occurrence’and’reduction’of’pharmaceuticals’and ... ·...
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Occurrence and Reduction of Pharmaceuticals and Personal Care Products (PPCPs) in Groundwater and
Wastewater of Cape Cod, MA Yunqi Zhang Brown University Advisor: Dr. Maureen Conte JC Weber Ecosystem Center, Marine Biological Laboratory Woods Hole, MA Abstract
This study aims to examine the existence of PPCPs in wastewater and groundwater on Cape Cod, MA and to compare the efficiency of PPCPs removal by two types of wastewater treatments, a sewage treatment facility and title V septic system. Samples were collected from the influent and effluent from the recently upgraded municipal wastewater sewage treatment plant, the influent and effluent from title V septic system, the wastewater just downstream from the Falmouth Hospital, and four groundwater sites around the community of Falmouth. Seven target compounds from pharmaceuticals and personal care products were examined in the organic extracts of the samples, including caffeine, clofibric acid, ibuprofen, 4-‐methylbenzylidene, 7-‐acetyl-‐1,1,2,4,4,7-‐hexamethyltetralin (AHTN), triclosan and β-‐estradiol. Target compounds were isolated using C18 disks and identified and quantified using the gas chromatography/mass spectrometry (GC/MS). GC/MS response curves for target compounds were achieved with standard addition and recovery from Naushon Island water, the most pristine site, to compensate for matrix effects. Six of the seven target compounds, clofibric acid, ibuprofen, caffeine, AHTN, triclosan and β-‐estradiol were detected in samples. 4-‐methylbenzylidene, the major compound in sunscreens, was not found in any samples. The Falmouth Wastewater Treatment Plant influent contained triclosan, AHTN, caffeine, ibuprofen, clofibric acid at concentrations of 7.1-‐108.8 μg/l, but none of these compounds was detected in FWTP effluent. Massachusetts Alternative Septic System Testing Center (MASSTC) influent contained triclosan, AHTN, caffeine and ibuprofen at concentrations of 8.0-‐115.0 μg/l, while only lower concentrations of triclosan, AHTN and ibuprofen, ranging between 1.5-‐16.9 μg/l, were found in the effluent.
In the hospital wastewater, triclosan, AHTN, caffeine, ibuprofen and clofibric acid were detected at 6.9-‐95.8 μg/l. Low concentrations of different compounds were detected in four groundwater samples at 0.04-‐0.7 μg/l. Results of this project demonstrate the occurrence of PPCPs in Cape Cod wastewater and groundwater. Results also demonstrate that 84% PPCPs removal in the title V septic system but more efficient (100%) removal by the upgraded sewage treatment. 1. Introduction
In recent years, the fate and effects of pharmaceuticals and personal care
products (PPCPs) entering the environment has gained increasing attention.
PPCPs include a large class of chemical contaminants that can originate from a
variety of products such as over-‐the-‐counter and prescription medications and
fungicides and disinfectants used for industrial, domestic, agricultural, and
livestock practices, and are introduced into the environment via human usage,
excretions and veterinary applications. (Daughton and Ternes, 1999).
Recent studies indicate the potential widespread occurrence of low-‐level
concentrations (ng-‐mg/l) of pharmaceuticals, hormones, other organic sewage
contaminants and their metabolites in the aquatic environment (Guillette, 1995;
Desbrow et al., 1998; Halling-‐Sørensen et al., 1998; Ternes, 1998; Daughton and
Ternes, 1999; Sedlak et al., 2000; Heberer, 2002, Kolpin et al., 2002; Lindström et
al., 2002; Boyd et al., 2003; Calamari et al., 2003; Koutsouba et al., 2003; Tixier et
al., 2003). Till 2007, over a hundred individual PPCPs in addition to antibiotics
and steroids have been identified in environmental samples and drinking water
and the number is still growing (EPA).
