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    Biological Transformation of Selenium in Soil-Plant Systems: Z-Q Lin and Gary Bañuelos

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    Gramoz Cubreli
    1) Selenium is an essential nutrient for animals but toxic at high concentrations. It exists in various chemical forms with different toxicities. Salicornia bigelovii (pickleweed) has an enhanced ability to transform selenium compounds compared to other plants. 2) Studies found that Salicornia can reduce selenate to organic forms like selenomethionine without microbes. Soil microbes also play a role, with one bacterium isolated from Salicornia soils, Shewanella putrefaciens, highly effective at volatilizing selenium. 3) Phytoremediation using Salicornia and other plants like canola and broccoli can help remove selenium from

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    Biological Transformation of Selenium in Soil-Plant Systems: Z-Q Lin and Gary Bañuelos

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    Gramoz Cubreli
    22 views47 pages
    1) Selenium is an essential nutrient for animals but toxic at high concentrations. It exists in various chemical forms with different toxicities. Salicornia bigelovii (pickleweed) has an enhanced ability to transform selenium compounds compared to other plants. 2) Studies found that Salicornia can reduce selenate to organic forms like selenomethionine without microbes. Soil microbes also play a role, with one bacterium isolated from Salicornia soils, Shewanella putrefaciens, highly effective at volatilizing selenium. 3) Phytoremediation using Salicornia and other plants like canola and broccoli can help remove selenium from

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    1) Selenium is an essential nutrient for animals but toxic at high concentrations. It exists in various chemical forms with different toxicities. Salicornia bigelovii (pickleweed) has an enhanced ability to transform selenium compounds compared to other plants. 2) Studies found that Salicornia can reduce selenate to organic forms like selenomethionine without microbes. Soil microbes also play a role, with one bacterium isolated from Salicornia soils, Shewanella putrefaciens, highly effective at volatilizing selenium. 3) Phytoremediation using Salicornia and other plants like canola and broccoli can help remove selenium from

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    22 views47 pages

    Biological Transformation of Selenium in Soil-Plant Systems: Z-Q Lin and Gary Bañuelos

    Uploaded by

    Gramoz Cubreli
    1) Selenium is an essential nutrient for animals but toxic at high concentrations. It exists in various chemical forms with different toxicities. Salicornia bigelovii (pickleweed) has an enhanced ability to transform selenium compounds compared to other plants. 2) Studies found that Salicornia can reduce selenate to organic forms like selenomethionine without microbes. Soil microbes also play a role, with one bacterium isolated from Salicornia soils, Shewanella putrefaciens, highly effective at volatilizing selenium. 3) Phytoremediation using Salicornia and other plants like canola and broccoli can help remove selenium from

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    Biological Transformation of Selenium in Soil-Plant Systems

    Z-Q Lin1 and Gary Bauelos2


    Sci. Program & Dept. of Biol. Sci. Southern Illinois Univ., Edwardsville 2USDA-ARS, Water Management Research Lab
    1Environ.

    Se

    Selenium

    A narrow margin between nutritionally required and toxic concentrations


    Essential for humans & animals Not essential for plants

    Chemical Forms of Se
    Se(VI), selenat Se(IV), selenite

    Se(0), elemental Se
    Se(-II), selenide
    e.g., Selenomethionine (SeMet); Dimethylselenide (DMSe)

    Toxicity of Se
    Toxicities of different chemical forms
    Toxic to fish: SeMet > selenite > selenate Elemental Se is not toxic because it is not water soluble. DMSe, a volatile Se compound, is less toxic to rats, compared with inorganic Se.

    Toxicity of Different Forms of Se to Fish

    T=0

    Se(-II)

    Se(IV)

    Se(VI)

    CK

    T=24 hrs

    What are the major chemical forms of Se accumulated in soilplant systems?

