mL/min)
0.0 50 50 1.0
1.5 50 50 1.0
2.5 30 70 1.0
5.5 30 70 1.0
7.0 10 90 1.0
9.0 10 90 1.0
11.0 50 50 1.0
8.3 Method Efficiency .
Before doing samples analysis, a test mix was purchased and ran to check the system suitability of the instrument and method parameters. The test mix that was purchased from Restek, RP Test Mix #1, contains analytes Uracil, Benzene, Napthalene, and
Biphenyl at concentrations of 0.02, 3.0, 0.5, 0.6 mg/mL, respectively. The chromatogram can be seen in Figure 8. Detection was at 254 nm and eluted at isocratic concentration of
75:25 Methanol:Water. Another test mix from Thermo, Test Mix RP5, was also analyzed.
The components of this test mix were Theophylline, p-Nitroaniline, Methyl Benzoate, 39
Phenetole, and o-Xylene. Detection for this test mix was at 254 nm and eluted at 60:40
Acetonitrile:Water isocratically.
1200 1200 1: 254 nm, 4 nm RESTEK RP TEST MIX Hitachi Elite DAD.10026 7-29-2011 3-28-09 PM.dat Name Retention Time 1000 1000 Resolution (USP)
800 800
600 600 mAU Napthalene 2.92 2.87 2.92 Napthalene mAU
400 400 Biphenyl 3.30 2.22 3.30 Biphenyl Benzene 2.47 4.10 Benzene 2.47 200 200 Uracil 1.87 0.00 1.87 Uracil
0 0 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 Minutes
Figure 10 : Restek Test Mix used to test system suitability on the HPLC DAD.
40
1200 1200 1: 254 nm, 4 nm Thermo test Mix RP5 110729 thermo test mix r.dat Name Retention Time 1000 1000 Resolution (USP)
800 800
600 600 mAU mAU
400 400 Methyl Benzoate 2.61 5.97 2.61 Benzoate Methyl
200 5.57 3.42 Phenetole 200 o-Xylene 4.51 6.24 4.51 o-Xylene Theophyline 1.44 0.00 1.44 Theophyline p-Nitroaniline 1.88 3.93 1.88 p-Nitroaniline
0 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 Minutes
Figure 11: Thermo Test Mix to test system suitability on the HPLC DAD.
The column plate number, or efficiency, changes with respect to the column, sample, and
77 other separation conditions. Particularly, the baseline width W b and retention time t R of a peak determine the value of theoretical plates, as shown in equation 1. The larger the value of N, the narrower the peaks in the chromatogram, and the better is the separation, other factors equal. The Efficiency (N), Resolution (R s), capacity factor (k), and selectivity ( α) were calculated as per equations 1-4 for the developed method. Good separation and resolution is essential for accurate quantification. Baseline resolution of
1.5 is favorable for peaks of similar size while resolution greater than 2 is favored as the critical resolution of the separation. The resolution and capacity factors were improved by changing the relative retention or selectivity of the analytes. The chromatogram and resolution can be found in figure 10. 41
1 k Equation :1 Rs = ()α −1 N 05.0 4 1+ k
2 tR Equation :2 N = 16 Wb
− tm tR Equation :3 k = t m
k2 Equation :4 α = k 1
42
3: 231 nm, 4 nm 250 ppb 8/10/11 18 Hypersil gold TRACER CAL direct 081011 MA 1mlmin 14.dat 18 Name Retention Time 16 Resolution (USP) 16
14 14
12 12
10 10 mAU mAU 8 8
6 6 Carbamazepine 2.77 0.00 2.77 Carbamazepine 4 4 Triclosan 7.80 2.27 7.80 Triclosan bisphenol A-d16 3.37 3.60 3.37 A-d16 bisphenol Triclocarban 7.39 23.44 7.39 Triclocarban 2 2
0 0
1 2 3 4 5 6 7 8 Minutes Figure 12: Chromatogram at 231 nm showing the four tracers retention time, theoretical plates, and resolution. The method obtained analyte resolution above 2.2, and efficiency from 4805 to 28199 from the first to last eluting peak.
8.4 Method Capabilities and Validation
Linearity was measured for this method from 1-100 ug/L. All compounds had a coefficient of determination (r 2) > 0.995, based on a minimum of 7 data points used in the regression of the calibration curve. Procedural recoveries with this method were 90%,
85%, and 80% for Carbamazepine, Triclocarban and Triclosan, respectively. Precision of the method was assessed by comparing repeatability and intermediate precision results with pre-determined criteria. For repeatability, the same QC sample was injected 7 times for intra-day precision, giving an RSD less than 16%. For intermediate precision, a QC sample was injected over 5 days, giving an RSD less than 9%. Repeatability and 43
Intermediate Precision results can be seen in Table 4 and 5. A QC sample was also
extracted 7 times and observed for procedural RSD, which was below 12% and can be
seen in table 6.
Table 4: Repeatability Study; injecting QC sample of 25 ug/L same day for Intra day Precision. QC QC QC QC QC QC QC %Rel 1 2 3 4 5 6 7 Average Stdev Stdev
Carbamazepine 231nm 7.00 9.55 10.0 7.87 8.59 9.28 11.1 9.05 1.36 15%
Triclocarban 260nm 8.12 8.47 7.89 7.82 8.43 8.21 8.00 8.13 0.253 3%
Triclosan 231nm 8.32 6.68 6.09 6.87 7.75 8.75 8.09 7.51 0.975 13%
44
Table 5: Intermediate Precision study by injecting QC sample of 25 ug/L over 6 days.
