&EPA United States Environmental Protection Agency Environmental Research Laboratory Corvallis OR 97330 EPA-600/3-80-012 January 1980 Research and Development Probable Effects of Acid Precipitation on Pennsylvania Waters ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8. "Special" Reports 9. Miscellaneous Reports This report has been assigned to the ECOLOGICAL RESEARCH series. This series describes research on the effects of pollution on humans, plant and animal spe- cies, and materials. Problems are assessed for their long- and short-term influ- ences. Investigations include formation, transport, and pathway studies to deter- mine the fate of pollutants and their effects. This work provides the technical basis for setting standards to minimize undesirable changes in living organisms in the aquatic, terrestrial, and atmospheric environments. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161. ------- EPA-600/3-80-012 January 1980 PROBABLE EFFECTS OF ACID PRECIPITATION ON PENNSYLVANIA WATERS by Dean E. Arnold Robert W. Light Valerie J. Dymond Pennsylvania Cooperative Fishery Research Unit 328 Mueller Laboratory University Park, Pennsylvania 16802 Contract Number B0835NAEX Project Officer Charles F. Powers Terrestrial Division Corvallis Environmental Research Laboratory Corvallis, Oregon 97330 CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY ~ OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CORVALLIS, OREGON 97330 ------- DISCLAIMER One of the principal reasons for the preparation of this report for the Environmental Protection Agency was to supply scientifically valid information which could be incorporated into the EPA S02-Particulate Matter criteria document, presently in the final stages of preparation. A strict requirement pertaining to'that document is that any scientific information used there must be published (or at least in press) by January 1, 1980. Because of this demanding time constraint, it was necessary that the contractor prepare this report in a shorter time than would ordinarily be attempted, and that it be published by EPA without undergoing peer review. We feel that early publica- tion of these results in order to stimulate the broadest scientific discussion prior to completion of the criteria document justified waiving our normally more rigorous prepublication review requirements. Publication, however, does not signify that the contents necessarily reflect the views and policies of EPA, nor does mention of trade names or commercial products constitute en- dorsement or recommendation for use. 11 ------- FOREWORD Effective regulatory and enforcement actions by the Environmental Protec- tion Agency would be virtually impossible without sound scientific data on pollutants and their impact on environmental stability and human health. Responsibility for building this data base has been assigned to EPA's Office of Research and Development and its 15 major field installations, one of which is the Corvallis Environmental Research Laboratory. The primary mission of the Corvallis Laboratory is research on the ef- fects of environmental pollutants on terrestrial, freshwater, and marine ecosystems; the behavior, effects and control of pollutants in lakes and streams and the development of predictive models on the movement of pollutants in the biosphere. This report has assembled evidence for increased acidity of a number of Pennsylvania streams, decreases of fish populations in many, and points to acid precipitation as a likely cause. Thomas A. Murphy, Director Corvallis Environmental Research Laboratory 111 ------- ABSTRACT The purpose of this project was to search for and identify any trends in water chemistry and fish communities in Pennsylvania waters which would indi- cate that acid precipitation was affecting them adversely. No new data col- lection was to be included. Five existing data bases, including original data collected by the authors, were examined for the existence of water analyses from the same or nearby locations separated by at least one year. (Analyses involving known or suspected influence of acid mine drainage were omitted.) Of 983 analysis reports which were usable, there were 314 cases with two or more such points. Of these 107 or 34% showed a decrease in pH, alkalinity, or both. Average decrease in pH was 0.4 units with a maximum case of 1.3 units. Average decrease in alkalinity was 15.1 mg/1 (as CaC03) with a maximum case of 105 mg/1. The average time span between earliest and latest sample was 8.5 years. When the data were separated by physiographic provinces, it became appar- ent that although the majority of the decreases occurred in streams on the relatively insoluble rocks of the Allegheny Plateau, there were also many cases in the ridge-and-valley province and other regions. Many of these decreases are to pH levels considered marginal for growth and reproduction of trout and other fishes. Seventy-one of the 107 analyses showing decreased pH or alkalinity in- cluded fish collection data. In 40 of these cases (58%), the number of fish species present decreased as well. This report was submitted in fulfillment of Contract Number B0835NAEX under the sponsorship of the U.S: Environmental Protection Agency. This report covers a period from May to October, 1979, and work was completed as of October 1, 1979. ------- CONTENTS Foreword iii Abstract iv Figures vi Tables vi Acknowledgements vii 1. Introduction 1 2. Conclusions 4 3. Recommendations 4 4. Materials and Methods 5 5. Results and Discussion 8 References 19 ------- FIGURES Number 1. Card form used for recording and analysis of available data 7 2. County map of Pennsylvania showing approximate boundaries of physiographic provinces and locations of waters showing decrease in pH or alkalinity or both 12 3. Stream map of Pennsylvania showing major drainage basins and locations of waters showing decrease in pH or alkalinity or both. . . 