PPCPs and their metabolites in the aquatic environments can affect water
quality and ecosystem health and potentially impact drinking water supplies
(Roefer etal. 2000; Trussell, 2001). The long-‐term effects of continuous, low-‐level
exposure to PPCPs and their metabolites are not well understood (Daughton and
Ternes, 1999). The major concerns have been the resistance to antibiotics and
disruption of aquatic endocrine systems by natural and synthetic sex steroids
(EPA). However, although there are no currently known adverse health effects
from such low-‐level exposures, we should still avoid being continuously exposed
to any levels of medications.
2. Materials and Methods
2.1. Target Compound Selection
A diverse group of PPCPs widely reported to occur in aquatic systems was
chosen for the project (Tab. 1). Compounds were chosen to represent different
groups of PPCPs, such as anti-‐inflammatory drug, antibacterial agent, sunscreens,
fragrances, stimulants, lipid regulator, and hormone. In each class, compounds
that are frequently reported in wastewater were considered. Triclosan, caffeine,
and ibuprofen were among the 30 most frequently detected organic wastewater
contaminants as reported by the US Geological Survey (Kolpin et al., 2002).
2.2. Sample Site Selection
For samples collection, I visited seven field sites and collected nine samples.
Five wastewater samples were collected from influent and effluent of a sewage
treatment plant, Falmouth Wastewater Treatment Plant (FWTP), Hospital
wastewater and influent and effluent of a Title V septic tank from Massachusetts
Alternative Septic System Testing Center (MASSTC). Four groundwater samples
were collected from Naushon Island, a pristine site, as well as three densely
populated areas, West Falmouth Harbor, Child’s River and Little Pond.
Naushon Island, part of the Elizabeth Islands, is just southwest offshore from
Falmouth (Fig. 1). The Island has a population of 30 people (2000 census), so it is
considered as the most pristine site in this study.
The Falmouth wastewater treatment plant (FWTP) is the main sewage
facility in Falmouth town. Approximately 4% of the town’s properties are
connected to the facility, including the wastewater from the Falmouth Hospital.
The original FWTP was constructed in the mid 1980’s and was an aerated lagoon
plant. It was recently upgraded and started to discharge again in 2005. The
wastewater is now treated with Sequencing Batch Reactors (SBRs) which
remove organic material and nitrogen through biological processes,
denitrification filters which physically remove solids and biologically remove
additional nitrogen as well as ultraviolet lights which disinfect the wastewater in
the upgraded facility.
West Falmouth Harbor is downstream of FWTP and receiving effluent from
FWTP. (Fig. 1) Based on the estimated travel time of wastewater from release as
FWTP effluent to reaching the sampling location, the groundwater collected from
West Falmouth Harbor is from wastewater discharged prior to the upgrade of
FWTP and additional septic inputs from the West Falmouth population.
The remaining 96% of the town of Falmouth utilizes septic tank systems for
the wastewater treatment and vast majority of those properties utilize a Title V
septic tank system. At the Massachusetts Alternative Septic System Testing
Center (MASSTC), there are different septic systems being tested and monitored,
including the Title V septic tank. The wastewater influent at MASSTC comes from
the nearby Massachusetts Military Reservation.
Two other groundwater sites receiving inputs from densely populated areas
in the watershed were selected. The Little Pond embayment system is located
within the Town of Falmouth and it is the headwater to a nutrient-‐rich shallow
coastal salt pond (Fig. 1). Most of the households on the Little Pond watershed
have on-‐site title V septic system. The nutrient and PPCPs loading to the Little
Pond results primarily from on-‐site disposal of wastewater from a population of
2700 (GIS). The Little Pond sample composites water collected at the west and
south shores of the Little Pond.
Child’s River arises from John’s Pond, a freshwater system, and empties into
Waquoit Bay (Fig. 1). It has been heavily contaminated by the release of
wastewater from on-‐site title V septic tanks within the watershed. The sample
collected here composites water collected on the east shore of the river.