%Rel Day 1 Day 2 Day 3 Day 4 Day 5 Average Stdev Stdev
Carbamazepin e 231nm 22.6 22.5 22.8 23.6 25.4 23.4 1.21 5%
Triclocarban 260nm 21.3 21.2 21.7 21.2 21.2 21.3 0.21 1%
Triclosan 231nm 22.3 23.1 25.4 26.6 26.7 24.8 2.02 8%
Table 6: Method Procedural RSD: Prepared QC sample seven times to observe RSD. Run Run Run Run Run Run %Rel 1 2 3 4 5 6 Average Stdev Stdev
Carbamazepine 231nm 24.7 24.4 22.8 23.4 22.7 22.6 23.4 0.91 4%
Triclocarban 260nm 21.3 21.3 21.7 21.2 21.3 21.7 21.4 0.27 1%
Triclosan 231nm 22.9 26.9 23.1 26.3 30.4 23.9 25.6 2.89 11%
8.5 Sample Extraction
The method involves sample pretreatment through usage of Solid Phase Extractions
(SPE). Since pharmaceutical and personal care products are found in the environment in low concentrations, such as in parts per trillion (ng/L), SPE is used as a concentration step. SPE was optimized based on the type of SPE sorbent, sample volume and elution volume. The four main steps that were done for SPE were conditioning of the sorbent, 45 application of the sample, rinsing and cleaning of the sample, and desorption and recovery of the analytes. The sorbent is conditioned to improve analyte retention reproducibility, followed by rinsing the sorbent with a weak solvent to displace undesired components from the matrix, then the analytes of interest are eluted from the sorbent using a strong solvent. 78 We tried different solvents for elution, such as methanol, acetone, and methyl tert-butyl ether (MTBE). Methanol and MTBE gave similar results, but due to MTBE’s toxicity, methanol was chosen. Methylene chloride was not tried as an elution solvent also due to its toxicity.
For the method, there is a concentration step of a factor of 250, since a 500 mL sample is concentrated to 2 mL. Five hundred milliliters of sample is collected in an amber glass bottle and taken for extraction on SPE. The SPE program uses Thermo C-18 6-mL cartridges with 1 g bed weight. The cartridges are conditioned with water then methanol sequentially, 500 mL of sample is extracted to the cartridge, the cartridge is dried under nitrogen for 15 min, and the sample eluted with 5 mL methanol. The elutant is then taken on a turbovap at 40 oC and put under nitrogen for 35 minutes under 8 psi until the sample evaporates to dryness. The final step consists of adding 2 mL of the starting HPLC solvent to the sample, vortexing, and then transferring to autosampler vials.
µ 10 g 1mL ()5µL mL 1000 µL 1.0 µg Equation :5 = 1L L ()500 mL 1000 mL
10.0 ug 25 µg Equation :6 * 250 = L L 46
9. Results
9.1 Wastewater
The fate of the chemical tracers was quantitated after the treatment process. In order for the compounds to be suitable as tracers, their presence has to be confirmed at wastewater locations and through the wastewater treatment process. All three tracers were detected before and after wastewater treatment.
Figures 11-13 show the tracers concentrations before and after wastewater treatment.
From the results it apparent that wastewater treatment does reduce the concentrations of the tracers, but there are still detects for all analytes in the wastewater effluent.
Concentrations found in wastewater effluent are from 0.4-5.0 µg/L for Carbamazepine,
0.05-0.09 for Triclocarban, and 0.29-0.47 µg/L for Triclosan. It is shown that
Carbamazepine, Triclocarban, and Triclosan are removed through the wastewater treatment by 43% to 93%, 86 to 89%, and 71 to 83%, respectively. Concentrations found in source water are in the ranges of 0.006-1.1 µg/L for Carbamazepine, 0.004 - 0.48 µg/L for Triclocarban, and 0.02-.058 µg/L for Triclosan.
47 20 300 WWI CBZ 18 Carbamazepine In Raw & Treated Water WWE CBZ Rain 250 16 Flow 14 200 12 10 150 8 100 (mgd) Flow 6
Concentratioin (ug/L) Concentratioin 4 50 2 0 0 9/21/2011 9/28/2011 10/14/2011 10/17/2011 10/21/2011 Date Figure 13 : Wastewater influent and effluent of Carbamazepine.
1.4 450 WWI TCB Triclocarban in Raw & Treated Water WWE TCB Rain 400 1.2 Flow 350 1 300
0.8 250
0.6 200 Flow (mgd) Flow 150
Concentratioin (ug/L) Concentratioin 0.4 100 0.2 50
0 0 9/21/2011 9/23/2011 9/26/2011 9/28/2011 Date Figure 14 : Wastewater influent and effluent of Triclocarban. 09/26/12 influent sample had interference, so no data available for this data point.
48
4 350 WWI TCS Triclosan in Raw & Treated Water 3.5 WWE TCS Rain 300
3 Flow 250 2.5 200 2 150 1.5 (mgd) Flow
Concentratioin (ug/L) Concentratioin 100 1
0.5 50
0 0 9/21/2011 9/23/2011 9/26/2011 9/28/2011 Date
Figure 15 : Wastewater influent and effluent of Triclosan.
