94: Point and NonPoint Source Pollution

KEITH LOAGUE1 AND DENNIS L CORWIN2

1 2

Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, US USDA-ARS, George E. Brown, Jr. Salinity Laboratory, Riverside, CA, US

The information age has ushered in a global awareness of complex environmental problems that do not respect political or physical boundaries: climatic change, ozone layer depletion, deforestation, desertication, and pollution from point and nonpoint sources. Among these global environmental problems, point and nonpoint source pollution represent a perfect example of a complex multidisciplinary problem that exists over multiple scales with tremendous spatial and temporal complexity. A point source of pollution discharges to the environment from an identiable location, whereas a nonpoint source of pollution enters the environment from a widespread area. The ability to accurately assess present and future point and nonpoint source pollution impacts on ecosystems ranging from local to global scales provides a powerful tool for environmental stewardship and guiding future human activities.

INTRODUCTION
The objective of this chapter is to introduce the subject of point and nonpoint source pollution, the entirety of which could easily ll several volumes. The point and nonpoint source problems are dened and important related legislation is identied in the following two subsections. Monitoring and modeling (with consideration for uncertainty) are discussed, relative to characterizing the impacts from point and nonpoint source pollution, in the section on assessment. Excerpts from three case studies are presented in the example section; two of the case studies are for nonpoint source pollution, the third case study is for point source pollution. It should be pointed out that the chapter is focused, with the exception of one of the case studies, on the United States.
Point versus Nonpoint Source Pollution

Point source pollutants, in contrast to nonpoint source pollutants, are associated, as the name suggests, with a point location such as toxic-waste spill site (see Figure 1). As such, point source pollutants are, compared to nonpoint source pollutants, characteristically (i) easier to control, (ii) more readily identiable and measurable, and (iii) generally more toxic. Nonpoint sources of pollution

(see Figure 1) are the consequence of agricultural activities (e.g. irrigation and drainage, applications of pesticides and fertilizers, runoff and erosion); urban and industrial runoff; erosion associated with construction; mining and forest harvesting activities; pesticide and fertilizer applications for parks, lawns, roadways, and golf courses; road salt runoff; atmospheric deposition; livestock waste; and hydrologic modication (e.g. dams, diversions, channelization, over pumping of groundwater, siltation). Point sources include hazardous spills, underground storage tanks, storage piles of chemicals, mine-waste ponds, deep-well waste disposal, industrial or municipal waste outfalls, runoff, and leachate from municipal and hazardous waste dumpsites, and septic tanks. Compared to point source pollution, nonpoint source pollution is more difcult, related to monitoring and enforcement of mitigating controls, due to the heterogeneity of soil and water systems at large scales. Characteristically, nonpoint source pollutants (i) are difcult or impossible to trace to a source, (ii) enter the environment over an extensive area and sporadic timeframe, (iii) are related (at least in part) to certain uncontrollable meteorological events and existing geographic/geomorphologic conditions, (iv) have the potential for maintaining a relatively long active presence on the global ecosystem, and (v) may result in longterm, chronic (and endocrine) effects on human health and soil-aquatic degradation.

Encyclopedia of Hydrological Sciences. Edited by M G Anderson. 2005 John Wiley & Sons, Ltd.

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Crop dusting (NPS)

Hazardouswaste disposal (PS/NPS) Soil erosion (NPS) Livestock Excessive waste fertilizer (NPS) Deforestation application (NPS) (NPS) Irrigation (NPS) Marine Chemical (NPS) waste (PS/NPS) application Strom-water to parks Mine-waste pond (PS) runoff and lawns Sewage(PS/NPS) treatment plant Construction Industrial Siltation erosion (PS) emission (NPS) (NPS) (NPS)

Septic system(PS) (NPS) Strip-mining

WATER QUALITY AND BIOGEOCHEMISTRY

Water table

Saturated zone

Water well

Underground storage tank (PS)

Underground mining (PS/NPS) Limestone (NPS) Road-salt runoff (PS) Deep-well waste disposal Landfill (PS) Freshwater aquifer Municipalsewage (PS) discharge

Water-bearing sandstone

Figure 1 Examples of point and nonpoint source pollution (Reproduced from Corwin et al. (1999) by permission of American Geophysical Union. Adapted from a map published by National Geographic Society, 1993). A color version of this image is available at http://www.mrw.interscience.wiley.com/ehs

POINT AND NONPOINT SOURCE POLLUTION

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Nonpoint source pollution was generally not recognized until the mid-1960s. Initially, nonpoint source pollution was associated entirely with pollution from storm water and runoff. Subsequently, nonpoint source pollution has expanded to encompass all forms of diffuse pollutants. Nonpoint pollutants are dened as contaminants of [air, and] surface and subsurface soil and water resources that are diffuse in nature and cannot be traced to a point location (Corwin and Wagenet, 1996). It is important to note the statutory denitions of point and nonpoint source pollution (see Novotny and Olem, 1994). In essence, point sources of pollution were originally dened as pollutants that enter the transport routes at discrete identiable locations and that can usually be measured, while nonpoint source pollution was everything else. Table 1 provides a list of statutory point and nonpoint sources of pollution compiled by Novotny and Olem (1994). There can be a ne line between point and nonpoint source pollution. The distinction depends entirely upon the scale of interest. One persons point source pollution can easily be another persons nonpoint source pollution. For example, a single quarter-section (65 ha), in a watershed of hundreds of thousands of hectares, might be considered a point source of nitrogen fertilizer, and, yet, within the area of interest, the fertilizer could be viewed as a nonpoint source because of the broadcasting of millions of granules of the active ingredient. The scale of reference ultimately determines whether a pollutant is viewed as coming from a point or nonpoint source. Historically, point source pollutants have received the greatest attention, both publicly and scientically, because of the conspicuous severity of their impacts at a localized point (e.g. Love Canal (Mercer et al., 1983) and Woburn (Harr, 1995)). However, over recent years, public, political, and scientic attention has shifted more and more toward pollutants that are widespread. This shift reects an awareness of the scope and potential impact of the nonpoint source pollution problem (see Corwin and Loague, 1996; Corwin et al., 1999).
A Bit of the Legal History, for the United States

