Właściwości chemiczne pofermentu i wpływ na dynamikę C i N w glebie Hiszpania 2012

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Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

Contents

lists

available

at

ScienceDirect

Agriculture,

Ecosystems

and

Environment

j o

u r

n

a l

h o m e p a g e :

w w w . e l s e v i e r . c o m / l o

c a t e / a g e e

Chemical

properties

of

anaerobic

digestates

affecting

C

and

N

dynamics

in

amended

soils

José

Antonio

Alburquerque

,

Carlos

de

la

Fuente,

María

Pilar

Bernal

Department

of

Soil

and

Water

Conservation

and

Organic

Waste

Management,

Centro

de

Edafología

y

Biología

Aplicada

del

Segura,

CSIC,

P.O.

Box

164,

30100

Murcia,

Spain

a

r

t

i

c

l

e

i

n

f

o

Article

history:

Received

11

October

2010

Received

in

revised

form

1

March

2011

Accepted

14

March

2011

Available online 8 April 2011

Keywords:
Anaerobic

digestion

Animal

slurries

Organic

matter

mineralisation

Biodegradability
Nitrogen

immobilisation

a

b

s

t

r

a

c

t

The

optimisation

of

digestate

recycling

as

fertilisers,

based

on

both

environmental

and

agricultural

crite-

ria,

requires

an

evaluation

of

the

effects

on

C

and

N

dynamics

in

soil.

In

the

present

paper,

six

digestates

from

several

anaerobic

co-digestion

experiments,

using

pig

or

cattle

slurry

as

the

main

substrate,

were

evaluated

in

short-term

incubations

in

soil.

Digestate

properties

such

as

dissolved

organic-C

(DOC),

biochemical

oxygen

demand

(BOD)

and

digestate

organic-C

mineralised

in

the

soil

during

the

first

7

days

represented

properly

the

digestate

biodegradability.

These,

together

with

their

ratios

with

respect

to

the

total

nitrogen

(TN)

concentration

in

the

digestate,

were

reliable

parameters

with

respect

to

defining

the

C

and

N

dynamics

in

the

soil

and

hence

the

N-fertiliser

potential

of

the

digested

materials.

Therefore,

highly

biodegradable

digested

materials,

represented

in

the

present

study

by

digestates

from

cattle

slurry–glycerine

mixtures

were

not

suitable

for

agricultural

use

as

they

caused

a

high

CO

2

–C

production

and

led

to

N-immobilisation

and/or

denitrification

after

their

application

to

soil.

Contrastingly,

for

less

biodegradable

digested

mate-

rials

(BOD

5

d

<

6.0

g

O

2

L

−1

fresh

weight,

DOC

<

5.5

g

L

−1

fresh

weight

and

DOC/TN

<

1.5),

less

CO

2

–C

was

evolved

and

ammonium

was

rapidly

nitrified

in

soil—being

an

available

N

source

for

crops.

© 2011 Elsevier B.V. All rights reserved.

1.

Introduction

Nowadays,

there

is

increasing

interest

in

Europe

in

the

imple-

mentation

of

anaerobic

digestion

in

productive

sectors

such

as

livestock

and

agroindustry,

where

vast

amounts

of

biodegradable

wastes

(animal

manure

and

slurries,

agricultural

and

food

industry

wastes,

etc.)

must

be

adequately

managed,

due

to

the

demand

for

renewable

energy.

Co-digestion

can

enhance

the

energy

produc-

tion

from

animal

manure

and

slurries,

as

co-digestible

materials

such

as

slaughterhouse

wastes,

glycerine

and

energy

crops

or

silage

can

increase

the

amount

of

biodegradable

organic

matter,

dilute

potential

toxic

compounds,

improve

the

nutrient

balance

and

favour

synergistic

effects

of

microorganisms,

thereby

raising

biogas

production

(

Álvarez

et

al.,

2010;

Holm-Nielsen

et

al.,

2009;

Pesta,

2007

).

However,

the

sustainability

of

biogas

production

also

depends

on

an

appropriate

end-use

of

the

digested

material

(digestate)—which

should

be

treated,

disposed

of

or

re-used

in

a

proper

way,

avoiding

any

negative

environmental

impact.

The

use

of

digestates

as

organic

fertilisers

in

agricultural

sys-

tems

seems

the

best

option

for

their

recycling

since

they

contain

considerable

amounts

of

residual

organic-C

and

plant

nutrients.

∗ Corresponding

author.

Tel.:

+34

968

396200;

fax:

+34

968

396213.

E-mail

addresses:

jalburquerque@cebas.csic.es

,

jalburquerquemendez@yahoo.es

(J.A.

Alburquerque).

Digestates

also

present

advantages

in

comparison

with

untreated

waste,

such

as

greater

microbial

stability

and

hygiene

and

a

higher

amount

of

N

present

as

ammonium

(

Al

Seadi,

2002;

Holm-Nielsen

et

al.,

2009

).

So,

land

spreading

of

digestate

can

lead

to

benefits

if

integrated

into

good

agricultural

practices,

by

controlling

the

N

application

rate

and

heavy

metal

load,

and

by

securing

digestate

hygiene

(

Al

Seadi,

2002;

Fuchs

et

al.,

2008;

Holm-Nielsen

et

al.,

2009

).

Nevertheless,

the

biodegradability

of

these

materials,

which

determines

organic

matter

(OM)

mineralisation

and

thus

nutrient

turnover

in

soil,

is

not

well

characterised.

The

complete

exhaustion

of

the

most

labile

organic

fraction

during

the

anaerobic

process,

in

order

to

obtain

digestates

with

a

high

stability

degree,

is

not

easy

to

achieve

at

the

industrial

level,

the

main

objective

of

the

anaerobic

co-digestion

being

the

pro-

duction

of

a

high

rate

of

biogas,

rich

in

methane.

This

process

is

conditioned

mainly

by

the

composition

of

the

raw

materials

and

the

development

of

the

anaerobic

process,

leading

in

some

cases

to

the

production

of

unstable

digested

materials

which

may

exert

negative

impacts

on

the

plant–soil

system

(

Abdullahi

et

al.,

2008;

Salminen

et

al.,

2001

).

In

this

context,

aerobic

respiration

indices

based

on

oxygen

uptake

are

considered

the

most

suitable

param-

eters

for

assessing

the

biodegradability

of

organic

amendments

(

Barrena

et

al.,

2006;

Copperband

et

al.,

2003

).

In

wastewaters

and

animal

slurries

the

biochemical

oxygen

demand

(BOD)

test

is

a

reliable

and

commonly

used

method

to

determine

readily

biodegradable

OM

(

APHA,

2005;

Brookman,

1997;

Williams,

1983

).

0167-8809/$

see

front

matter ©

2011 Elsevier B.V. All rights reserved.

doi:

10.1016/j.agee.2011.03.007

background image

16

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

Although

there

is

no

threshold

value

established

as

a

stability

and

quality

criterion

for

the

agricultural

use

of

waste

materials

based

on

BOD

data,

it

is

possible

with

some

caution

to

compare

it

with

the

limits

established

in

the

solid

waste

field

based

on

oxygen

uptake

rate

and/or

cumulative

oxygen

consumption

indices.

