Skip to main content
Log in

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

  • Published:
Archives of Environmental Contamination and Toxicology Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1

Similar content being viewed by others

References

  • 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, OK

  • Aley TJ (1976) Hydrology and surface management. In: Aley T, Rhodes D (eds) The national cave management symposium proceedings. Speleobooks, Albuquerque

    Google Scholar 

  • 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, OK

  • 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 64:1464–1471

    Article  CAS  Google Scholar 

  • 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 23:1640–1648

    Article  CAS  Google Scholar 

  • 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 61:610–622

    Article  CAS  Google Scholar 

  • 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 37:1024–1033

    Article  CAS  Google Scholar 

  • Ankley GT, Brooks BW, Huggett DB, Sumpter JP (2007) Repeating history: pharmaceuticals in the environment. Environ Sci Technol 41:8211–8217

    Article  CAS  Google Scholar 

  • 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 68:46–50

    CAS  Google Scholar 

  • 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 42:153–162

    Article  CAS  Google Scholar 

  • 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 24:464–469

    Article  CAS  Google Scholar 

  • Collier AC (2007) Pharmaceutical contaminants in potable water: potential concerns for pregnant women and children. EcoHealth 4:164–171

    Article  Google Scholar 

  • 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 27:1788–1793

    Article  CAS  Google Scholar 

  • 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 67:1911–1918

    Article  CAS  Google Scholar 

  • 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 25:151–158

  • Culver DC (1982) Cave life: evolution and ecology. Harvard University Press, Cambridge

    Google Scholar 

  • Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107(Suppl 6):907–938

    Article  CAS  Google Scholar 

  • 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 27:83–90

    Article  Google Scholar 

  • Don J, Mendoza M, Pritchard J (2008) Pharmaceuticals lurking in U.S. drinking water. Associated Press. http://www.msnbc.msn.com/id/23503485. Accessed 10 Sept 2008

  • 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 9:1329–1336

    Article  CAS  Google Scholar 

  • 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 2005-5140

  • Graening GO, Brown AV (2003) Ecosystem dynamics and pollution effects in an Ozark cave stream. J Am Water Res Assoc 39:1497–1507

    Article  CAS  Google Scholar 

  • Hale RC, La Guardia MJ, Harvey E, Gaylor MO, Mainor TM (2006) Brominated flame retardant concentrations and trends in abiotic media. Chemosphere 64:181–186

    Article  CAS  Google Scholar 

  • 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 42:1452–1457

    Article  CAS  Google Scholar 

  • Hansen LG (1999) The ortho side of PCBs: occurrence and disposition. Kluwer, Boston

    Google Scholar 

  • Heberer T (2002) Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17

    Article  CAS  Google Scholar 

  • 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, OH

  • 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 43:229–235

    Article  CAS  Google Scholar 

  • 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 36:1886–1892

    Article  CAS  Google Scholar 

  • 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 47:427–439

    Article  CAS  Google Scholar 

  • Katsoyiannis A, Samara C (2004) Persistent organic pollutants (POPS) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal. Water Res 38:2685–2698

    Article  CAS  Google Scholar 

  • 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 36:1202–1211

    Article  CAS  Google Scholar 

  • 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 328:119–130

    Article  CAS  Google Scholar 

  • 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 72:1145–1151

    Article  CAS  Google Scholar 

  • 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, DC

  • Mudge SM, Lintern DG (1999) Comparison of sterol biomarkers for sewage with other measures in Victoria Harbour, BC, Canada. Estuar Coast Shelf Sci 48:27–38

    Article  Google Scholar 

  • National Pesticide Information Center (2007) Fipronil fact sheet. National Pesticide Information Center, Oregon State University, Corvallis, OR

  • NatureServe (2008) NatureServe Explorer: an online encyclopedia of life [web application]. Version 4.5. NatureServe, Arlington, VA. http://www.natureserve.org/explorer. Accessed 1 Sept 2008

  • Omernik JM (1987) Ecoregions of the conterminous United States. Map (scale 1:7, 500, 000) revised August 2002. Ann Assoc Am Geogr 77:118–125

    Article  Google Scholar 

  • 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 68:55–63

    Google Scholar 

  • 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 18:129–138

    Article  CAS  Google Scholar 

  • 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 54:695–705

    Article  CAS  Google Scholar 

  • Poulson TL, White WB (1969) The cave environment. Science 165:971–981

    Article  Google Scholar 

  • Proudlove GS (2001) The conservation status of hypogean fishes. Environ Biol Fishes 62:201–213

    Article  Google Scholar 

  • Quednow K, Puttmann W (2008) Organophosphates and synthetic musk fragrances in freshwater streams in Hessen/Germany. Clean-Soil Air Water 36:70–77

    Article  CAS  Google Scholar 

  • 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 34:1521–1528

    Article  CAS  Google Scholar 

  • 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 42:296–312

    Article  CAS  Google Scholar 

  • 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 42:1324

    Article  CAS  Google Scholar 

  • 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 36:1751–1756

    Article  CAS  Google Scholar 

  • Simon KS, Buikema AL (1997) Effects of organic pollution on an Appalachian cave: changes in macroinvertebrate populations and food supplies. Am Midl Nat 138:387–401

    Article  Google Scholar 

  • Sjödin A, Marsh G, Bergman A (1999) Polybrominated diphenyl ethers: environmental contaminants of concern. The Standard, Cambridge Isotope Laboratories 4:1–2

  • Smith GR, Burgett AA (2005) Effects of three organic wastewater contaminants on American toad, Bufo americanus, tadpoles. Ecotoxicology 14:477–482

    Article  CAS  Google Scholar 

  • Stanley JK, Ramirez AJ, Chambliss CK, Brooks BW (2007) Enantiospecific sublethal effects of the antidepressant fluoxetine to a model aquatic vertebrate and invertebrate. Chemosphere 69:9–16

    Article  CAS  Google Scholar 

  • Stuer-Lauridsen F (2005) Review of passive accumulation devices for monitoring organic micropollutants in the aquatic environment. Environ Pollut 136:503–524

    Article  CAS  Google Scholar 

  • US Census Bureau (2001) Census 2000 brief: population change and distribution: 1990–2000. Report CK2BR/01–2. US Census Bureau, Washington, DC

  • 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, DC

  • 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 80:497–501

    Article  CAS  Google Scholar 

  • 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 7:500–508

    Article  CAS  Google Scholar 

  • 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 68:1683–1691

    Article  CAS  Google Scholar 

  • 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 42:4331–4337

    Article  CAS  Google Scholar 

  • 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 41:4555–4560

    Article  CAS  Google Scholar 

  • 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, DC

  • 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 34:372–380

    Article  CAS  Google Scholar 

Download references

Acknowledgments

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.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Joseph R. Bidwell.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 214 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bidwell, J.R., Becker, C., Hensley, S. et al. Occurrence of Organic Wastewater and Other Contaminants in Cave Streams in Northeastern Oklahoma and Northwestern Arkansas. Arch Environ Contam Toxicol 58, 286–298 (2010). https://doi.org/10.1007/s00244-009-9388-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00244-009-9388-6

Keywords

Navigation