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)