2.3. Sample Collection
Groundwater samples were collected using a wellpoint sampler or directly
pumped from built-‐in wells. The wellpoint sampler was driven about 1 meter
into the sand within 5 meters of the shoreline. C-‐flex tubing was connected from
the wellpoint sampler to a vacuum collection flask and a vacuum of 10 psi was
achieved using a manual pump. The initial sandy water was discarded. Once the
sample was clear of debris, the salinity was checked in the first 200-‐300ml of
water. If the salinity was 0-‐3 ppt, collection continued; otherwise, we moved to
new location until finding freshwater. At sites with wells, a battery operated geo
pump was used to create the vacuum. The deepest well at the sites was used for
collection. The pump was purged for 10 minutes before collecting the 4L sample.
All samples were collected in acid-‐washed, solvent-‐rinsed 4 liter glass bottles to
minimize the wall absorption. Bottles were kept on ice when transported back to
lab.
Naushon Island groundwater was collected with the wellpoint sampler at
Kettle Cove. West Falmouth Harbor groundwater was collected from 8.6m deep
built-‐in well located on the east shore. Little Pond groundwater sample was
collected at two different spots along the shore using the wellpoint sampler.
Child’s River sample composited water collected via both the wellpoint sampler
and 2.2m deep built-‐in well along the east shore.
2.4. Sample Filtration and Acidification
The flowchart of methods in lab is shown as Fig. 2. In the lab, samples were
pumped through 0.7μm glass fiber filters (47mm in diameter) to remove
particulate matter. Wastewater samples were first pre-‐filtered through 10μm
filters and 1.6μm glass fiber filters. Subsamples (23mm diameter) were taken
from one GF/F filter per sample, dried overnight and packed for CN and isotope
analyses. The rest of the filter was immersed in 1:1 methanol:DCM and stored at
-‐32˚C until particulate extraction.
After the filtration, 12N HCl was used to acidify the filtered samples to a pH
between 2 to 3 and samples were refridgerated at 4°C until extraction.
2.5. PPCP isolation
The targeted PPCP compounds were isolated from water samples using
Supelco ENVI™-‐DSK cotadecyl (C18) disks. The disks consist of a glass fiber disk
embedded with surface-‐modified silica and they are hydrolytically stable at low
pH.
Using the 47mm glass filtration assembly, the C18 disks were cleaned with
10ml of elution solution (1:1 Methanol:methyl chloride) and dried under high
vacuum. The disks were conditioned with 10ml methanol, followed by 10ml
water to match the sample matrix before sample addition. Samples were poured
into the filtration reservoir and low vacuum was applied to achieve a flow rate of
75-‐100 ml/minute. After each entire water sample was passed through the disk,
the disk was dried under high vacuum to remove as much water as possible
prior to eluting the analytes.
A setup of a 47 mm Teflon filter holder assembled with vacuum adapter and
75ml collection pear flask was used to extract the compounds from the disk. 1μg
of 21 fatty alcohol, an internal standard, was applied to the disk just before
elution. Target compounds were extracted from the C18 disks by eluting with
20ml methanol, 20ml 1:1 methanol:DCM and 20ml of methylene chloride (DCM).
The organic extracts in the pear flasks were roto-‐evaporated to just dryness,
resuspended in 3ml of 1:1 methanol:DCM and then transferred to 13mm test
tubes for transesterification.
2.6. Trans-‐esterification and TMS-‐Derivatization
Trans-‐esterification reaction was used to derivatize target PPCPs with
carboxylic acid group, including clofibric acid and ibuprofen (Tab. 1). Extracts
were evaporated using a Savant centrifugal evaporator at 1-‐2 torr vacuum. Two
ml of trans-‐esterification reagent (10% methanolic HCl, made with 10:1
anhydrous methanol:acetyl chloride) was added to each tube. N2 gas stream was
used to remove air.
The trans-‐esterification reaction required incubation in the 55°C oven
overnight. The transesterified products were extracted by adding 1.5ml of 5%
aqueous sodium chloride to each tube and extracting with 2ml of DCM, followed
by two 1mL DCM extraction rinses. The DCM extracts were passed through a
column containing combusted sodium sulfate to remove water into clean 13mm
test tubes.