Table 7: Analyte concentration ranges for river and wastewater samples.
Penn Treaty WW WW Frankford Park Influent Effluent Arsenal (ug/L) (ug/L) (ug/L) (ug/L)
Carbamazepine 0.047-0.738 1.59- 0.4 - 5.0 0.086-1.80 13.58 1
Triclocarban 0.0051- 0.49-0.76 0.05 - 0.09 0.023 0.017
Triclosan 0.012-0.44 1.40-1.76 0.29 - 0.47 0.023
.
1 With this method, Carbamazepine has been getting a lot of interferences due to its mid-polarity. Method has to be slightly modified for Carbamazepine. 49
2.5 CBZ in River Samples Before and After WWTP 2
1.5 F.A. Upstream P.T. Downstream Rain 1
0.5 Concentratioin (ug/L) Concentratioin 0 1 1 1 1 11 1 1 1 1 0 0 /2 /20 /20 /2 /20 8 /3 7 /2 /30 0 /1 /19 9 9 1 10/5/2011 0 10/12/2011Date 10/14/2011 1 10 Figure 16: Carbamazepine river values before and after treated wastewater discharge.
9.2 Source Water
Samples were measured at the Wissahickon Creek, which receives contributions from
wastewater effluent. Samples were collected along the Creek and into the Schuylkill
River, where the Wissahickon Creek combines with the Schuylkill, to see any apparent
impact.
50
1.2 Source Water 1
0.8 Carbamazepine Triclocarban 0.6 Triclosan Rain
0.4 Concentration (ug/L) Concentration 0.2
0
8 3 3 /3 /5 / /5 /5 5 /5 /8 /28 5 /28 5 5 5 5 6 8 5 6/2 9 5/5 6 0 5 6/28 18 1 7 0 0503 54 54 76 6 ke 79 1 21 a W0 W0 018 8 S7 W S107 W WS7 WS0 Int WS1879 5WS18 WS1 W WS07 SN SN WS1 W W WS12 xter WSN Ba
Location Queen Lane Intake 6/28 Figure 17: Graph of Source water values for Carbamazepine, Triclocarban, and Triclosan. The sample locations are organized by locations upstream to downstream and by date for each location.
51
Table 8: Table showing the concentrations for Carbamazepine, Triclocarban, and Triclosan measured in source water samples. (nd= no detection)
CBZ TCB TCS Sample Location ug/L ug/L ug/L
SC1331 6/28 nd nd nd
SC1331 8/9 nd nd nd
NEW 6/28 2 0.006 nd nd
WSNW018 5/3 1.110 0.298 0.578
WSNW018 5/5 0.181 0.357 0.400
WSNW018 6/28 0.352 0.482 0.400
WS1879 5/3 0.209 0.067 0.023
WS1879 5/5 0.054 0.042 0.275
WS1879 6/28 0.179 0.109 0.031
WS1210 0503 0.087 0.110 nd
WS1210 5/5 0.136 0.089 0.040
WS1075 5/5 0.033 0.023 nd
WS754 53 0.085 0.021 nd
WS754 5/5 0.185 0.004 0.072
WS076 5/8 0.126 nd nd
WS076 6/28 nd nd nd
Queen Lane Intake 6/28 0.093 nd nd
Belmont Intake 6/28 nd nd nd
2 This sample is upstream at the Wissahackon, before wastewater discharge.
52
10. Discussion of the Results
10.1 Source water and wastewater
Delaware River samples from Frankford Arsenal and Penn Treaty before and after wastewater effluent from the Northeast Wastewater Treatment Plant were not good locations to compare water quality. These locations were chosen because they were easily accessible, but they were about 2 miles from the Northeast Wastewater Treatment plant.
There are also other contributions from New Jersey and other small creeks possibly affecting water quality. It was difficult to sample locations within close proximity to the wastewater plant since many areas need permits for access. It was hypothesized that the amount of tracers found at Frankford Arsenal would be minimal or less than Penn Treaty
Park, since the Northeast Treatment Plant discharges treated wastewater, which mixes with the source water and flows downstream passing Penn Treaty Park. The results seem random with no apparent pattern. Also, the locations are not so close to the plant, making it difficult to see the effect of the Northeast Wastewater Treatment Plant’s discharge of treated wastewater. Possible discharges from New Jersey or the Frankford Creek could have compromised results, as well as run off during rain events. However, the actual wastewater samples after treatment showed incomplete removal of the chemical tracers, confirming these tracers usage as tracers. But unfortunately, we could not quantitatively assess wastewater contribution to the Delaware River.
Discrete sampling locations on the Wissahickon Creek were chosen as a screening monitoring program. Essentially, the concentrations should decrease going downstream due to dilution factors, which is what the results show. Rain can affect sample trends 53 since rain causes land run-off, possibly discharging chemicals that are in fertilizer land applications or soils. Since Triclocarban or Triclosan are chemicals highly adsorbed to soil and are possibly found in fertilizer, run-off may increase their concentration in the source water during rain events. It would have been favorable to acquire wastewater effluent directly from the wastewater treatment plant then along the Wissahickon, but this may be done in the future when we acquire permits that will allow a more thorough analysis.