Dif-

ferent

methodologies

for

characterising

the

biological

stability

of

organic

materials

have

been

used,

such

as

SOUR

(specific

oxygen

uptake

rate

as

the

maximum

rate

of

oxygen

consumption),

OD

20

h

(cumulative

oxygen

demand

for

the

first

20

h

of

the

test;

Lasaridi

and

Stentiford,

1998

)

and

DRI

24

h

(dynamic

respiration

index,

which

is

the

average

oxygen

uptake

rate

at

24

h

of

maximum

biological

activity;

Adani

et

al.,

2004

).

Also,

little

information

is

available

about

the

degree

of

stabil-

ity

of

digestates

and

their

C

and

N

dynamics

in

amended

soils

(

Sánchez

et

al.,

2008;

Tambone

et

al.,

2009

).

The

information

gained

from

decomposition

studies

in

digestate-treated

soil

(OM

mineral-

isation,

N

mineralisation–immobilisation,

etc.)

may

be

useful

for

assessing

N

availability,

and

for

optimising

the

digestate

applica-

tion

rate

to

agricultural

soils.

Thus,

defining

the

main

digestate

properties

affecting

such

C

and

N

dynamics

in

soil

can

help

achieve

the

sustainable

use

of

digestates

as

fertilisers

in

soil–plant

system,

which

will

have

both

agricultural

and

environmental

benefits.

The

present

paper

evaluates

the

dynamics

of

C-mineralisation

and

inorganic-N

in

soil

amended

with

six

digestates

produced

from

representative

anaerobic

co-digestion

processes

in

Spain.

These

effects

were

investigated

in

aerobic

incubation

experiments,

an

appropriate

tool

to

evaluate

the

feasibility

of

the

use

of

organic

amendments

in

agricultural

soils

(

Qiu

et

al.,

2008;

Trinsoutrot

et

al.,

2000

).

Based

on

these

considerations,

the

main

objective

of

this

paper

is

to

identify

the

most

relevant

parameters

related

to

digestate

composition

for

assessing

the

maximum

benefits

of

these

materials

as

fertilisers.

2.

Materials

and

methods

2.1.

Incubation

experiments

in

soil

Six

digestates

were

collected

as

representative

samples

from

anaerobic

co-digestion

experiments

based

on

cattle

or

pig

slurry

mixed

with

agro-industrial

wastes

(co-digestion

mixtures):

cat-

tle

slurry

+

4%

glycerine

(CG4),

cattle

slurry

+

6%

glycerine

(CG6),

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage

(CMS),

cattle

slurry

+

5%

orange

peel

waste

(CO),

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treatment

plant

+

6.5%

biodiesel

wastewaters

(PSB),

and

pig

slurry

+

0.6%

pasteurised

slaughter-

house

waste

(PS).

Digestates

were

sampled

directly

after

anaerobic

digestion

(without

post-treatments),

stored

at

a

temperature

<4

C

and

processed

quickly

to

prevent

any

chemical

or

biological

alter-

ation.

Their

main

characteristics

and

the

specifications

of

anaerobic

co-digestion

performance

are

shown

in

Table

1

.

CMS

and

PSB

sam-

ples

came

from

industrial-scale

co-digestion

processes,

while

the

rest

of

the

samples

came

from

laboratory-scale

experiments,

run

mainly

to

optimise

the

production

of

biogas

through

anaerobic

co-digestion.

From

an

agricultural

soil

at

La

Alberca

(Murcia,

Spain),

soil

was

taken

from

the

top

20

cm,

air-dried

and

sieved

to

2

mm

before

use.

Its

main

characteristics

were:

24%

CaCO

3

,

pH

7.5

and

electrical

conductivity

(EC)

1.72

dS

m

−1

(both

saturated

paste,

with

water),

24.3

g

kg

−1

OM,

14.1

g

kg

−1

total

organic-C

(TOC)

and

1.85

g

kg

−1

total

nitrogen

(TN),

with

14.8%

clay,

22.3%

silt

and

62.9%

sand.

The

digested

materials

were

mixed

thoroughly

with

the

soil

in

a

proportion

of

4

g

of

fresh

digestate

per

100

g

of

dry

soil

(equiva-

lent

to

a

field

application

of

96

m

3

ha

−1

).

This

application

rate

was

selected

in

order

to

avoid

excessively

low

inputs

of

organic-C

to

the

soil

with

some

digestate

samples,

which

could

limit

the

accu-

racy

of

the

C-mineralisation

study,

while

keeping

the

N

addition

(140–380

kg

N

ha

−1

)

realistic

for

the

requirements

of

agricultural

crops

(

MARM,

2010

).

The

digestate-soil

mixtures

were

incubated

in

darkness

under

aerobic

conditions,

at

26

±

1

C

for

56

days.

Each

treatment

was

run

in

triplicate,

and

soil

without

digestate

was

used

as

the

control.

Soil

moisture

was

maintained

at

60%

of

the

water-holding

capac-

ity

during

incubation,

with

deionised

water.

To

follow

N

dynamics,

a

set

of

destructive

samples

of

the

digestate-soil

mixtures

were

placed

in

50-mL

tubes

without

drainage

holes;

then,

they

were

closed

with

parafilm

which

allows

gas

exchange

to

retain

soil

moisture

and

avoid

anaerobic

conditions

(

de

la

Fuente

et

al.,

2010

).

Periodically,

three

replicates

per

treatment

were

removed

from

the

incubator

(at

0,

2,

7,

14,

28,

42

and

56

days)

for

analysis

of

inorganic-

N

(NH

4

–N

and

NO

3

–N).

Since

the

digestate

samples

were

mixed

homogeneously

with

the

soil

at

the

time

of

application

and

there

was

no

airflow

at

the

soil

surface

during

incubation,

N-loss

through

volatilisation

was

negligible—as

demonstrated

by

de

la

Fuente

et

al.

(2010)

.

Net

organic-N

mineralisation

was

evaluated

by

the

accu-

Table

1

Main

characteristics

of

the

digestate

samples

(mean

value

±standard

deviation,

data

expressed

on

a

fresh

weight

basis).

