Antibiotics in Our Streams How Much is There and Where Are They Coming From? Colorado State...

Antibiotics in Our StreamsAntibiotics in Our StreamsHow Much is There and Where Are They How Much is There and Where Are They

Coming From?Coming From?

Colorado State UniversityColorado State University

Kenneth CarlsonKenneth Carlson

([email protected])([email protected])

Sung-Chul KimSung-Chul Kim

Shinwoo YangShinwoo Yang

October, 2005October, 2005

Annual Antimicrobials UsageAnnual Antimicrobials Usage 2002 Animal Health Industry Sales

Total Pounds Total Pounds

(Thousands)(Thousands)Percent of Total (%)Percent of Total (%)

Human UsesHuman Uses

Disease TreatmentDisease Treatment

Other Human UseOther Human Use

3,0003,000

1,5001,50099

55

Livestock UsesLivestock Uses

Therapeutic – All SpeciesTherapeutic – All Species

Nontherapeutic – Cattle, Swine, Nontherapeutic – Cattle, Swine, Poultry Poultry

2,0002,000

24,50024,50066

7777

OthersOthers

Companion AnimalsCompanion Animals 1,0001,000 33

Total Antimicrobials UseTotal Antimicrobials Use 32,00032,000 100100

Sources, Distribution and Sinks Sources, Distribution and Sinks of of

Pharmaceuticals in the Pharmaceuticals in the EnvironmentEnvironment

Sources from: K Kummerer, Pharmaceuticals in the Sources from: K Kummerer, Pharmaceuticals in the Environment, SpringerEnvironment, Springer

Human Used Pharmaceuticals:Human Used Pharmaceuticals: STP as point sourceSTP as point source

Veterinary Pharmaceuticals:Veterinary Pharmaceuticals: Manure as fertilizer Manure as fertilizer Soil Soil Surface Runoff or Surface Runoff or Leaching through sub-surfaceLeaching through sub-surface

Risk to Drinking Water andRisk to Drinking Water and Watershed EcologyWatershed Ecology

Main ObjectivesMain Objectives Monitoring Occurrence of Human and Animal Monitoring Occurrence of Human and Animal

Antibiotics in Water and SedimentAntibiotics in Water and Sediment

Monitoring Occurrence in Animal Waste Lagoons Monitoring Occurrence in Animal Waste Lagoons and Manureand Manure

Evaluating Transport Pathways and MechanismsEvaluating Transport Pathways and Mechanisms

Evaluating Fate of Antibiotics and Waste Evaluating Fate of Antibiotics and Waste Management Management

Practice (BMPs)Practice (BMPs)

NH2

OHO

O OHOH

O

OH

NCH3 CH3R1R2

R3R4

12

3

4

5

6

7

89

1011

1214

15

16

17ABCD

13

pKaa Compounds R1 R2 R3 R4

pK1 pK2 pK3 Oxytetracycline(OTC) OH OH CH3 H 3.3 7.3 9.1

Chlortetracycline(CTC) H OH

Cl

3.3 7.4

9.3

Minocycline(MNC) H H H 2.8 5.0 7.8 Demeclocycline(DMC) H OH H Cl

Melocycline(MCC) OH CH2 - Cl Tetracycline(TC) H OH CH3 H 3.3 7.7 9.7

Doxycycline(DXC) OH H CH3 H 3.5 7.7 9.5

TetracyclinesTetracyclines

Name

R Name R pKa

Sulfathiazole (STZ)

S

N

Sulfametho-xazole (SMX)

ON

CH3

Sulfamerazine (SMR)

N

N

CH3

Sulfachloro-

pyridazine

(SCP)

NN Cl

Sulfamethazine (SMT)

