The North Coast Karst Aquifer System of Puerto Rico is the islands most productive aquifer.

The characteristics that make it highly productive also make it vulnerable to contamination. This
research, which addresses the historical contamination of groundwater resources in the northern
karst region was conducted through integration of spatial hydrogeologic and contaminant
concentration data in the La Plata-Arecibo area. The study used GIS technologies and focused on
phthalates and chlorinated volatile organic compounds (CVOCs) and phthalates due to their
ubiquitous presence in the environment as well as their presence in listed and potential superfund
sites in Puerto Rico and U.S. and potential for exposure and health impacts. Results show an
extensive historical contamination of the groundwater resources in the northern karst aquifers.
Long-term contamination indicates the aquifers large capacity for storing and releasing
contaminants and reflects a long-term potential for exposure. The degradation of this important
water resource has resulted in a subsequent reduction of the extraction capacity and an increase
in the cost of use.
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Introduction
The north coast karst aquifer (Figure 1), which comprises 19% of the island, is the most
extensive and productive fresh-water aquifer in Puerto Rico (Lugo et. al, 2004; Veve and
Taggart, 1996). This aquifer serves as a significant source of water for domestic, industrial, and
agricultural uses (DNER, 2008). Groundwater in the region also discharges to surface water
features, contributing to the ecological integrity of stream, wetlands, costal lagoons, and
estuaries.

Figure 1
Hydrogeology of Puerto Rico
The north coast karst groundwater system contains two major aquifers (Lugo et. al, 2004): the
upper water-table aquifer is within the Aymamn and Aguada Limestones and alluvial deposits
along the coastal areas; the lower aquifer occurs within various members of the Cibao Formation
and the Lares Limestone (Figures 1 and and2).2). The upper aquifer is connected to the surface
throughout most of its outcrop area. The lower aquifer is confined toward the coastal zone coast
and outcrops to the south of the upper aquifer, where it is recharged. Groundwater in both
aquifers flows from recharge areas toward discharge areas near the coast, streams, wetlands,
springs, and other surface-water features (Renken et. al, 2002). Extraction wells are used for
domestic, industrial, and agricultural purposes, with the largest fraction used for public supply,
followed by the industrial and agricultural sectors (Molina, 2009). Groundwater is mostly
extracted from the upper aquifer because it is the most accessible for drilling and pumping, but
several industrial wells (and a few for public water supply) tap the lower aquifer.

Figure 2
Hydrogeologic cross section of the North Central Coast of Puerto Rico. Modified from Veve and
Taggart, 1996.
The high productivity of the northern karst aquifers is imparted by well-developed conduit
porosity and highly transmissive zones developed by dissolution of soluble rocks, primarily
limestone and dolomite, in which groundwater flows (Figure 3).

Figure 3
Karst formations
The same characteristics that make karst groundwater systems highly productive and suitable for
industrial development make them highly vulnerable to contamination (Gppert and
Goldscheider, 2008), and impart an enormous capacity to store and convey contaminants from
sources to potential exposures zones. As a result, karst aquifers serve as an important route for
exposing humans and wildlife to contaminants.
The aquifers productivity, among other reasons, led many pharmaceutical, chemical, and
manufacturing industries to settle in the north coast area, with subsequent growth in population
and urban development. Many of these industries rely on the use of hazardous materials, which
can enter the karst groundwater from accidental spills and deliberate disposal. Urban growth
brought construction of municipal landfills and clandestine waste disposal sites. Many of the
clandestine sites were developed in sinkhole depressions, which serve as a direct route of
contaminants into the underlying groundwater formations. The unintended consequence of the
industrial and urban development has therefore been extensive contamination of the groundwater
resources in the northern karst aquifer. The degradation of this important resource has
subsequently resulted in a reduction of the extraction capacity and the cost of use.
The study focuses on chlorinated volatile organic compounds (CVOCs) and phthalates because
of their ubiquitous presence in the environment as well as their presence in listed and potential
superfund sites in Puerto Rico and U.S. and potential for exposure and health impacts. CVOCs,
including TCE, PCE, Chloroform, 1,1,2-Thrichloroethane, Carbontetrachloride, Methylene
Chloride, 1,1-Dichloroethane, 1,1,1-Trichloroethane, 1,2-Dichloroethane, 1,1-Dichloroethylene,
and 1,2-Transdichloroethylene are commonly used industrial solvents, degreasers, and paint and
spot removers. Many phthalates are contained in commonly used products, including plastics,
food packaging, home furnishings, paints, clothing, medical devices, and cosmetic products
(NIH, 2006). In landfills, phthalates-containing materials can degrade and serve as a potential
source of phthalate contamination for groundwater. Indeed, phthalates have been commonly
found in landfill leachates, including many listed in the NPL (ATSDR, 2002, Bauer and
Herrmann, 1998; Randal et al., 1994). Some phthalates are considered endocrine disruptors, and