15 TABLES 1. Summary of decreases in pH, alkalinity, and number of fish species found for Pennsylvania as a whole 8 2. pH, alkalinity, and number of fish species for Pennsylvania waters showing decreases as described in test 9 3. Water chemistry and fish population records summarized by physiographic province 14 4. Water chemistry and fish population records summarized by major watershed 5. Selected waters showing serious symptoms of acidification 17 VI ------- ACKNOWLEDGEMENTS The authors wish to thank the following for consent and aid in obtaining data and ideas for this report: Edwin L. Cooper of The Pennsylvania State University; Delano Graff, Robert Hesser, Fred Johnson, Rickalon Hoopes, Bruce Hoi lender, and Richard Snyder of the Pennsylvania Fish Commission; and Karl Shaeffer of the Pennsylvania Department of Environmental Resources. Funds for the study were provided by the Corvallis Environmental Research Laboratory of the U.S. Environmental Protection Agency. The contract was supervised by Dr. Charles F. Powers, whom we thank for his cooperation. Additional funds and supplies were provided by the Pennsylvania Fish Commission, the U.S. Fish and Wildlife Service, and The Pennsylvania State University, Department of Biology. vn ------- INTRODUCTION In just a few years, the problem of acid precipitation has grown from a suspicion held by a few scientists to a matter of international concern char- acterized by large conferences, a large amount of new research effort (only part of which is receiving adequate financial support), and large numbers of review articles in both the popular and scientific press (most recently, see Likens et a!. , 1979). No one is sure of either its extent or its time of beginning. Indeed, it undoubtedly has been developing since the dawn of the industrial age. The increasing acidity in precipitation has been linked to anthropogenic sources, i.e. coal combustion, petroleum combustion, and nonferrous metal production (Kellogg et al., 1972). The major cause of the acidification has been the addition of S02 (sulfur dioxide) from the combustion of fossil fuels and the subsequent production of the strong acid H2S04 (sulfuric acid). This transformation may take several pathways (Kellogg et al., 1972; Brosset, 1973). A second strong acid, HN03 (nitric acid), has also been forming at increasing rates in the atmosphere. The formation of this acid also stems from fossil fuel combustion, especially'automobile exhausts. Thus the highest concentrations of HN03 are evident around metropolitan areas. Both of these strong acids are now present in such high concentration that the natural buffering capacity of the atmosphere is no longer able to neutralize their effects. The pH of pure rainwater saturated with carbon dioxide should be 5.7, but the addition of strong acids to the atmosphere is driving it down well below this level (Johnson, Reynolds, and Likens, 1972). Only recently have the effects of increasing acidity been appearing in the aquatic ecosystem. The problem facing us now is that (due to safety and other problems with the use of nuclear power and our difficulties in imple- menting either conservation or alternative energy sources), the use of fossil fuels is increasing, thus compounding the acid precipitation effect. Man contributes about one-half as much sulfur to the atmosphere as does nature now, and it has been predicted that by the year 2000 the amount will be equal (Kellogg et al_. , 1972). Estimates are that by the year 1995, 350 new coal- fired plants will be built and that sulfur emissions will increase by 2 mil- lion tons, corresponding to a threefold increase in coal usage (Carter, 1979). Increased acidity has been reported primarily in the northern hemisphere. The river systems on the west coast of Sweden have decreased 1.8 units in pH since the 1930s (Schofield, 1976). In 18 Norwegian lakes there has been a doubling of sulfate since the 1950s (Aimer et a^L , 1974). Similar increases in acidity have been- found in parts of Scandinavia and in numerous lakes west of Sudbury, Ontario, with increases of 200- and 100-fold respectively (Beamish and Harvey, 1972; Likens and Bormann, 1974). In the northeastern United States, the increase in acidity began to be noticed about twenty years ago and ------- now the pH of the precipitation ranges between 2.1 and 5 (Likens and Bormann, 1974; Newman, 1975). After analysis of the literature it becomes apparent that the main thrust of acid precipitation research has been directed at lake ecosystems, not at streams. This may be because, due to low turnover rates, the effects of acidification should be more obvious in lakes than in streams. However, we feel that the effects on streams may prove to be equally as serious as those on lakes, especially in the susceptible areas of the Appalachians. For a thorough review of the literature covering studies prior to 1976, consult Wright (1976). The Pennsylvania Cooperative Fishery Research Unit has been studying factors influencing production of native trout in infertile streams of the Allegheny Plateau for over 5 years. One of the common features of these streams is their low pH and alkalinity. These are usually between 