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Antibiotics in NM Waters

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    ANTIBIOTICS

    IN NEW MEXICO WASTEWATER

    AND GROUND WATER

    New Mexico Environment Department

    Ground Water Quality Bureau

    New Mexico Department of Health

    Scientific Laboratory Division

    Jerzy Kulis

    Dennis McQuillan

    Timothy ChapmanDouglas Mawhinney

    Rick Meyerhein

    September 22, 2003

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    EMERGING THREAT

    Antibiotic residues in natural waters are ofgrowing concern worldwide:up to 90% of pharmaceutical doses pass through

    humans or animalsmany antibiotics are not destroyed by conventional

    wastewater treatment

    have adverse ecological impact (e.g., antibiotic-resistant bacteria)

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    MAIN SOURCES

    Homes (treatment, disposal of unused

    medication)

    Hospitals, nursing homes (treatment,disposal of unused medication)

    Animal feeding operations (treatment,

    growth promotion) Pharmaceutical manufacturers

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    TRANSPORT & FATE

    Some antibiotics (e.g., penicillin) easily degrade inthe environment; some (e.g., tetracyclines) resistconventional wastewater treatment

    Some antibiotics (e.g., sulfonamides,tetracyclines) bind to manure or soil particles

    Subject to photolysis, hydrolysis, redox processes,biodegradation, sorption, and volatilization

    Ozonation and activated carbon filtration havebeen demonstrated to remove some antibioticsfrom drinking water.

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    2000-02 SURVEY OF DRUG

    RESIDUES IN NM WATERS

    Analgesics, antibiotics (tetracyclines and macrolides), anti-

    convulsants, anti-depressants, anti-inflammatory, hormones

    Treated sewage effluent, surface water receiving treated sewage

    effluent, groundwater contaminated by sewage, drinking water Drug residues detected in 11 out of 15 sewage effluent samples and in

    4 out of 23 surface water samples at low ng/L (ppt) up to 4.6 ug/L

    (ppb) levels

    Antibiotics (oxytetracycline and/or tetracycline) detected in 6 sewageeffluent samples at levels from 0.66 to 4.6 ug/L

    All samples were analyzed by the SLD, except for antibiotics

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    OBJECTIVES OF THIS STUDY

    Develop in-state capabilities to analyze

    antibiotics in water samples (SLD)

    Conduct a limited sampling for antibiotics

    in wastewater from different sources and in

    contaminated ground water (NMED)

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    DEVELOPMENT OF

    ANALYTICAL METHODS

    Factors considered in developing a preliminary list

    of antibiotics of interest: analytical capabilities of the SLD

    availability of laboratory standards

    frequency of occurrence in US waters

    Experimental extractions and analyses resulted in a

    final list of antibiotics of interests:best combination of recovery rate, accuracy, precision,

    detection limits, and frequency of occurrence in US

    waters

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    ANALYTICAL METHODS

    Samples collected into amber-glass bottles, kept on

    ice until delivered to SLD, no preservation

    Extraction from water using Solid Phase Extraction

    (SPE) cartridges at both acidic and alkaline pH

    Separation of antibiotics using high performance

    liquid chromatography (HPLC)

    Detection using tandem mass spectroscopy (MS/MS)with electrospray ionization (ESI)

    Detection limits at or below 1 ppb

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    PROBLEMS ENCOUNTERED

    Erythromycin appeared to partially dehydrate during the

    analytical process giving rise to several products compound

    removed from the preliminary list

    Tetracyclines appear to form complexes with metals makingthem difficult to extract with SPE

    Chlortetracycline gives very poor analytical response

    compound removed from the preliminary list

    Different compounds need different pH for optimum recoveryduring SPE (e.g., penicillin G requires acidic pH)

    Clogging of the SPE cartridges with dairy wastewater samples

    requires centrifuging

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    THE FINAL LIST OF

    ANTIBIOTICS OF INTEREST

    11compounds belonging to 6 classes

    Beta-lactams (penicillin G, penicillin V)

    Floroquinolones (ciprofloxacin, norfloxacin,ofloxacin)

    Lincosamides (lincomycin)

    Macrolides (tylosin)

    Sulfonamides (trimethoprim, sulfamethazine,sulfamethoxazole,)