Table 1 Statutory point and nonpoint sources of pollution (after Novotny and Olem, 1994) Statutory Point Sources Municipal and industrial wastewater efuents Runoff and leachate from solid waste disposal sites Runoff and inltrated water from concentrated animal feeding operations Runoff from industrial sites not connected to storm sewers Storm sewer outfalls in urban centers with populations of more than 100 000 Combined sewer overows Leachate from solid waste disposal sites Runoff and drainage water from active mines, both surface and underground, and from oil elds Other sources, such as discharges from vessels, damaged storage tanks, and storage piles of chemicals Runoff from construction sites that are larger than 2 ha Statutory Nonpoint Sources Return ow from irrigated agriculture Other agricultural and silvicultural runoff and inltration from sources other than conned concentrated animal operations Unconned pastures of animals and runoff from range land Urban runoff from sewered communities with a population of less than 100 000 not causing a signicant water quality problem Urban runoff from unsewered areas Runoff from small and/or scattered (less than 2 ha) construction sites Septic tank surfacing in areas of failing septic tank systems and leaching of septic tanks efuents Wet and dry atmospheric deposition over a water surface (including acid rainfall) Flow from abandoned mines (surface and underground), including inactive roads, tailing, and spoil piles Activities on land than generate wastes and contaminants, such as: Deforestation and logging Wetland drainage and conversion Channeling of streams, building of levees, dams causeways, and ow-diversion facilities on navigable waters Construction and development of land Interurban transportation Military training, maneuvers, and exercises Mass outdoor recreation

Up until the 1800s, the rural environment remained largely pristine in contrast to the lth of the urban areas as exemplied by historic centers such as ancient Rome, and, in the Middle Ages, London and Paris. By the mid-1800s, the sewage and runoff of the urban areas that polluted the surface waters became associated with waterborne disease. The concern for public health led to the rst awareness of the repercussions of the environmental degradation and the close association of humankinds well being to environmental quality, thereby heralding the rst environmental activist period. By the twentieth

century, sewage systems and sewage treatment plants came into being. Public interest in the environment through the rst half of the twentieth century was almost negligible primarily because the epidemics associated with the Middle Ages had been controlled or eliminated, and because the use of chemical insecticides and fertilizers did not occur to an appreciable extent until the late 1950s. Once humanmade chemicals, such as DDT (1,1,1-trichloro-2,2-bis-(4chloropheny)-ethane)), were introduced in the mid-1950s

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WATER QUALITY AND BIOGEOCHEMISTRY

and the dumping of outows from post-World War II factories continued unabated, pollution of soil and water resources rapidly increased. The book Silent Spring by Rachel Carson in 1962, which revealed the spread and potential danger of toxic human-made chemicals to the unwitting public, is heralded as initiating the second environmental activist period. Freeze (2000) astutely points out that environmental policy and perspective over the last half century have been driven by the prevailing socio-politico-economic climate. The environmental pendulum, as Freeze refers to it, has swung from underkill to overkill and from concern that breeds action to disillusionment that breeds reaction. Table 2 provides a timetable of some of the signicant environmental and statutory events that have shaped the last six decades and an overview of the pendulum swing from the environmental perspective to a retrospective from the New Right. The positive result of the environmental activism of the 1960s and the 1970s was the formation of the Environmental Protection Agency (EPA) in 1970 and the Clean Water Act (CWA) of 1972 (Public Law 92500). It should be pointed out, however, that the CWA called for zero discharge into surface waters, which, in actuality, shifted the onus of pollution from surface water to soil and groundwater. Prior to the CWA, the Refuse Act of 1899 and the Water Pollution Control Act of 1948 (Public Law 80845) were used to control water pollution from industrial sources, but these archaic statutes were generally ineffective in controlling pollution.

The CWA was intended to be a comprehensive water quality program. For example, under the CWA, each State was to establish water quality standards based upon a total maximum daily load (TMDL), which is the amount of a pollutant that a body of water can handle from all sources. Once a TMDL is established, it is used as a basis for putting limits on the amount of that pollutant that can be discharged into the system. In reality, most of the emphasis of the CWA was placed on controlling point source rather than nonpoint source pollution (Novotny and Olem, 1994). The CWA established three crucial tasks (Novotny and Olem, 1994): (i) the regulation of point source discharge, (ii) the regulation of oil spills and other hazardous substances, and (iii) nancial assistance for wastewater treatment plant construction. The most signicant contribution of the CWA was the formulation of a means of enforcement through the National Pollution Discharge Elimination System (NPDES). This system has served as the basic mechanism for enforcing the implementation of pollution abatement of point sources and some nonpoint sources legally classied as point sources (Novotny and Olem, 1994). The Water Quality Act (Clean Water Act) of 1987 (Public Law 10024) provided three sections (Section 319, 402, and 404) that are signicant to the control of nonpoint source pollution. Of these, Section 319 most directly applies to nonpoint pollution, requiring each State to prepare a State Nonpoint Source Assessment Report, and provides the incentive of matching Federal funds to encourage States to develop and implement management programs.