4.5-5.5 and 0-10 mg/1 (as CaC03) respectively. Although it is recognized that nearly any source of hydrogen ions will upset the pH of such pure-water streams, acid precipitation and/or acid from headwater bogs seem the most likely causes of the low pH. Samples taken early in our studies indicated that (a) the pH is equally low above and below the headwater bog areas; (b) the water emerging from springs on the hillsides has a pH as low as that in the streams; and (c) the pH of rainfall in the area is consistently near 3.8, lower than the streams (and, in fact, lower than the rainfall values for this area indicated in various published reviews such as Likens et a^L (1979), which does not even include the Allegheny Plateau region of Pennsylvania and West Virginia among those areas "sensitive" to acid precipitation). These factors all seem to lend support to the assumption that acid precipitation is the primary factor in the acidification of Pennsylvania's unpolluted streams. The factors involved in our area seem to be similar to those evaluated by Seip and Tollan (1978) in concluding that acid precipitation must be the prime cause of the well-known acidification of rivers and lakes in southern Norway. The majority of the sensitive streams identified in the present study are located on forested land, usually in public ownership, and are subject to few significant human influences. Although there may be occasional exceptions, we believe that acid precipitation is the most probable cause of acidification in the streams we have identified; and that there are many more streams in the state, equally affected, which we were unable to identify simply because of missing or inadequate data. The most immediate danger from stream and lake acidification is, of course, to fish populations and to their food. Although most of the published reports on this topic involve fish populations in lakes, we believe that similar cause-effect relationships are likely for stream fish. Complete losses of fish populations have been reported in several areas of Europe (Aimer et aJL , 1974), and in Ontario (Beamish and Harvey, 1972), among other places. In most cases these losses were preceded by symptoms such as poor recruitment, failure of females to reach spawning condition, heavy mortality of eggs and/or larvae, deformed fins, shortening of gill covers, and rising concentrations of toxic elements such as aluminum and mercury. In ------- Pennsylvania waters, we suspect that the harmful effects to fish populations will occur through such immediate symptoms (i.e., through reduced growth and reproduction) and/or through interference with the food supply, rather than from direct toxicity of acidic water. Two earlier investigators from our group completed limited studies on the production of periphyton algae and of insect larvae- in poorly-buffered, acidic streams. Bender (1978) reported that pH affects species composition of peri- phyton algae but not species number or diversity, and that total biomass and productivity were not limited. Certain species become dominant only in acidic streams. Hale (1978) showed that in an acidic stream, detritus-feeding in- sects were dominant, while in a similar stream of neutral pH, herbivorous species dominated. The significance of these findings to fish production is not known. We are also currently investigating the significance of mineral nutrition of fish as related to these acidified streams. ------- CONCLUSIONS Although the data upon which this report is based are not sufficiently strong to define statistically valid relationships, it seems clear that there is a definite overall trend toward increasing acidity in many Pennsylvania streams, with the loss of components of the fish populations in many. Field experiments wi-th static limestone beds are being carried out on a number of streams in which the pH is at or near lethality for trout. Precipitation chemistry data are lacking, but elimination of streams possibly affected by acid mine drainage suggests acid precipitation as a likely cause of the ob- served changes. RECOMMENDATIONS A program of investigation should be undertaken to supplement the data utilized in this report with the information needed to document the current conditions and trends indicated for Pennsylvania streams, and their causes. A list is presented illustrating probable worst conditions existing at present in Pennsylvania surface waters not affected by acid mind drainage. These waters should be monitored for changes in biological or chemical systems related to increasing acidity. ------- MATERIALS AND METHODS - This study was funded in early May 1979 with a completion date for this report of September 30. With less than 5 months available for the work, it was necessary to limit the study to existing data in locations known to us. Much as we would like to have made field checks of many of the streams re- ported (and plan to in the near future), the available time did not permit it. Five data banks were identified and used in the study, as follows: 1. Data collected and compiled by the Pennsylvania Cooperative Fishery Research Unit in connection with various studies of trout production in infertile streams over the past five years. These data exist in punch- card form but in a non-standard local format. 2. Collection station files of The Pennsylvania State University Fish Col- lection. These include over 1000 locations throughout the state and have been organized by Dr. Edwin L. Cooper, curator. Most of the collections which have water quality data were made during the 1960s (for description see Cooper and Wagner, 1973). Although part of the data is available on compter tape, it is in a non-standard local format and not in a conven- ient form for machine retrieval of the data needed for the present study. 