Parameter

CG4

CG6

CMS

CO

PSB

PS

BOD

24

h

(g

L

−1

)

7.5

±

1.5

35.0

±

3.0

1.6

±

0.2

0.5

±

0.1

0.7

±

0.1

1.1

±

0.1

BOD

5

d

(g

L

−1

)

37.5

±

3.5

52.5

±

3.5

5.9

±

0.7

1.3

±

0.1

2.2

±

0.2

2.3

±

0.2

pH

5.64

±

0.01

7.35

±

0.03

7.50

±

0.01

7.86

±

0.01

8.20

±

0.02

7.95

±

0.03

EC

(dS

m

−1

)

14.5

±

0.3

11.7

±

0.2

25.7

±

0.8

8.7

±

0.2

30.3

±

0.9

21.1

±

0.1

DM

(g

L

−l

)

38.3

±

0.5

72.9

±

5.8

90.1

±

0.2

24.4

±

0.3

19.5

±

0.1

21.0

±

2.4

OM

(g

L

−l

)

26.4

±

0.1

56.4

±

0.9

66.4

±

0.2

18.0

±

0.1

8.5

±

0.1

11.4

±

0.2

TOC

(g

L

−l

)

17.8

±

0.1

42.8

±

0.1

33.7

±

0.5

9.4

±

0.1

5.9

±

0.1

5.8

±

0.1

DOC

(g

L

−l

)

10.6

±

0.3

27.6

±

0.9

5.4

±

0.1

1.2

±

0.1

2.4

±

0.1

1.2

±

0.1

TN

(g

L

−l

)

1.88

±

0.02

2.32

±

0.07

3.97

±

0.02

1.44

±

0.01

3.96

±

0.03

2.89

±

0.02

NH

4

–N

(g

L

−l

)

0.97

±

0.03

0.89

±

0.01

2.43

±

0.01

0.76

±

0.01

3.46

±

0.04

2.21

±

0.01

TOC/TN

ratio

9.5

±

0.1

18.5

±

0.5

8.5

±

0.1

6.6

±

0.1

1.5

±

0.1

2.0

±

0.1

Anaerobic

co-digestion

performance

Operation

Discont

Discont

Cont

Discont

Cont

Cont

Scale

L

L

I

L

I

L

Temperature

(

C)

35

35

38.5

38

37

35

HRT

(days)

40

40

25

28

21

20

BOD

24

h

and

BOD

5

d

:

24-h

and

5-d

biochemical

oxygen

demand,

respectively.

EC:

electrical

conductivity,

DM:

dry

matter,

OM:

total

organic

matter,

TOC:

total

organic-C,

DOC:

dissolved

organic-C

and

TN:

total

nitrogen.

Discont:

discontinuous

operation,

Cont:

continuous

operation,

L:

laboratory-scale

(2–6

L

digester),

I:

industrial-scale

(3000

m

3

digester)

and

HRT:

hydraulic

residence

time

CG4:

cattle

slurry

+

4%

glycerine,

CG6:

cattle

slurry

+

6%

glycerine,

CMS:

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage,

CO:

cattle

slurry

+

5%

orange

peel

waste,

PSB:

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treatment

plant

+

6.5%

biodiesel

wastewaters,

and

PS:

pig

slurry

+

0.6%

pasteurised

slaughterhouse

waste.

background image

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

17

mulation

of

inorganic-N

in

the

soil,

since

small

changes

in

organic

pools

are

usually

difficult

to

detect

and

gaseous

losses

were

consid-

ered

negligible

under

these

experimental

conditions

(

de

la

Fuente

et

al.,

2010

).

Net

N-mineralisation

(net

N-min)

in

each

treatment

(in

digestate

amended

and

non-amended

soil)

was

calculated

by

subtracting

the

soil

inorganic-N

content

at

day

0

from

the

amount

present

in

soil

after

56

days

of

incubation,

and

expressed

as

␮g

inorganic-N

g

−1

dry

soil.

The

N-mineralisation

from

the

digestates

(N

m

)

was

calculated

as:

N

m

(%)

=

100

×

[(inorg

N

56

d

inorg-N

0

d

)

soil

+

digestate

(inorg

-

N

56

d

inorg-N

0

d

)

soil

]/added

TN.while

nitrification

(nitrate

conver-

sion)

was

determined

as

the

percentage

of

the

added-N

from

the

digestate

that

had

been

converted

into

nitrate

after

56

days.

NC

(%)

=

100

×

[(NO

3

-N

56

d

NO

3

-N

0

d

)

soil

+digestate

(NO

3

-N

56

d

NO

3

-N

0

d

)

soil

]

/added

TN.

The

dynamics

of

C-mineralisation

was

determined

in

a

sepa-

rate

set

of

incubations

lasting

56

days,

using

500-mL,

hermetically

closed

glass

vessels.

A

small

vial

with

10

mL

of

0.1

M

NaOH

was

placed

inside

each

vessel

to

trap

the

CO

2

evolved

during

the

incuba-

tion,

and

empty

vessels

were

used

as

blanks.

These

were

opened

for

several

minutes

when

the

NaOH

vials

were

replaced,

to

maintain

adequate

aerobic

conditions.

The

CO

2

was

measured

periodically

(after

2,

4,

7,

14,

28,

42

and

56

days),

by

titration

of

the

NaOH

solution

with

0.1

M

HCl

in

an

excess

of

BaCl

2

to

precipitate

car-

bonates.

The

mineralisation

of

the

organic-C

from

the

digestates

(C

m

)

was

calculated

as

the

difference

between

the

CO

2

–C

evolved

in

the

amended

soils

and

that

produced

in

the

control

(unamended)

soil,

and

was

expressed

as

a

percentage

of

the

TOC

added

with

the

digestates.

The

data

for

the

C-mineralisation

from

the

diges-

tates

were

fitted

to

kinetic

functions

by

the

non-linear

least-square

technique

(Marquardt–Levenberg

algorithm),

using

the

Sigma-Plot

computer

programme

(SPSS

Inc.).

The

statistical

significance

of

the

curve-fitting,

residual

mean

square

(RMS)

and

F-values

were

also

calculated.

2.2.

Analytical

methods

The

following

parameters

were

determined

in

the

digestate

samples:

EC

and

pH

(directly,

after

sample

homogenisation);

mois-

ture

content,

after

drying

to

constant

weight

at

105

C;

the

volatile

solids,

which

reflect

the

OM

content,

by

loss

on

ignition

at

500

C

for

24

h.

The

TOC

and

TN

were

measured

by

automatic

microanalysis

(EuroVector

elemental

analyser,

Milan,

Italy)

of

freeze-dried

sam-

ples

and

the

dissolved

organic-C

(DOC)

using

an

automatic

analyser

for

liquid

samples

(TOC-V

CSN

Analyzer,

Shimadzu)

after

sample

filtration

(0.45

␮m

pore-diameter).

Ammonium

was

extracted

by

steam-distillation

of

fresh

samples

alkalised

with

MgO,

trapped

in

boric

acid

and

titrated

with

HCl.

The

5-day

biochemical

oxy-

gen

demand

(BOD

5

d

)

was

measured

with

a

respirometric

Oxitop

®

IS

6

(WTW,

Germany)

based

on

pressure

measurement,

which

is

automatically

transformed

into

mg

O

2

L

−1

.

In

the

Oxitop

®

system,

cumulative

oxygen

consumption

measurements

were

made

each

day

during

a

5-day

period.

The

soil

TOC

and

TN

were

determined

with

an

automatic

microanalyser.

The

CaCO

3

content

was

measured

with

a

Bernard

calcimeter.

As

incubation

progressed,

a

two-step

sequential

extrac-

tion

procedure

was

carried

out

for

inorganic-N

determination:

ultrapure

water

(1:5

w/v)

for

NO

3

-N

and

2

M

KCl

(1:5

w/v)

for

NH

4

–N.

The

NO

3

–N

was

measured

using

a

nitrate-ion

selective

electrode

(

USEPA,

2007

),

while

NH

4

–N

was

determined

by

a

colori-

metric

method

based

on

Berthelot’s

reaction

(

Sommer

et

al.,

1992

).