N

N

CH3

CH3

Sulfadimeth-

oxine

(SDM) N

N

CH3O

CH3O

NH2

S

O

O

NH

R

SulfonamidesSulfonamides

MacrolidesMacrolides

H

CH3 H

OH

O

CH3

O

CH3

CH3

O

CH3

O

OH

CH3

O

OHCH3

OH OCH3

OCH3

OHCH3

NCH3CH3

C

OCH3

H

CH3 H

OH

O

CH3

H3CO-H2C-H2C-O-H2C-O-N

CH3

CH3

O

CH3

O

OH

CH3

O

OHCH3

OH OCH3

OCH3

OHCH3

NCH3CH3

C

OCH3

O

C2H3 O

CH3

O

CH3OH

O

CH3

O

O CH3

CHOOH

O

NCH3 CH3

OOH

CH3

OH

CH3

OHO

CH3

OCH3

OCH3

Erythromycin

Tylosin

Roxithromycin

IonophoresIonophores

HCH3

O

O

OH

O O

O

H5C2

HCH3

CH3

H

O

OH

OH

CH3CH3O

CH3

H

CH3

CH3

OHCH3

H3C

1

23

4

5

6

78

91 0

1 1

1 2 1 3

1 4

1 5

1 6

1 71 8

1 9

2 0

2 12 2

2 3

2 4

2 5

2 6

2 7

2 82 9

HCH3

O

O

OH

O O

O

H5C2

HCH3

CH3

H

O

OH

OH

CH3CH3O

H

CH3

CH3

OHCH3

H3C

1

23

4

5

6

78

910

11

12 13

14

15

16

1718

19

20

2122

23

24

25

26

27

2829

CH3OH3C

CH3

H

O

O

O

OH CH3

CH3

H

O

OH

O

CH3

H

OHOH

CH3

CH3

CH3 CH2OH

12

3

4

5

6

78

9

10 11

12 13

14 15

16 17

18 19

20

2122

23

24

25

Monensin

Salinomycin Naracin

Main ObjectivesMain Objectives Monitoring Occurrence of Human and Animal Monitoring Occurrence of Human and Animal

Antibiotics in Water and SedimentAntibiotics in Water and Sediment

Monitoring Occurrence in Animal Waste Lagoons Monitoring Occurrence in Animal Waste Lagoons and Manureand Manure

Evaluating Transport Pathways and MechanismsEvaluating Transport Pathways and Mechanisms

Evaluating Fate of Antibiotics and Waste Evaluating Fate of Antibiotics and Waste Management Management

PracticePractice

Solid Phase Extraction (SPE) Solid Phase Extraction (SPE) ProcedureProcedure

HLBHLB

3mL MeOH3mL HCL(5%,v/v)

3mL DI

3mL MeOH3mL HCL(5%,v/v)

3mL DI

Flow Rate2mL/min

Flow Rate2mL/min

33mLDI Water

33mLDI Water

22.5mLMeOH

22.5mLMeOH

Schematic Diagram of the Sediment Sample Schematic Diagram of the Sediment Sample PreparationPreparation

SampleSample(Air dried)(Air dried)

Pre-ExtractionPre-Extraction

Clean-upClean-up(SPE)(SPE)

Evaporation and ReconstitutionEvaporation and Reconstitution

HPLC/MS/MS AnalysisHPLC/MS/MS Analysis

TCs and SAs:TCs and SAs:Mcllvaine Buffer Solution (pH 4.0)Mcllvaine Buffer Solution (pH 4.0)

MLs and IPs:MLs and IPs:Ammonium Hydroxide Buffer (pH 10.0)Ammonium Hydroxide Buffer (pH 10.0)

Nitrogen Gas Water Bath (50Nitrogen Gas Water Bath (50C)C)5050l Sample + 70l Sample + 70l mobile phase Al mobile phase A

High Performance Liquid Chromatography High Performance Liquid Chromatography Tandem Mass Spectrometry (HPLC/MS/MS)Tandem Mass Spectrometry (HPLC/MS/MS)

EquipmentEquipment HP 1100 HPLC equipped with Thermostatted Auto Sampler and HP 1100 HPLC equipped with Thermostatted Auto Sampler and

variable UV detectorvariable UV detector

ThermoFinnigan LCQ Duo ion trap mass spectrometerThermoFinnigan LCQ Duo ion trap mass spectrometer