10.2 Mixing Ratio of Analytes
Comparisons of analyte relations were done as scatter graphs to see any pattern of analyte relationships that may be present. If there is a correlation relationship between the analyte responses, this can be used to predict values of other similar compounds. Also, having a correlation can help discern the source of contamination. For example, having a strong linear correlation between Carbamazepine and Triclocarban or Triclosan from wastewater can be strong, while from CSO there could be a weaker correlation. In source water, rain events can cause run-off, causing Triclocarban and Triclosan to be found in increased concentration in source water. Having their values deviate from the correlation may indicate influence from wastewater or run-off. However, the values of Triclocarban or Triclosan may be also weakly correlated to Carbamazepine due to the half-lives of
Triclocarban and Triclosan when going downstream for a longer period of time. When there is treated waste discharge going downstream, it can be assessed how far along the wastewater was in the water, this can be assessed based on the half-time for Triclocarban and Triclosan. The values of Triclocarban or Triclosan may be a lot weaker due to their 54 half life values, whereas Carbamazepine is quite stable going downstream. This pattern will be observed in the future continuation of the project.
An equation for the correlation between the analytes was established for the best-fit procedures by linear regression in a scatter plot to see any data trends. Based on samples that were collected, the strongest correlation we found was between Triclocarban and
Triclosan, with an r 2 of 0.871 in wastewater samples, while for source water, the r 2 correlation was 0.574. However, for Carbamazepine, the linear regression for comparison to Triclocarban was 0.410 while it is only 0.317 to Triclosan. So, there was not a strong correlation for Carbamazepine found with the current samples. More samples, though, need to be collected for a more thorough comparison.
2 Triclocarban Versus Triclosan in Wastewater 1.8
1.6
1.4
1.2
1 y = 1.9984x + 0.2469 2 Triclosan 0.8 R = 0.8709
0.6
0.4
0.2
0 0 0.2 0.4 0.6 0.8 Triclocarban
Figure 18: Scatter Plot of Triclocarban versus Triclosan in wastewater. The plot shows a possitve correlation and linear regression r 2 value of 0.871. 55
0.7 Triclocarban Versus Triclosan in Source Water 0.6
0.5
0.4
Triclosan 0.3 y = 0.9358x + 0.058 R2 = 0.5739 0.2
0.1
0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 Triclocarban Figure 19: Scatter plot of Triclocarban versus Triclosan in source water. The plot shows a positive correlation with a linear regression r 2 of 0.574.
11. Troubleshooting
There were a few issues that were encountered during the method development stages.
Triclosan began appearing in method blanks and also could not achieve a linear response during calibration. The area response per unit concentration seemed to follow a random relation. Initially it was thought that the concentrations are outside the linear dynamic range of the instrument, but this was not the case. When researching about Triclosan during early stages of method development, it was declared that Triclosan was photosensitive. Only amber glassware was used and preventative measures were taken to eliminate any direct light to prevent degradation. Even though freshly opened vials and fresh calibration curves were established within one hour of opening the vial, we still had a random response of Triclosan area to concentration. Further reading suggested that 56
Triclosan sticks to glass. Since glass micro pipettes were used to add the internal standard, we switched the pipette to a Gilson automatic plastic pipette that can withstand organic solvents. Also, all glassware was rinsed with methylene chloride after being washed since the wash room might have Triclosan in the dish wash soap. After muffling glassware at 400 oC and cleaning all glassware with methylene chloride, as well as using a plastic pipette, the calibration curve response was linear and method blanks were clear.
An issue also occurred when developing the SPE method. The first step of the method was to condition the cartridge with water and organic solvent before the sample matrix was extracted. After the samples were eluted and evaporated to dryness, HPLC starting solvent was added to the tubes in preparation for HPLC analysis. However, there were small white particles at the bottom of the tube. Initially it was thought that one of the analytes was immiscible in the solvent but this was contradicted what chemical databases indicated for the analytes. An experiment was done with four extractions on the automatic SPE. The extraction method was the same for all samples; the first two SPE cartridges were from Sigma Aldrich Supelclean C-18, while the other two from Waters
Oasis HLB. The Waters Oasis did not have any residue after preconcentration, while the
Supelclean did. So it was then believed that is was from the silica C-18 particles. Then the conditioning step was increased from 3 mL to 10 mL on the Supelclean, and there was no residue in the final extract. This issue was fixed by just increasing the conditioning solvent. The problem was possibly due to the C-18 packing and needed more conditioning solvent. The Supelclean C-18 was no longer used and we no longer had a contract with Waters, so Thermo Hypersil C-18 cartridges, which gave similar results as compared to the Waters Oasis HLB, were used for this method. This issue 57 could have been avoided by just starting out with 10 mL conditioning solvent, since increasing the conditioning solvent should not affect analysis.
After the SPE procedure is preformed and the samples are eluted with 5 mL methanol, sample elutants are taken on the turbovap for about 35 minutes at 40 oC and under 8 psi nitrogen. Some samples took a shorter time than 35 minutes, while other samples took more time. It was thought that the nitrogen lines are not all clear or do not have all the same psi pressure going to the samples, or that some samples have still water in the cartridge before elution due to the nitrogen lines on the automatic SPE. This issue was not solved and did not cause problems in the analysis. It was preferred for all samples to have the same drying time to eliminate any variability in sample analysis, but the times were denoted for the samples and the samples taken for HPLC analysis.