All

values

refer

to

soil

dried

at

105

C

for

24

h.

2.3.

Statistical

analyses

Basic

statistical

analyses

of

data,

correlation

coefficients

and

regression

equations

were

calculated

using

the

SPSS

18.0

pro-

gramme

for

Windows.

The

normal

distribution

of

the

data

was

checked

by

the

Shapiro–Wilk’s

test;

when

data

failed

this

test,

they

were

adjusted

to

a

normal

distribution

through

log-transformation.

3.

Results

and

discussion

3.1.

Digestate

microbial

stability

In

the

present

study,

all

digestate

samples

showed

an

initial

phase

of

maximum

respirometric

activity

within

the

first

24

h

of

testing.

As

a

result,

the

BOD

24

h

accounted

for

20,

67,

27,

39,

30

and

47%

of

the

BOD

5

d

for

CG4,

CG6,

CMS,

CO,

PSB

and

PS,

respectively

(

Table

1

).

This

indicated

the

presence

of

an

easily

biodegradable

organic

fraction

probably

including

decaying

microbial

biomass

from

the

digestate.

When

the

BOD

24

h

data

were

expressed

as

the

average

oxygen

uptake

rate

(mg

O

2

g

−1

OM

h

−1

),

the

following

results

were

obtained:

1.0,

1.2,

3.2,

3.9,

11.8

and

25.9

for

CMS,

CO,

PSB,

PS,

CG4

and

CG6,

respectively.

Our

results

exceed

the

limit

value

established

by

Adani

et

al.

(2004)

of

0.5

mg

O

2

g

−1

OM

h

−1

as

the

average

oxygen

uptake

over

a

24-h

period

of

the

most

intense

biological

activity

(DRI

24

h

)

for

highly

stable

materials

(mature

compost);

only

the

CMS

digestate

behaved

like

a

material

of

medium

stability

(limit

of

1.0

mg

O

2

g

−1

OM

h

−1

).

By

using

the

less

restrictive

classification

proposed

by

Ponsá

et

al.

(2010)

and

based

on

DRI

24

h

data,

the

CMS,

CO

and

PSB

showed

a

low

biodegradabil-

ity

(<2

mg

O

2

g

−1

DM

h

−1

):

0.8,

0.9

and

1.4

mg

O

2

g

−1

DM

h

−1

,

respectively.

The

PS

had

a

moderate

biodegradability

(2–5

mg

O

2

g

−1

DM

h

−1

)

of

2.1

mg

O

2

g

−1

DM

h

−1

and

the

CG

samples

showed

a

high

biodegradability

(>5

mg

O

2

g

−1

DM

h

−1

):

8.2

and

20.0

mg

O

2

g

−1

DM

h

−1

for

CG4

and

CG6,

respectively.

These

results

are

in

agreement

with

those

of

Orzi

et

al.

(2010)

and

Tambone

et

al.

(2009)

,

who

compared

stability

data

from

digested

and

non-digested

materials

based

on

cumulative

oxygen

demand

after

20

h

using

the

SOUR-test

(OD

20

h

).

They

noted

clear

decreases

in

the

OD

20

h

from

235

to

264

mg

O

2

g

−1

DM

in

the

non-digested

mixtures

to

30–95

mg

O

2

g

−1

DM

after

anaerobic

digestion,

the

latter

values

being

comparable

to

those

shown

by

stabilised

materials.

When

these

values

were

compared

to

the

BOD

24

h

data

obtained

in

this

work

(

Table

2

),

the

CG

samples

showed

values

of

oxygen

demand

similar

to

those

reported

for

non-digested

mixtures,

while

the

rest

of

the

digestates

had

lower

values,

within

the

range

proposed

for

stabilised

materials.

These

results

can

be

attributed

to

the

high

content

in

CG

digestates

of

OM

easily

degradable

by

microorganisms

(DOC,

Table

1

),

which

greatly

affected

the

degree

of

stability

of

the

digestate.

The

DOC

accounted

for

60,

64,

16,

13,

41

and

21%

of

the

TOC

for

CG4,

CG6,

CMS,

CO,

PSB

Table

2

Biochemical

oxygen

demand

(BOD)

values,

expressed

as

mg

O

2

g

−1

DM,

obtained

after

24

h

and

2,

3,

4

and

5

days

of

testing.

Digestate

BOD

24

h

BOD

2

d

BOD

3

d

BOD

4

d

BOD

5

d

CG4

195.8

456.9

587.4

718.0

979.1

CG6

479.9

514.2

651.3

685.6

719.8

CMS

18.0

33.3

45.8

55.5

66.0

CO

20.5

32.8

41.0

45.1

53.2

PSB

33.4

54.0

82.3

100.3

110.5

PS

50.0

73.8

85.7

97.6

107.1

CG4:

cattle

slurry

+

4%

glycerine,

CG6:

cattle

slurry

+

6%

glycerine,

CMS:

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage,

CO:

cattle

slurry

+

5%

orange

peel

waste,

PSB:

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treat-

ment

plant

+

6.5%

biodiesel

wastewaters,

and

PS:

pig

slurry

+

0.6%

pasteurised

slaughterhouse

waste.

background image

18

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

Incubation

time

(da

ys)

0

7

14

21

28

35

42

49

56

Cumulative CO

2

-C ev

olv

e

d (µg C

g

-1

)

0

250

500

750

1000

1250

1500

1750

2000

2250

Soil

Soil

+ CG6

Soil

+ P

S

Soil+ CO

Soil

+ CG4

Soil+ CMS

Soil

+ P

SB

Incuba

tio

n time (da

ys)

0

7

14

21

28

35

42

49

56

Cumulativ

e mi

neralised-C (% of

T

O

C)

0

10

20

30

40

50

60

70

80

90

100

110

CG6

PS

CO

CG4

CMS

PSB

(a)

(b)

Fig.

1.

Cumulative

CO

2

–C

evolved

from

soil

during

incubation

(mean

value

±standard

deviation;

where

absent,

bars

fall

within

symbols)

(a)

and

cumulative

mineralised-C

from

digestate

samples

added

to

soil:

symbols

are

experimental

data

(mean

value

±standard

deviation,

n

=

3)

and

lines

represent

the

curve-fitting

(b).

CG4:

cattle

slurry

+

4%

glycerine,

CG6:

cattle

slurry

+

6%

glycerine,

CMS:

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage,

CO:

cattle

slurry

+

5%

orange

peel

waste,

PSB:

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treatment

plant

+

6.5%

biodiesel

wastewaters,

and

PS:

pig

slurry

+

0.6%

pasteurised

slaughterhouse

waste.

and

PS,

respectively.

Therefore,

the

higher

such

percentage

was,

the

lower

microbial

stability

exhibited.

Although

a

significant

correlation

between

the

BOD

24

h

and

BOD

5

d

data

was

obtained

(P

<

0.01),

indicating

that

both

param-

eters

can

be

used

to

characterise

the

microbial

stability

of

the

digested

materials,

the

5-day

measurement

can

give

more

reliable

information

since

the

tested

materials

usually

maintained

a

high

respirometric

activity

beyond

the

first

24

h

of

testing.