    Tetracyclines (oxytetracycline)

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    SAMPLING LOCATIONS

    Selected based on their potential to have highlevels of antibiotics in wastewater or groundwater

    Wastewater from 8 dairies, 5 municipalwastewater treatment plants (WWTPs), 2hospitals, and a nursing home

    Ground water from contaminant plumes from3 dairies and a WWTP

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    DAIRY

    WASTEWATER

    SAMPLING RESULTS

    Antibiotics detected

    Not detected

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    DAIRY WASTEWATER

    SAMPLING RESULTS

    Midway Dairy (Portales) lincomycin 6.6

    ug/L (ppb)

    J-Lu Dairy (Portales) lincomycin 0.7 ug/LBright Star Dairy, Daybreak Dairy (Vado) -

    ND

    J&M Dairy, Haflinger Dairy (Artesia) NDYorktown Dairy (Roswell) ND

    Cheyenne Dairy (Dexter) - ND

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    NON-DAIRY

    WASTEWATER

    SAMPLING RESULTS

    Antibiotics detected

    Not detected

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    NON-DAIRY WASTEWATER

    SAMPLING RESULTS Country Cottage (nursing home, Hobbs) ofloxacin 23.5

    ug/L

    Hagerman WWTP - trimethoprim 1.4 ug/L,

    sulfamethoxazole 1.0 mg/L, ofloxacin 0.4 ug/L,

    ciprofloxacin 0.2 ug/L Portales WWTP trimethoprim 1.0 ug/L, ofloxacin 1.0 ug/L,

    sulfamethoxazole 0.4 ug/L

    Santa Fe WWTP ofloxacin 1.0 ug/L, ciprofloxacin 1.0 ug/L

    St. Vincent Hospital (Santa Fe) ofloxacin 4.9 ug/L

    Socorro WWTP ND

    Socorro Hospital ND

    Magdalena WWTP - ND

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    GROUND WATER

    SAMPLING RESULTS

    Antibiotics detected

    Not detected

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    GROUND WATER

    SAMPLING RESULTS

    Bright Star Dairy, Daybreak Dairy (Vado)

    ND

    J&M Dairy (Artesia) ND

    Magdalena WWTP - ND

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    DISCUSSION: DAIRY

    WASTEWATER

    No evidence of widespread antibiotic residues

    Only lincomycin was detected (in 2 dairies out of

    8 sampled): commonly used to treat foot warts and mastitis in

    lactating cows

    in this study, not detected in human wastewater

    possible use as a tracer of animal wastewater?

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    DISCUSSION: NON-DAIRY

    WASTEWATER

    Majority of WWTPs had at least one detectable antibiotic

    Ofloxacin present in all facilities that had detectable antibiotics used to treat urinary tract infections, pneumonia, bronchitis, prostate

    and skin infections

    highest levels in wastewater from one hospital and a nursing home

    possible use as a tracer of human wastewater?

    Simultaneous detections of trimethoprim and sulfamethoxazole

    match their mode of use

    often used together to treat urinary tract infections, pneumonia,protozoan infections, and by people with HIV to prevent infections

    suggests a similar fate in the environment

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    DISCUSSION: GROUND WATER

    No antibiotic detections in ground water

    from 4 sampled facilities

    BUT

    None of these facilities had detectable

    levels of antibiotics in wastewater

    Unable to determine if antibiotics can leach

    into ground water

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    CONCLUSIONS: ANALYTICAL

    METHODS

    Analytical capabilities for a number of

    antibiotics have been developed by SLD

    Future work:expand the list of antibiotics that can be

    analyzed, with emphasis on tetracyclines

    lower the detection limits down to low pptrange

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    CONCLUSIONS: THE SURVEY

    Antibiotics detectable in some dairy wastewater

    but not widespread

    Majority of human wastewater contain antibiotic

    residues

    Ofloxacin and lincomycin should be investigated

    for a possible use as tracers of human and animal

    wastes More field sampling is needed to characterize the

    fate of antibiotics in the environment and threat to

    ground water

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    ACKNOWLEDGMENT

    This study was funded in part by a grant

    from the U.S. Environmental Protection

    Agency, pursuant to Section 319 of theFederal Clean Water Act.


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