One last issue encountered was for the HPLC sample analysis. The method gradient started at 50:50 Water:CAN at 1mL/min. Some samples analyzed appeared to have a high abundance of polar analytes, causing the solvent peak to be very large and interfere with the Carbamazepine peak, which was the first eluted peak. The solvent peak was large and as the peak abundance was decreasing, there would be a very small or absent peak appearance for Carbamazepine. For the same sample, a known concentration of
Carbamazepine was spiked, and recoveries were very low. This issue was lessened when changing the method gradient starting conditions to 40:60 instead of 50:50 water:ACN.
Another approach which will be done in the future is to decrease the C-18 bed weight, since having a higher than necessary bed weight might attract unnecessary compounds.
58
12. Conclusion
This study had initial goals of identifying the quality of wastewater and CSOs by establishing a method for detection of tracers and further establishing a monitoring program. It is essential to understand water quality to help ensure healthy and clean waters. It is even more important to identify the source of pollutant contamination, which can be further used to reduce sources of contamination. Using wastewater tracers for a water quality monitoring program helps determine the presence of wastewater as well as other unidentified sources of wastewater. Tracer techniques help monitor priority pollutants or un-disinfected pathogens in the case of CSOs to rivers and ground water.
Due to the importance of water quality, this method has been established and used as a screening for future more thorough analysis.
A method for simultaneous determination of three tracers has been developed using
SPE-HPLC-DAD detection. Experiments show detection of all three tracers in wastewater and surface water. This method has shown Carbamazepine, Triclocarban, and
Triclosan are suitable to be used as tracers. Occurrence was evaluated and the concentrations quantitated. Tracers were monitored before and after treatment and in source water at the Wissahickon. More samples need to be collected at a higher frequency and for a longer period of time to monitor water quality throughout wet and dry conditions.
59
13. Future Proposals
The method can be improved by enhancing the sensitivity of the method for non wastewater samples. A more thorough survey should be done by collecting more samples throughout Philadelphia’s watershed to trace the pathway of pollutants from the wastewater treatment plant waterway. Sample collection will be done during dry and wet weather. Other parameters such as pH, VOC, TOC, pesticides, hormones and metals will be measured as well.
Currently, a method is being implemented for Acesulfame-K using HPLC with post column derivatization and Fluorescence detection to be used simultaneously with the
HPLC-DAD tracer method. A three column switcher has been installed on the HPLC and future samples will be analyzing four rather than three wastewater tracers. In the future, we would like to collect samples at areas of wastewater effluent discharge and areas of combined sewer overflow and compare water parameters for a better understanding of water quality. It would be interesting to observe water quality affected by CSO and compare it after the “Green City, CleanWaters” program establishes green space in trying to help storm management. We can evaluate how effective this green waters program is in helping water quality.
One way we would like to quantitate wastewater contamination in the continuation of this program is by calculating mixing ratios and dilution contributions. For example, samples will be taken from the Wissahickon Creek near a wastewater outfall and the tracers will be monitored as they travel downstream. Since the Wissahickon merges with the
Schuylkill River, we would measure the amount of tracers found at the Schuylkill before 60 and after Wissahickon Creek combines to the Schuylkill. Other factors will be considered such as flow and dilution to help quantitate the wastewater contribution. The following approach will be used to calculate how much contribution of wastewater is applied to source water can be found in equation 7.
Tracers found at Wissahicko n Equation :7 Contributi on = Tracers found at Schuylkill + Tracers found atWissahic kon 61
Figure 20 : Partial Inventory of Infrastructure Locations in Wissahickon Creek within Montgomery County, 2005. The figure shows bridges, dams, and outfalls. This will be a good guide to know where to sample near outfalls. 62
Figure 21: Map of Philadelphia showing areas of combined sewer overflow and the river or creek that are being affected by the outfall. 63
The Philadelphia Water Department has completed or is in the process of designing: 79
• 124 Stormwater Tree Trenches • 13 Porous Paving Projects • 16 Stormwater Planters • 9 Swales • 17 Stormwater Bumpouts • 2 Stormwater Wetlands • 27 Rain Gardens • 1 Green Roof • 3 Stormwater Basins • 33 Downspout Planters • 21 Infiltration/Storage Trenches • 8 Other Projects
Figure 22: Map of locations which the “Green City, Clean Water” program has or intends to build green space.
Figure 22 shows areas where these projects will be established within Philadelphia. Sampling near these locations before and after they are established might be a good way areas to evaluate their effectiveness. 64
References
(1) Ort, C.; Lawrence, M. G.; Rieckermann, J.; Joss, A. Sampling for pharmaceuticals and personal care products (PPCPs) and illicit drugs in wastewater systems: are your conclusions valid? A critical review. Environ. Sci. Technol. 2010 , 44 , 6024-6035.
(2) Halling-Sørensen, B.; Nors Nielsen, S.; Lanzky, P. F.; Ingerslev, F.; Holten Lützhøft, H. C.; Jørgensen, S. E. Occurrence, fate and effects of pharmaceutical substances in the environment- A review. Chemosphere 1998 , 36 , 357-393.
(3) Ternes, T. A.; Meisenheimer, M.; McDowell, D.; Sacher, F.; Brauch, H. J.; Haist- Gulde, B.; Preuss, G.; Wilme, U.; Zulei-Seibert, N. Removal of pharmaceuticals during drinking water treatment. Environ. Sci. Technol. 2002 , 36 , 3855-3863.