The

cumula-

tive

data

followed

a

linear

tendency

over

time

in

all

samples

after

the

first

24

h

of

BOD

testing,

reaching

steady

rates

without

showing

clear

decreases

indicating

exhaustion

of

the

easily

biodegradable

OM

fraction

in

the

digestate

(

Table

2

).

The

BOD

5

d

values

varied

considerably

among

the

digestate

sam-

ples

(

Table

1

).

Considering

that

BOD

5

d

values

for

slurry

and

silage

effluents

can

be

in

the

range

of

10–80

g

L

−1

(

Brookman,

1997

)

and

BOD

reductions

of

around

70%

can

be

reached

after

anaerobic

diges-

tion

(

Smith

et

al.,

2007

),

the

values

found

in

the

present

study

can

be

considered

normal

for

digestates

with

the

exception

of

CG

samples

which

were

clearly

higher.

3.2.

Carbon

mineralisation

of

digestates

in

soil

The

addition

of

digestate

to

the

soil

caused

a

rapid

development

of

microbial

activity,

reflected

by

the

high

release

of

CO

2

–C

dur-

ing

the

first

days

of

incubation

(

Fig.

1

a).

This

was

related

to

the

presence

of

an

easily

degradable

organic

fraction

in

the

digestate

samples,

already

detected

in

the

BOD

test,

with

clear

differences

among

samples

(the

organic

load

and

its

microbial

stability).

Sub-

sequently,

the

CO

2

–C

production

rates

decreased

rapidly

during

the

first

two

weeks,

reaching

nearly

constant

values

at

the

end

of

the

incubation

(<10

␮g

C

g

−1

soil

and

day),

similar

to

those

obtained

in

the

unamended

soil

as

the

easily

mineralisable

OM

sources

were

exhausted.

The

amount

of

CO

2

–C

evolved

from

digestate-treated

soil

after

56

days

of

incubation

(mineralised-C)

increased

significantly

in

the

order

(mean

value):

639

<

653

<

730

<

948

<

1027

<

1679

␮g

C

g

−1

soil

for

soil

treated

with

CO,

PS,

PSB,

CMS,

CG4

and

CG6,

respec-

tively

(

Fig.

1

a).

The

TOC

mineralised

from

the

digestate

(C

m

)

also

reflected

the

different

biodegradability

of

the

OM

present

in

the

digestates

(

Fig.

1

b).

At

the

end

of

the

incubation,

CO

showed

the

lowest

percentage

of

C

m

(16%

of

TOC),

followed

by

CMS

and

PS

(30

and

34%,

respectively),

which

were

much

lower

than

for

the

CG4

and

CG6

digestates

(60

and

63%

of

TOC,

respectively).

Thus,

CMS,

PS

and,

especially,

CO

showed

a

more

recalcitrant

nature

than

the

digestates

from

the

glycerine

mixtures,

in

agreement

with

the

BOD

and

DOC

results.

Also,

more

than

100%

of

the

TOC

added

with

PSB

had

been

mineralised

after

56

days

of

incubation,

indicating

degra-

dation

of

native

soil

TOC

during

incubation

(priming

effect).

Bernal

and

Kirchmann

(1992)

found

that

the

addition

to

soil

of

anaerobi-

cally

treated

pig

manure

led

to

105%

mineralised-C

after

70

days,

related

to

the

presence

of

a

high

amount

of

easily

degradable

OM.

The

addition

to

soil

of

organic

materials

with

a

low

C/N

ratio,

such

as

PSB

(

Table

1

),

favours

high

C-mineralisation

rates

as

noted

by

Riffaldi

et

al.

(1996)

.

Our

results

agree

well

with

those

obtained

by

Bernal

and

Kirchmann

(1992)

and

Kirchmann

and

Lundvall

(1993)

for

soil

treated

with

fresh

and

aerobically

or

anaerobically

treated

ani-

mal

slurry

and

manures,

from

similar

incubation

experiments.

The

percentages

of

TOC

evolved

from

these

materials

after

70

days

of

incubation

ranged

from

23

to

105%,

depending

on

the

biodegradability

of

the

OM

and

the

presence

of

highly

available

organic

compounds

to

microorganisms

under

aerobic

condi-

tions.

Such

compounds

can

accumulate

in

digested

materials

when

degradation

of

complex

substrates

into

simple

and

water-

soluble

compounds

(hydrolysis)

and

their

subsequent

degradation

to

produce

methane

(methanogenesis)

are

not

completely

bal-

anced

during

anaerobic

digestion,

leading

to

the

production

of

unstable

materials

(

Drennan

and

DiStefano,

2010;

Pesta,

2007;

Schievano

et

al.,

2010

).

The

presence

of

such

intermediate

products

could

enhance

soil

microbial

activity

and

oxygen

demand

when

digestates

are

added

to

soil,

resulting

in

oxygen

depletion

and

N-immobilisation

(

Bernal

and

Kirchmann,

1992;

Kirchmann

and

Lundvall,

1993

).

The

dynamic

of

C-mineralisation

from

the

CG4

and

CG6

diges-

tates

in

the

soil

fitted

to

a

combined

first-

and

zero-order

kinetic

model

(

Table

3

),

which

suggests

the

presence

of

two

different

pools

of

OM

in

these

digestate

samples

of

different

degradability:

a

labile

pool,

which

was

quickly

decomposed

in

soil

during

an

initial,

intense

phase

of

microbial

respiration

(about

50%

of

the

added

TOC,

with

high

k

values),

and

another,

more

resistant

to

microbial

degra-

dation

and

hence

mineralised

at

a

low,

constant

rate

with

time.

In

the

CG

samples,

the

addition

of

glycerine

as

co-digestion

substrate

may

have

increased

the

labile

pool

of

TOC,

resulting

in

high

insta-

bility

with

regard

to

microbial

breakdown.

The

high

percentage

of

background image

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

19

Table

3

Parameters

of

the

kinetic

models

used

to

describe

C-mineralisation

of

the

digestates

(

±

standard

error)

and

the

statistical

significance

of

the

non-linear

curve-fitting

(RMS:

residual

mean

square,

F-value

of

the

ANOVA).

Combined

first-

and

zero-order

function:

C

m

=

C

R

(1

e

−k

R

t

)

+

At

Digestate

C

m

(%

of

TOC)

C

R

k

R

A

RMS

F

CG4

59.8

±

2.4

52.0

±

0.6

0.330

±

0.011

0.143

±

0.017

0.498

3015

*

CG6

63.0

±

0.8

46.5

±

0.5

0.362

±

0.013

0.305

±

0.015

0.436

3577

*

First

order

function:

C

m

=

C

0

(1

− e

−kt

)+B

Digestate

C

m

(%

of

TOC)

C

0

k

B

RMS

F

CMS

30.1

±

1.2

28.9

±

0.6

0.078

±

0.004

0.757

1447

*

CO

16.1

±

3.8

16.4

±

0.3

0.272

±

0.023

0.425

574

*

PSB

108

±

4.4

106

±

10

0.025

±

0.005

30.2

±

1.9

4.625

568

*

PS

34.2

±

4.8

35.5

±

1.5

0.289

±

0.049

8.119

133

*

CG4:

cattle

slurry

+

4%

glycerine,

CG6:

cattle

slurry

+

6%

glycerine,

CMS:

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage,

CO:

cattle

slurry

+

5%

orange

peel

waste,

PSB:

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treatment

plant

+

6.5%

biodiesel

wastewaters,

and

PS:

pig

slurry

+

0.6%

pasteurised

slaughterhouse

waste.

