Occurrence of Organic Wastewater and Other Contaminants in Cave Streams in Northeastern Oklahoma and Northwestern Arkansas

  • Joseph R. BidwellEmail author
  • Carol Becker
  • Steve Hensley
  • Richard Stark
  • Michael T. Meyer


The prevalence of organic wastewater compounds in surface waters of the United States has been reported in a number of recent studies. In karstic areas, surface contaminants might be transported to groundwater and, ultimately, cave ecosystems, where they might impact resident biota. In this study, polar organic chemical integrative samplers (POCISs) and semipermeable membrane devices (SPMDs) were deployed in six caves and two surface-water sites located within the Ozark Plateau of northeastern Oklahoma and northwestern Arkansas in order to detect potential chemical contaminants in these systems. All caves sampled were known to contain populations of the threatened Ozark cavefish (Amblyopsis rosae). The surface-water site in Oklahoma was downstream from the outfall of a municipal wastewater treatment plant and a previous study indicated a hydrologic link between this stream and one of the caves. A total of 83 chemicals were detected in the POCIS and SPMD extracts from the surface-water and cave sites. Of these, 55 chemicals were detected in the caves. Regardless of the sampler used, more compounds were detected in the Oklahoma surface-water site than in the Arkansas site or the caves. The organic wastewater chemicals with the greatest mass measured in the sampler extracts included sterols (cholesterol and β-sitosterol), plasticizers [diethylhexylphthalate and tris(2-butoxyethyl) phosphate], the herbicide bromacil, and the fragrance indole. Sampler extracts from most of the cave sites did not contain many wastewater contaminants, although extracts from samplers in the Oklahoma surface-water site and the cave hydrologically linked to it had similar levels of diethylhexyphthalate and common detections of carbamazapine, sulfamethoxazole, benzophenone, N-diethyl-3-methylbenzamide (DEET), and octophenol monoethoxylate. Further evaluation of this system is warranted due to potential ongoing transport of wastewater-associated chemicals into the cave. Halogenated organics found in caves and surface-water sites included brominated flame retardants, organochlorine pesticides (chlordane and nonachlor), and polychlorinated biphenyls. The placement of samplers in the caves (near the cave mouth compared to farther in the system) might have influenced the number of halogenated organics detected due to possible aerial transport of residues. Guano from cave-dwelling bats also might have been a source of some of these chlorinated organics. Seven-day survival and growth bioassays with fathead minnows (Pimephales promelas) exposed to samples of cave water indicated initial toxicity in water from two of the caves, but these effects were transient, with no toxicity observed in follow-up tests.


DEHP Triclosan Chlordane PBDE Congener Polar Organic Chemical Integrative Sampler 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors thank Dr. Steven Zaugg of the USGS National Water Quality Laboratory, Denver, Colorado for assistance in analyzing extracts and helpful review of the manuscript. Similarly, we thank Dr. David Alvarez of the USGS Columbia Environmental Research Center for his review of an initial version of the article and feedback regarding presentation of the data. The views described herein are those of the authors and do not necessarily reflect the views of the US Geological Survey or the US Fish and Wildlife Service. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the US government. Funding for this study was provided in part by a grant from the Oklahoma Water Resources Research Institute.

Supplementary material

244_2009_9388_MOESM1_ESM.doc (214 kb)
Supplementary material 1 (DOC 214 kb)