(4) U. Olofsson; S. Lundstedt; P. Haglund Behavior and fate of anthropogenic substances at a Swedish sewage treatment plant. Water Science & Technology- WST 2010 , 62.12 .
(5) Ternes, T.; Bonerz, M.; Schmidt, T. Determination of neutral pharmaceuticals in wastewater and rivers by liquid chromatography–electrospray tandem mass spectrometry. Journal of Chromatography A 2001 , 938 , 175-185.
(6) Ort, C.; Lawrence, M. G.; Reungoat, J.; Mueller, J. F. Sampling for PPCPs in wastewater systems: comparison of different sampling modes and optimization strategies. Environ. Sci. Technol. 2010 , 44 , 6289-6296.
(7) Heberer, T. Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol. Lett. 2002 , 131 , 5-17.
(8) Göbel, A.; McArdell, C. S.; Joss, A.; Siegrist, H.; Giger, W. Fate of sulfonamides, macrolides, and trimethoprim in different wastewater treatment technologies. Sci. Total Environ. 2007 , 372 , 361-371.
(9) EPA Pharmaceuticals and Personal Care Products (PPCPs). www.epa.gov/ppcp/ .
(10) Fent, K.; Weston, A. A.; Caminada, D. Ecotoxicology of human pharmaceuticals. Aquatic Toxicology 2006 , 76 , 122-159.
(11) Jones, O. A. H.; Voulvoulis, N.; Lester, J. N. Potential ecological and human health risks associated with the presence of pharmaceutically active compounds in the aquatic environment. Critical Reviews in Toxicology 2007 , 34(3) , 335-350.
(12) De Lange, H. J.; Noordoven, W.; Murk, A. J.; Lurling, M.; Peeters, E. T. H. M. Behavioural responses of Gammarus pulex (Crustacea, Amphipoda) to low concentrations of pharmaceuticals. Aquatic Toxicology 2006 , 78(3) , 209-216. 65
(13) Gagne, F.; Blaise, C.; Andre.C. Occurrence of pharmaceutical products in a municipal effluent and toxicity to rainbow trout (Oncorhynchs mykiss) hepatocytes. Ecotoxicology and Environmental Safety 2006 , 64(3) , 329-336.
(14) Flaherty, C. M.; Dodson, S. I. Effects of pharmaceuticals on Daphnia survival, growth, and reproduction. Chemosphere 2005 , 61(2) , 200-207.
(15) Schwab, B. W.; Hayes, E. P.; Fiori, J. M.; Mastrocco, F. J.; Roden, N. M.; Cragin, D.,; Meyerhoff, R. D.; D'aco, V. J.; Anderson, P. D. Human Pharmaceuticals in US surface waters: A human health risk assessment. Regulatory Toxicology and Pharmacology 2005 , 43(2) , 296-312.
(16) Webb, S.; Ternes, T.; Gilbert, M.; Olejniczak, K. Indirect human exposure to pharmaceuticals via drinking water. Toxicology letters 2003 , 142(3) , 157-167.
(17) Nicholas, T. Pharmaceuticals and Personal Care Products in Ground Water from Municipal Lagoon Treatment. Boise State University, 2010 .
(18) Weyrauch, P.; Matzinger, A.; Pawlowsky-Reusing, E.; Plume, S.; von Seggern, D.; Heinzmann, B.; Schroeder, K.; Rouault, P. Contribution of combined sewer overflows to trace contaminant loads in urban streams. Water Res. 2010 , 44 , 4451- 4462.
(19) Benotti, M.; Brownawell, B. Distributions of pharmaceuticals in an urban estuary during both dry- and wet- weather conditions. Environmental science & technology 2007 , 41 , 5795-5802.
(20) Focazio, M. J.; Kolpin, D. W.; Barnes, K. K.; Furlong, E. T.; Meyer, M. T.; Zaugg, S. D.; Barber, L. B.; Thurman, M. E. A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States — II) Untreated drinking water sources. Sci. Total Environ. 2008 , 402 , 201-216.
(21) Hao, C. e. a. Determination of pharmaceuticals in environmental waters by liquid chromatography/electrospray ionization/tandem mass spectrometry. Analytical and bioanalytical chemistry 2006 , 384 , 505-513.
(22) Loos, R.; Gawlik, B. M.; Locoro, G.; Rimaviciute, E.; Contini, S.; Bidoglio, G. EU- wide survey of polar organic persistent pollutants in European river waters. Environmental Pollution 2009 , 157 , 561-568.
(23) Zhang, Z.; Hibberd, A.; Zhou, J. L. Analysis of emerging contaminants in sewage effluent and river water: Comparison between spot and passive sampling. Anal. Chim. Acta 2008 , 607 , 37-44. 66
(24) Cunningham, V. L.; Perino, C.; D’Aco, V. J.; Hartmann, A.; Bechter, R. Human health risk assessment of carbamazepine in surface waters of North America and Europe. Regulatory Toxicology and Pharmacology 2010 , 56 , 343-351.
(25) Gasser, G.; Rona, M.; Voloshenko, A.; Shelkov, R.; Lev, O.; Elhanany, S.; Lange, F. T.; Scheurer, M.; Pankratov, I. Evaluation of micropollutant tracers. II. Carbamazepine tracer for wastewater contamination from a nearby water recharge system and from non-specific sources. Desalination 2011 , 273 , 398-404.