‘–’:

parameter

not

included

in

the

curve-fitting.

C

m

:

mineralised-C

(%

of

TOC)

after

56

days

of

incubation,

and

t:

incubation

time

(days).

In

the

combined

first-

and

zero-order

function:

C

R

,

rapid

potentially

mineralisable-C

(%

of

TOC);

k

R

,

rapid

rate

constant

(day

−1

);

A

(%

of

TOC

day

−1

),

slowly

mineralisable-C

rate

(equivalent

to

“C

S

×

k

S

”;

C

S

:

slowly

mineralisable-C

and

k

S

:

the

slow

rate

constant).

In

the

first

order:

C

0

,

potentially

mineralisable-C

(%

of

TOC)

and

k,

rate

constant

(day

−1

).

The

constant

term

(B)

indicates

the

initial

mineralisation

flux

detected

in

the

PSB

sample

(%

of

TOC).

*

Significant

at

probability

level

P

<

0.001.

TOC

from

CG

digestates

evolved

as

CO

2

–C

during

the

first

stage

of

incubation

is

typical

of

non-treated

animal

manure

and

slurries

(

Dendooven

et

al.,

1998;

Kirchmann

and

Lundvall,

1993

),

identify-

ing

them

as

unstable

materials.

The

C-mineralisation

of

the

CMS,

CO

and

PS

digestates

fitted

better

to

a

first-order

kinetic

model,

with

a

potentially

mineralisable-C

of

16.4–35.5%

(

Table

3

),

indicat-

ing

the

existence

in

these

digestates

of

a

predominant

proportion

of

OM

that

is

hardly

degradable

under

both

anaerobic

and

aerobic

conditions.

The

PSB

dynamic

of

C-mineralisation

needed

an

inde-

pendent

parameter

(B)

to

show

the

initial

flux

of

CO

2

–C

evolved

(30%

of

the

TOC

added),

suggesting

the

elevated

presence

of

an

OM

fraction

susceptible

to

rapid

mineralisation

(

Riffaldi

et

al.,

1996

).

Although

this

digestate

had

the

lowest

OM

concentration,

it

was

highly

unstable

according

to

the

BOD

5

d

test

(

Table

2

).

3.3.

Nitrogen

dynamics

in

digestate-treated

soil

As

shown

in

Fig.

2

,

all

the

digestates

supplied

NH

4

–N

to

the

soil.

During

the

first

week

of

incubation,

the

inorganic-N

concen-

tration

decreased

in

most

of

the

amended

soils,

due

mainly

to

a

reduction

in

NH

4

–N.

However,

during

the

initial

stage

of

incuba-

tion,

the

NO

3

–N

concentration

also

decreased

in

soil

treated

with

CG

samples

(

Fig.

2

).

The

initial

inorganic-N

had

decreased

after

7

days

and

accounted

for

8,

17,

22

and

60

␮g

N

g

−1

soil

for

soil

treated

with

CO,

PS,

PSB

and

CMS,

respectively,

while

the

decrease

was

even

faster

after

CG4

or

CG6

addition:

74

and

115

␮g

N

g

−1

soil,

respectively

(after

2

days,

Fig.

2

).

Such

initial

decreases

in

inorganic-

N

could

be

due

to

microbial

immobilisation,

since

a

concomitant

strong

C-mineralisation

was

found

in

all

treated

soils

(

Fig.

1

),

which

0

14

28

42

56

µg N g

-1

0

50

100

150

200

250

300

µg N g

-1

0

50

100

150

200

250

300

350

Soil+CG4

Soil+PS

B

0

14

28

42

56

Soil+PS

Soi

l

0

14

28

42

56

Soil+CG6

Soil+CMS

14

28

42

56

Soil+CO

Soil

Incubation time (days)

NO

3

-N

NH

4

-N

Inorganic-

N (NH

4

-N + NO

3

-N)

Fig.

2.

Evolution

of

inorganic-N

in

a

soil

treated

with

digestates

during

incubation

(mean

value

±standard

deviation;

where

absent,

bars

fall

within

symbols).

CG4:

cattle

slurry

+

4%

glycerine,

CG6:

cattle

slurry

+

6%

glycerine,

CMS:

cattle

slurry

+

4.3%

cattle

manure

+

11.6%

maize–oat

silage,

CO:

cattle

slurry

+

5%

orange

peel

waste,

PSB:

pig

slurry

+

1.0%

sludge

from

a

slaughterhouse

wastewater

treatment

plant

+

6.5%

biodiesel

wastewaters,

and

PS:

pig

slurry

+

0.6%

pasteurised

slaughterhouse

waste.

background image

20

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

also

indicates

high

activity

of

soil

microorganisms.

Kirchmann

and

Lundvall

(1993)

also

detected

an

initial

period

of

inorganic-

N

immobilisation,

of

up

to

200

␮g

N

g

−1

soil,

after

amending

soil

with

animal

slurries.

A

significant,

inverse

correlation

(r

=

−0.949

at

P

<

0.01)

between

the

net

N-mineralisation

and

mineralised-C

(microbial

respiration)

was

obtained

in

the

present

study

(data

at

56

days).

The

addition

to

soil

of

high

amounts

of

easily

degradable

OM

in

the

digestates

should

induce

a

quick

development

of

the

microbial

population,

immobilising

inorganic-N

for

tissue

synthesis

(

Kirchmann

and

Lundvall,

1993;

Qiu

et

al.,

2008

).

Although

preferential

microbial

immobilisation

of

NH

4

over

NO

3

is

generally

accepted,

microbial

assimilation

of

NO

3

as

a

N

source

can

occur

(

Drury

et

al.,

1991;

Myrold

and

Posavatz,

2007

).

But,

N-losses

by

denitrification

cannot

be

discounted

in

the

soils

treated

with

CG4

or

CG6,

which

sup-

plied

high

amounts

of

unstable

OM

to

the

soil

and

produced

intense

microbial

respiration

(CO

2

–C

production,

Fig.

1

a).

This

high

respi-

ration

during

the

first

days

of

incubation

could

have

reduced

the

oxygen

concentration

in

the

soil

system,

leading

to

N-losses

by

den-

itrification

(

Clemens

and

Huschka,

2001;

Dendooven

et

al.,

1998

).

After

the

immobilisation

period,

inorganic-N

increased,

indicating

re-mineralisation

and

nitrification.

The

net

N-mineralisation

after

56

days

of

incubation

was:

+7,

−2,

+18,

−15,

−39

and

−77

␮g

N

g

−1

soil,

for

soil

amended

with

CO,

PS,

PSB,

CMS,

CG4

and

CG6,

respectively

(

Fig.

2

).