3. Stream survey files of the Pennsylvania Fish Commission. These are mostly in raw format on data sheets or in report letters. They include data from the 1940s to the present. A statewide fishery survey which will take several years to complete is now in progress and much of the data generated has been entered into a computer file. The access program for this file is not yet operational, and the file does not include information from earlier surveys. 4. Stream surveys and spot measurements by the Pennsylvania Department of Environmental Resources and its predecessor agencies. These are primar- ily from the 1970s and were usually made in response to reports of pollu- tion problems. However, they complement the Fish Commission data by being mainly from the lower, more developed parts of watersheds, while the Fish Commission surveys are primarily of the upper, less developed sections. These files are all in letter or field data sheet form. 5. Stream monitoring data of the Pennsylvania Department of Environmental Resources. These data are generated routinely by periodic sampling of specific stations throughout the state, and cover the last several years. It is in the standard STORET computer format, but was of limited use to us because the printout we obtained gave the data in terms of averages, masking trends of the time span in which we were interested. It is possible that more intense manipulation of the field would yield data ------- usable for detecting trends in pH and alkalinity, but shortage of time and money prevented our attempting this. Because of the widely-varying formats used in these data bases, and the necessity to do time-consuming major programming jobs to use them with com- puter techniques, we decided to forego the advantages of machine data manipu- lation for the advantages of manual methods. A standard 4 x 6-inch card was developed (Figure 1) for recording the pertinent data for several samples from a given location. As we proceeded with examination of each data bank (in the order given above), each sample location was evaluated to determine whether it justified starting a new card or if it was sufficiently close (generally within one mile with no major tributaries or other influences between) to an already-recorded station to be listed on the same card. The major time con- sumption of the study was connected with the laborious task of identifying and matching these station locations, many of which were labeled with place names not on the USGS topographic maps or other references available. (Note: we urge other workers to record and report their collection station data with standard coordinates using place names found on the USGS maps!) If such geographic matching could not be done the sample was eliminated from further consideration; this also was done if the sulfate or iron concentrations of the sample were significant (indicating possible acid mine drainage contamination) or if the sampling site was located in an area known to have mine drainage problems. Data actually recorded included name of water body, county, drainage basin, location of sampling site, dates, collectors, collector's code for the site, pH, conductivity, alkalinity, acidity, sulfate, whether or not fish were collected (or collection attempted), and if so, number of species found. This process generated a total of 983 cards representing different water bodies or locations within a stream system. Almost all these were streams, reflecting the small number of lakes within Pennsylvania and the little attention that has been given to their study. From these cards, all those were removed that did not meet the following criteria: there must be at least two samples (data points) and these must be separated in time by at least one year; either the pH or the alkalinity or both must show a decrease. Data from the remaining cards were used to generate the remaining tables and figures of this report. ------- P.C.F.R.U. - E.P.A. Study of Acid Precipitation Effects, 1979 Water Body County Card of Drainage Sampling Site Date Collector Coil's Code PH Conductivity Alkalinity Acidity Sulfate Fish Collection (+ = present) N ( 0 = no try) 0 (- = absent) T E S Figure 1. Card form used for recording and analysis of available data. ------- RESULTS AND DISCUSSION A total of 983 cards were generated. Of these, 314 had two or more data points meeting the specified criteria, and were examined for trends. A de- crease in pH, alkalinity, or both was found in 107 cases (40%). Seventy-one (66%) of these 107 records also had data from fish collections, and in 41 (58%) of these the number of species of fish present had decreased. A summary of the data on a statewide basis is presented in Table 1. TABLE 1. SUMMARY OF DECREASES IN pH, ALKALINITY, AND NUMBER OF FISH SPECIES FOUND FOR PENNSYLVANIA AS A WHOLE. Parameter pH (units) Alkalinity (ppm CaC03) Number of fish species Mean of Earliest Data (Range) 7.31 (5.8—8.8) 41.7 (5—200) 10.3 (2—22) Mean of Most Recent Data (Range) 6.94 (4.9—8.3) 26.6 (2—186) 8.7 (1-21) Mean Net Change (Range) -0.37 (-1.3 — +0.2) -15.1 (-105 — +18) -1.53 (-15 - +8) Average time span between earliest and most recent data =8.5 years (range 1—27). The data extracted for the 107 stations showing decreases are presented in Table 2. Since it is difficult to detect overall