    Chemical Speciation of Se by X-ray absorption spectroscopy (XAS)


    XAS is one of the most advanced techniques that currently available for chemical speciation of Se and other environmentally important trace elements.
    Element specific Direct determination & non-destructive Various complex environmental substrates

    Chemical Speciation in Environmental Samples by XAS

    Se X-ray Absorption Spectra


    2.5

    Normalized Absorbance

    STANDARDS
    2.0

    1.5

    Se(VI) Se(IV) Se(0) SeMet

    1.0

    Sediment (0-2 cm)


    0.5

    0.0 12650

    12660

    12670

    12680

    12690

    Energy (eV)

    Factors Affecting Se Transformation in Soil-Plant Systems


    Sulfate
    Chemical similarity between selenate & sulfate Anaerobic microbial reduction of selenate Enhanced Se methylation in alkaline soils Adsorption of selenite Se bioavailability Root exudates

    Redox potential

    pH

    Organic matter

    Soil moisture

    Plants & associated microbial communities in soil

    Selenium pollution sources & predominant chemical forms


    Industry
    Oil refinery wastewater with selenite

    Agriculture
    Drainage water with ~90% of selenate

    The San Joaquin Valley:

    One of the most productive agriculture areas Subsurface tile-drainage contains Se & other salts.

    Soils contain high levels of Se

    East

    West

    Drainage Water Reuse System


    - Zero Discharge of Drainage Water into Environment

    Solar Evaporator 52 ha Cotton Alfalfa

    7.6 ha

    Halophytes Field

    192 ha

    Salt-tolerant Trees and Grasses

    Lin et al., 2002, Water Research

    The Halophyte Study Field


    Cordgrass (Spartina sp.)

    Pickleweed (Salicornia bigelovii)

    g Se m d
    100 200 300 400 500 0

    -2

    -1

    Sa lic or ni a

    C or d gr a ss

    Sa ltg ra ss

    At rip le x N at iv

    Maximum Rates of Se Volatilization

    gr

    as s

    Distribution of Salicornia bigelovii Torr. in the U.S.


    (Data from USDA)

    Why Does Salicornia Volatilize More Se Than Other Species ?


    Unique physiological processes in Salicornia? Volatilization by microbes associated with Salicornia? Interaction of Salicornia and microbes in soil?

    Major Steps of Se Volatilization Pathway in Plant

    Dimethyl selenide Methyl-SeMet Se-Methionine

    Selenate

    APSe

    Selenite

    Se-Cysteine

    DMSe

    Hypothesis:
    SeMet Selenite

    Salicornia

    SeMet DMSe

    SeMet

    Soil Microbes

    Selenate in Soil

    Selenate

    Selenate

    Question 1:
    Does Salicornia have an enhanced capacity of reducing selenate into organoselenium (SeMet) compounds?

    Salicornia was supplied with selenate or selenite. Experiments were conducted under sterile vs non-sterile conditions. Se speciation in Salicornia shoots & roots was determined by XAS.

    Lee & Lin et al. 2001. Planta

    Findings:
    Compared with other species, Salicornia has an enhanced capacity to reduce selenate into organic forms.
    Salicornia reduced >65% of selenate or selenite into SeMet in tissues.
    Chemical reduction of selenate without the presence of microbes.

    Question 2:
    Will chemical forms of selenium (e.g., selenate, selenite, SeMet) affect rates of Se volatilization in the soil-Salicornia system?

    Plants Treated With: Selenate, Selenite, or Selenomethionine

    Salicornia bigelovii Torr.

    Se Volatilization Measurements

    Finding:
    The soil-Salicornia system volatilized organic SeMet ~20 times faster than inorganic selenate (or ~15 times with selenite).