(26) Guo, Y. C.; Krasner, S. W. Evaluation of wastewater impact on drinking water sources using caffeine, carbamazepine, and primidone as tracers. Metropolitan Water District of Southern California .
(27) TSCA Chemical Substances Inventory U.S. Environmental Protection Agency; Washington D.C., 2003 .
(28) McAvoy, D. C. Measurement of triclosan in wastewater treatment systems. Environmental toxicology and chemistry 2002 , 21 , 1323.
(29) Singer, H. 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.
(30) Adolfsson-Erici, M.; Pettersson, M.; Parkkonen, J.; Sturve, J. Triclosan, a commonly used bactericide found in human milk and in the aquatic environment in Sweden. Chemosphere 2002 , 46 , 1485-1489.
(31) Li, X.; Ying, G.; Su, H.; Yang, X.; Wang, L. Simultaneous determination and assessment of 4-nonylphenol, bisphenol A and triclosan in tap water, bottled water and baby bottles. Environ. Int. 2010 , 36 , 557-562.
(32) Zhao, J.; Ying, G.; Liu, Y.; Chen, F.; Yang, J.; Wang, L. Occurrence and risks of triclosan and triclocarban in the Pearl River system, South China: From source to the receiving environment. J. Hazard. Mater. 2010 , 179 , 215-222.
(33) Thomas A, T. Occurrence of drugs in German sewage treatment plants and rivers. Water Res. 1998 , 32 , 3245-3260.
(34) Scheytt, T.; Mersmann, P.; Lindstädt, R.; Heberer, T. Determination of sorption coefficients of pharmaceutically active substances carbamazepine, diclofenac, and ibuprofen, in sandy sediments. Chemosphere 2005 , 60 , 245-253.
(35) Kosjek, T.; Andersen, H. R.; Kompare, B.; Ledin, A.; Heath, E. Fate of carbamazepine during water treatment. Environ. Sci. Technol. 2009 , 43 , 6256-6261. 67
(36) Arye, G.; Dror, I.; Berkowitz, B. Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils. Chemosphere 2011 , 82 , 244-252.
(37) Faigle, J. W.; Feldmann, K. F. Pharmacokinetic data of carbamazepine and its major metabolites in man, University Park Press, London 1976 , 159-165E.
(38) Bendz, D.; Paxéus, N. A.; Ginn, T. R.; Loge, F. J. Occurrence and fate of pharmaceutically active compounds in the environment, a case study: Höje River in Sweden. J. Hazard. Mater. 2005 , 122 , 195-204.
(39) Clara, M.; Strenn, B.; Kreuzinger, N. Carbamazepine as a possible anthropogenic marker in the aquatic environment: investigations on the behaviour of Carbamazepine in wastewater treatment and during groundwater infiltration. Water Res. 2004 , 38 , 947-954.
(40) Gebhardt, W.; Schröder, H. F. Liquid chromatography–(tandem) mass spectrometry for the follow-up of the elimination of persistent pharmaceuticals during wastewater treatment applying biological wastewater treatment and advanced oxidation. Journal of Chromatography A 2007 , 1160 , 34-43.
(41) Tizaoui, C.; Grima, N.; Hilal, N. Degradation of the antimicrobial triclocarban (TCC) with ozone. Chemical Engineering and Processing: Process Intensification 2011 , 50 , 637-643.
(42) Perencevich, E. N.; Wong, M. T.; Harris, A. D. National and regional assessment of the antibacterial soap market: A step toward determining the impact of prevalent antibacterial soaps. Am. J. Infect. Control 2001 , 281-283.
(43) TCC Consortium TCC Consortium. 2002 , IUCLID data set, report 201-14186B, 2002 .
(44) Snyder, E. H.; O’Connor, G. A.; McAvoy, D. C. Toxicity and bioaccumulation of biosolids-borne triclocarban (TCC) in terrestrial organisms. Chemosphere 2011 , 82 , 460-467.
(45) Snyder, E. H.; O'Connor, G. A.; McAvoy, D. C. Fate of 14C–triclocarban in biosolids-amended soils. Sci. Total Environ. 2010 , 408 , 2726-2732.
(46) Heidler, J. Partitioning, Persistence, and Accumulation in Digested Sludge of the Topical Antiseptic Triclocarban during Wastewater Treatment. Environ. Sci. Technol. 2006 , 40 , 3634-3639.
(47) Snyder, E. H.; O'Connor, G. A.; McAvoy, D. C. Measured physicochemical characteristics and biosolids-borne concentrations of the antimicrobial Triclocarban (TCC). Sci. Total Environ. 2010 , 408 , 2667-2673. 68
(48) Thompson, A.; Griffin, P.; Stuetz, R.; Cartmell, E. The fate and removal of triclosan during wastewater treatment. Water Environ. Res. 2005 , 77 , 63-67.
(49) Environmental Protection Agency Triclosan Facts. http://www.epa.gov/oppsrrd1/REDs/factsheets/triclosan_fs.htm (accessed March, 2010).
(50) Levy, C. W.; Roujeinikovai, A.; Sedelnikova, S.; Baker, P. J.; Stuitje, A. R. Molecular basis of triclosan activity. Nature 1999 , 398 , 383-384.