TMS-‐derivatization was used to prepare compounds for GC/MS analysis,
replacing hydroxyl groups on the organic compounds with a trimethylsilyl
group. Given the sensitivity of the derivatization reagent, BSTFA, to moisture,
samples were placed in GC autosampler vials and completely dried under a
stream of N2 prior to derivatization. Derivatization was achieved by dissolving
the dried sample residue in 25μl pyridine and 25μl BSTFA under nitrogen. The
closed vials were sealed with Teflon tape before heated at 55°C oven for an hour.
The derivatized samples were dried under N2 stream and resuspended in 100μl
DCM for GC/MS analysis.
2.7. GC/MS conditions
Samples were analyzed by Agilent GC/MS under the following conditions.
The GC oven was operated from 50°C (5-‐minute hold) at 5°C/minute to 320°C
(20-‐minute hold). Tab. 2 summarizes the properties of target PPCPs on GC/MS.
2.8. Quantification
Standard calibration line of each compound was used to convert peak areas
of the most intensive ion of each compound into concentration. Compound
identification was confirmed by GC retention time and qualifier ions as shown in
Tab. 2. During quantification, dilution factors, 1:100, 1:1000 and 1:12000, were
included.
Quantification of the total organics in each sample was conducted by
comparing the area under all peaks after 10 minutes with that of the internal
standard.
2.9. Standards and Recovery
A PPCP standard mix was made with 7 compounds at concentration of 200
μg/ml and the exact concentrations of each are shown in Tab. 1. 1μg, 2μg and
6μg of PPCP standard mix were analyzed on GC/MS to get standard calibration
lines for the feature ion peaks of each compound. The standard calibration lines
for the most intensive ion of all compounds were shown in Fig. 3 and the R2 of all
compounds were all greater than 0.9 (Tab. 3).
Due to the diverse sample matrices, spiked recoveries were measured for
each compound. 100ml of Naushon Island water sample was spiked with 0.8μg
of PPCP standard mix. The spiked sample was extracted and analyzed using the
solid-‐phase extraction, trans-‐esterification, derivatization, and GC/MS as
described previously. Result was compared to the result of 0.8μg standard mix
without extraction.
Recoveries for target compounds range from 30% up to 100% (Tab. 4). The
low recoveries of some target compounds might be attributed to the presence of
dissolved organic matter and other matrix complexities.
3. Results
The portioning of target PPCPs in aqueous extraction and particulate
extraction is indicated in Fig. 4. The occurrence of target PPCPs in each sample
combining results from both extractions is shown in Fig. 5. Among the 7 target
PPCPs, β-‐estradiol, triclosan, AHTN, caffeine, ibuprofen and clofibric acid were all
detected in groundwater and wastewater at different concentration up to
115.0μg/l (Tab. 5). However, 4-‐Methyl-‐benzylidene was not detected in any
samples. Four compounds including triclosan, AHTN, caffeine and ibuprofen
were detected in MASSTC influent at concentration of 8.0-‐115.0μg/l, while three
of these compounds were detected in the effluent at lower concentration of 1.6-‐
16.9μg/l. The septic system’s efficiency on PPCPs removal ranges from 81% to
100% depending on the individual compounds (Tab. 6). Five compounds
including triclosan, AHTN, caffeine, ibuprofen and clofibric acid were detect in
hospital wastewater at concentration of 6.9-‐95.8μg/l. Same compounds were
detected in FWTP influent at concentration of 8.0-‐108.8μg/l while none of these
compounds were detected in FWTP effluent. The comparison between septic
system influent and effluent is shown in Fig. 6 and the PPCPs removal efficiency
of the sewage treatment plant is indicated in Fig. 7. Different compounds were
detected in four groundwater samples at low concentrations from 0.04 to 0.7
μg/l (Fig. 8)
Concentrations of total organics in each sample are shown in Fig. 9. All three
of the wastewater influents are heavily organics loaded at concentration of
1646-‐3804 μg/l (Tab. 7), but both the sewage treatment plant and the septic
system effectively removed over 90% of organic matters in the wastewater (Tab.
