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Discussion
Sampling of groundwater in the vicinity of three tile beds
shows that a number of pharmaceutical compounds and
triclosan were present in groundwater at elevated concen-
trations as the result of infiltration of septic system wastewater
into the subsurface. The results also indicate that, based on
the long distances from the infiltration lines, a number of
FIGURE 1. Concentration of diclofenac and salicylic acid (ng compounds are mobile in the subsurface. Striking differences
L-1) in shallow (and deep) wells at Point Pelee. were observed between the number of detections, the
centrations may be overestimated by close to a factor of 2 concentrations, and the transport distances both within a
(Table SI-5). The spatial changes in concentrations at this given site and from site to site. The highest number of
site, however, are much larger than these analytical uncer- detections and highest concentrations were observed at Long
tainties, thus the results provide an indication of pharma- Point (e.g., ibuprofen, naproxen, and gemfibrozil), compared
ceutical persistence and transport at this site. Nine trace with Point Pelee where virtually no compounds were
organic compounds, including ibuprofen, salicylic acid, detected. At Long Point, several compounds, including
gemfibrozil, naproxen, triclosan, ketoprofen, diclofenac, ibuprofen, salicylic acid, naproxen, and bezafibrate, were
indomethacin, and bezafibrate were detected in the plume present in groundwater at concentrations similar to those
(Figure 2). Concentrations of ibuprofen were the highest, in observed in raw and partially treated effluent from Canadian
the thousands of ng L-1 range. Concentrations of naproxen municipal wastewater treatment plants (5). Many of the
and gemfibrozil were observed in the hundreds and thou- concentrations are similar to and, in many cases, several
sands of ng L-1 in the plumes, and salicylic acid, ketoprofen, orders of magnitude higher than pharmaceutical concentra-
diclofenac, and indomethacin were present at concentrations tions observed in surveys of surface water in Canada (22)
ranging mostly from 1 to 30 ng L-1. Elevated concentrations and elsewhere (2, 22, 23). Some pharmaceutical compounds
of several pharmaceutical compounds far from the tile bed are known to degrade through photolysis reactions (1), a
indicate groundwater transport is occurring. Salicylic acid process that would be limited in the subsurface environment,
and ketoprofen were both observed 20 m down gradient of possibly contributing to the relatively high persistence in
the tile bed, whereas diclofenac and indomethacin were this setting.
observed 10 m down gradient of the edge of the tile bed. For pharmaceutical compounds in their neutral form,
Gemfibrozil, naproxen, and ibuprofen were detected through- organic partitioning may affect their transport in ground-
out almost the entire depth of the aquifer and extend 20 m water. However, the pKa values of the compounds range from
or more down gradient of the edge of the tile bed. 2.8 to 7.9 (Table 1), indicating that under the pH values
Seven of the nine target compounds detected in ground- observed at all three field sites, all of the compounds except
water at Long Point also were detected in the septic tank at triclosan, and fenofibrate will be completely dissociated. The
the time of groundwater sampling. Ketoprofen and diclofenac anionic nature of these compounds suggests that mecha-
were present in the plume, but were not detected in the tank nisms other than hydrophobic sorption are likely influencing
at the time of the groundwater sampling, but they were their attenuation.
