Nick BastaProfessor of Soil and Environmental ChemistrySchool of Environment and Natural Resources

Ohio State University

Ecological Effects of Land Application of Biosolids

Workshop on Microconstituents and Ecological Impacts of Biosolids and Effluent Reuse; June 26, 2008

Environmental Science / Ecosystem ScienceTerrestrial Wildlife and Ecology

mammals, avian (including migratory birds)reptiles,

Soil Science (including soil ecology)Carbon Management and Sequestration Center

Wetland Science / ecosystemsOlentangy River Wetland Research Park

Forest EcosystemsStream, Lake Ecosystems and FisheriesEnvironmental Social Science

School of Environment and Natural ResourcesOhio State University

ORWRP

Research programSoil/Environmental contaminant chemistry; ecotoxicologyDevelopment and evaluation of remediation technologiesof contaminated landBeneficial use of industrial by-products via land applicationBiogeochemical cycling of trace elements in soils

School of Environment and Natural ResourcesSoil Environmental Chemistry Program

Today’s Presentation

Contaminant Exposure (bioavailability)in Contaminated Soil Systems and Ecological Effects

Use of Soil Amendments and Biosolids to ReduceContaminant Exposure / Ecological Effects

Long-term Ecological Effects of Biosolids Applicationto Agricultural Land

Soil Environmental Chemistry,Contaminant Bioavailability, and Toxicity

Soil / contaminant chemistry affects availability,contaminant transmission, and human and ecological risk

Total ContaminantContent in Soil

Soluble / Available Soil Contaminant

Insoluble / UnavailableSoil Contaminant

High LowPotential Bioavailability / Toxicity

Potential Human/Ecological Risk

Soil Chemistry affects Contaminant Partitioning and Availability

Soil Chemical PropertiespH, OC, Clay, etc

Soil Chemical Properties and Solid Phases affect Contaminant Solubility / Bioavailability

Surface Chemistry - Adsorption Reactions in Soil

Pb2+

Soluble Pb

SOM

Fe

Fe

O

OH

OH2+

+ H2AsO4-

Fe

Fe

O

OH

O OH

OH

O

AsSoluble

Insoluble

Insoluble

O

CO

OSOM

OH

CO

O +

Ca10(PO4)6(OH)2 + xPb2+ Ca10-xPbx(PO4)6(OH)2 + xCa2+

Precipitation Reactions in Soil

Soluble Insoluble

Soil / contaminant chemistry affects availability,contaminant transmission, and ecological risk

Contaminant Exposure in Soil Systemsand Ecological Effects

Low pHLow OCLow Clay

High pHHigh OCMod Clay

High pHHigh OCMod Clay

Mod pHLow OCMod Clay

Low pHHigh OCMod Clay

Soil Chemical Properties / Solid Phase Components affect Solubility, Bioavailability, and Toxicity

5 pots of the same Zn contaminated soil

All pots have same total soil Zn but different bioavailable Zn

Soil ContaminantSoil Contaminant

Herbivore PathwayHerbivore Pathway

Carnivore PathwayCarnivore Pathway

Plant

Invertebrate Shrew

How Do We Adjust for the Effect of Soil on Contaminant Transmission to Ecological Receptors?

Environmental Security and Technology Certification ProgramStrategic Environment Resource Development Program(DOD, DOE, USEPA consortium)USEPA National Center for Ecological Assessment

Ohio State University; US Army Edgewood Chem. Biol. Ctr; Oak Ridge National Laboratory; Stanford Univ.; Univ. of Missouri; USEPA National Risk Management Lab; USEPA National Exposure Research Lab; Auburn Univ.;

Quantifying the Effect of Soil Chemical Propertieson Soil Ecotoxicity for Ecological Risk Assessment

contaminated soil research (not biosolids)

Research Projects

CAl + Fe oxide (FEAL, mol/kg)

0.00

0.05

0.10

0.15

0.20

BCation Exchange Capacity (CEC, cmolc/kg)

0

15

30

45

AOrganic Carbon (% OC)