6).
Total dissolved nitrogen concentrations and nitrogen concentrations on
particulates are shown in Tab. 8. Wastewater samples, highly nitrogen enriched
from human waste have nitrogen concentrations that are three orders of
magnitude higher than Naushon Island and one order of magnitude higher than
other groundwater samples (Tab. 8).
4. Discussion
4.1. Total organics and Nitrogen
Both the total organics of samples and the nitrogen data exhibited similar
trend as the PPCPs. MASSTC influent, hospital wastewater and FWTP influent
have the highest concentrations of total organics from 1600μg/l to 3800μg/l
(Tab. 7) and highest concentrations of total dissolved nitrogen (TDN) around
30mg/l (Tab. 8). The concentrations of total organics in the effluent samples
from septic system and sewage facility were one order of magnitude lower than
the influent, while those in the groundwater samples were two to three orders of
magnitude lower than the influent. TDN was effectively reduced in FWTP
effluent while TDN increased in MASSTC effluent compared to the influent.
Therefore, sewage treatment plant is proved to have not only better efficiency on
PPCPs removal but also nitrogen reduction. Naushon Island sample, the most
pristine sample, contained the lowest concentration of organics at 8μg/l as well
as the lowest TDN at 84.2μg/l (Tab. 8).
Partitioning of nitrogen between the aqueous solution and particulates was
also shown in Tab. 7. Most of the nitrogen went into the aqueous solution during
filtration, while one or two orders of magnitude lower concentrations of nitrogen
were captured in particulates (Tab. 8).
4.2. PPCPs
Partitioning of target PPCPs in aqueous solution and in particulates
Most of the target PPCPs were filtered through GF/F into aqueous solution
while some were captured on filters based on the properties of the target PPCPs.
As shown in Fig. 4, most of clofibric acid, ibuprofen, caffeine, AHTN and small
amount of triclosan were mostly extracted in aqueous solution while large
quantities of triclosan and very low amount of AHTN were detected in
particulates. The following discussion sections are based on the total extraction
data combining the aqueous solution and the particulates (Fig. 5).
Wastewater Influents
In the influent from the title V septic system at MASSTC, four of the seven
target PPCPs, triclosan, AHTN, caffeine, and ibuprofen were detected at
concentrations ranging from 8.0 to 115.0μg/l (Tab. 5). The wastewater comes
from the military reservation next to MASSTC where the average population age
is around 30. The highest concentration of ibuprofen at 115.0μg/l could be
attributed to the abundant consumption of ibuprofen in the military reservation
population.
In the influent from the sewage treatment plant (FWTP) contained five of the
seven target PPCPs-‐ triclosan, AHTN, caffeine, ibuprofen and clofibric acid-‐ at
concentrations of 7.1-‐108.8μg/l (Tab. 5). Similar compositions of PPCPs were
detected in the hospital wastewater, but at relatively lower concentrations
ranging from 6.9 to 95.8μg/l. In contrast to the MASSTC influent, the clofibric
acid, a lipid regulator, was detected in both the FWTP influent and hospital
wastewater. Its presence could be associated with the higher population age of
around 55 in the general Falmouth population. In FWTP influent, ibuprofen was
again detected at the highest concentration 108.8μg/l, followed by triclosan,
antibacterial agent, at 98.9μg/l. Therefore, based on the data of FWTP influent
and MASSTC influent, ibuprofen is consumed in large quantities regardless of the
population age.
Wastewater Effluents
In the effluent of the septic system, 84% of the target PPCPs were removed
(Tab. 6) and 24μg/l of PPCPs left including ibuprofen, β-‐estradiol and triclosan
(Tab. 5). Although title V septic system only partially reduced these three PPCPs,
it completely removed caffeine from the influent.