(51) McMurry, L. M.; Oethinger, M.; Levy, S. B. Triclosan targets lipid synthesis. Nature 1998 , 394 , 531-532.
(52) Ying, G.; Yu, X.; Kookana, R. S. Biological degradation of triclocarban and triclosan in a soil under aerobic and anaerobic conditions and comparison with environmental fate modelling. Environmental Pollution 2007 , 150 , 300-305.
(53) Bester, K. Triclosan in a sewage treatment process—balances and monitoring data. Water Res. 2003 , 37 , 3891-3896.
(54) Canosa, P.; Rodriguez, I.; Rubí, E.; Cela, R. Optimization of solid-phase microextraction conditions for the determination of triclosan and possible related compounds in water samples. Journal of Chromatography A 2005 , 1072 , 107-115.
(55) Perlman, H. The USGS Water Resources of th United States. http://ga.water.usgs.gov/edu/wuww.html (accessed Jan 5, 2012).
(56) Wikipedian http://en.wikipedia.org/wiki/Sewage_treatment . http://en.wikipedia.org/wiki/Sewage_treatment (accessed June 12, 2012).
(57) Philadelphia Water Department Water Infrastructure Management. http://www.phillywatersheds.org/watershed_issues/infrastructure_management (accessed March 10, 2012).
(58) Philadelphia Water Department Making News: Green City, Clean Waters Media Roundup. http://www.phillywatersheds.org/making-news-green-city-clean-waters- media-roundup (accessed March 10, 2012).
(59) U.S. Environmental Protection Agency Combined Sewer Overflows Demographics. Combined Sewer Overflows (accessed March 15, 2012).
(60) Marsalek, J.; Kok, S. Stormwater management and abatement of combined sewer overflow pollution. Water Qual Res J Can 1997 , 32(1) , 1-5. 69
(61) Even, S.; Mouchel, J.; Servais, P.; Flipo, N.; Poulin, M.; Blanc, S.; Chabanel, M.; Paffoni, C. Modelling the impacts of Combined Sewer Overflows on the river Seine water quality. Sci. Total Environ. 2007 , 375 , 140-151.
(62) Wikipedia Combined sewer. http://en.wikipedia.org/wiki/Combined_sewer (accessed January 20, 2012).
(63) PennPraxis Green2015: An Action Plan for the First 500 Acres. http://planphilly.com/green2015 (accessed March 10, 2012).
(64) Riechel, M. Impact Assessment of Combined Sewer Overflows on the Berlin River Spree. Technical University Berlin 2009 .
(65) Passerat, J.; Ouattara, N. K.; Mouchel, J.; Vincent Rocher; Servais, P. Impact of an intense combined sewer overflow event on the microbiological water quality of the Seine River. Water Res. 2011 , 45 , 893-903.
(66) Gasperi, J.; Garnaud, S.; Rocher, V.; Moilleron, R. Priority pollutants in wastewater and combined sewer overflow. Sci. Total Environ. 2008 , 407 , 263-272.
(67) Gasperi, J.; Zgheib, S.; Cladière, M.; Rocher, V.; Moilleron, R.; Chebbo, G. Priority pollutants in urban stormwater: Part 2 – Case of combined sewers. Water Res. .
(68) Lee, H.; Swamikannu, X.; Radulescu, D.; Kim, S.; Stenstrom, M. K. Design of stormwater monitoring programs. Water Res. 2007 , 41 , 4186-4196.
(69) Benotti, M. J.; Brownawell, B. J. Distributions of pharmaceuticals in an urban estuary during both dry- and wet-weather conditions. Environ. Sci. Technol. 2007 , 41 , 5795-5802.
(70) EPA Combined sewer overflow (CSO) Control Policy. Federal Register, 59 FR 18688. April 19, 1994.
(71) EPA National Combined Sewer Overflow (CSO) Control Strategy. US Environmental Protection Agency, Washington, DC, USA 1989 , 54 FR 37370 .
(72) Petersen, L.; Minkkinen, P.; Esbensen, K. H. Representative sampling for reliable data analysis: Theory of Sampling. Chemometrics Intellig. Lab. Syst. 2005 , 77 , 261- 277.
(73) Gy, P. M. The analytical and economic imporatance of correctness in sampling. Anal. Chim. Acta 1986 , 190 , 13-23.
(74) Daughton, C. G.; Ruhoy, I. S. Environmental footprint of pharmaceuticals: the significance of factors beyond direct excretion to sewers. Environmental toxicology and chemistry 2009 , 28(12) , 2495-2531. 70
(75) Meyer, V. R. In Pitfalls and Errors of HPLC in Pictures; 2006; , pp 188.
(76) Wikipedian Wissahickon Creek. http://en.wikipedia.org/wiki/Wissahickon_Creek (accessed May 9th, 2012).
(77) Snyder, L. R. In Introduction to Mordern Liquid Chromatography; John Wiley & Sons, Inc., Ed.; 2010; Vol. Third Edition, pp 912.
(78) Poole, C. F.; Gunatilleka, A. D.; Sethuraman, R. Contributions of theory to method development in solid-phase extraction. Journal of Chromatography A 2000 , 885 , 17- 39.
(79) Philadelphia Water Department Green Stormwater Infrastructure Project Map. http://phillywatersheds.org/biggreenmap (accessed May 31, 2012).