detected in the 10s of ng/L range at a later date. The extent of transport of the pharmaceutical compounds
Lake Joseph Groundwater. The groundwater down was observed to be correlated to the oxidation–reduction
gradient from the Lake Joseph infiltration bed had slightly conditions that developed in the wastewater plumes (Table
depressed pH conditions (∼5.9). Aerobic conditions, observed 4). At Point Pelee, two compounds, salicylic acid and
below the tile bed become more reducing down gradient diclofenac were detected at one sampling point where NO3-
along the groundwater flow path. The presence of an aerobic reducing conditions are present. Of the five compounds
zone upgradient of the tile bed suggests that aerobic detected at Lake Joseph, none were present in aerobic zones,
all were present in NO3-reducing zones, and three were Various aspects of system design may be contributing
detected in more reduced areas. Finally, at Long Point, all to variations in the degree of attenuation. The effluent
of the pharmaceuticals detected were observed in NO3-, loading rate is highest at Long Point, and lowest at Lake
Mn(IV)-, and Fe(III)-reducing zones. No pharmaceuticals Joseph (Table 2). The higher loading rates at Long Point
were detected in groundwater at the one sampling point would result in faster flow rates and decreased residence
where SO4-reducing conditions prevailed, and only triclosan times relative to the other two sites. This difference may
was detected in aerobic zones. The results are similar to those account for the limited degree of attenuation observed at
reported by Swartz et al. (12), where preferential removal of Long Point. In addition, the depth to the water table is
estrogenic and other organic wastewater compounds was least at Long Point (Table 2), further contributing to
observed in oxic zones of a plume relative to suboxic/anoxic reduced transport times in the vadose zone, where much
zones, suggesting enhanced degradation under oxidizing aerobic oxidation takes place.
conditions. The mobility and persistence of the compounds analyzed
In addition to differences in oxidation–reduction condi- in this study suggest that there may be a concern for their
tions in the plumes, differences in properties of the aquifer unintended human ingestion if drinking water is obtained
material at each site may also contribute to the transport of from water supply wells located close to septic system
the pharmaceutical compounds. The Point Pelee aquifer sand infiltration beds. Typically, separation distances between
has a higher surface area and higher organic carbon content wells and tile beds are based on the distances required for
than the other tile bed sites (Table 2), suggesting surface the removal of pathogens, such as E. coli, and do not consider
reactions also may be contributing to the limited transport the transport of other pathogens, pharmaceutical com-
of pharmaceuticals at this site. pounds, or other trace substances.
TABLE 4. Presence of pharmaceutical compounds in different oxidation–reduction zones at the septic system sitesa, (+)
indicates that the compound was observed, and (-) indicates that it was not observed
Point Pelee Long Point Lake Joseph
NO3 Fe- NO3- Mn- Fe- SO4- NO3- Mn-
reducing reducing aerobic reducing reducing reducing reducing aerobic reducing reducing methanogenic
clofibric acid - - - - - - - - + - +
ibuprofen - - - + + + - - + + +
salicylic acid + - - + + - - - - - -
gemfibrozil - - - + + + - - + - -
naproxen - - - + + + - - + + -
triclosan - - + - - - - - + - -
ketoprofen - - - + + + - - - - -
diclofenac + - - + + + - - - - -
indomethacin - - - + + + - - - - -
bezafibrate - - - + + + - - - - -
a
Zones defined according to Christensen et al. (21).
Similarly, there is potential for unmonitored release of designs that will promote wastewater oxidation may assist
PhACs to natural ecosystems at locations where septic system in minimizing persistence of these compounds.
plumes containing elevated concentrations of pharmaceuti-
cal compounds are discharging to surface water bodies. Many Acknowledgments
nontarget species have the potential to be exposed to Funding for this project was provided by Environment
pharmaceutical compounds in these settings, and may be Canada, NSERC, the Canadian Water Network, and Ontario
susceptible to adverse effects at very low concentrations. and NSERC graduate scholarships. The authors thank the
These effects may be magnified in settings where there are Canadian National Institute for the Blind, Long Point
multiple tile beds, such as in intensely developed lakeshore Provincial Park, and Point Pelee National Park for access
settings. to the sites. We thank H. Steer, J. Schachtschneider, S.
The field observations suggest that the persistence of Cagampan, J. Birks, J. Voralek, and C. Ardau for their
pharmaceutical compounds is closely related to the support in the laboratory and field. This manuscript
oxidation–reduction conditions that are established in the benefited greatly from the comments of an anonymous
wastewater disposal area. Optimization of septic system reviewer.