trends in such a table, and because the effect is diluted by a number of increases in one parameter or another, we sought more meaningful methods of presentation. ' Pennsylvania water chemistry is strongly influenced by topography, due to the very different types of rocks and soils exposed by different landforms. In many cases, the same stream undergoes a change of one or two hundred ppm in alkalinity, for example, within a few hundred yards as it leaves an inert sandstone mountainside and flows into a valley floor of highly reactive lime- stone. This sort of phenomenon may make it seem meaningless to sort stream data by major watersheds. We first chose to divide the state's counties into groups separated by lines denoting the major physiographic provinces, although in three cases it was necessary to divide a county between two provinces. A map indicating the location of "decrease" stations and these physiographic provinces is presented in Figure 2. 8 ------- TABLE 2. pH, ALKALINITY, AND NUMBER OF FISH SPECIES FOR PENNSYLVANIA WATERS SHOWING DECREASES AS DESCRIBED IN TEXT. NA = data not available. Asterisk indicates that intermediate data exist which, if used, would indicate a decrease in the number of fish species. Earliest Data Location Name Conewago Creek 1 Conewago Creek 2 South Branch Conewago Creek Opossum Creek Little Sewickly Creek Antietam Creek Northkill Creek Poplar Run Sugar Creek South Branch Towanda Creek Chest Creek 1 Chest Creek 2 North Creek Aquashicola Creek Sand Springs Run Black Moshannon Creek Cherry Run Cold Stream Elk Creek Laurel (Whetstone) Run Little Fishing Creek Six Mile Run Pickering Creek Valley Creek Canoe Creek Chest Creek Gifford Run Little Clearfield Creek Mosquito Creek Panther Run West Branch Susquehanna River Cooks Run Tangascootack Creek Beaver Run Armstrong Creek 1 Armstrong Creek 2 Stoney Creek 1 Stoney Creek 2 Belmouth Run Youghiogheny River East Standing Stone Creek Globe Run Trough Creek County Adams Adams Adams Adams Allegheny Berks Berks Blair Bradford Bradford Cambria Cambria Cameron Carbon Carbon Centre Centre Centre Centre Centre Centre Centre Chester Chester Clarion Clearfield Clearfield Clearfield Clearfield Clearfield Clearfield Clinton Clinton Columbia Dauphin Dauphin Dauphin Dauphin Elk Fayette Huntingdon Huntingdon Huntington Year 69 70 69 70 70 69 72 47 69 69 67 67 47 67 65 66 64 66 65 61 70 76 69 69 67 67 72 66 53 74 67 61 50 49 69 69 69 64 63 71 61 61 60 PH 7.3 7.0 7.5 7.5 7.7 7.7 8.1 7.6 8.7 7.8 7.6 7.7 7.7 7.6 6.6 7.3 6.9 7.0 8.3 7.1 8.1 7.2 7.5 8.2 6.7 7.7 6.3 7.3 6.0 5.8 7.3 6.9 7.5 7.3 7.2 7.0 6.6 6.9 6.7 7.2 7.3 6.9 7.1 Alka- linity 37 91 123 60 86 122 85 120 85 45 45 79 21 29 20 8 10 15 120 11 65 NA 45 200 18 39 NA 40 NA NA 17 NA NA 20 13 7 5 5 5 11 12 6 28 No. Fish Species 20 17 21 17 6 16 NA NA 14 16 10 15 NA 18 6 4 4 6 8 11 9 NA 13 3 2 12 1 11 NA NA 2 5 NA NA 14 16 10 13 3 8 7 11 8 Year 77 77 77 77 73 76 74 67 78 78 70 69 63 71 76 71 77 72 76 78 78 78 77 76 76 69 79 71 79 79 74 78 66 76 76 76 74 74 78 73 76 76 67 Latest Data PH 7.1 7.2 7.7 7.2 7.2 7.3 7.6 7.0 7.8 7.1 7.2 7.1 6.8 6.9 6.5 6.5 6.5 6.2 8.3 6.9 7.4 6.5 7.2 8.3 7.0 7.5 5.5 7.1 4.9 5.2 6.9 6.4 6.9 7.0 6.3 6.7 6.0 6.4 6.7 6.8 6.9 6.3 6.9 Alka- linity 36 37 60 40 60 62 70 15 62 35 41 22 20 26 3 10 2 NA 108 10 46 NA 36 186 12 32 0 38 0 NA 2 NA NA 14 9 6 10 10 3 8 5 8 18 No. Fish Species 18 17 6 17 NA 11 NA 7 NA 15 NA NA 8 NA 3 2 NA NA 7 5 8 NA 21 8 1 NA NA NA NA NA NA NA 5 14 11 14 7 5 2 4 10 8 9 Time Span 8 7 8 7 3 7 2 20 9 9 3 2 16 4 11 5 13 6 11 17 8 2 8 7 9 2 7 5 26 5 7 17 16 27 7 7 5 10 15 2 15 15 7 PH -0.2 +0.2 +0.2 -0.3 -0.5 -0.4 -0.5 -0.6 -0.9 -0.7 -0.4 -0.6 -0.9 -0.7 -0.1 -0.8 -0.4 -0.8 0 -0.2 -0.7 -0.7 -0.3 +0.1 +0.3 -0.2 -0.8 -0.2 -1.1 L -0.6 -0.4 -0.5 -0.6 -0.3 -0.4 -0.3 -0.6 -0.5 0 -0.4 -0.4 -0.6 -0.2 Net Change Alka- linity -1 -54 -63 -20 -@6 -60 -15 -105 -23 -10 -4 -57 -1 -3 -17 +2 -8 NA -12 -1 -19 NA -9 -14 -6 -7 NA -2 NA NA -15 NA NA -6 -4 -1 +5 +5 -2 -3 -7 +2 -10 No. Fish Species -2 0 -15 0 NA -5 NA NA NA -1 NA NA NA NA -3 -2 NA NA -1 -6 -1 NA +8 +5 -1 NA NA NA NA NA NA NA NA NA -3 -2 -3 -8 -1 -4 +3 -3 + 1 (continued) ------- Table 2. (continued) Earliest Data Location Name Five Mile Run Mill Creek North Fork Redbank Creek Tuscarora Creek 1 Tuscarora Creek 2 Little Swatara Creek Tulpehocken Creek Jordan Creek Little Wapwallopen Creek Neslopeck Creek North Branch Bowman s Creek Little Bear Creek Slate Run Trout Run Kinzua Creek Jacks Creek Brodhead Creek Cocolamus Creek Fowler Hollow Run McCabes Run Sherman Creek 1 Sherman Creek 2 Little Bushkill Creek Middle Branch Saw Creek Allegheny River 1 Allegheny River 2 Mill Creek Reed Run Swift Run Blue Hole Run Clear Shade Creek Fall Creek Jones Mill Run Pole Branch Run Rock Run East Branch Tunkhannock Creek North Branch Wyal using Salt Lick Creek Cowanesque River Four Mile Run Francis Branch Slate Run Long Run Stoney Fork 1 Stoney Fork 2 County Jefferson Jefferson Jefferson Juniata Juniata Lebanon Lebanon Lehigh Luzerne Luzerne Luzerne Lycoming Lycoming Lycomi ng McKean Miff Tin Monroe Perry Perry Perry Perry Perry Pike Pike Pike Potter Potter Potter Potter Snyder Somerset Somerset Somerset Somerset Sullivan Sullivan Susquehanna Susquehanna Susquehanna Tioga Tioga Tioga Tioga Tioga Tioga Year 55 67 67 69 69 57 68 69 69 66 ' 64 64 64 65 63 69 69 53 64 64 69 64 65 65 65 52 52 71 62 64 65 65 65 65 64 54 69 69 69 69 64 64 64 64 71 PH 7.3 7.3 7.3 8.4 8.6 7.6 8.0 8.0 6.9 6.7 6.7 6.8 7.4 6.6 6.9 7.6 8.1 7.6 6.5 7.5 8.2 6.5 7.6 7.3 6.8 8.8 6.9 7.2 7.2 6.5 6.7 7.1 7.3 7.3 6.8 6.9 7.5 7.4 7.5 7.7 7.3 7.5 7.4 8.0 7.4 