have recently been associated with decreased gestation length (Latini 2003), reproductive and
neurological damage, and the rise of preterm birth (CERHR, 2006). Exposure to TCE has been
related to several adverse health effects, including cardiac, neurological, hepatic, renal, dermal,
immunological, and reproductive effects, increased birth defects, perinatal mortality, cancer,
decreased birth weights (ATSDR, 2011), and risk for spontaneous abortion (Lipscomb and
Fenster 1991, Khattak 1999, Ha and Cho 2002).
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Methods
The historical contamination of groundwater resources in the northern karst aquifer of Puerto
Rico was assessed and integrated using GIS (geographic information systems) technologies. The
general approach involved collection, analysis, indexing, and segregation of historical and spatial
data. Historical (since 1980) and spatial data was collected for hydrogeology, known and
potential sources of contamination, and concentrations of contaminants in the La Plata-Arecibo
study area. Sources for the data include the Environmental Protection Agency (EPA) local offices
and reports, U.S. Geological Survey, P.R. Environmental Quality Board, P.R. Department of
Natural and Environmental Resources (PR DNER), and the P.R. Aqueduct and Sewer Authority
(PRASA). The data was revised and validated for accurateness and system representativeness
and integrated in the data repository for subsequent analysis. Data characteristics were overlain
and analyzed within the context of a number of basemaps using ArcGIS 8.3 (ESRI, 2003). This
GIS platform uses intelligent data models for representing geographical features, and provides
the necessary tools to create and work with spatially-distributed data. The spatial analyst
extension for ArcGIS was used to perform the analysis.
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Historical Contamination in the Northern Karst Region

Among heavily affected physiographical areas along Puerto Ricos north coast is the La PlataArecibo hydrogeophysical system, which extends between the Rio La Plata and Rio Grande de
Arecibo watersheds (Figures 1 and and4).4). Included in this region, the municipalities of
Arecibo, Barceloneta, Vega Baja, Vega Alta, and Toa Baja have been affected by a long history
of toxic spills and chemical waste and industrial solvent release into the subsurface (EPA, 2011;
Hunter and Arbona, 1995; Zach et al., 1987). The municipalities in the La Plata-Arecibo
hydrogeophysical region are coincidentally among the areas with highest groundwater extraction
(Molina and Gomez-Gomez, 2008).

Figure 4
La Plata-Arecibo hydrogeophysical area

Serious contamination has prompted inclusion in the National Priority List (NPL) of 10 sites
within La Plata-Arecibo hydrogeophysical region since 1983 (Figure 4, Table 1) and 15
corrective action sites within the Resource Conservation and Recovery Act (RCRA). With an
estimated area of 285 mi2, this would reflect a linear density of a NPL site every mile, making
the region one with the highest superfund densities in the U.S. Seven of these NPL sites are still
active, but the others could have contributed to contamination at the system level. Five of these
sites (Barceloneta Landfill, Scorpio Recycling, Upjohn, Vega Alta Landfill, and the Vega Baja
Landfill) have been contaminated with chlorinated solvents, including: TCE, Dichloroethene,
Chloroform, Carbon tetrachloride, tetrachloroethene, tetrachloroethane, and dichloroethane, and
methylene chloride. Four of the sites (Pesticide Warehouse III, Scorpio Recycling, and the Vega
Baja Landfill, and the Barceloneta Landfill) have reported phthalate contamination, mostly with
Dibutyl phthalate (DBP) and Di (2-ethylhexyl) phthalate (DEHP). Unofficial information from
EPA suggest that more sites are being considered in the area for further inclusion in the list, most
associated with unlined landfills (Figure 5). Recently the EPA issued orders to close landfills in
Toa Baja, Florida, Vega Baja, Aguadilla, and Santa Isabel, due mainly to substantial concern
about the drinking water quality associated with the landfills (EPA, 2006). Also, in the northern
area of Puerto Rico, these landfills are typically located in karst areas where pollutants can get
directly to the ground water.

Figure 5
Historical (19822008) contamination of CVOCs and phthalates in both shallow and deeply
confined aquifers.

