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Book with abstracts from the COST Action 0905 meeting in ... - UMB

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Fig 1, 190x show<strong>in</strong>g biochar’s variously<br />

sized pores (A.) and longitud<strong>in</strong>al, vertically<br />

cut cross-section of those pores at 550x<br />

magnification (B.).<br />

Columns were leached upwards <strong>from</strong> <strong>the</strong>ir<br />

base cont<strong>in</strong>uously <strong>with</strong> de-ionised water (pH<br />

5.5) at 0.1 ml m<strong>in</strong> -1 flow rate, ma<strong>in</strong>ta<strong>in</strong>ed by<br />

a peristaltic pump. Two of <strong>the</strong> columns<br />

conta<strong>in</strong><strong>in</strong>g biochar were l<strong>in</strong>ked <strong>in</strong> parallel to<br />

<strong>the</strong> preced<strong>in</strong>g two columns conta<strong>in</strong><strong>in</strong>g soil to<br />

allow biochar to <strong>in</strong>tercept contam<strong>in</strong>ated<br />

eluate directly leached <strong>from</strong> <strong>the</strong> soil<br />

columns. Eluate samples (10 ml) <strong>from</strong> soil<br />

were collected prior to pass<strong>in</strong>g through <strong>the</strong><br />

biochar columns, by means of a small outlet<br />

at <strong>the</strong> jo<strong>in</strong>t between columns which<br />

rema<strong>in</strong>ed closed at all times except dur<strong>in</strong>g<br />

sample collection. The rema<strong>in</strong><strong>in</strong>g two<br />

biochar filled columns were leached by <strong>the</strong><br />

same method, but <strong>in</strong>dependently of <strong>the</strong> soil<br />

columns, to provide a biochar control.<br />

Columns were leached for 8 weeks <strong>in</strong> total.<br />

For <strong>the</strong> first 5 weeks (fractions 1-5) eluate<br />

was collected <strong>from</strong> all of <strong>the</strong> columns. In<br />

fractions 6, 7 and 8 (weeks 6, 7 and 8)<br />

leach<strong>in</strong>g of soil columns was term<strong>in</strong>ated, but<br />

both <strong>the</strong> <strong>in</strong>tercept<strong>in</strong>g biochar and biochar<br />

control columns cont<strong>in</strong>ued to be leached as<br />

previously described. Arsenic, Cd, and Zn<br />

concentrations <strong>in</strong> <strong>the</strong> eluate samples were<br />

determ<strong>in</strong>ed by ICP-MS. For <strong>the</strong> SEM/EDX<br />

analyses samples of soils and biochar both<br />

before and after leach<strong>in</strong>g were dried and<br />

encased <strong>in</strong> epoxy res<strong>in</strong>, stuck to microscope<br />

slide, covered <strong>with</strong> colloidal graphite to<br />

ensure conductivity and analysed <strong>with</strong> a Jeol<br />

6400 SEM microscope equipped <strong>with</strong> an<br />

Oxford detector. Images of EDX dot maps<br />

of As, Zn, Cd and SEM images of biochar<br />

structure were acquired and processed <strong>with</strong><br />

INCA software (Oxford Inst.).<br />

Results<br />

Arsenic concentrations were by far <strong>the</strong><br />

lowest of all elements measured <strong>in</strong> <strong>the</strong> eluate<br />

<strong>from</strong> <strong>the</strong> soil (< 10 µg l -1 ), but did <strong>in</strong>crease<br />

slightly when soil eluate was passed through<br />

biochar (Fig 2a & b), suggest<strong>in</strong>g a<br />

cumulative effect given that concentrations<br />

were also very low <strong>from</strong> <strong>the</strong> biochar alone.<br />

Unlike arsenic, cadmium and z<strong>in</strong>c<br />

concentrations <strong>in</strong> eluate <strong>from</strong> soil were high,<br />

especially <strong>in</strong> <strong>the</strong> first 2 leach<strong>in</strong>g fractions<br />

(200-500 µg l -1 <strong>in</strong> each fraction) which<br />

resulted <strong>in</strong> cumulative removals of ~ 4 mg<br />

Cd per kg -1 and ~ 2.5 mg Zn per kg -1 of soil<br />

over <strong>the</strong> 5 fractions of <strong>the</strong> column test.<br />

Biochar rapidly and significantly (p < 0.05)<br />

rapidly reduced concentrations of both Cd<br />

and Zn as it <strong>in</strong>tercepted contam<strong>in</strong>ated eluate<br />

<strong>from</strong> <strong>the</strong> soil columns (Fig 2e & h). Given<br />

biochar’s large surface area (Fig 1)<br />

SEM/EDX detected greater sorption of As,<br />

Cd and Zn on biochar’s surface follow<strong>in</strong>g<br />

<strong>the</strong> column test, corroborat<strong>in</strong>g <strong>the</strong> leach<strong>in</strong>g<br />

test results. Fur<strong>the</strong>rmore, this microanalyses<br />

also confirmed de-sorption <strong>from</strong> <strong>the</strong> surfaces<br />

of soil, illustrat<strong>in</strong>g <strong>the</strong> relocation of soluble<br />

contam<strong>in</strong>ants <strong>from</strong> soil to biochar.<br />

Discussion<br />

Biochar alone was free <strong>from</strong> significant<br />

amounts of As, Cd and Zn <strong>in</strong> water-soluble<br />

form and would be safe to use as a soil<br />

treatment <strong>with</strong>out itself contribut<strong>in</strong>g to any<br />

environmental toxicity effects. Its structure<br />

might expla<strong>in</strong> some of <strong>the</strong> effects observed<br />

as oxidation could occur most rapidly on<br />

outer surfaces, followed by <strong>in</strong>terior pores,<br />

which might result <strong>in</strong> differential element<br />

retention between surface and <strong>in</strong>terior sites<br />

as a result of shift<strong>in</strong>g CEC for example.<br />

None<strong>the</strong>less, biochar has proven to be<br />

effective at reduc<strong>in</strong>g high concentrations of<br />

soluble Cd and Zn orig<strong>in</strong>at<strong>in</strong>g <strong>from</strong> a<br />

contam<strong>in</strong>ated soil and we can now more<br />

affirmatively say that sorption is one of <strong>the</strong><br />

mechanism by which those metals are<br />

reta<strong>in</strong>ed.

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