Alka- linity 25 39 38 79 72 81 180 93 12 8 10 10 30 15 20 57 22 115 10 35 38 15 20 30 NA 35 33 24 28 10 20 15 15 25 15 9 40 23 30 58 40 25 40 70 63 No. Fish Species NA 16 16 15 22 NA 2 14 19 NA 2 3 7 5 15 9 12 NA 5 15 19 10 13 10 7 NA NA 9 14 3 3 9 3 5 2 NA 13 18 10 12 2 NA 12 6 6 Year 72 78 74 72 72 69 72 72 78 69 77 74 78 70 67 70 78 69 77 75 78 77 78 76 76 70 70 77 76 77 77 76 77 77 76 73 77 78 78 77 73 71 69 76 76 Latest Data PH 7.0 7.3 7.1 7.8 7.3 7.5 8.0 7.5 6.8 6.4 6.2 6.8 7.2 6.6 6.9 7.3 7.3 7.8 6.0 6.9 7.4 6.4 6.3 6.2 6.2 7.5 7.1 7.1 7.1 6.3 6.5 6.3 6.5 7.0 6.2 6.4 7.0 6.8 7.2 7.4 7.3 7.0 7.2 7.8 7.4 Alka- linity 12 26 20 40 28 68 160 40 10 6 2 4 15 10 12 46 18 40 2 10 56 4 7 3 8 12 12 12 12 2 4 5 3 15 3 10 20 18 24 32 23 23 20 72 52 No. Fish Species 4 7 9 11 13 19 NA NA 18 9 2 4 8 2 NA NA 8 18 6 6 17 13 8 8 8 18 19 10 9 3 2 5 2 5 3 2 13 11 17 13 4 5 5 7 6 Time Span 17 11 7 3 3 12 4 3 9 3 13 10 14 5 4 1 9 16 13 11 9 13 13 11 11 18 18 6 14 13 12 11 12 12 12 19 8 9 9 8 9 7 5 12 5 PH -0.3 0 -0.6 -0.6 -1.3 -0.1 0 -0.5 -0.1 -0.3 -0.5 0 -0.2 0 0 -0.3 -0.8 +0.2 -0.5 -0.6 -0.8 -0.1 -1.3 -1.1 -0.6 -1.3 +0.2 -0.1 -0.1 -0.2 -0.2 -0.8 -0.8 -0.3 -0.6 -0.5 -0.5 -0.6 -0.3 -0.3 0 -0.5 -0.2 -0.2 0 Net Change Alka- linity -13 -13 -18 -39 -44 -13 -20 -53 -2 -2 -8 -6 -15 -5 -8 -11 -4 -75 -8 -25 +18 -11 -13 -27 NA -23 -21 -12 -16 -8 -16 -10 -12 -10 -12 +1 -20 -5 -6 -26 -17 -2 -20 +2 -11 No. Fish Species NA* -9 -7 -4 -9 NA NA NA -T NA 0 + 1 + 1 -3 NA NA* -4 NA + 1 -9 -2 +3 -5 -2 +1 NA NA + 1 -5 0 -1 -4 -1 0 +1 NA 0 -7 +7 +1 +2 NA -7 + 1 0 (continued; ------- Table 2. (continued) Earliest Data Location Name Straight Run Tioga River 1 Tioga River 2 Laurel Run Weikert Run Little Sandy Creek Four Mile Run Oyberry Creek Lackawaxen Creek Shadigee Creek Wallenpaupack Creek West Branch Dyberry Creek Four Mile Run Bowmans Creek North Branch Mehoopany Creek Tunkhannock Creek 1 Tunkhannock Creek 2 Toms Run West Branch Codorus Creek County Tioga Tioga Tioga Union Union Venango Warren Wayne Wayne Wayne Wayne Wayne Westmoreland Wyomi ng Wyomi ng Wyomi ng Wyomi ng York York Year 64 73 71 64 64 65 54 69 69 69 69 65 67 64 69 66 66 70 70 PH 7.4 7.3 6.4 6.8 6.8 7.7 7.3 7.2 7.6 7.3 7.2 8.2 7.3 6.8 7.9 8.0 8.0 7.1 7.3 Alka- 1 inity 35 8 10 15 15 100 73 30 30 35 17 30 38 15 32 32 30 14 137 No. Fish Species 6 7 NA 8 9 12 NA 16 11 11 13 11 19 10 8 NA NA 6 7 Year 76 78 78 77 77 77 75 77 78 76 78 77 77 77 77 69 69 77 78 Latest Data pH 7.1 6.4 5.3 6.7 6.5 7.8 7.1 7.1 7.1 7.2 6.7 7.1 7.4 6.8 7.2 7.4 7.6 6.9 7.5 Alka- linity 22 6 3 7 5 42 24 20 17 28 12 22 21 2 24 44 33 11 98 No. Fish Species 5 8 NA 9 4 5 6 13 17 13 15 10 20 7 8 12 18 10 5 Time Span 12 5 7 13 13 12 21 8 9 7 9 12 10 13 8 3 3 7 8 PH -0.3 -0.9 -1.1 -0.1 -0.3 +0.1 -0.2 -0.1 -0.5 -0.1 -0.5 -1.1 +0.1 0 -0.7 -0.6 -0.4 -0.2 +0.2 Net Change Alka- linity -13 -2 -7 -8 -10 -58 -49 -10 -13 -7 -5 -8 -17 -13 -8 +8 +3 -3 -39 No. Fish Species -1 +1 NA + 1 -5 -7 NA -3 +6 +2 +2 -1 +1 -3 0 NA NA +4 -2 NA = Data not available. * = Intermediate data indicate a decrease in number of species. ------- Figure 2. County map of Pennsylvania showing approximate boundaries of physiographic, provinces and locations of waters showing decrease in pH or alkalinity or both. Key to numbers: 1) Coastal-Piedmont province; 2) Pocono-Anthracite province; 3) Ridge and Valley province; 4) Allegheny Plateau province (see Table 3). Scale 1:2,500,000. ------- The four provinces which we have delineated follow both topographic and geologic features, and for our purposes may be described as follows: 1. Coastal—Piedmont. Flat to rolling hills, Cambrian limestone and dolo- mite, some areas of Triassi.c shales and sandstones and Ordovician/ Precambrian metamorphic rocks. 2. Pocono-Anthracite. High rolling mountains mostly of Devonian shale and sandstone; occasional limestone exposures in association with coal seams. 3. Ridge and Valley. Long, high, parallel ridges of Devonian sandstones giving rise to infertile waters locally called "freestone streams." Valley floors of Ordovician and Cambrian limestones, dolomites, and shales with streams becoming relatively fertile and alkaline as they flow off the ridges into the valleys. 4. Allegheny Plateau. High, rolling mountains in irregular patterns. Cyclic sequences of Pennsylvania sandstones, limestones, shales, clays, and coals; but most higher elevations, especially in northern part, overlain by sandstone and shale beds of low solubility. The approximate boundaries of our four physiographic provinces are shown in Figure 2, along with the locations of streams snowing decreases in pH, alkalinity, or both. A summary of the relevant data is presented in Table 3. Divided in this way, the available data still show no striking irregularity. Total number of streams identified is closely related to the size of the province, and the proportion showing decreases in pH, alkalinity, and/or fish species number is relatively constant. However, this in itself may be impor- tant, indicating that either the distribution of susceptible streams, or of acid precipitation, or both, are statewide. Resolution of this point will require statistical analysis for which neither time nor funds were available at this writing. We expect to perform this analysis and publish the results in the near future. Although earlier questioned, the obvious alternative method of examining the data is by major watershed. The major watersheds of Pennsylvania, along with the locations of the "decrease" streams, are shown in Figure 3. A summary of the data sorted by watershed is presented in Table 4. This arrangement