Xterra MS CXterra MS C1818 (2.1 (2.150mm, 2.550mm, 2.5m pore size, end-capped)m pore size, end-capped)

Optimized HPLCOptimized HPLC

ConditionConditionColumnColumn

TemperatuTemperaturere

((C)C)

Flow Flow RateRate

(ml/min)(ml/min)

Mobile Phase Conditions:Mobile Phase Conditions:

Mobile Phase A (99.9% DI+ 0.1% Formic Acid)Mobile Phase A (99.9% DI+ 0.1% Formic Acid)

Mobile Phase B (99.9% ACN + 0.1% Formic Acid)Mobile Phase B (99.9% ACN + 0.1% Formic Acid)

Mobile Phase C (100% MeOH)Mobile Phase C (100% MeOH)

Tetracyclines Tetracyclines (TCs)(TCs)

Sulfonamides Sulfonamides (SAs)(SAs)

1515 0.320.32 A: 96% + B: 4%: 0 (min) A: 96% + B: 4%: 0 (min) A: 70% + B: 30%: 29 A: 70% + B: 30%: 29 (min) (min) A: 96% + B: 4%: 30 (min) A: 96% + B: 4%: 30 (min)

Macrolides (MLs)Macrolides (MLs) 4545 0.320.32 A: 80% + B: 20%: 0 (min) A: 80% + B: 20%: 0 (min) A: 65% + B: 35%: 13 A: 65% + B: 35%: 13 (min) (min) A: 80% + B: 20%: 14 (min) A: 80% + B: 20%: 14 (min)

Ionophore Ionophore PolyethersPolyethers

(IPs)(IPs)

1515 0.250.25 A: 50% + C: 50%: 0 (min) A: 50% + C: 50%: 0 (min) A: 10% + C: 90%: 1 A: 10% + C: 90%: 1 (min) (min) A: 50% + C: 50%: 20 (min) A: 50% + C: 50%: 20 (min)

Optimized MSOptimized MS

ConditionConditionNitrogen Gas used for drying and nebulizingNitrogen Gas used for drying and nebulizing

Spray Voltage – 4.5VSpray Voltage – 4.5V

Capillary Voltage – 21VCapillary Voltage – 21V

Capillary Temperature - 165Capillary Temperature - 165°C°C

Quality Assurance: Quality Assurance: Recovery,Limit of Quantification (LOQ)Recovery,Limit of Quantification (LOQ)

RecoveryRecovery

Range (%)Range (%)TCsTCs SAsSAs MLsMLs IPsIPs

AqueousAqueous

(0.1,1,5 (0.1,1,5 g/L)g/L)102 - 124102 - 124 77 – 12477 – 124 89 – 11489 – 114 82 – 11782 – 117

SedimentSediment

(1,30,90 (1,30,90 g/kg)g/kg)

33 -11533 -115 62 - 10862 - 108 53 - 12853 - 128 51 - 10551 - 105

Lowest calibration curve point based on signal/noise 3 (0.01 Lowest calibration curve point based on signal/noise 3 (0.01 g/L and 1 g/L and 1 g/kg )g/kg )Standard Deviation Standard Deviation Student’s t-variate for one sided Student’s t-variate for one sided tt-test at the 95% confidence -test at the 95% confidence intervalinterval

LOQLOQ TCsTCs SAsSAs MLsMLs IPsIPs

AqueousAqueous

((g/L)g/L)0.01 – 0.040.01 – 0.04 0.01 – 0.020.01 – 0.02 0.01 – 0.030.01 – 0.03 0.012 – 0.012 –

0.0270.027

SedimentSediment

((g/kg)g/kg)0.3 – 2.50.3 – 2.5 0.3 – 1.70.3 – 1.7 0.5 – 1.70.5 – 1.7 0.4 – 3.60.4 – 3.6

Recovery Ratio Recovery Ratio ==

Detect Response of Spiked Sample prior to SPEDetect Response of Spiked Sample prior to SPE

100100Detect Response of Spiked Sample after SPEDetect Response of Spiked Sample after SPE