  1. Adornato TG (2005) Assessment of contamination in caves located at the Ozark Plateau National Wildlife Refuge, Oklahoma, Project # 1261-2N46. Final report submitted to the Oklahoma Ecological Services Office, US Fish and Wildlife Service, Tulsa, OKGoogle Scholar
  2. Aley TJ (1976) Hydrology and surface management. In: Aley T, Rhodes D (eds) The national cave management symposium proceedings. Speleobooks, AlbuquerqueGoogle Scholar
  3. Aley TJ (2005) Groundwater recharge area delineation and vulnerability mapping of Star cave and nearby hydrologically associated springs, Delaware County, Oklahoma: Final report submitted to the Oklahoma Ecological Services Office, US Fish and Wildlife Service, Tulsa, OKGoogle Scholar
  4. Allinson G, Mispagel C, Kajiwara N, Anan Y, Hashimoto J, Laurenson L, Allinson M, Tanabe S (2006) Organochlorine and trace metal residues in adult southern bent-wing bat (Miniopterus schreibersh bassanii) in southeastern Australia. Chemosphere 64:1464–1471CrossRefGoogle Scholar
  5. Alvarez DA, Petty JD, Huckins JN, Jones-Lepp TL, Getting DT, Goddard JP, Manahan SE (2004) Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments. Environ Toxicol Chem 23:1640–1648CrossRefGoogle Scholar
  6. Alvarez DA, Stackelberg PE, Petty JD, Huckins JN, Furlong ET, Zaugg SD, Meyer MT (2005) Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream. Chemosphere 61:610–622CrossRefGoogle Scholar
  7. Alvarez DA, Cranor WL, Perkins SD, Clark RC, Smith SB (2008) Chemical and toxicologic assessment of organic contaminants in surface water using passive samplers. J Environ Qual 37:1024–1033CrossRefGoogle Scholar
  8. Ankley GT, Brooks BW, Huggett DB, Sumpter JP (2007) Repeating history: pharmaceuticals in the environment. Environ Sci Technol 41:8211–8217CrossRefGoogle Scholar
  9. Ayebo A, Breuer GM, Cain TG, Wichman MD, Subramanian P, Reynolds SJ (2006) Sterols as bio-markers for waste impact and source characterization in stream sediment. J Environ Health 68:46–50Google Scholar
  10. Barnabe S, Beauchesne I, Cooper DG, Nicell JA (2008) Plasticizers and their degradation products in the process streams of a large urban physicochemical sewage treatment plant. Water Res 42:153–162CrossRefGoogle Scholar
  11. Brooks BW, Chambliss CK, Stanley JK, Ramirez A, Banks KE, Johnson RD, Lewis RJ (2005) Determination of select antidepressants in fish from an effluent-dominated stream. Environ Toxicol Chem 24:464–469CrossRefGoogle Scholar
  12. Collier AC (2007) Pharmaceutical contaminants in potable water: potential concerns for pregnant women and children. EcoHealth 4:164–171CrossRefGoogle Scholar
  13. Coogan MA, La Point TW (2008) Snail bioaccumulation of triclocarban, triclosan, and methyltriclosan in a North Texas, USA, stream affected by wastewater treatment plant runoff. Environ Toxicol Chem 27:1788–1793CrossRefGoogle Scholar
  14. Coogan MA, Edziyie RE, La Point TW, Venables BJ (2007) Algal bioaccumulation of triclocarban, triclosan, and methyl-triclosan in a North Texas wastewater treatment plant receiving stream. Chemosphere 67:1911–1918CrossRefGoogle Scholar
  15. Crunkilton R (1984) Subterranean contamination of Meramec Spring by ammonium nitrate and urea fertilizer and its implication on rare cave biota. Proceedings of the 1984 National Cave Management Symposium. J Missouri Speleol Soc 25:151–158Google Scholar
  16. Culver DC (1982) Cave life: evolution and ecology. Harvard University Press, CambridgeGoogle Scholar
  17. Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107(Suppl 6):907–938CrossRefGoogle Scholar
  18. Di Domenico A, Ferri F, Fulgenzi AR, Iacovella N, Larocca C, Miniero R, Rodriguez F, Ditella ES, Silvestri S, Tafani P, Baldassarri LT, Volpi F (1993) Polychlorinated biphenyl, dibenzodioxin, and dibenzofuran occurrence in the general environment in Italy. Chemosphere 27:83–90CrossRefGoogle Scholar
  19. Don J, Mendoza M, Pritchard J (2008) Pharmaceuticals lurking in U.S. drinking water. Associated Press. Accessed 10 Sept 2008
  20. Ellis J, Shah M, Kubachka KM, Caruso JA (2007) Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection. J Environ Monit 9:1329–1336CrossRefGoogle Scholar
  21. Galloway JM, Haggard BE, Meyers, MT, Green WR (2004) Occurrence of pharmaceuticals and other organic wastewater constituents in selected streams in Northern Arkansas. US Geological Survey, Scientific Investigations Report 2005-5140Google Scholar
  22. Graening GO, Brown AV (2003) Ecosystem dynamics and pollution effects in an Ozark cave stream. J Am Water Res Assoc 39:1497–1507CrossRefGoogle Scholar