of the data does reveal some interesting trends, although their real meaning is not at all certain. For example, the proportion of the identified streams showing decreases in pH or alkalinity is quite low in the Allegheny River drainage, but the proportion of "decrease" streams showing a decrease in fish species number is quite high. The latter proportion is also quite high in the Delaware and Susquehanna below Sunbury (main stem) drainages as well as in the Monongahela-Youghiogheny system, although the data for the latter are very limited. Since the latter three drainages are not areas which we suspected of being very susceptible to acid precipitation, we are reluctant to speculate on the meaning of these trends in the data. Nevertheless, it seems clear that there is a definite overall trend of many streams becoming more acidic and/or less alkaline, and losing some fish populations at the same time. We hope that we or some other agency will be 13 ------- TABLE 3. WATER CHEMISTRY AND FISH POPULATION RECORDS SUMMARIZED BY PHYSIOGRAPHIC PROVINCE. Total Number* of Streams Examined (Percent 1. 2. 3. 4. Province Coastal -Piedmont Pocono- Anthracite Ridge and Valley Allegheny Plateau Totals of Grand Total) 55 45 62 152 314 (18%) (14%) (20%) (48%) Number Decreasing in pH, Al or 13 14 23 57 107 kalinity, Both (24%) (31%) (37%) (37%) Number with Fish Data 9 12 18 32 71 Number with Decrease in Fish 4 7 12 18 41 Species (44%) (58%) (67%) (56%) Having two or more data points and no evidence of mine drainage. TABLE 4. WATER CHEMISTRY AND FISH POPULATION RECORDS SUMMARIZED BY MAJOR WATERSHED. 1. 2. 3. 4. 5. 6. 7. 8. 9. Watershed (Numbers as in Figure 3) Lake Erie Ohio below Pittsburgh Monongahel a- Youghi ogheny Allegheny West Branch Susquehanna Susquehanna below Sunbury Potomac North Branch Susquehanna Delaware Totals Total Number* Locations Examined 7 3 9 48 66 79 3 44 55 314 Number Decreasing in pH, Alkalinity, or Both 0 1 4 14 29 28 0 15 16 107 (33%) (44%) (29%) (44%) (35%) (34%) (29%) (34%) Number with Fish Data 0 0 4 9 13 23 0 10 12 71 Number with Decrease in Fish Species 0 0 3 7 6 14 0 4 7 41 (75%) (78%) (46%) (61%) (40%) (58%) (58%) Having two or more data points and no evidence of mine drainage. ------- 80 Km Figure 3. Stream map of Pennsylvania showing major drainage basins and locations of waters showing decrease in pH or alkalinity or both. Key to numbers: 1) Lake Erie; 2) Ohio below Pittsburgh; 3) Monongahela-Youghiogheny; 4) Allegheny; 5) West Branch Susquehanna; 6) Susquehanna below Sunbury; 7) Potomac; 8) North Branch Susquehanna; 9) Delaware (see Table 4). Scale 1:2,500,000. ------- able to institute a program of investigation which will supplement the avail- able data with information needed to document the current condition and trend of many of these streams. We would be the first to admit that measurements of pH and alkalinity on a single stream during one day or one year can be highly variable; that it is very likely many of the data we used were generated in different ways and with different degrees of accuracy; and that the two meas- urements available in many of our cases are hardly enough to establish a statistically valid trend. However, we feel that the weight of the evidence becomes strong when so many of these cases, however imperfect, point in the same direction. Many chances for mitigation of ecological "disasters" have been lost because no one was willing to make a commitment until statistically unquestionable proof was not only in hand but widely accepted. We hope that will not be the case with the acid precipitation problem. As a start in what we hope is the right direction, we have been experi- menting with static limestone beds and other devices to mitigate the problems caused by acidification of Pennsylvania's fragile mountain trout streams. In the process of this work we have documented water quality in a number of streams which approaches the lower lethal limit of pH for brook trout, one of the most hardy of the native species. Since our study has been centered in the Quehanna Wilderness Area of Clearfield County, most of these streams are located there, but we can not believe that there are not others equally frag- ile and/or degraded in other areas. Naturally air quality control will be their best hope. In Table 5 we present a list of streams identified either in our earlier work or from the present study which illustrates the probable worst conditions existing at present in Pennsylvania streams and lakes which are not affected by acid mine drainage. We suggest that these streams should be watched closely to document whatever changes in their ecosystems have or will occur. 16 ------- TABLE 5. SELECTED WATERS SHOWING SERIOUS SYMPTOMS OF ACIDIFICATION (data from 1978-1979; N = number of samples). Name Gifford Run Mosquito Creek Deer Creek Pebble Run Panther Run Tioga River Tuscarora Creek *Allegheny River *West Branch Dyberry Creek Lower Duck Pond (Tributary of Mosquito Creek) Sandy Creek Meeker Run County Clearfield Clearfield and Elk Clearfield Elk Clearfield Tioga Juniata Potter Wayne Clearfield Clearfield Clearfield and Cameron Mean pH (N) (range) 5.26 .(26) (4.6-5.9) 5.22 (13) (4.7-5.9) 5.23 (10) (4.8-5.5) (4.66 (15) (4.4-5.0) 5.26 (15) (4.9-5.7) 6.85 (2) (6.4-7.3) 8.03 (3) (7.3-8.6) 8.15 (2) (7.5-8.8) 7.65 (2) (8.2-7.1) 5.26 (7) (4.9-5.4) 5.33 (11) (4.7-5.6) 4.8 (1) (4.8) Mean Alkalinity (N) (range) 1.5 (12) (0-9.1) 0.6 (5) 0-2.85) 0 (5) (0-0) 0 (5) (0-0) 0 (8) (0-0) 7 (2) (6-8) 61(3) (28-83) 48.5 (2) (12-85) 76.5 (2) (66-87) 0 (3) (0-0) 0.15 (12) (0-1.81) 4.05 (1) (4.05) * These streams, while not exhibiting abnormally low pH or alkalinity, did exhibit significant changes in these or in fish populations over the time period examined, and thus will bear watching. 