These

values

were

equivalent

to

net

N-mineralisation

from

the

digestate

(N

m

)

of

−10,

−15,

−8,

−19,

−68

and

−96%

for

CO,

PS,

PSB,

CMS,

CG4

and

CG6,

respectively,

indicating

the

proportion

of

the

TN

from

the

digestate

samples

which

had

been

immobilised

in

the

soil.

The

PSB,

CMS,

CO

and

PS

samples

led

to

fast

NO

3

-N

produc-

tion

in

the

soil

after

an

initial

lag

phase

(related

to

adaptation

and/or

immobilisation

periods)

and,

concomitantly,

to

a

decrease

in

NH

4

–N,

due

to

nitrification

(

Fig.

2

).

The

percentage

of

TN

added

in

digestates

that

had

converted

into

nitrate

after

56

days

(nitrate

conversion:

NC),

was

44%,

50%,

59%

and

84%

for

CO,

CMS,

PS-MW

and

PSB,

respectively.

These

results

indicate

the

N-fertiliser

value

of

the

digestates,

as

nitrate

is

the

main

form

of

N

taken

up

by

plants

from

the

soil.

3.4.

Characteristics

of

the

digestate

defining

the

C

and

N

dynamics

in

soil

The

digestate

composition

and

stability

parameters

(BOD

5

d

and

C-mineralisation

in

soil)

were

highly

interrelated

(

Table

4

),

with

highly

significant

correlations

between

DOC

and

BOD

24

h

and

BOD

5

d

and

the

7-day

C-mineralisation

from

digestate

(C

7

d

).

The

latter

is

in

agreement

with

the

results

presented

by

Trinsoutrot

et

al.

(2000)

,

who

related

the

amount

of

TOC

mineralised

from

crop

residues

after

7

days

of

incubation

in

soil

mainly

to

the

water-

soluble

organic

fraction

added

with

the

amendments.

In

addition,

DOC,

BOD

24

h

,

BOD

5

d

and

C

7

d

correlated

significantly

with

key

parameters

which

define

C

and

N

turnover

in

soil

after

digestate

addition,

such

as

mineralised-C

and

both

N

m

and

NC;

however,

for

the

two

latter

parameters,

the

DOC/TN

and

C

7

d

/TN

ratios

showed

the

most

significant

correlations

(

Table

4

).

These

results

suggest

that

DOC,

BOD

5

d

and

C

7

d

,

which

represent

the

most

labile

organic

fraction

of

the

digested

materials,

together

with

their

ratios

with

respect

to

the

TN,

can

be

considered

reliable

criteria

to

assess

C

and

N

dynamics

in

soil

after

digestate

addition.

Although

the

com-

position

of

the

digestates

differed

quite

a

lot

in

the

present

study,

significant

regression

equations

were

obtained,

which

allows

cau-

tious

prediction

of

the

C-mineralisation

and

N-fertilising

potential

of

these

materials

in

soil,

especially

from

BOD

data

(in

mg

L

−1

),

avoiding

time

consuming

procedures

of

mineralisation

tests

in

soil:

Mineralised-C

(

␮g

C

g

−1

soil)

=

523.4

×

log

BOD

24

h

812.9;

r

2

=

0.903

(P

<

0.01).

N

m

(%)

=

−51.0

×

logBOD

24

h

+

135.4;

r

2

=

0.970

(P

<

0.001).

N

m

(%)

=

−51.6

×

logBOD

5

d

+

160.8;

r

2

=

0.915

(P

<

0.01).

NC

(%)

=

−69.8

×

logBOD

24

h

+

262.0;

r

2

=

0.892

(P

<

0.01).

NC

(%)

=

−87.7

×

log(DOC/TN)

+

46.5;

r

2

=

0.915

(P

<

0.01).

According

to

the

BOD,

DOC

and

DOC/TN

data,

digestates

from

cattle

slurry–glycerine

mixtures

(CG

samples)

constitute

a

group

clearly

different

from

the

rest

of

the

digestates

and

represent

highly

biodegradable

materials,

indicating

that

anaerobic

co-digestion

in

this

case

did

not

produce

stable

materials.

The

CG

digestates

were

characterised

by

the

highest

DOC

concentrations

(>10

g

L

−1

fresh

weight,

accounting

for

>59%

of

TOC),

DOC/TN

>

5,

BOD

5

d

>

37

g

L

−1

fresh

weight

and

the

lowest

percentages

of

TN

as

NH

4

–N

(52

and

38%

for

CG4

and

CG6,

respectively).

These

digestates

were

charac-

terised

by

an

intense

initial

period,

with

a

high

respiration

activity,

after

their

addition

to

soil—during

which

N

was

mainly

immo-

bilised.

This

limits

their

N-fertilising

potential

and

hence

their

possible

use

in

agriculture,

since

further

stabilisation

is

necessary

before

their

use.

In

contrast,

the

CO

and

PS

samples

showed

the

lowest

DOC

con-

centrations

(1.2

g

L

−1

each,

accounting

for

only

12

and

21%

of

TOC

for

CO

and

PS,

respectively)

and

a

high

stability

degree

according

to

the

BOD

5

d

test

(

Table

1

),

which

led

to

the

lowest

CO

2

–C

produc-

tion

in

the

soil

(

Fig.

1

a).

These

digestates

showed

DOC/TN

ratios

<1,

clearly

lower

than

those

of

the

CG

samples,

and

high

percent-

Table

4

Significant

correlations

found

among

parameters

related

to

digestate

composition,

and

C-

and

N-mineralisation

dynamics

(n

=

6).

Parameters

C

7

d

C

7

d

/TN

Mineralised-C

DOC

DOC/TN

BOD

24

h

BOD

5

d

Net

N-min

N

m

NC

C

7

d

1

C

7

d

/TN

0.932

**

1

Mineralised-C

0.948

**

0.889

*

1

DOC

0.995

***

0.914

*

0.943

**

1

DOC/TN

0.957

**

0.991

***

0.912

*

0.951

**

1

BOD

24

h

0.969

**

0.945

**

0.950

**

0.943

**

0.944

**

1

BOD

5

d

0.975

**

0.944

**

0.880

*

0.959

**

0.953

**

0.966

**

1

Net

N-min

0.937

**

−0.943

**

−0.949

**

0.915

*

−0.940

**

0.986

***

0.936

*

1

N

m

0.946

**

−0.977

**

−0.918

*

0.914

*

−0.961

**

0.985

***

0.956

**

0.969

**

1

NC

0.884

*

−0.981

**

−0.878

*

0.855

*

−0.956

**

0.944

**

0.908

*

0.962

**

0.975

**

1

C

7

d

:

7-day

C-mineralisation

from

digestate

(mg

L

−1

fresh

digestate

weight),

mineralised-C:

the

amount

of

CO

2

–C

evolved

from

digestate-treated

soil

after

56

days

of

incubation

(

␮g

C

g

−1

dry

soil),

DOC:

dissolved

organic

carbon

(mg

L

−1

fresh

digestate

weight),

BOD

24

h

:

24-h

biochemical

oxygen

demand

(mg

O

2

L

−1

fresh

digestate

weight),

BOD

5

d

:

5-day

biochemical

oxygen

demand

(mg

O

2

L

−1

fresh

digestate

weight),

TN:

total

nitrogen

(mg

L

−1

fresh

digestate

weight),

net

N-min:

the

net

N-mineralisation

in

the

amended

soils

after

56

days

of

incubation

(

␮g

N

g

−1

dry

soil),

N

m

:

nitrogen

mineralisation

after

56

days

of

incubation

(%

of

TN

from

digestate)

and

NC:

nitrate

conversion

as

a

percentage

of

added

TN

that

had

been

converted

into

nitrate

from

digestate

after

56

days

of

incubation

in

soil

(%

of

TN

from

digestate).