  23. Hale RC, La Guardia MJ, Harvey E, Gaylor MO, Mainor TM (2006) Brominated flame retardant concentrations and trends in abiotic media. Chemosphere 64:181–186CrossRefGoogle Scholar
  24. Hale RC, Kim SL, Harvey E, La Guardia MJ, Mainor TM, Bush EO, Jacobs EM (2008) Antarctic research bases: local sources of polybrominated diphenyl ether (PBDE) flame retardants. Environ Sci Technol 42:1452–1457CrossRefGoogle Scholar
  25. Hansen LG (1999) The ortho side of PCBs: occurrence and disposition. Kluwer, BostonGoogle Scholar
  26. Heberer T (2002) Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17CrossRefGoogle Scholar
  27. Henry TR, De Vito MJ (2003) Non-dioxin-like PCBs: effects and consideration in ecological risk assessment. US Environmental Protection Agency, Office of Research and Development-Ecological Risk Support Center, Cincinnati, OHGoogle Scholar
  28. Huggett DB, Brooks BW, Peterson B, Foran CM, Schlenk D (2002) Toxicity of select beta adrenergic receptor-blocking pharmaceuticals (B-blockers) on aquatic organisms. Arch Environ Contam Toxicol 43:229–235CrossRefGoogle Scholar
  29. Ikonomou MG, Rayne S, Addison RF (2002) Exponential increases of the brominated flame retardants, polybrominated diphenyl ethers, in the Canadian arctic from 1981 to 2000. Environ Sci Technol 36:1886–1892CrossRefGoogle Scholar
  30. Jones-Lepp TL, Alvarez DA, Petty JD, Huckins JN (2004) Polar organic chemical integrative sampling and liquid chromatography-electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents. Arch Environ Contam Toxicol 47:427–439CrossRefGoogle Scholar
  31. Katsoyiannis A, Samara C (2004) Persistent organic pollutants (POPS) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal. Water Res 38:2685–2698CrossRefGoogle Scholar
  32. Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999–2000: a national reconnaissance. Environ Sci Technol 36:1202–1211CrossRefGoogle Scholar
  33. Kolpin DW, Skopec M, Meyer MT, Furlong ET, Zaugg SD (2004) Urban contribution of pharmaceuticals and other organic wastewater contaminants to streams during differing flow conditions. Sci Total Environ 328:119–130CrossRefGoogle Scholar
  34. Li XM, Zhang QH, Dai JY, Gan YP, Zhou J, Yang XP, Cao H, Jiang GB, Xu MQ (2008) Pesticide contamination profiles of water, sediment and aquatic organisms in the effluent of Gaobeidian wastewater treatment plant. Chemosphere 72:1145–1151CrossRefGoogle Scholar
  35. Meyer MT, Lee EA, Ferrell GM, Bumgarner JE, Varns J (2007) Evaluation of offline tandem and online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry for analysis of antibiotics in ambient water and comparison to an independent method. US Geological Survey Scientific Investigations Report 2007-5021. US Geological Survey, Washington, DCGoogle Scholar
  36. Mudge SM, Lintern DG (1999) Comparison of sterol biomarkers for sewage with other measures in Victoria Harbour, BC, Canada. Estuar Coast Shelf Sci 48:27–38CrossRefGoogle Scholar
  37. National Pesticide Information Center (2007) Fipronil fact sheet. National Pesticide Information Center, Oregon State University, Corvallis, ORGoogle Scholar
  38. NatureServe (2008) NatureServe Explorer: an online encyclopedia of life [web application]. Version 4.5. NatureServe, Arlington, VA. Accessed 1 Sept 2008
  39. Omernik JM (1987) Ecoregions of the conterminous United States. Map (scale 1:7, 500, 000) revised August 2002. Ann Assoc Am Geogr 77:118–125CrossRefGoogle Scholar
  40. Panno SV, Hackley KC, Kelly WR, Hwang HH, Wilhelm FM, Taylor SJ, Stiff BJ (2006) Potential effects of recurrent low oxygen conditions on the Illinois Cave amphipod. J Cave Karst Stud 68:55–63Google Scholar
  41. Pawlowski S, Ternes TA, Bonerz M, Rastall AC, Erdinger L, Braunbeck T (2004) Estrogenicity of solid phase-extracted water samples from two municipal sewage treatment plant effluents and river Rhine water using the yeast estrogen screen. Toxicol In Vitro 18:129–138CrossRefGoogle Scholar
  42. Petty JD, Huckins JN, Alvarez DA, Brumbaugh WG, Cranor WL, Gale RW, Rastall AC, Jones-Lepp TL, Leiker TJ, Rostad CE, Furlong ET (2004) A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants. Chemosphere 54:695–705CrossRefGoogle Scholar
  43. Poulson TL, White WB (1969) The cave environment. Science 165:971–981CrossRefGoogle Scholar
  44. Proudlove GS (2001) The conservation status of hypogean fishes. Environ Biol Fishes 62:201–213CrossRefGoogle Scholar
  45. Quednow K, Puttmann W (2008) Organophosphates and synthetic musk fragrances in freshwater streams in Hessen/Germany. Clean-Soil Air Water 36:70–77CrossRefGoogle Scholar