Sampling Sites DescriptionSampling Sites DescriptionSampling Site 1:Sampling Site 1:

Pristine watershedPristine watershed

Sampling Site 2:Sampling Site 2:

Rural landscapeRural landscape


Urban influencedUrban influenced

Wastewater Reclamation Wastewater Reclamation FacilityFacility


Heavily agricultural Heavily agricultural influenced areainfluenced area


Both urban and agricultural Both urban and agricultural

influenced area influenced area Sampling Sites Dairy ■ Feedlots ▲ Ranches USGS Gages ★

Site 2 - Site 2 - AqueousAqueous

Site 2

Tetracyclines

TC CTC OTC DMC MCC DXC

Con

cent

ratio

n (

g/L

)

0.00

0.01

0.02

0.03

0.04

0.05

0.06

May-03April-04August-04February-05

Site 2

Sulfonamides

STZ SMR SMT SCP SMX SDM

Con

cent

ratio

n (

g/L

)0.00

0.01

0.02

0.03

0.04

0.05


Site 2

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/L

)

0.00

0.01

0.02

0.03

0.04


Site 2

Ionophore Polyethers

MNS SLM NRS

Con

cent

ratio

n (

g/L

)

0.000

0.005

0.010

0.015

0.020

0.025

0.030


No observedNo observedconcentrationconcentrationin May and Aprilin May and Aprilexcept Narasinexcept Narasin

Local small farmLocal small farmmight contributemight contributethe detection of the detection of NarasinNarasin

Higher Higher concentrationconcentrationin February within February withhigh detect high detect frequencyfrequencyFor TCs and SAsFor TCs and SAs

Site 3 - AqueousSite 3 - Aqueous

Site 3

Tetracyclines


Con

cent

ratio

n (

g/L

)

0.00

0.02

0.04

0.06

0.08

0.10

0.12


Site 3

Sulfonamides


Con

cent

ratio

n (

g/L

)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Site 3

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/L

)

0.0

0.1

0.2

0.3

0.4

0.5


Site 3


MNS SLM NRS

Con

cent

ratio

n (

g/L

)

0.00

0.01

0.02

0.03

0.04


Higher concentrationHigher concentrationof human usedof human usedantibiotics orantibiotics orantimicrobialsantimicrobials

High concentration ofHigh concentration ofETM-H2O in low flowETM-H2O in low flowand cold temperatureand cold temperature


Site 4

Tetracyclines


Con

cent

ratio

n (

g/L

)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


Site 4

Sulfonamides


Con

cent

ratio

n (

g/L

)0.00

0.02

0.04

0.06

0.08

Site 4

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/L

)

0.00

0.02

0.04

0.06

0.08

0.10


Site 4


MNS SLM NRS

Con

cent

ratio

n (

g/L

)

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035


3 IPs were detected3 IPs were detected


Site 5

Tetracyclines


Con

cent

ratio

n (

g/L

)

0.0

0.1

0.2

0.3

0.4

Site 5

Sulfonamides

STZ SMR SMT SCP SMX SDMC

once

ntra

tion

( g

/L)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

Site 5

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/L

)

0.00

0.05

0.10

0.15

0.20

0.25


Site 5


MNS SLM NRS

Con

cent

ratio

n (

g/L

)

0.00

0.01

0.02

0.03

0.04


Higher concentrationHigher concentrationof MNS in Mayof MNS in May

Site 2 - Site 2 - SedimentSediment

Site 2

Tetracyclines


Con

cent

ratio

n (

g/k

g)

0

10

20

30

40

50


Site 2

Sulfonamides


once

ntra

tion

( g

/kg)

0

1

2

3

4

5

6

7


Site 2

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/k

g)

0.00

2.00

4.00

6.00

8.00

10.00

12.00

14.00


Site 2


MNS SLM NRS

Con

cent

ratio

n (

g/k

g)

0.0

0.5

1.0

1.5

2.0

2.5

3.0


No measurement forNo measurement forMLs and IPs MLs and IPs in Februaryin February

More frequent detectionMore frequent detectioncompared to aqueouscompared to aqueous