Table 2 Timetable of environmental and statutory events (after Freeze, 2000) Environmental perspective Chemical Revolution Age of Carelessness Age of Awakening Age of Awareness and Action Age of Disillusion Age of Reaction Throwaway society Conservation, wilderness protection Limits to growth Environmental events US Federal response Prevalent environmental concepts Inuential books New right retrospective

Decade 1940s 1950s 1960s 1970s

EPA (established, 1970) Earth Day Love CWA, SDWA, Canal TSCA, RCRA, PP list, NOR

A Sand County Chemical Almanac Revolution Leopold (1949) Age of Economic Prosperity Silent Spring Age of Social Carson (1962) Upheaval The Closing Circle Commoner (1971) Earth in the Balance Gore (1992)
Age of Overreaction Age of Vindication Age of Reason

1980s 1990s

Three mi Island CERCLA, HSWA, Soft energy paths SARA Earth Summit PPA in Rio Sustainable yield

CERCLA = Comprehensive Environmental Response, Compensation, and Liability Act; CWA = Clean Water Act; EPA = Environmental Protection Agency; HSWA = Hazardous and Solid Waste Amendments (to RCRA); NOR = National Organics Reconnaissance; PPA = Pollution Prevention Act; PP list = Priority Pollutant List; RCRA = Resource Conservation and Recovery Act; SARA = Superfund Amendments Reauthorization Act; SDWA = Safe Drinking Water Act; TSCA = Toxic Substances Control Act.

POINT AND NONPOINT SOURCE POLLUTION

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Section 319 establishes a regulatory link between nonpoint source pollution and groundwater quality; specically requiring States to develop best management practices (BMPs) that consider the impact of management on both surface water and groundwater quality. Examples of BMPs include grassy waterways, buffer strips, reduced application rates for pesticides and fertilizers, and the proper storage and disposal of animal wastes. Besides the CWA, there are a plethora of Federal statutory laws concerning the environment, oodplain management, the US Department of Agriculture, and mining that affect point and nonpoint source pollution and water quality (e.g. National Environmental Policy Act; Federal Environmental Pesticide Control Act; Rare and Endangered Species Act; Safe Drinking Water Act; Federal Insecticide, Fungicide, and Rodenticide Act; Toxic Substance Control Act; The Wild and Scenic River Act; Coastal Zone Management Act; Flood Control Act (and amendments); National Flood Insurance Programs; Flood Disaster Protection Act; Rural Development Act; The Food Security Act; Surface Mining Control and Reclamation Act; Federal Land Policy and Management Act). Novotny and Olem (1994) provide an excellent discussion of the laws, regulations, and policies related to point and nonpoint sources of pollution. Table 3 shows the relative importance of pollutants with respect to their source. Domenico

and Schwartz (1990) provide a list of the EPA priority pollutants.

ASSESSMENT OF POINT AND NONPOINT SOURCE POLLUTION

Assessment involves the determination of change of some constituent over time and space. This change can be measured in either real time or simulated with a model. Real-time measurements reect the activities of the past, whereas simulations can provide useful glimpses into the future. Both means of assessment are valuable. Related to real-time measurement and monitoring, the distribution and trends of pesticides in the atmosphere (Majewski and Capel, 1995), groundwater (Barbash and Resek, 1996), surface water (Larson et al., 1997), and uvial sediments and aquatic biota (Nowell et al., 1999) have been carefully assessed. For more than 10 years, the US Geological Surveys (USGS) National Water Quality Assessment (NAWQA) program (see http://water.usgs.gov/nawqa) has played a key role in the assessment of nonpoint source contamination from various pollutants to both surface water and groundwater, with studies in more than 50 major river basins and aquifers (Gilliom, 2001). An example of the importance of real-time measurement is the eld

Table 3 Relative importance of pollutant concentration in soil-water systems (after Peirce et al., 1998) Suspended solids and sediment M H N H H H L L-M M N M-H N-L L H N M L-M Toxic metals H N-L N N-H M-H N-L N-L N N-L N N L-H L-M L-H L L-H N-M Trace elements M N-L N N-H M-H N-L H H-L N-L N N N-H L-M L-H L N-M N-M Salinity/ TDS M N H N-H M-H N H N-L N-L N N N-H N N N N N-H

Nonpoint source Urban storm runoff Construction Highway de-icing Instream hydrologic modication Noncoal mining Agriculture Nonirrigated crop production Irrigated crop production Pasture and range Animal production Forestry Growing Harvesting Residuals management On-site sewage disposal Instream sludge accumulation Direct precipitation Air pollution fallout Natural background

BOD L-M N N N N M L-M L-M H N L-M L-H M H N L L-H

Nutrients L L N N N H H H M L L-M L-M H M-H N-M L-M M

Pesticides L N N N N H M-H N N-L L L N L M-H L L-M N

Pathogens H N N N N N-L N N-L L-H N-L N L-H H L N-L N-L N-L

N = Negligible; L = Low; M = Moderate; H = High; TDS = Total Dissolved Solids.