In the FWTP effluent, 100% of target PPCPs were removed after sewage
treatment (Tab. 6). The upgraded sewage facility has a better efficiency on PPCPs
removal than the septic tanks since the septic treatment only contains a leaching
field while the wastewater goes through SBR, denitrification filters as well as UV
treatment at FWTP.
Groundwater
Low concentrations of different target PPCPs at 0.04-‐0.7μg/l were detected
in four groundwater samples. In Naushon water, 0.5μg/l of β-‐estradiol and
0.5μg/l of caffeine were found (Tab. 5). West Falmouth Harbor contained 0.5μg/l
of triclosan and 0.5μg/l of β-‐estradiol. Child’s River sample had detectable
caffeine at 0.5μg/l and triclosan at 0.04μg/l while 0.7μg/l of clofibric acid and
0.5μg/l of AHTN were found in Little Pond. Compared the groundwater samples
with 0.54-‐1.2μg/l target PPCPs to the effluent from septic system, PPCPs must be
either degraded or diluted traveling from septic tanks to the seepage face. Since
all four samples contain compounds that were not detected in septic system
effluent like clofibric acid and β-‐estradiol, the groundwater must have additional
PPCPs sources than the wastewater from septic treatment.
Acknowledgement
I would like to specially acknowledge the advisory and support from Dr.
Maureen Conte, JC Weber and Dr. Ken Foreman on my project. I also want to
appreciate the help and support from Rich McHorney, Fiona Jevon, Tyler
Messerschmidt and Nick Barrett.
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Appendix Tab. 1. Target compounds and their properties
CAS #
Molecular structure
Stock Concentration (μg/l)
Commercial Use Chemical Name
Clofibric acid 882-‐09-‐7
228.77
Metabolite of lipid regulator
2-‐(4-‐Chlorophenoxy)-‐2-‐methyl-‐propanoic acid
Ibuprofen 15687-‐27-‐1
202.22 Anti-‐inflammatory
α-‐Methyl-‐4-‐(2-‐methylpropyl) benzene-‐acetic acid
Caffeine 58-‐08-‐2
244.43 Stimulant
3,7-‐Dihydro-‐1,3,7-‐trimethyl-‐1H-‐purine-‐2,6-‐dione
AHTN 1506-‐02-‐1
241.71 Sunscreen 6-‐Acetyl-‐1,1,2,4,4,7-‐hexamethyltetralin
4-‐Methyl-‐benzylidene
36861-‐47-‐9
233.54 Fragrance 4-‐Methylbenzylidene
Triclosan 3380-‐34-‐5
281.88 Antibacterial, disinfectant
5-‐Chloro-‐2-‐(2,4-‐dichlorophenoxy) phenol
β-‐Estradiol 50-‐28-‐2
234.22 Steroid, birth control
(17β)-‐Estra-‐1,3,5 (10)-‐triene-‐3,17-‐diol
Tab. 2 Target PPCPs’ properties on GC/MS
Compound Name Molecular Weight
Retention time (min) Target Ion
Qualifier ion
1 2 Clofibric acid-‐TMS 286 31.26 128 228 169 Ibuprofen-‐TMS 278 32.17 161 220 177
Caffeine 194 38.69 194 109 67 AHTN 258 39.59 243 159 258
4-‐Methyl-‐Benzylidene 254 43.26 254 128 171
Triclosan-‐TMS 360 44.61 200 347 360 β-‐Estradiol-‐TMS 416 53.56 285 416 129
Tab. 3. R2 of standard calibration lines
Target PPCPs
Estradiol Triclosan 4-‐Methyl-‐Benzylidene
AHTN Caffeine Ibuprofen Clofibric Acid
R2 0.9442 0.9702 0.9595 0.9622 0.9093 0.9759 0.9526