Site 3

Tetracyclines


Con

cent

ratio

n (

g/k

g)

0

20

40

60

80

100

120


Site 3

Sulfonamides


once

ntra

tion

( g

/kg)

0

2

4

6

8

Site 3

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/k

g)

0

5

10

15

20

25

30


Site 3


MNS SLM NRS

Con

cent

ratio

n (

g/k

g)

0

1

2

3

4


Higher concentrationHigher concentrationIn February for TCs andIn February for TCs andSAsSAs

No IPs except NarasinNo IPs except Narasin


Site 4

Tetracyclines


Con

cent

ratio

n (

g/k

g)

0

5

10

15

20

25

30


Site 4

Sulfonamides


once

ntra

tion

( g

/kg)

0

2

4

6

8

10

12

14

16

Site 4

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/k

g)

0

2

4

6

8

10

12

14

16

18


Site 4


MNS SLM NRS

Con

cent

ratio

n (

g/k

g)

0

5

10

15

20

25

30

35


Higher Higher concentrationconcentrationin August for in August for SMT,SMT,ETM-HETM-H22O, and IPsO, and IPs

High High concentrationconcentrationOf CTC, STZ, and Of CTC, STZ, and TLSTLS


Site 5

Tetracyclines


Con

cent

ratio

n (

g/k

g)

0

20

40

60

80

Site 5

Sulfonamides


once

ntra

tion

( g

/kg)

0

2

4

6

8

Site 5

Macrolides

ETM-H2O RTM TLS

Con

cent

ratio

n (

g/k

g)

0

2

4

6

8

10

12

14


Site 5


MNS SLM NRS

Con

cent

ratio

n (

g/k

g)

0

5

10

15

20

25

30

35


Combination of human usedCombination of human usedAnd veterinary medicinesAnd veterinary medicines

Summary of Measured Concentration at Summary of Measured Concentration at watershedwatershed

WaterWater SedimentSediment

CompounCompoundsds

Frequency Frequency of of

Detection Detection (%)(%)

Detected Concentration (Detected Concentration (g/L)g/L) Frequency Frequency of of

Detection Detection (%)(%)

Detected Concentration (Detected Concentration (g/kg)g/kg)