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WATER QUALITY AND BIOGEOCHEMISTRY

characterization of the April 1977 accidental spill of approximately 1900 L of the pesticide EDB (ethylene dibromide) within approximately 20 m of a well that provided drinking water to the village of Kunia on the Hawaiian island of Oahu. The point source area around this spill would eventually become a Superfund site.
Modeling

A distinct advantage of simulation is that it can be used to alter the occurrence or future impact of detrimental conditions. Obviously, simulation cannot replace real data. It should also be pointed out that eld observations and simulation are not mutually exclusive entities. Simulation requires considerable information to establish (i) the problem of interest (e.g. climatic data, land-cover characteristics, spatial distributions of near-surface soil-hydraulic properties) and (ii) test (in some cases) the models performance (e.g. spatial and temporal distribution of chemical concentrations). The use of mathematical models for assessing point and nonpoint sources of pollution, especially after ground truth comparisons, lls in information gaps, identies critical areas and chemicals for future monitoring, and provides the what if capability needed for both regulation and remediation. By denition, a mathematical model integrates existing knowledge into a framework of rules, equations, and relationships for the purpose of quantifying how a system behaves. As long as a model is applied over the range of conditions from which it was developed, it serves as a useful tool for prognostication. When sufcient information exists to characterize point and nonpoint pollution at a given time, a model can be calibrated (e.g. adjusting model parameter values within a reasonable range so that simulated concentrations closely match observed concentrations) and subsequently employed to make predictions (Loague and Green, 1991). When sufcient information does not exist, a model can still be used in a what if mode to address questions related to potential impacts (Abrams and Loague, 2000). Models can range in complexity from the simplest empirical equation to complex sets of partial-differential equations that are only solvable with numerical approximation techniques. Addiscott and Wagenet (1985) present a categorization for models on the basis of a conceptual approach, distinguishing between deterministic and stochastic, and mechanistic and functional. The key distinction between deterministic and stochastic models is, according to Addiscott and Wagenet (1985), that deterministic models presume that a system or process operates such that the occurrence of a given set of events leads to a uniquely denable outcome while stochastic models presuppose the outcome to be uncertain. Stochastic models consider the statistical credibility of both input conditions and model predictions, whereas deterministic models ignore any uncertainties in

their formulation. The second level of model distinction is between mechanistic and functional models. As described by Addiscott and Wagenet (1985), mechanistic is taken [here] to imply that the model incorporates the most fundamental mechanisms of the process, as presently understood, whereas the term functional is used for models that incorporate simplied treatments of solute and water ow and make no claim to fundamentality, but do, thereby, require less input data and computer expertise for use. Three categories of, for example, deterministic models are: (i) regression models, (ii) overlay and/or index models, and (iii) transient-state solute transport models. Regression models generally use multiple linear regression techniques to relate various causative factors. Overlay and/or index models, which can be property or process based, compute an index of pollutant mobility. Transient-state, processbased models are capable of simulating the movement of a pollutant in a dynamic ow system. Transient-state, process-based models describe some or all of the processes involved in, for example, solute transport (e.g. advection, dispersion, diffusion, and retardation). Corwin et al. (1997) summarize several geographical information system (GIS) based nonpoint source pollution modeling efforts.
Uncertainty

There can be considerable uncertainty in modeling point and nonpoint source pollution. So, why model? In general, there are two idealized uses for simulation. The rst is the prediction (or forecasting) of future events based upon a calibrated and validated model. The second use is the development of concepts for the design of future experiments to improve the understanding of processes. There are three sources of error inherent to modeling: (i) model error, (ii) input error, and (iii) parameter error. Model error results in the inability of a model to simulate the given process, even with the correct input and parameter estimates. Input error is the result of errors in the source terms (e.g. soil-water recharge, chemical application rates). Input error can arise from measurement, juxtaposition, and/or synchronization errors. Parameter error has two possible connotations. For models requiring calibration, parameter error usually is the result of model parameters that are highly interdependent and nonunique. For models with physically based parameters, parameter error results from an inability to represent aerial distributions on the basis of a limited number of point measurements. The aggregation of model error, input error, and parameter error is the total (or simulation) error. For multipleprocess and comprehensive model simulation, error is complicated further by the propagation of error between model components. In general, the methods for characterizing uncertainty can be grouped into three categories (Loague and Corwin, 1996): (i) rst-order analysis, (ii) sensitivity analysis, and

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(iii) Monte Carlo analysis. First-order analysis is a simple technique for quantifying the propagation of uncertainty from input parameter to the model output. The rst-order approximation of functionally related variables is obtained by truncating a Taylor-series expansion (about the mean) for the function after the rst two terms. Sensitivity analysis is used to measure the impact that changing one factor has on another. The sensitivity of a models output to a given input parameter is the partial derivative of the dependent variable with respect to the parameter. Monte Carlo analysis is a stochastic technique of characterizing the uncertainty in complex hydrologic response model simulations. The Monte Carlo method considers each model input parameter to be a random variable with a probability density function (PDF). Monte Carlo simulations are based upon a large number of realizations, from every input parameter distribution, created through sampling the different PDFs with a random number generator. A separate hydrologic response simulation is made for each parameter realization. The number of possible simulations, based upon all the combinations of parameter realizations, is innite; therefore, a nite number of cases (e.g. several hundred) are usually investigated. Estimates of the average simulated hydrologic response, and the associated uncertainty, are made from the combined outputs of the simulations (i.e. the total ensemble of the different realizations). Loague and Corwin (1996) provide examples of rst-order uncertainty analysis, sensitivity analysis, and Monte Carlo simulation.