17 ------- REFERENCES Aimer, B., W. Dickson, C. Eckstrom, E. Hornstrom, and U. Miller. 1974. Effects of acidification on Swedish lakes. Ambio 3(1):30-36. Beamish, R. J. , and H. H. Harvey. 1972. Acidification of the LaCloche Moun- tain lakes, Ontario, and resulting fish mortalities. J. Fish. Res. Bd. Canada 29(8):1131-1143. Bender, P. M. 1978. Studies on the periphyton communities of two infertile mountain streams with differing pH. M.S. Thesis, The Pennsylvania State University, University Park, 42 pp. Brosset, C. 1973. Air-borne acid. Ambio 2(l):2-9. Carter, L. J. 1979. Uncontrolled S02 emissions bring acid rain. Science 204(4398):1179, 1181-1182. Cooper, E. L. and C. C. Wagner. 1973. The effects of acid mine drainage on fish populations. Pages 73-124 Ln R. L. Butler, E. L. Cooper, J. K. Crawford, D. C. Hales, W. G. Kimmel and C. C. Wagner, Fish and food organisms in acid mind waters of Pennsylvania. U.S. Env. Prot. Agency. Ecol. Res. Ser., Rep. No. EPA-R3-73-032. U.S. Government Printing Office, Washington, D.C. 158 pp. Hale, A. B. 1978. A comparative study of the insect communities in two woodland streams with differing pH, with notes on the growth and fecun- dity of two species of Leuctra (Plecoptera). M.S. Thesis, The Pennsyl- vania State University, University Park. 50 pp. Johnson, N. M. , R. C. Reynolds and G. E. Likens. 1972. Atmospheric sulfur: its effect on the chemical weathering of New England. Science 177(4148): 514-516. Kellogg, W. W. , R. D. Cadle, E. R. Allen, A. L. Lazrus and E. A. Martell. 1972. The sulfur cycle. Science 175(4022):587-596. Likens, G. E. and F. H. Bormann. 1974. Acid rain: a serious regional en- vironmental problem. Science 184(4142):1176-1179. Likens, G. E., R. F. Wright, J. N. Galloway and T. J. Butler. 1979. Acid rain. Sci. Amer. 241(4):43-51. Newman, L. 1975. Acidity in rainwater: has an explanation been presented? Science 958(4191):957-958. 19 ------- Schofield, C. L. 1976. Acid precipitation: effects on fish. Ambio 5(5-6): 228-230. Schofield, C. L. 1977. Acid precipitation's destructive effects on fish in the Adirondacks. New York's Food Life Sci. 10(3):12-15. Seip, H. M. and A. Tollan. 1978. Acid precipitation and other possible sources for acidification of rivers and lakes. Sci. Total. Env. 10(3): 253-270. Vermeulen, A. J. 1978. Acid precipitation in The Netherlands. Env. Sci. Tech. 12(9):1016-1021. Wright, R. F. 1976. Acid precipitation and its effects on freshwater eco- systems: an annotated bibliography. Proc. 1st Int. Symp. Acid Precip. For. Ecos. , U.S.D.A. Forest Serv. Gen Tech. Rep. NE-23:619-678. 20 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing} 1. REPORT NO. EPA-6QO/3-80-012 3. RECIPIENT'S ACCESSION NO. 4. TITLE AND SUBTITLE Probable Effects of Acid Precipitation on Pennsylvania Waters 5. REPORT DATE January 1980 issuing date 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) Dean E. Arnold, Robert W. Light, and Valerie J. Dymond 8. PERFORMING ORGANIZATION REPORT NO. 3. PERFORMING ORGANIZATION NAME AND ADDRESS Pennsylvania Cooperative Fishery Research Unit 328 Mueller Laboratory Jniversity Park, PA 16802 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. B0835NAEX 12. SPONSORING AGENCY NAME AND ADDRESS Environmental Research Laboratory J.S. Environmental Protection Agency :orvallis, OR 97330 13. TY.PE OF REPORT^AND PERIOD COVERED Final, Flay-October T979 14. SPONSORING AGENCY CODE EPA/600/02 15. SUPPLEMENTARY NOTES the purpose of this project was to search for and identify any trends in water :hemistry and fish communities in Pennsylvania waters which would indicate that acid Drecipitation was affecting them adversely. No new data collection was to be included. Five existing data bases, including original data collected by the authors, were sxamined for the existence of water analyses from the same or nearby locations separated ay at least one year. (Analyses involving known or suspected influence of acid mine drainage were omitted.) Of a total of 983 analysis reports which were usable, there re 314 cases with two or more such points. Of these 107 or 34% showed a decrease in pH, alkalinity, or both. Average decrease in pH was 0.4 units with a maximum case of .3 units. Average decrease in alkalinity was 15.1 mg/1 (as CaC03) with a maximum case 3f 105 mg/1. The average time span between earliest and latest sample was 8.5 years. When the data were separated by physiographic provinces, it became apparent that although the majority of the decreases occurred in streams on the relatively insoluble ocks of the Allegheny Plateau, there were also many cases in the ridge-and-valley province and other regions. Many of these decreases are to pH levels considered marg- inal for growth and reproduction of trout and other fishes. Seventy-one of the 107 analyses showing decreased pH or alkalinity included fish collection data. In 40 of these cases (58%), the number of fish species present de- creased as well. 7. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.lDENTIFIERS/OPEN ENDED TERMS COSATI Field/Group Acidification, Precipitation, Stream Pollution, Fisheries Acid precipitation Acid rain Atmospheric deposition 08-H 18. DISTRIBUTION STATEMENT Release to Public 19. SECURITY CLASS (ThisReport) Unclassified 21. NO. OF PAGES 20. SECURITY CLASS (Thispage) Unclassifipd _2L 22. PRICE EPA Form 2220-1 (Rev. 4-77) 21 ------- |