  46. Rodgers-Gray TP, Jobling S, Morris S, Kelly C, Kirby S, Janbakhsh A, Harries JE, Waldock MJ, Sumpter JP, Tyler CR (2000) Long-term temporal changes in the estrogenic composition of treated sewage effluent and its biological effects on fish. Environ Sci Technol 34:1521–1528CrossRefGoogle Scholar
  47. Schwab BW, Hayes EP, Fiori JM, Mastrocco FJ, Roden NM, Cragin D, Meyerhoff RD, D’Aco VJ, Anderson PD (2005) Human pharmaceuticals in US surface waters: a human health risk assessment. Regul Toxicol Pharmacol 42:296–312CrossRefGoogle Scholar
  48. Shah VG, Dunstan RH, Geary PM, Coombes P, Roberts T, Von Nagy-Felsobuki E (2008) Erratum to “Evaluating potential applications of faecal sterols in distinguishing sources of faecal contamination from mixed faecal samples (Water Res 41 (2007) 16)”. Water Res 42:1324CrossRefGoogle Scholar
  49. Silva E, Rajapakse N, Kortenkamp A (2002) Something from “nothing”: eight weak estrogenic chemicals combined at concentrations below NOECs produce significant mixture effects. Environ Sci Technol 36:1751–1756CrossRefGoogle Scholar
  50. Simon KS, Buikema AL (1997) Effects of organic pollution on an Appalachian cave: changes in macroinvertebrate populations and food supplies. Am Midl Nat 138:387–401CrossRefGoogle Scholar
  51. Sjödin A, Marsh G, Bergman A (1999) Polybrominated diphenyl ethers: environmental contaminants of concern. The Standard, Cambridge Isotope Laboratories 4:1–2Google Scholar
  52. Smith GR, Burgett AA (2005) Effects of three organic wastewater contaminants on American toad, Bufo americanus, tadpoles. Ecotoxicology 14:477–482CrossRefGoogle Scholar
  53. Stanley JK, Ramirez AJ, Chambliss CK, Brooks BW (2007) Enantiospecific sublethal effects of the antidepressant fluoxetine to a model aquatic vertebrate and invertebrate. Chemosphere 69:9–16CrossRefGoogle Scholar
  54. Stuer-Lauridsen F (2005) Review of passive accumulation devices for monitoring organic micropollutants in the aquatic environment. Environ Pollut 136:503–524CrossRefGoogle Scholar
  55. US Census Bureau (2001) Census 2000 brief: population change and distribution: 1990–2000. Report CK2BR/01–2. US Census Bureau, Washington, DCGoogle Scholar
  56. US EPA (US Environmental Protection Agency) (2002) Short-term methods for estimating the chronic toxicity of effluents and receiving waters to freshwater organisms, 4th edn. EPA-821-R-02-013. US Environmental Protection Agency, Washington, DCGoogle Scholar
  57. Venne LS, Anderson TA, Zhang B, Smith LM, McMurry ST (2008) Organochlorine pesticide concentrations in sediment and amphibian tissue in playa wetlands in the Southern High Plains, USA. Bull Environ Contam Toxicol 80:497–501CrossRefGoogle Scholar
  58. Vrana B, Paschke H, Paschke A, Popp P, Schuurmann G (2005) Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater. J Environ Monit 7:500–508CrossRefGoogle Scholar
  59. Wang YW, Zhang QH, Lv JX, Li A, Liu HX, Li GG, Jiang GB (2007) Polybrominated diphenyl ethers and organochlorine pesticides in sewage sludge of wastewater treatment plants in China. Chemosphere 68:1683–1691CrossRefGoogle Scholar
  60. Xia K, Luo MB, Lusk C, Armbrust K, Skinner L, Sloan R (2008) Polybrominated diphenyl ethers (PBDEs) in biota representing different trophic levels of the Hudson River, New York: from 1999 to 2005. Environ Sci Technol 42:4331–4337CrossRefGoogle Scholar
  61. Xie ZY, Ebinghaus R, Temme C, Lohmann R, Caba A, Ruck W (2007) Occurrence and air-sea exchange of phthalates in the arctic. Environ Sci Technol 41:4555–4560CrossRefGoogle Scholar
  62. Zaugg SD, Smith SG, Schroeder MP, Barber LB, Burkhardt MR (2002) Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory: determination of wastewater compounds by polystyrene-divinylbenzene solid-phase extraction and capillary-column gas chromatography/mass spectrometry: US Geological Survey Water Resources Investigations Report 01-4186. US Geological Survey, Washington, DCGoogle Scholar
  63. Zeng F, Cui KY, Xie ZY, Liu M, Li YJ, Lin YJ, Zeng ZX, Li FB (2008) Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China. Environ Int 34:372–380CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  • Joseph R. Bidwell
    • 1
    Email author
  • Carol Becker
    • 2
  • Steve Hensley
    • 3
  • Richard Stark
    • 4
  • Michael T. Meyer
    • 5
  1. 1.Department of ZoologyOklahoma State UniversityStillwaterUSA
  2. 2.Oklahoma Water Science CenterUnited States Geological SurveyOklahoma CityUSA
  3. 3.Ozark Plateau National Wildlife RefugeUnited States Fish and Wildlife ServiceVianUSA
  4. 4.Oklahoma Ecological ServicesUnited States Fish and Wildlife ServiceTulsaUSA
  5. 5.Organic Geochemistry Research LaboratoryUnited States Geological SurveyLawrenceUSA

Personalised recommendations