THREE EXAMPLES
There are thousands of documented cases of point and nonpoint source pollution, far too many to list here. Three examples (from the rst authors work) that combine eld observations and modeling are briey discussed in this section. The second example (II) is a local-scale legacy assessment of point source pollution from three Manufactured Gas Plants. The rst (I) and third (III) examples are both for nonpoint source pollution. Example I is a regionalscale legacy assessment associated with agrochemical use in Californias Central Valley. Example III is a regional-scale assessment focused on the future management of forested areas on the Canary Island of Tenerife. Assessments of the type shown in Examples I, II, and III can be useful for regulatory decisions and remediation efforts. It is worth pointing out that both examples I and II were undertaken related to major civil actions.
Example I: Nonpoint Source Pollution, the Fresno Case Study

Joaquin Valley in California. More than two decades after its cancellation, DBCP-contaminated groundwater persisted as a problem in the San Joaquin Valley. The objective of the Fresno Case study (Loague et al., 1998a,b) was to address, from a simulation perspective supported by eld observations, if label recommended NPS applications were likely to be the principal source of the DBCP groundwater contamination in Fresno County. The San Joaquin Valley, at the southern end of Californias Central Valley, extends in a southeasterly direction for approximately 400 km from just south of Sacramento. Eastcentral Fresno County, situated between the San Joaquin River to the north and the Kings River to the south, is the largest agricultural county in the valley. The spatial distribution of DBCP use in the study area, between 1960 and 1977 (see Figure 2a), was estimated using land-cover maps for different years. The numerical model used for the 1D simulations (Loague et al., 1998a) of dissolved phase DBCP concentration proles in the unsaturated zone was PRZM-2 (Mullins et al., 1993). The potential fate and transport of DBCP between the surface and the water table for multiple NPS applications, related to different and changing land use between 1960 and 1977, was quantitatively estimated for 1172 elements for a 35-year period. The aggregate of the DBCP concentrations loaded to the water table for each grid element make up the annual loading les for the 3D saturated transient transport simulations. The numerical models used for the 3D simulations (Loague et al., 1998b) of saturated subsurface uid ow and DBCP transport are MODFLOW (McDonald and Harbaugh, 1988) and MT3D (Zheng, 1992), respectively. Recharge to the water table for the saturated simulations was estimated as the residual (precipitation plus irrigation minus evapotranspiration) in the PRZM-2 water-balance simulations. The area focused upon for the saturated simulations was represented by a 3D nite-difference grid made up of 76 440 elements (i.e. 2184 1 km2 surface elements with 35 layers). The 13-step approach used by Loague et al. (1998a,b) to simulate the impact of multiple DBCP applications under changing land use and groundwater pumping/recharge in the Fresno study area are summarized in Table 4. Figure 2(b) shows a 1999 snapshot of the simulated DBCP loading water table from the Fresno Case study. The simulation results from the Fresno Case study lead to the following general comments (Loague et al., 1998a,b): The areas most likely to facilitate DBCP leaching through the entire unsaturated soil prole were targeted. The rst appearance of DBCP above the detectable limit at the water table was simulated as most likely occurring between 1961 and 1965. The estimated DBCP concentrations reaching the saturated subsurface exceed the maximum contaminant level (MCL) at several locations at different times. The

Between the late 1950s and the time of its statewide cancellation in August of 1977, there was widespread use of DBCP (1,2-dibromo-3-chloropropane) throughout the San

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WATER QUALITY AND BIOGEOCHEMISTRY

11957'30" 11955' 11952'30" 11950' 11947'30" 11945' 11942'30" 11940' 11937'30" 11935' 11932'30" 11930' 11927'30" 11925' 3700'

3657'30"

3655'

3652'30"

3650'

3647'30"

3645'

3642'30"

3640'

Total DBCP Applications 19601977 (kg ha ) 030 3150 5170 7190 91110 111130 131150 151170 Latitude/longitude 1Km grid Rivers/canals Highways/roads

(a)

11957'30" 11955' 11952'30" 11950' 11947'30" 11945' 11942'30" 11940' 11937'30" 11935' 11932'30" 119 30" 11927'30" 11925' 3700'

3657'30"

3655'

3652'30"

3650'

3647'30"

3645'

3642'30"

3640'

(b)

DBCP at the Water table 1980 (g L 1) >0.241 0.1210.150 0.2110.240 0.0910.120 0.1810.210 0.0610.090 0.0310.060 0.1510.180

0.0010.030

Latitude/longitude 1 Km grid

Rivers/canals Highways/roads

Figure 2 Components of the Fresno Case study example (i.e. Example I) of nonpoint source pollution (After Loague et al., (1998a) 1998, with permission from Elsevier). (a) Aggregate of the estimated DBCP applications. (b) Simulated 1990 DBCP loading at the water table (Note, this snapshot is taken from a continuous simulation animation). A color version of this image is available at http://www.mrw.interscience.wiley.com/ehs

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Table 4 Steps used in the Fresno Case study (after Loague et al., 1998a,b) 1. Approximate the climatic history (1950 1994). 2. Approximate the distribution of soils. 3. Approximate the land-cover history (1958 1994). 4. Approximate the average irrigation history (1960 1994). 5. Approximate the water table depth history (1960 1994). 6. Simulate (with PRZM-2) transient unsaturated uid ow and DBCP transport (1960 1994). 7. Abstract the DBCP concentration at the water table for each element (1960 1994). 8. Approximate the geology. 9. Approximate the distribution of saturated hydraulic conductivity. 10. Approximate the recharge history (1960 1994). 11. Approximate the pumping history (1960 1994). 12. Simulate (with MODFLOW) groundwater ow (1960 1994). 13. Simulate (with MT3D) saturated transient DBCP transport (1960 1994).