Tab. 4. Recovery rate of target compounds
Target PPCPs
Estradiol Triclosan 4-‐Methyl-‐Benzylidene
AHTN Caffeine Ibuprofen Clofibric Acid
Recovery Rate
100% 80% 58% 38% 48% 30% 34%
Tab 5. PPCPs in groundwater and wastewater of Cape Cod
Sites Estradiol (μg/l)
Triclosan (μg/l)
4-‐MBC (μg/l)
AHTN (μg/l)
Caffeine (μg/l)
Ibuprofen (μg/l)
Clofibric acid (μg/l)
MASSTC Influent ND 8.0 ND 8.9 17.3 115.0 ND
MASSTC Effluent ND 1.5 ND 16.9 ND 6.0 ND
Hospital wastewater ND 95.8 ND 7.7 20.7 51.6 6.9
FWTP Influent ND 98.9 ND 8.0 31.7 108.8 7.1
FWTP Effluent ND ND ND ND ND ND ND
Naushon Island 0.7 ND ND ND 0.5 ND ND
West Falmouth Harbor 0.5 0.5 ND ND ND ND ND
Child's River ND ND ND ND 0.5 0.04 ND Little Pond ND ND ND 0.5 ND ND 0.7
Tab. 6. Removal efficiency of sewage treatment plant and septic system
FWTP MASSTC Total
Organics 95.1% 91.5%
PPCP1 100% 84% Triclosan 100% 81.3% AHTN 100% 0
Caffeine 100% 100% Ibuprofen 100% 94.8%
Clofibric Acid 100% N/A
Tab. 7. Total organics in groundwater and wastewater of Cape Cod
Total organics
(µg/l) MASSTC Influent 1645.7
MASSTC Effluent 140.1 Hospital
Wastewater 3804.4
FWTP Influent 1935.7
FWTP Effluent 95.5
Naushon Island 8.4
West Falmouth Harbor 16.2
Little Pond 39.6
Child's River 30.0
Tab. 8. Nitrogen concentrations of aqueous and particulates in groundwater and wastewater of Cape Cod
Total Dissolved Nitrogen (µg/l)
Particulate Nitrogen (µg/l)
MASSTC Influent 35618.4 1238.7
MASSTC Effluent 58696.1 119.2 Hospital
Wastewater 29104.5 584.9
FWTP Influent 29909.2 994.6
FWTP Effluent 2121.2 51.5
Naushon Island 84.2 41.5
West Falmouth Harbor 2088.3 10.5
Little Pond 2530.8 122.4
Child's River 5741.8 29.0
Fig. 1. Samples collection sites on Cape Cod
Fig. 2. Analytical procedure for analyzing PPCPs
Fig. 3. Standard calibration lines for 7 target compounds
Fig. 4 Partitioning of target PPCPs in aqueous extraction and particulates extraction
Fig. 5 PPCPs’ concentration in wastewater and groundwater samples
0 20 40 60 80
100 120 140 160 180
Con
cent
ratio
n (µ
g/L)
Clofibric acid
Ibuprofen
Caffeine
AHTN
4-MBC
Triclosan
Estradiol
Fig. 6 Efficiency of PPCPs removal of Title V septic system
149
24
0
50
100
150
200
250
MASSTC Insluent MASSTC Efsluent
Concentration (µg/L) Closibric acid
Ibuprofen
Caffeine
AHTN
4-‐MBC
Triclosan
Estradiol
Fig. 7 Efficiency of PPCPs removal of upgraded Falmouth Wastewater Treatment Plant (FWTP)
0
254
0
50
100
150
200
250
FWTP Insluent FWTP Efsluent
Concentration (µg/L)
Closibric acid
Ibuprofen
Caffeine
AHTN
4-‐MBC
Triclosan
Estradiol
Fig. 8 PPCPs in groundwater samples
0
5
10
15
20
25
MASSTC Efsluent
Naushon West Falmouth Harbor
Child's River
Little Pond
Concentration (µg/L) Closibric acid
Ibuprofen
Caffeine
AHTN
4-‐MBC
Triclosan
Estradiol
Fig. 9. Total organics in groundwater and wastewater of Cape Cod
1646
140
3804
1936
95 8 16 40 30 0
500 1000 1500 2000 2500 3000 3500 4000
Concentration (µg/L)