0

1

2

3

DpH

Soil1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

0

2

4

6

8

U.S. EPA NCEA StudyU.S. EPA NCEA Study

22 soils with wide range of properties / constituents

soils spiked with one level ofAs, Pb, Zn, or Cd

ecotoxicological endpointslettuce, earthworms

Bradham et al. 2006. Environ. Tox. Chem. 25(3):769-775

Dayton et al. 2006. Environ. Tox. Chem 25(3):719-725

Soil Chemical Properties affected Phytotoxicity

0

10

20

30

40

50

60

70

80

Bernow B

Canis

teo

Dennis

ADen

nis B

Doughtery

AEfa

w AHan

lon A

Haske

llKirk

land A

Luton A

Mansi

c A

Mansi

c BOsa

ge A

Osage B

Perkin

s

Pond Cre

ek A

Pond Cre

ek B

Pratt

APra

tt B

Richfie

ld B

Summ

it A

Summ

it B

% G

row

th R

elat

ive

to C

on

tro

l

Lettuce grown in soil spiked with 250 mg/kg As

22 soils with a wide range of properties

Similar results for Pb, Cd, Zn

Soil

Soil Chemical Properties affect Pb BioaccumulationEarthworm Bioassay

0

100

200

300

400

500

600

700

800

900

Luto

nOsa

ge B

Osage

AKirk

land

Canist

eoSum

mit B

Man

sic A

Summ

it ADen

nis B

Dennis

AHan

lonM

ansic

BNor

geRich

field

Taloka

Dough

tery

Pond

Creek

B

Pond

Creek

ATell

erPra

tt B

Pratt

ABer

now

Soil

Inte

rnal

Con

cent

ratio

n (m

g P

b kg

-1dr

y w

t.)

Earthworms in soil spiked with 2000 mg/kg Pb

22 soils with a wide range of properties

Similar results for Cd, Zn, As

Remedial Techniques for Soil Property Multicollinearity

Many soil properties are inherently strongly intercorrelated(soil pH, CEC, organic carbon, clay content, etc)

Usual Multiple Regression Techniques will produce highly inaccurate ecotoxicological endpoints

Solution: specialized methodsStructural equation modelingPath analysisMultiple Regression ModelsRidge regression

Ridge Regression

Using Soil Chemical Properties toAdjust/Predict Soil Ecotoxicological Endpoints

Advanced Statistical ApproachesAdvanced Statistical Approaches

Prediction Equations used to Model Food Chain and Contaminant Transmission

Soil AvailableContaminant

Earthworm ShrewContaminant

SolubilityBioavailabilityto earthworm

Oral or GastrointestinalBioavailability

to ShrewDermal bioavailabilityand/or Oral Bioavailability

How do you measure effects from ingestionof contaminated soil?

Soil Contaminant Oral Bioavailability Soil Ingestion Exposure Pathway

Risk = [Soil]Risk = [Soil](BW) (AT)(BW) (AT)

(EF) (ED) (IR)(EF) (ED) (IR) (BIO)

How do we measure BIO for children?

for other ecological receptors ?

OSU In Vitro Gastrointestinal MethodAn Inexpensive, Fast, Accessible Alternative

in vitro “(bio)availability” = dissolved contaminant= bioaccessible contaminant

stomach phaseintestinal phase

Sequential extraction, 3737ooCC

U.S. EPA, Guidance for Evaluating the Oral Bioavailability of Metals in Soils for Use in Human Health Risk AssessmentOSWER 9285.7-80, May 2007; RBALP IVG accepted for Pb, others under consideration for Pb and As.

Rodriguez et al. 1999. ES&T 33:642-649

OSU IVG correlation with in vivoAs with dosing vehicle

As without dosing vehicleBasta et al., 2007. J. Environ.Health Sci. Part A 42:1275-1181.

Pb with/out dosing vehicleSchroder et al., 2004

J. Environ. Qual., 33:513-521.

Cd with/out dosing vehicleSchroder et al., 2003.

ES&T 37:1365-1370.

Rel

ativ

e B

ioav

aila

ble

As,

%

% Bioaccessible As

0 10 20 30 400

10

20

30

40

50

60

RBA As = 0.942 IVG RBA As = 0.942 IVG --7.11 r = 0.91**7.11 r = 0.91**

Basta et al. 2003. Grant R825410 Final Report. submitted to U.S. EPA ORD

OSU IVG Bioaccessibility Method

Ecotoxicological Risks Associated with Land Treatment of Petrochemical Wastesfrom Petrochemical-Contaminated Soils

Prior Use of in vitro methods for estimatingecotoxicological risks from ingestion of contaminated soil

Landfarming of Petrochemical WasteResulted in Soil Contamination

Oily/acid petrochemical sludge pit

Heavily vegetated landfarmcreates an attractive

“ecological nuisance”

Organic chemical wastesHF- octane productionPb - tetraethylleadcatalysts (Zn, Cr, V, other metals)

Contaminant Indicator SpeciesContaminant Indicator SpeciesCotton Rats (Cotton Rats (Sigmodon hispidusSigmodon hispidus))

small mammal with a critical functional role small mammal with a critical functional role in terrestrial food chainin terrestrial food chain

19.92 μg day -1

146.7 μg day-1

11.4%. .