Table 5 Steps used in the simulations of three former manufacture gas plants (after Abrams and Loague, 2000) 1. 2. 3. 4. 5. 6. 7. 8. 9. Approximate the climatic history (MGP inception* 2000). Approximate the soil properties for each site. Approximate the operational history of each MGP. Simulate (with LEACHM) unsaturated uid ow and dissolved naphthalene transport for subsurface sources (MGP inception 2000). Abstract the dissolved naphthalene concentration at the water table for each source (MGP inception 2000). Approximate the geology. Approximate the distribution of saturated hydraulic conductivity of each site. Simulate (with MODFLOW) groundwater ow for each site (MGP inception 2000). Simulate (with MT3D) saturated dissolved naphthalene transport for each site (MGP inception 2000).

rst appearance above the MCL was between 1965 and 1970 (note, by 1990, the concentrations are below the MCL). Relative to the size of the study area, the extent and duration of the estimated DBCP contamination was small. DBCP concentrations are a function of the spatial and temporal variations in (i) the application rates, (ii) the application frequency, (iii) the unsaturated prole thickness, (iv) the soil-hydraulic properties, and (v) the near-surface sorption. The DBCP plume evolves (grows and retracts) with time owing to the loading rates at the water table.
Example II: Point Source Pollution, Three Manufactured Gas Plants

From the early 1800s to about 1950, manufactured gas plants (MGPs) were operated in the United States to produce gas from coal or oil. By the time they began to close down, when the distribution of natural gas became more economical, approximately 2000 MGPs had been constructed throughout the USA. The contamination legacy resulting from the production of manufactured gas poses a signicant and ongoing groundwater quality problem. The disposal of by-products from the manufacturing process at MGPs contributed to the contamination of MGP sites. Although coal tar was perhaps the most abundant manufacturing by-product, it was not always considered waste as it was sold for multiple uses (e.g. dyes, explosives, pesticides, pharmaceutical preparations, pipe coatings, plastics, road tar, roong pitch, and wood preservatives). Because of its commercial value, coal tar was usually stored in holding tanks. After a MGP was decommissioned, the coal

tar was often left in the holding tanks. Fifty years later, many of these holding tanks remained as point sources of contamination. The purpose of the study reported by Abrams and Loague (2000) was to address, in a what if (forensic) mode, using all available data, if contamination emanating from the holding tanks at three former MGP sites (located in Indiana), could cause undesirable impacts to groundwater quality. The nine-step approach used by Abrams and Loague (2000) to simulate the subsurface transport of dissolved naphthalene, under variable precipitation for 150 years, is summarized in Table 5. The numerical model used for the 1D unsaturated naphthalene transport simulations in this study was a slightly modied version of LEACHM (Hutson and Wagenet, 1992). The characterization, through simulation, of the temporally variable naphthalene loading histories at the water table was used for the input to subsequent 3D simulations of saturated subsurface uid ow with MODFLOW (McDonald and Harbaugh, 1988) and solute transport with MT3D (Zheng, 1992). The simulation results reported by Abrams and Loague (2000) indicate that accidental releases of dissolved naphthalene, from the holding tanks at the three former MGP sites, most likely resulted in severe, negative groundwater quality impacts. Figure 3 illustrates, for one of the three sites, components of effort reported by Abrams and Loague (2000). The assumptions made by Abrams and Loague (2000) in conducting these simulations had little impact on the overall conclusion that leaks from the holding tanks can reasonably be expected to lead to groundwater contamination. The sensitivity analyses performed by Abrams and Loague (2000) support this conclusion. It is interesting to note that the approaches used in Examples I (see Table 4)

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WATER QUALITY AND BIOGEOCHEMISTRY

h5 = 226.16m

h = h1,5

hr1 = 226.37m h = hr River 0 100 m hr2 = 226.46 m h = h2,3 h3 = 227.09 m

h = h4,5 y 1 z (a) B
226

3 2

h4 = 228.62 m

h = h3,4

A 0 5 10 15 Depth (m)

B Depth of horizontal slice

227

Hydrostratigraphic unit and saturated hydraulic conductivity

22 8

Fill (0.03 m d1) Alluvium (0.4 m d1) Till (0.03 m d1) A

(b)

Advection

Advection and dispersion

Naphthalene concentration(g L1) 100 10 1 0.1 0.01

(c)

Figure 3 Components of the manufactured gas plant example (i.e. Example II) of point source pollution (Reproduced from Abrams and Loague (2000), by permission of Springer). (a) Site map showing nite-difference grid and boundary-value problem. (b) Site map and vertical cross section showing the spatial distribution of hydrostratigraphic units and saturated hydraulic conductivity values. (c) Snapshots from two saturated-zone solute transport simulations (Note, these snapshots are taken from continuous simulation animations). A color version of this image is available at http://www.mrw.interscience.wiley.com/ehs

and II (see Table 5) are very similar. The major differences between the nonpoint and point source pollution examples are the scale of the two problems and the characterization of the sources (i.e. dispersed and well dened).