    Chemcial Forms of Se in Top Soil with Salicornia

    Se(VI) Se(IV) SeMet Se(0)

    Se volatilization by soil bacterial strains isolated Maximum from theRates Salicornia saltgrass fields of Se & Volatilization
    500

    400

    g Se m-2 d-1

    300

    200

    100

    0
    ni or Sa lic ltg Sa ra ss a

    76% of the total Se accumulated in Salicornia roots were SeMet-like organic compounds, while saltgrass accumulated 48% of SeMet-like compounds

    Salicornia root

    Saltgrass root

    Question 3:
    What is the role of soil microbes in Se volatilization?
    Is there a special microbial community associated with Salicornia? Are there any microbes that have an enhanced capacity to volatilize Se?

    Soil Microbial Study


    Soil samples were collected from the Salicornia and saltgrass fields. Cultureable bacteria were studied only. 5 identical bacterial strains were isolated and identified by 16 S rDNA technique.

    Volatilization of Se by Bacteria Isolated From the Salicornia and/or Saltgrass fields

    Se volatilization by soil bacterial strains isolated from the Salicornia & saltgrass fields
    g volatile Se per 500 ml culture per day
    300 Common 250 200 150 100 50 0 Species-specific

    c Ba

    illu

    t ub s s B

    ilis s lo ha d

    a ur

    ns an s illu t

    ac hr

    is ut p a re

    s ien c fa eu Ps

    illu c a

    c Ba

    ew Sh

    ell n a

    on m do

    as

    t pu

    ida

    Finding:
    Shewanella putrefaciens, a Salicorniaassociated bacterial strain, volatilized more Se than any others.

    Volatilization of Se into the Air


    An environmentally-important pathway of Se removal
    Volatile Se compound, DMSe, is less toxic Se removed from polluted ecosystem Less hazardous waste

    Transport of Volatile Se in the Atmosphere

    Lin et al., 2000, JEQ

    Phytoremediation Approaches:

    Phytoextraction

    Phytovolatilization

    Phytostabilization

    Phytodegradation

    Rhizodegradation

    Salicornia:

    A succulent, crunchy, and tasty vegetable; known as samphire, sea beans, or sea asparagus.

    Selenium accumulation in Canola & Broccoli


    Canola:
    In soil: ~ 2.5 ppm
    Extractable soil Se: ~0.5 ppm In irrigation water: ~ 0.25 ppm

    In seed: ~ 1 ppm
    Canola oil: ~ 1 ppm Seed by-products: ~ 1 ppm

    Dried leaves: 2-5 ppm

    Broccoli:
    In florets: ~ 4 ppm

    Dr. Gary Bauelos evaluates canola plants grown for cleaning seleniumrich soils. In studies on livestock, he is testing the potential use of high-selenium canola forage as feed.

    Growing Canola in the San Joaquin Valley, California

    Se-laden Drainage Sediment & Phytoremediation Studies

    Bauelos & Lin, 2004, Ecotoxicology & Environ. Safety

    Se Volatilization in Drainage Sediment


    100 80

    Bare Soil In a Brassica Field

    g Se m d-1
    -2

    60

    40

    20

    May

    Jun

    Jul

    Aug

    Sep

    Oct

    Nov

    Dec

    Jan

    Feb

    Time (2002-03)

    # of measurements (n) varied from 3 to 11 in each month.

    Phytoremediation: A Perspective of Ecosystem Ecology

    Salicornia is a staple food for the endangered salt marsh harvest mouse.

    ACKNOWLEDGEMENTS
    Graduate Students, Ramya Nadella, Bikram Shrestha, Shawn Lipe, SIU Edwardsville Irvin Arroyo, USDA-ARS, Water Management Research Lab Drs. N. Terry, A. Tagmount, H. Mohamed, A. Lee, UC Berkeley A. Illes, B. moose Peterson, H. Castle for the adapted illustration & photos California State Agricultural Research Initiative Grant (to Bauelos) The Joint Interagency (DOE/NSF/EPA/ONR) Phytoremediation Research Program
    U.S. DOE, Grant No. DE-FG02-03ER63621 (to Lin)

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