Table 1
NPL sites in the La Plata-Arecibo Study Area

Groundwater contamination
Water quality surveys in Puerto Rico have shown a vast contamination of the northern karst
aquifer (Guzmn-Ros et al., 1986). Of great concern has been the contamination with
chlorinated chemicals, which have been measured in a large percentage of sample wells.
Extensive contamination resulted in the closure of 41% of drinking water supply wells in the
north coast aquifer by 1987 (Zack et al., 1987). Since then, more than 27 other water supply
wells have been closed (PRDoH, 2010), and industrial facilities have had to implement advanced
water treatments, incurring in additional costs.
Initial assessment of groundwater contaminants since 1980 in the La Plata-Arecibo
hydrogeophysical study area on Puerto Ricos north coast indicates widespread contamination of

phthalates and CVOCs at the systems level (Figure 5). Although some contamination is observed
in areas not associated with listed superfund sites or landfills, a high density of contaminants are
found around these sites. Analysis of the data indicate that 71% of wells sampled for CVOCs
(136 wells) and 47% of wells sampled for phthalates (DHP, DEP, DBP; 19 wells) show detection.
Both contaminants have been detected in 44% of the wells sampled for CVOCs and Phthalates
(9).
Superposition of the approximate groundwater surface level over the contamination data in the
area (Figure 6) points toward greater association with the sites, as a large number of the wells
reporting contamination are found dispersed around the downstream areas of the sites.
Dispersion around the groundwater downstream areas can be attributed to temporal changes in
flow regimes, which can modify the direction and magnitude of water and contaminant transport.

Figure 6
Phthalate (a) and VOC (b) Groundwater Contaminant in la Plata-Arecibo Study Area since 1980.
Contour levels obtained from Renken et al, 2002.
Initial assessment shows contamination of CVOCs and phthalates in both upper and lower
aquifers. The contamination of the upper aquifers is easily attributed to historical contamination
from surface-related spills and discharges. However, contamination of the lower aquifers reflects
long-term storage and dispersion of contaminants in the system. When a lower aquifer is
disconnected from the surface by a confining unit, and no recent contamination is observed in the
outcrops, it is postulated that remaining contamination is from liquid-waste injections made prior
to the 1970s, after which these injections were banned (Zack et. al, 1987). Long-term storage of
contaminants in the karst aquifers is also consistent for the upper aquifers in areas that have been
contaminated since the early 1980s (e.g., Upjohn Superfund site). Preliminary data assessment
from field sampling and analysis during MarchApril, 2011, show persistent contamination of
CVOCs in 56% of wells/springs sampled for CVOCs (16).
Figure 7 shows results of potential flow path for the Vega Alta region applying a very simple
analysis using ARCGIS and Spatial Analyst (Steele, 2011). Initial assessment indicates much
greater dispersion around a potential source than accounted for by Fickian dispersion. The
analysis assumes steady flow conditions, and does not incorporate dispersion caused by velocity
fields varying in magnitude and direction. Incorporation of temporal changes in flow and
detection will significantly enhance the analysis. It is also likely that more than one source has
contributed to the contamination, and historical potential sources must be incorporated.

Figure 7
Longitudinal Path (a) and Fickian Distribution (b) of contamination from a superfund site in the
Vega Alta region.

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Concluding remarks
The groundwater systems in the karst region of northern Puerto Rico are highly productive and
offer important freshwater resources for human consumption, ecological integrity, and industrial
and urban development. Their vulnerability to contamination in a region that has experienced
growth in industrial and urban development has resulted in a large number and high density of
contaminated sites with the unintended consequence of an extensive contamination of the
groundwater resources.
Spatial and historical distributions of contaminants in the northern karst aquifer show that
transport processes in these aquifers are extremely complex and may be highly influenced by
hydrologic conditions. Long-term contamination indicates a large capacity of aquifers for storing
and releasing contaminants and reflects a long-term potential exposure.
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Acknowledgments
This project is supported by Grant Award Number P42ES017198 from the National Institute of
Environmental Health Sciences. The content is solely the responsibility of the authors and does
not necessarily represent the official views of the National Institute of Environmental Health
Sciences or the National Institutes of Health.
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Biographies

Dr. Ingrid Padilla is an associate professor in Environmental and Water Resources Engineering in
the Department of Civil Engineering and Surveying and the Director of the Environmental
Engineering laboratory (EEL) at the University of Puerto Rico, Mayagez. She has been at the
University of Puerto Rico since 2001. Prior to that, she worked with Greg Morris and Associates
and the U.S. Geological Survey. Dr. Padilla holds a PhD from the University of Arizona; an MS
from the University of Michigan; and a BS from the University of Maryland. She has directed
laboratory, field-scale, and modeling environmental engineering and ground-water investigations
in the academic, government, and private sectors, and has been awarded with numerous scientific
grants (NSF, NIH, DoD, DoE, EPA). She can be contacted at ude.rpu@llidap.dirgni.

Celys Irizarry and Katherine Steele are current and former graduate students, respectively, in
Environmental and Water Resources Engineering at the Department of Civil Engineering and
Surveying the University of Puerto Rico, Mayagez