MeanMean StandarStandard d

DeviatioDeviationn

MaximuMaximumm

MinimuMinimumm

MeanMean StandarStandard d

DeviatioDeviationn

MaximuMaximumm

MinimuMinimumm

TCTC 4242 0.020.02 0.010.01 0.030.03 0.010.01 8080 17.917.9 24.324.3 102.7102.7 1.11.1

CTCCTC 4545 0.080.08 0.070.07 0.210.21 0.010.01 8080 10.810.8 9.29.2 30.830.8 1.11.1

OTCOTC 3737 0.180.18 0.400.40 1.211.21 0.010.01 8080 14.814.8 13.913.9 56.156.1 2.42.4

DMCDMC 3030 0.030.03 0.010.01 0.050.05 0.020.02 8080 6.96.9 5.55.5 23.623.6 2.12.1

MCCMCC 4747 0.030.03 0.030.03 0.100.10 0.010.01 8080 24.324.3 21.521.5 72.072.0 4.34.3

DXCDXC 3333 0.020.02 0.010.01 0.050.05 0.010.01 6565 15.715.7 10.110.1 38.938.9 2.22.2

STZSTZ 3333 0.010.01 0.010.01 0.030.03 0.010.01 7070 3.33.3 2.32.3 5.45.4 1.31.3

SMRSMR 3030 0.020.02 0.020.02 0.060.06 0.010.01 1515 4.84.8 2.32.3 6.86.8 2.32.3

SMTSMT 1010 0.020.02 0.000.00 0.020.02 0.020.02 2525 4.74.7 5.25.2 13.713.7 1.01.0

SCPSCP 55 0.030.03 0.000.00 0.030.03 0.030.03 2525 2.72.7 0.50.5 3.23.2 1.91.9

SMXSMX 6060 0.110.11 0.090.09 0.320.32 0.040.04 2525 1.61.6 0.30.3 1.91.9 1.21.2

SDMSDM 3333 0.020.02 0.020.02 0.040.04 0.010.01 3030 3.83.8 2.12.1 6.86.8 1.71.7

ETM-H2OETM-H2O 6565 0.120.12 0.130.13 0.450.45 0.020.02 7575 10.010.0 7.67.6 25.625.6 1.31.3

RTMRTM 00 0.000.00 0.000.00 0.000.00 0.000.00 3030 2.12.1 1.91.9 5.95.9 1.11.1

TYLTYL 55 0.050.05 0.000.00 0.050.05 0.050.05 5353 3.03.0 2.82.8 9.39.3 1.11.1

MNSMNS 5050 0.0090.009 0.0010.001 0.0360.036 0.0020.002 4040 13.813.8 11.211.2 31.531.5 2.42.4

SLMSLM 4343 0.0020.002 0.0020.002 0.0070.007 0.0010.001 4040 9.19.1 11.011.0 30.130.1 1.81.8

NRSNRS 3737 0.0180.018 0.0160.016 0.0380.038 0.0010.001 4040 6.46.4 4.24.2 16.316.3 2.82.8

Pseudo Partitioning Pseudo Partitioning CoefficientCoefficient

Pseudo Partitioning Coefficient Pseudo Partitioning Coefficient (L/kg) =(L/kg) =

Sediment Concentration Sediment Concentration ((g/kg)g/kg)

Aqueous Concentration (Aqueous Concentration (g/L)g/L)CompoundsCompounds RangeRange AverageAverage ReferenceReference

CTCCTC 623 - 1160623 - 1160 891891 670 – 1620670 – 1620

SMXSMX 20 - 2820 - 28 2424 0.6 – 4.90.6 – 4.9

ETM-H2OETM-H2O 72 - 39772 - 397 243243 8.3 – 1288.3 – 128

MNSMNS 1000 - 20501000 - 2050 15251525 --

PPC: MNS > CTC > ETM-H2O > SMXPPC: MNS > CTC > ETM-H2O > SMX

Sources from: J Tolls, Environmental Science and Technology (2001), 35, 3397 - 3406Sources from: J Tolls, Environmental Science and Technology (2001), 35, 3397 - 3406

Animal Waste Animal Waste OperationsOperations

Operation Lagoon Water Manure

Dairy 7 7

Beef 6 5

Hog 10 5

Sheep 2 4

Turkey 0 2

Animal Waste Animal Waste OperationsOperationsConcentration in lagoon water

Samples OTC CTC TC MNSug/L ug/L ug/L ug/L

MDL 1.79 1.33 2.09 0.86

Dairy A 5.04 1.71 9.89Dairy B 17.46 4.78 11.48Dairy C 10.62 1.56Dairy D 2.25Dairy EDairy F 2.95 12.45Dairy G 2.41Beef A 3.27 51.80 7.44 101.34Beef B 7.85 54.56Beef C 2.08 6.94 502.34Beef D 3.53 3.02 8.61 75.32Beef E 2.31 43.27Beef F 2.52 395.76Hog A 7.53 12.93Hog B 2.36 6.23Hog C 11.30 1193.00 6.47Hog D 12.77 2.54Hog E 135.43 16.95Hog F 99.52 14.40Hog G 1524.82 9498.69 26.47Hog H 1310.23 9450.37 24.83Hog I 6.65 2.58Hog J 8.05 2.40

Sheep 1 1.60 6.29Sheep 2


Samples STZ SCP SDM SMR SMT SMXug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.81 0.87 1.03 1.02 0.94 0.58

Dairy A 3.83 4.41 0.95 0.61Dairy B 1.01 16.80 1.02 2.91 0.59Dairy C 1.76 2.34Dairy DDairy EDairy F 28.04Dairy G 1.82Beef A 1.44 2.43 0.64Beef B 1.17Beef CBeef D 3.83Beef E 2.14 0.96 0.70Hog A 2.07Hog B 4.43Hog C 1941.53 66.07Hog D 1.77Hog E 3.80 2.96 1.12Hog F 3.88 4.53 2.70 1.26Hog G 2079.27 270.73 1.59 9.44Hog H 2430.30 280.58 2.31 8.05Hog IHog J 1.51 1.19