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F exposure from incidental ingestion of soil associated with dietary (soiled food) and non-dietary pathways

88.6%88.6%

DietarypathwayDietary

pathway

Non-dietary pathwayNon-dietary pathway

Incidental ingestion of soil is a major contaminantexposure pathway for cotton rats

Soil Remediation by in situ Soil Amendments

Pb2+

Available

Unavailable

Pb

BiosolidsBiosolids Biosolids

O

O

OH

Treat soil to reduce contaminant solubility/availability to ecological and human receptors

adjust soil pHincrease clay/oxide contentadd organic matter, etc.

In Situ Chemical Immobilization of Pb

Immobilization of Pb Contaminated SoilPhosphates / P Fertilizer

Hydroxyapatite + available Pb

Ca10(PO4)6(OH)2 + xPb2+

Lead pyromorphiteLow bioavailability

Ca10-xPbx(PO4)6(OH)2 + xCa2+

Hydroxyapatite (Ma et al., 1995; Laperche et al., 1997)

Soluble phosphate fertilizerBasta and McGowen, 2004; McGowen et al., 2000

Before AfterBunker Hill, ID; Joplin, MO; Leadville, CO; othersBunker Hill, ID; Joplin, MO; Leadville, CO; othershttp://faculty.washington.edu/slb/Brown, Chaney, et al. 2004. J. Environ. Qual. 33:522-531.

Large-Scale Ecological Restoration Using BiosolidsUniversity of Washington, USDA-ARS, USEPA

Soil Remediation Using ByproductsLarge-Scale Field Studies

Palmerton, PA, 1980; Dead Ecosystem on Blue Mountain.

Palmerton, PA, 1999: Looking down revegetated Blue Mountain.

Soil Remediation in Picher, OK using ByproductsUniv. of Washington, USEPA ERT, OSU

72 plots on Pb, Zn, Cd contaminated landAlkaline BiosolidsBiosolids CompostCommercial phosphorus fertilizerAl-Drinking water residualsFe-Drinking water residuals

Seeded with Bermudagrass

Soil Remediation in Picher, OK using ByproductsUniv. of Washington, USEPA ERT, OSU

Soil Remediation and Ecological Restoration

“Ecological Revitalization” of contaminated Superfund sites

http://www.cluin.org/ecotools/

Ecological RestorationSoil Amendments

•biosolids•manures•compost•pulp sludges•yard /wood waste•lime•wood ash•coal combustion products•sugar beet lime•foundry sand•steel slag•FGD•water treatment residuals•etc

http://www.cluin.org/products/tpm/

Ecological RestorationEvaluating Contaminant Remediation

Technology Performance MeasuresStep 1 – Selecting the Goal of the Soil Amendment Application

Step 2 – Selecting the Exposure Pathway of ConcernStep 3 – Select the Performance EndpointStep 4 – Select What You Want To MeasureStep 5 – Select the Performance Measurement

TPM to Evaluate Amended SoilTPM to Evaluate Amended SoilReductions in Bioavailability and Ecological ExposureReductions in Bioavailability and Ecological Exposure

TPM for herbivore pathway: plant bioassay / metal bioaccumulationTPM for carnivore: earthworm bioassay / bioaccumulationTPM for both pathways: plant/worm ingestion- in vitro GI methods

Soil ContaminantSoil Contaminant

Herbivore Pathway

Carnivore Pathway

Shrew

Remediated Site

AlkalineBiosolids

Control N-ViroSoil

RockPhosphate

Non-alkalineBiosolids

Zn

Fra

ctio

n, m

g k

g-1

2000

4000

6000

Ca(NO3)2NaOAcEDTA HNO3

Chemical Immobilization and Phytotoxicityin Treated Pb/Zn Smelter-Contaminated Soils

Chemical Immobilization and PhytotoxicityChemical Immobilization and Phytotoxicityin Treated Pb/Zn Smelterin Treated Pb/Zn Smelter--Contaminated SoilsContaminated Soils

Basta, Gradwohl, Snethen, and Schroder. 2001. J. Environ. Qual. 30:1222-1230.

0

20

40

60

80

100

0 48 96 144 192 240 288 336

Time (h)

Cu

mu

lati

ve M

ort

alit

y (%

)

Alkaline Biosolids (LSB)

Control

Rock Phosphate (RP)

Non-Alkaline Biosolids (BS)

Condor, Lanno, and Basta. 2001. J. Environ. Qual. 30:1231Condor, Lanno, and Basta. 2001. J. Environ. Qual. 30:1231--1237.1237.

Earthworm Toxicity TestingZn, Pb, Cd Contaminated Smelter Soil

0

10

20

30

40

50

None LSB RP BSZn-smelter treated soils

Ca(NO3)2- extractable Zn, mmol/kg

No toxicity to Eisenia fetida in alkaline biosolids treated soil !

Quantifying Efficacy of In Situ Remediation Treatments:Treatment Effects on Ecological Risk

r2 = 0.61P < 0.01

0

10

20

30

40

50

60

70

80

90

100

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

Soil organic carbon (%)

Co

coo

n p

rod

uct

ion

(%

)

Organic Matter Amendments Increase Earthworm Cocoon Production

More Earthworms!