Example III: Nonpoint Source Pollution, the Forested Areas of Tenerife

It is widely known that the use of pesticides in modern agriculture can result in groundwater contamination.

POINT AND NONPOINT SOURCE POLLUTION

1437

The impact of pesticide use in forestry has received considerably less attention. Pesticide use in forest management falls into two main categories. The rst category consists of applying herbicides, soil insecticides, and fumigants for site preparation before reforestation, using herbicides to control undesired vegetation during initial tree growth, and applying insecticides and fungicides to prevent and control sporadic outbreaks of pests. The second category of pesticide use in forest management is the application of herbicides to clear rebreaks and road edges. Pesticide applications in forest management began during the late 1950s and early 1960s, with chlorinated insecticides, such as DDT. In many cases, organochlorines are still manufactured today for use in less developed countries. The focus of the study reported by Diaz Diaz and Loague (2001) was to estimate the potential for groundwater contamination on the Canary Island of Tenerife resulting from the use of pesticides for forest management purposes. In Tenerife, there are currently no guidelines for the use of pesticides in forested areas despite the ongoing use of some chemicals. Diaz Diaz and Loague (2001) used an index-based model to rank the leaching potential of 50 pesticides that are or could be used for forest management in Tenerife forests. Once the pesticides having the greatest leaching potential were identied, regional-scale groundwater vulnerability assessments with consideration for uncertainty were generated using soil, climatic, and chemical information in a GIS framework for all of the pine forest areas. On the basis of the leaching potential ranking, Diaz Diaz and Loague (2001) suggest that, for the pine forest areas of Tenerife (see Figure 4a), the potential leachers are picloram (potassium salt of 4-amino-3,5,6-trichloro-2pyridinecarboxylic acid), tebuthiuron (N -(5-(1,1-dimethyl)1,3,4-thiadiazol-2-yl)-N ,N -dimethylurea), carbofuran (2,3dihydro-2,2-dimethyl-7-benzofuranyl-n-methylcarbamate), triclopyr (triethylamine salt of 3,5,6-trichloro-2-pyridinyloxyacetic acid), and hexazinone (3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4-(1H ,3H )-dione). Following the identication of the ve potential leachers, Diaz Diaz and Loague (2001) prepared regional-scale groundwater vulnerability assessments in a GIS-driven format, for the pine forest areas of Tenerife. Two hot spots were identied on the northern side of the study area, their locations corresponding to soils classied as Inceptisols and high recharge rates. The uncertainties in the leaching assessments, related to the uncertainties in the soil, recharge, and pesticide data, were shown to be signicant. Figure 4(b) illustrates the distribution of soils and recharge across the pine forest areas of Tenerife. Figure 4(c) shows the regional-scale groundwater vulnerability assessments, and their uncertainty, for picloram and carbofuran.

Pine forest 1995 Fires 1998 Fire

0 10 km (a)

Soil orders

Recharge mm/year 0250 250500 500750

Entisols Inceptisols (b) Li Li + SLi

Picloram

Li < 0.2 0.2 < Li < 0.5 0.5 < Li

Carbofuran

(c)

Figure 4 Components of the Tenerife example (i.e. Example III) of nonpoint source pollution (Reproduced from Diaz Diaz and Loague (2001), by permission of Alliance Communications). (a) Distribution of pine forest areas, showing the locations of res in 1995 and 1998. (b) Distribution of soil orders (left) and average recharge rates (right) for the pine forest areas in (a). (c) Distribution of groundwater vulnerability estimates (left) and groundwater vulnerability estimates with consideration of uncertainty (right) for two pesticides [notes: the leaching index (Li) values range between zero and one, the larger the value, the more likely it is that the pesticide will leach; the uncertainty is represented by one standard deviation (S) in Li]. A color version of this image is available at http://www.mrw.interscience.wiley.com/ehs

EPILOGUE AND FOOD FOR THOUGHT

This article only provides an introduction to the huge subject of point and nonpoint source pollution. The value of real-time measurements for assessing point and nonpoint sources of pollution and the heroic contributions of the NAWQA program are stressed. The use (and types) of

1438 WATER QUALITY AND BIOGEOCHEMISTRY

mathematical models as well as the characterization of uncertainties associated with modeling point and nonpoint source problems are covered, illustrated by three examples. There has been no effort in the allotted space here to address the exposure/human-health outcome question as it relates to point and nonpoint source pollution. Unquestionably, point and nonpoint sources of pollution pose a potentially serious long-term health threat. The EPA, CDC (Center for Disease Control and Prevention), NIH (National Institutes for Health), and the USGS (and their counterparts in Canada and Europe) have each focused considerable energy on developing the linkages between environmental indicators (contaminants), exposure routes, and humanhealth outcomes. Nevertheless, there is a feeling amongst some scientists and policymakers that the perceived severity of the threats resulting from point and nonpoint source pollution, relative to human health, must be better documented. This view is clearly expressed in Al Freezes (2000) book The Environmental Pendulum. Anyone interested in this controversy should investigate further. The reader interested in point and nonpoint source pollution may also want to read the following chapters: Chapter 3, Hydrologic Concepts of Variability and Scale, Volume 1; Chapter 10, Concepts of Hydrologic Modeling, Volume 1; Chapter 66, Soil Water Flow at Different Spatial Scales, Volume 2; Chapter 69, Solute Transport in Soil at the Core and Field Scale, Volume 2; Chapter 78, Models of Water Flow and Solute Transport in the Unsaturated Zone, Volume 2; Chapter 79, Assessing Uncertainty Propagation Through Physically based Models of Soil Water Flow and Solute Transport, Volume 2; Chapter 91, Water Quality, Volume 3; Chapter 100, Water Quality Modeling, Volume 3; Chapter 122, Rainfall-runoff Modeling: Introduction, Volume 3; Chapter 131, Model Calibration and Uncertainty Estimation, Volume 3; Chapter 152, Modeling Solute Transport Phenomena, Volume 4; Chapter 153, Groundwater Pollution and Remediation, Volume 4 and Chapter 150, Unsaturated Zone Flow Processes, Volume 4.