Sheep 1 64.23 2.47 0.60Sheep 2 132.68


Samples TLS ETM-H2O RTMug/L ug/L ug/L

MDL 0.46 0.65 0.59

Dairy A 1.16Dairy B 4.05 3.05 19.20Dairy C 0.51Dairy D 9.60 0.74Dairy E 19.53 7.95 4.58Dairy F 5.88Dairy G 4.84Beef A 102.52 7.39 43.66Beef B 0.90 0.68Beef C 11.69Beef D 27.88Beef E 37.59Beef F 36.78 0.67Hog A 0.69 0.63Hog BHog C 12.58 3.76 1.09Hog D 60.01 4.25Hog E 5.04Hog F 2.27Hog G 0.46Hog HHog IHog J

Sheep 1Sheep 2 1.80 1.40 1.06

Animal Waste Animal Waste OperationsOperationsConcentration in liquid manure

Samples OTC CTC TC MNSug/kg ug/kg ug/kg ug/kg

MDL 2.43 1.93 2.27 1.96

Dairy/Fresh 16.32 8.87 45.00Dairy/Fresh 42.43 33.38Dairy/Fresh 38.62 34.56Dairy/Fresh 15.73 356.62Dairy/Fresh 5130.42 2.47 1045.52Dairy/Fresh 5.58 39.01 78.53Dairy/Fresh 620.92 31.34 83.00Beef/Fresh 4.58 345.67Beef/Fresh 20.59 380.77 585.34 542.57Beef/Fresh 6.05 10.28 983.56Beef/Fresh 22.93 234.49 184.97 456.30Beef/Fresh 8.29 30.71 36.78Hog Fresh 11.94 23.88 128.44Hog Fresh 91.73 23138.27 1115.56Hog Fresh 1076.27 634.89 394.06Hog Fresh 372.78 148.60 284.15Hog Fresh 176779.21 22837.04 808.12

Sheep Fresh 172.33 3622.96 343.53Sheep Fresh 5.90 5.07 26.45Sheep Fresh 34.04 9990.72 3071.49Sheep Fresh 175832.67 9.64 10896.72Turkey/Old 160.53 26.91Turkey/Old 18.69 308.70 37.78

Animal Waste Animal Waste OperationsOperations

Actual concentration in liquid manureSamples STZ SCP SDM SMR SMT SMX

ug/kg ug/kg ug/kg ug/kg ug/kg ug/kg

MDL 1.35 1.43 1.54 1.17 1.62 1.08

Dairy/Fresh 16.51 7.85 1.75Dairy/Fresh 7.04 1.67Dairy/Fresh 11.49 1.89Dairy/Fresh 8.57Dairy/Fresh 24.32 3.04 647.85 2.64 3.57Dairy/Fresh 46.39 9.53 3.01 1.47Dairy/Fresh 2.74 11.67Beef/Fresh 12.77 3.25Beef/Fresh 127.47 2.18 12.11 5.30 7.28Beef/Fresh 19.70 6.31 2.82Beef/Fresh 257.78 8.43 2.49Beef/Fresh 7.88 5.97Hog Fresh 14.75 1.72 3.07 3.59Hog Fresh 17.40 3.19 2.71Hog Fresh 4.76 5.73Hog Fresh 36.69 38.38 1.81 1.50Hog Fresh 1.74

Sheep Fresh 1.37Sheep Fresh 12.96 419.21 1.96Sheep Fresh 4.19 1.82 2.01Sheep Fresh 10.19 248.42 2.73 1.80Turkey/Old 31.35 69.86 3.18 6.47Turkey/Old 5.51 6.17 1.68

Column Leaching ExperimentsColumn Leaching Experiments

PurposesPurposes Evaluating potential mobility of antibioticsEvaluating potential mobility of antibiotics Estimating partition coefficient (Kd)Estimating partition coefficient (Kd) Comparing surface runoff field experimentComparing surface runoff field experiment