*

Significant

at

probability

level

P

<

0.05.

**

Significant

at

probability

level

P

<

0.01.

***

Significant

at

probability

level

P

<

0.001.

background image

J.A.

Alburquerque

et

al.

/

Agriculture,

Ecosystems

and

Environment

160 (2012) 15–

22

21

ages

of

TN

as

NH

4

–N

(>50%),

which

improve

the

soil

N

balance

(44

and

59%

of

added

TN

for

CO

and

PS,

respectively,

was

converted

into

nitrate

with

low

N-immobilisation),

representing

an

available

N

source

for

plants.

Based

on

the

characteristics

of

such

diges-

tates,

DOC

<

1.5

g

L

−1

(<25%

of

TOC),

BOD

5

d

<

2.5

g

L

−1

,

C

m

<

35%

and

DOC/TN

<

1

can

be

used

to

define

a

high

quality

digestate

appropri-

ate

for

use

as

a

fertiliser.

The

characteristics

of

the

PSB

and

CMS

digestates

showed

a

higher

similarity

to

CO

and

PS

(stable

digested

materials)

than

to

the

CG

samples

(highly

unstable).

The

PSB

sample

showed

a

relatively

low

BOD

5

d

value,

in

accordance

with

its

low

TOC

content

(5.9

g

L

−1

fresh

weight);

however,

it

was

highly

labile

(41%

of

TOC

as

DOC)

and

had

the

highest

percentage

of

TN

as

NH

4

–N

(87%).

This,

combined

with

its

low

DOC/TN

ratio

(0.6),

could

explain

the

observed

priming

effect

on

C-mineralisation

when

PSB

was

added

to

soil;

however,

negative

effects

on

the

soil

N

dynamic

were

not

seen.

Finally,

the

CMS

sample

showed

an

acceptable

degree

of

stability

considering

its

much

higher

organic

load

relative

to

CO

and

PS

(33.7

g

TOC

L

−1

fresh

weight,

only

16%

as

DOC);

however,

it

showed

a

relatively

high

CO

2

–C

production

at

the

end

of

the

incubation,

similar

to

that

resulting

from

CG4

addition

to

soil.

The

CMS

sample

had

a

DOC/TN

ratio

of

1.4

with

61%

of

its

TN

as

NH

4

–N,

leading

to

a

percentage

conversion

of

TN

into

nitrate

of

about

50%.

Therefore,

digestate

properties

such

as

DOC

<

5.5

g

L

−1

(<45%

of

TOC),

BOD

5

d

<

6.0

g

L

−1

and

DOC/TN

<

1.5

can

be

established

as

less

restrictive

quality

cri-

teria

compared

with

those

defined

previously

for

stable

digested

materials.

The

suitable

land

application

of

these

digestates

may

require

some

precautions

depending

on

the

land

use

and

manage-

ment.

A

curing

or

maturation

period

may

be

necessary

in

order

to

increase

digestate

stability

or

to

allow

digestates

to

stabilise

in

soil

before

sowing.

4.

Conclusions

Our

results

demonstrate

that

digestate

composition

and

stabil-

ity

degree

can

vary

greatly

depending

on

the

raw

materials

used

for

co-digestion

and

process

characteristics.

Therefore,

the

anaerobic

co-digestion,

including

the

selection

of

co-substrates,

must

guaran-

tee

that

a

certain

degree

of

OM

stability

of

the

digested

material

is

reached

in

order

to

avoid

detrimental

effects

on

the

plant–soil

sys-

tem.

These

are

mainly

conditioned

by

the

biodegradability

of

the

digested

material

obtained,

which

determines

whether

the

diges-

tate

can

be

used

directly

(highly

stable),

after

a

curing/maturation

period

(moderately

stable)

or

after

aerobic

post-treatments

to

achieve

stabilisation

(highly

unstable).

In

this

context,

the

biochemical

oxygen

demand

(BOD

24

h

or

BOD

5

d

),

dissolved

organic-C

(DOC)

together

with

the

DOC/TN

can

be

considered

the

most

reliable

parameters

to

describe

digestate

biodegradability

and

hence

provide

a

quick

estimation

of

the

main

effects

on

C

and

N

turnover

produced

by

digestate

addition

to

soil.

Highly

unstable

and

easily

biodegradable

materials,

represented

in

our

study

by

digestate

from

cattle

slurry–glycerine

mixtures

(BOD

5

d

>

37

g

O

2

L

−1

fresh

weight,

DOC

>

10

g

L

−1

fresh

weight

and

DOC/TN

>

5),

gave

rise

to

a

strong

CO

2

–C

production

and

a

loss

of

N-fertiliser

value

through

N-immobilisation

in

soil.

These

materials

need

more

extensive

biological

treatment,

such

as

aerobic

stabilisa-

tion,

in

order

to

reduce

potential

detrimental

impacts.

In

contrast,

ammonium

in

the

more

stable

digested

materials

was

oxidised

by

nitrifiers

in

the

very

short

term.

These

less

biodegradable

digested

materials

(BOD

5

d

<

6.0

g

O

2

L

−1

fresh

weight,

DOC

<

5.5

g

L

−1

fresh

weight

and

DOC/TN

<

1.5)

showed

a

scaled

degree

of

stability,

from

highly

stabilised

materials,

which

can

be

used

directly

in

soils

as

fertilisers,

to

moderately

stabilised

materials,

which

may

need

a

curing/maturation

period

or

stabilisation

in

the

soil

before

sowing.

Acknowledgements

This

research

was

funded

by

the

“Ministerio

de

Ciencia

e

Inno-

vación,

Plan

Nacional

I+D+I

2008-2011”

and

FEDER

Funds

“Fondo

Europeo

de

Desarrollo

Regional,

una

manera

de

hacer

Europa”,

in

the

framework

of

the

project

“singular

estratégico

PROBIOGAS”:

sub-project

3

Agronomical

evaluation

of

digestates;

and

subproject

8,

Co-digestion

of

citric

and

farm

residues

(Refs.:

PSS-120000-2008-58;

PSS-120000-2008-62).

The

authors

thank

all

the

research

groups

involved

in

the

project

PROBIOGAS

(

http://www.probiogas.es

),

especially

the

GIRO

and

AINIA

Technological

Centres,

the

Univer-

sity

of

Oviedo,

San

Ramón

Group

and

Treatments

of

Juneda

Society

(Tracjusa)

for

providing

the

digested

materials

used

in

this

work.

The

authors

wish

to

thank

Dr.

D.J.

Walker

for

the

English

revision.

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