0.0

0.5

1.0

1.5

2.0

2.5

In-VitroPb

aa

b

c

b

Did the Amendments Decrease Soil Ingestion Risk? in-vitro Pb GI Bioavailability

in Amended Soil

Control Alk.Biosolids

NViro PO4 BiosolidsBasta et al., 2001. J. Environ. Qual. 30:1222-1230

Soil Contaminant

Soluble

Released In Gut

Bioaccumulated in Organism

Drinking Water

Ingestion of Soil

Food Chain

Combination Amendment

Biosolids + Phosphorus Fertilizer (for Zn / Pb / Cd)

Best Amendment to Reduce Bioavailability / Mobility and Transmission via Exposure Pathways

Brown, S.L., H. Compton, and N.T. Basta. 2007. Field Test of In Situ Soil Amendments at the Tar Creek National Priorities List Superfund Site J. Environ. Qual. 36:1627-1634.

Nick Basta, Shane Whitacre, SENRRoman Lanno, Dept. of Entomology

Plots established by Dr. Terry Logan in 1992 One time application of biosolids. 10 application rates ranging from 0 to 300 Mg/ha

Long-Term Ecological and Environmental Benefitsfrom Land Application of Biosolids

Plots established by Dr. Terry Logan in 1992 One time application of biosolids10 application rates ranging from 0 to 300 Mg/ha

Experimental Design

Percent MortalityReproduction (cocoons, juveniles)Contaminant Bioaccumulation

Dry matter growthbioaccumulationgermination

Earthworms

Eisenia andrei

Ecological Test Species

Perennial Ryegrass

Lolium perenne L.

Ecological Test Species

6630.2792.735.58300

*Mehlich 3 Extraction

4560.2091.986.67150

630.1151.207.000

P* (mg/kg)Total N (%)Organic C (%)pHBiosolids, Mg/ha

Soil Properties / Nutrients

Long Term Improvement in Soil Quality and Fertility

Biosolid Plots

Zn

50

100

150

200

250

300

350

400

As

12.0

12.5

13.0

13.5

14.0

14.5

15.0

Cd

0

1

2

3

4

5

6

Cr

15

20

25

30

35

40

Cu

20

30

40

50

60

70

80

90

Mo

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

Ni

Biosolid application rate (Mg/ha)

0 50 100 150 200 250 30019

20

21

22

23

24

25

26

Pb

0 50 100 150 200 250 30040

45

50

55

60

65

70

Soil Metal Content for OSU Logan Biosolids Study, all in mg/kg

Soil Metal Contents

Zn Cd

As Cr

Cu Mo

Ni Pb

Increase in Zn, Cu, Pb, Cd

Mg/ha Zn Cu Pb Cd

0 109 24 43 0.60

300 374 85 67 4.90

metal in mg/kg soil

0 Mg/ha 150 Mg/ha 300 Mg/ha

Large increase in dry matter growth with Biosolids Application Rate

Effect of Biosolids on Ryegrass Dry Matter Growth

Metal Bioaccumulation in Perennial Ryegrass

Concentrations of two metals increased in Ryegrass grown on plots amended with biosolids:Zn: 36 mg/kg for 0 Mg/ha

111 mg/kg for 300 Mg/ha

Cu: 3.7 mg/kg for 0 Mg/ha4.7 mg/kg for 300 Mg/ha

Cu sufficiency for Ryegrassis 5 mg/kg

Biosolids improved micronutrient status of soil and improved soil and plant nutrition for Cu and Zn

Cocoon production of Eisenia andrei in reproduction test

05

10

15202530

35

0 0* 60 150 300 300*

Application rate

To

tal c

oco

on

s / 1

0 w

orm

s

Cocoons Day 14

Cocoons Day 28

Cocoons Total

* No food

Soil Ecotoxicity- Invertebrates

Biosolids had no effect on cocoon production

Hatchling production of Eisenia andrei in reproduction test

0

20

40

60

80

0 0* 60 150 300 300*

Application rate

To

tal h

atch

ling

s / 1

0 w

orm

s

Hatchlings Day 14

Hatchlings Day 28

Hatchlings Total

* No food

Biosolids had no effect on hatchling production

Soil Ecotoxicity- Invertebrates

• Biosolids increased concentrations of several metals in amended soil

• Biosolids improved soil quality and fertility

• Long term increase in ryegrass dry matter growth

• Improved Cu and Zn in ryegrass (removed deficiency)

• No effect on reproduction in E. andrei

Summary

Kottman Hall

Thank you for your attentionMore information? Please contact:

Nick Basta, SENR OSU basta.4@osu.edu