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Corwin D.L. and Loague K. (Eds.) (1996) Applications of GIS to the Modeling of Non-Point Source Pollutants in the Vadose Zone, Special Publication 48, Soil Science Society of America: Madison. Corwin D.L., Loague K., and Ellsworth T.R. (Eds.) (1999) Assessment of Non-Point Source Pollution in the Vadose Zone, Geophysical Monograph 108, AGU Press: Washington. Corwin D.L., Vaughan P.J. and Loague K. (1997) Modeling nonpoint source pollutants in the vadose zone with GIS. Environmental Science and Technology, 31, 2157 2175. Corwin D.L. and Wagenet R.J. (1996) Applications of GIS to the modeling of non-point source pollutants in the vadose zone: a conference overview. Journal of Environmental Quality, 25, 403 411. Diaz Diaz R. and Loague K. (2001) Assessing the potential for pesticide leaching for the pine forest areas of Tenerife. Environmental Toxicology and Chemistry, 20, 1958 1967. Domenico P.A. and Schwartz F.W. (1990) Physical and Chemical Hydrogeology, John Wiley & Sons: New York. Freeze R.A. (2000) The Environmental Pendulum: A Quest for the Truth About Toxic Chemical, Human Health and Environmental Protection, University of California Press: Berkeley. Gilliom R.J. (2001) Pesticides in the hydrologic system what do we know and whats next? Hydrological Processes, 15, 3197 3201. Gore A. (1992) Earth in the Balance: Ecology and the Human Spirit, Houghton Mifin: New York. Harr J. (1995) A Civil Action, Vintage Books: New York. Hutson J.L. and Wagenet R.J. (1992) LEACHM: A ProcessBased Model of Water and Solute Movement, Transformations, Plant Uptake, and Chemical Reactions in the Unsaturated Zone (Version 3), Research Series 92 3 , Department of Soil, Crop, and Atmospheric Sciences, New York State College of Agriculture and Life Sciences, Cornell University: Ithaca. Larson S.J., Capel P.D. and Majewski S.S. (1997) Pesticides in Surface Waters: Distribution, Trends, and Governing Factors, Ann Arbor Press: Chelsea. Leopold A. (1949) A Sand County Almanac, Oxford University Press: New York. Loague K., Abrams R.H., Davis S.N., Nguyen A. and Stewart I.T. (1998b) A case study simulation of DBCP groundwater contamination in Fresno County, California: 2. Transport in the saturated subsurface. Journal of Contaminant Hydrology, 29, 137 163. Loague K. and Corwin D.L. (1996) Uncertainty in regional-scale assessments of non-point source pollutants. In Applications of GIS to the Modeling of Non-Point Source Pollutants in the Vadose Zone, Corwin D.L. and Loague K. (Eds.), Special Publication 48, Soil Science Society of America: Madison, pp. 131 152. Loague K. and Green R.E. (1991) Statistical and graphical methods for evaluating solute transport models: overview and application. Journal of Contaminant Hydrology, 7, 51 73. Loague K., Lloyd D., Nguyen A., Davis S.N. and Abrams R.H. (1998a) A case study simulation of DBCP groundwater contamination in Fresno County, California: 1. Leaching through the unsaturated subsurface. Journal of Contaminant Hydrology, 29, 109 136.

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Majewski S.S. and Capel P.D. (1995) Pesticides in the Atmosphere: Distribution, Trends, and Governing Factors, Ann Arbor Press: Chelsea. McDonald M.G. and Harbaugh A.W. (1988) A Modular ThreeDimensional Finite-Difference Groundwater Flow Model, Scientic Software Group: Washington. Mercer J.W., Silka L.R. and Faust C.R. (1983) Modeling groundwater ow at Love Canal, New York. Journal of Environmental Engineering, 109, 924 942. Mullins J.A., Carsel R.F., Scarbough J.E. and Ivery A.M. (1993) PRZM-2, A Model for Predicting Pesticide Fate in the Crop Root and Unsaturated Soil Zones: Users Manual for Release 2, EPA-600/R-93/046, USEPA Environmental Research Laboratory: Athens.

Novotny V. and Olem H. (1994) Water Quality Prevention, Identication, and Management of Diffuse Pollution, Van Nostrand Reinhold: New York. Nowell L.H., Capel P.D. and Dileanis P.D. (1999) Pesticides in Stream Sediments and Aquatic Biota: Distributions, Trends, and Governing Factors, CRC Press: Boca Raton. Peirce J.J., Weiner R.F. and Vesilind P.A. (1998) Environmental Pollution and Control, Fourth Edition, ButterworthHeinemann: Boston. Zheng C. (1992) MT3D: A Modular Three-Dimensional Model for Simulation of Advection, Dispersion, and Chemical Reactions of Contaminants in Groundwater Systems (Version 1.5), S.S. Papadopulos and Associates: Bethesda.