Expected ResultsExpected Results Mobility: Sulfonamides > Macrolides > Mobility: Sulfonamides > Macrolides >

Ionophores > Ionophores > Tetracyclines Tetracyclines Kd values: Tetracyclines > Ionophores > Kd values: Tetracyclines > Ionophores >

Macrolides > Macrolides > Sulfonamides Sulfonamides

Mass Loading From Local Irrigation Mass Loading From Local Irrigation Ditches to WatershedDitches to Watershed ID Site name or

description

Averaged MeanStream Flow (cfs) a

A Eaton Canal 195

B Local Ditch -

C Eaton Canal 195

DGraham Seep Ditch

3

E Greeley #2 Canal 119

FGraham Seep Ditch

3

G Eaton Canal 195

H Greeley #2 Canal 119

I Greeley #2 Canal 119

M Agricultural Area 45

NUrban and agricultural combined area

a Averaged mean stream flow of canal or ditch was provided by Cache la Poudre River water commitioner and river mean stream flow was adapted from U.S. Geological Survey (USGS). Unknown data is not shown.

Inflow Inflow TC: 153.4TC: 153.4

CTC: 266.4CTC: 266.4OutflowOutflowTC: 2.5TC: 2.5

CTC: 2.9CTC: 2.9Mass Flux Mass Flux

TC: 1.6TC: 1.6CTC: 1.1CTC: 1.1

Inflow Inflow STZ: 6.2STZ: 6.2

SMT: 151.3SMT: 151.3OutflowOutflowSTZ: 0.3STZ: 0.3SMT: 3.0SMT: 3.0

Mass Flux Mass Flux STZ: 4.6STZ: 4.6

SMT: 2.0SMT: 2.0

Inflow Inflow ETM-HETM-H

22O: 48.2O: 48.2

TLS: 118.3TLS: 118.3OutflowOutflow

ETM-HETM-H22O: 2.1O: 2.1

TLS: 4.2TLS: 4.2Mass FluxMass Flux

ETM-HETM-H22O: 4.4O: 4.4

TLS: 3.5TLS: 3.5

InflowInflow MNS: 13.0MNS: 13.0SLM: 6.0SLM: 6.0NRS: 12.6NRS: 12.6OutflowOutflowMNS: 0.3MNS: 0.3SLM: 0.3SLM: 0.3NRS: 0.6NRS: 0.6

Mass FluxMass Flux MNS: 1.9MNS: 1.9SLM: 5.0SLM: 5.0NRS: 4.5NRS: 4.5

Unit of Inflow and Outflow: ton/yr, Mass Flux: %Unit of Inflow and Outflow: ton/yr, Mass Flux: %

ConclusionConclusionss

Occurrence frequency high in semi-arid watershedOccurrence frequency high in semi-arid watershed

Sediment-partitioned concentrations much higherSediment-partitioned concentrations much higher

With different site characteristics and land use, With different site characteristics and land use, concentration of human and animal antibiotics concentration of human and animal antibiotics varies significantly – BMPs can be developedvaries significantly – BMPs can be developed

Surface runoff may contribute to the release of Surface runoff may contribute to the release of antibiotics or antimicrobials to the antibiotics or antimicrobials to the environmentenvironment

Local irrigation ditches might act as intermediate Local irrigation ditches might act as intermediate transport pathways transport pathways

AcknowledgemAcknowledgementent

Colorado State UniversityColorado State University

Dr Amy PrudenDr Amy Pruden

Dr Jessica DavisDr Jessica Davis

Kathy DoeskenKathy Doesken

Support:Support:

United States Department of Agriculture United States Department of Agriculture (USDA)(USDA)

National Integrated Water Quality ProgramNational Integrated Water Quality ProgramIntegrated Research, Education, and Extension Competitive Grants Integrated Research, Education, and Extension Competitive Grants

ProgramProgram

Antibiotics in Our Streams How Much is There and Where Are They Coming From? Colorado State...

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