Organic

Matter Turnov

er

Root Exudat

es

Fall or harvest

Aphorizon

EBhorizon

Bthorizon

pH 5.68 5.75 4.27

------------------ cm ----------------Depth 0-30 30-70 70-130

Particle sizes: ------------------g kg-1 -------------< 2 m 68 126 1482-20 m 127 114 9720-200 m 805 760 755

Nutrients: --------------- g kg-1 ----------------Total C 30.10 1.41 0.76Total N 2.01 0.09 0.05Total P 0.80 0.41 0.23

Aluminium andiron fractions

------------- mmole kg-1 -----------

Alcbd

† 133 115 71Al

ox

‡ 111 81 62Fe

cbd80 77 83

Feox

62 22 32†: cbd acronym for citrate-bicarbonate-dithionite.‡: ox acronym for oxalate.

Table 1. Soil characteristics of Burrehøjvej field soil.

Sorption of Dissolved Organic C and P to Agricultural Top- and Subsoil

INTRODUCTIONDissolved organic matter (DOM) mobility is a major factor affecting the export of nutrients from soils to surface waters. E.g. nitrogen (N) and phosphorus (P) in DOM can make up a significant fraction of total dissolved concentrations of N and P in soil pore water.

DOM concentrations are observed to decrease considerably with depth in forest soil profiles which is presumed to be caused by sorption of DOM to the soil. Several laboratory adsorption experiments demonstrate that sorption of DOM increases with decreasing pH; however, only limited data are available for agricultural soils.

The aim of the present study was to investigate the sorption of DOM to agricultural top- and subsoil material at two pH levels, and describing the sorption behavior with the approach of the initial mass isotherm.

Sorption experiments

Six series of sorption experiments were conducted with two pH levels (pH 5 and 7) for each of the Ap, EB, and Bt horizons. A sorption series comprised six bottles (250 ml Blue Cap) with a soil:solution ratio of 1:10, and with initial concentrations of DOM of 0, 0.4, 0.8, 1.7, 3.4 and 4.7 mmol C L-1, respectively. A 10 mM NaCl solution was used as background electrolyte throughout. All sorption experiments were carried out in duplicate.

The amount of DOC, dissolved inorganic phosphorus (DIP), and total dissolved phosphorus (TDP) in solution was measured after 1, 120, 1440 and 4320 minutes of reaction by withdrawing 10 ml of suspension, centrifugation (4000 g) and filtering through 0.45 mm Millipore filters.

Figure 1. Effect of pH and time of reaction on DOC isotherms for the

Ap and Bt horizons. Left: pH 7, right: pH 5. Each data point represents the average of two replicates.

Ap horizon pH 5

-25

-15

-5

5

15

25

35

45

0 2 4 6

Ap horizon pH 7

-25

-15

-5

5

15

25

35

45

0 2 4 6

Sor

bed

DO

C [m

mol

e / k

g so

il] 1 minute

2 hours

24 hours72 hours

-25

-15

-5

5

15

25

35

45

0 2 4 6

Bt horizon pH 5

-25

-15

-5

5

15

25

35

45

0 2 4 6

DOC concentration [mmole / L]

Bt horizon pH 7

-25

-15

-5

5

15

25

35

45

0 2 4 6

DOC concentration [mmole / L]

Sorb

ed D

OC

[mm

ole

/ kg

soil]

Figure 2. Effect of pH and time of reaction on DOP isotherms for the

Ap and Bt horizons. Left: pH 7, right: pH 5. Each data point represents the average of two replicates.

M.Sc. Ph.D. stud. Birgitte Gjettermann1,2,Ph.D., Merete Styczen1,Assoc. Prof., Søren Hansen2, Prof., Dr. agro, Ph.D., Ole K. Borggaard2,Prof., Ph.D., Hans Chr. B. Hansen2.

1: DHI Water and Environment2: The Royal Veterinary and Agricultural University

Ap horizon pH 5

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

Ap horizon pH 7

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

Sor

bed

DO

P [m

mol

e / k

g so

il]

1 minute2 hours

24 hours72 hours

EB horizon pH 5

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

Bt horizon pH 5

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

DOP concentration [mmole / L]

Bt horizon pH 7

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0 0.01 0.02 0.03 0.04

DOP concentration [mmole / L]

Sor

bed

DO

P [m

mol

e / k

g so

il]

RESULTS

Dissolved

Organic Matter

MATERIAL AND METHODSThe soil used is located at the Burrehøjvej field at Research Center Foulum in the central part of Jutland. In the previous 9 years (1994-2002) the soil has been covered by grass-clover and grassed by dairy cattle. The soil is classified as a Humic Hapludult. Bulk soil material from the genetic Ap, EB, and Bt horizons were collected from appropriate depths.

A stock solution of DOM to be used in the sorption experiments was prepared by extraction of the A-horizon material using a chelating, sodium saturated resin, Chelex® 100 Resin (from Bio-Rad).

Figure 3. Relation between dissolved molar DOC / DOP – ratios as

functions of dissolved DOC concentration for Ap-, EB-, and Bt-horizons at pH 7 (left) and pH 5 (right). Dots correspond to averages over the four times of reaction for every sample.

Information of DaisyGIS and DAISY can be found at the following web sites:

DaisyGIS: http://www.dhisoftware.com/daisygis/DAISY: http://www.dina.kvl.dk/~daisy/

Figure 4. Initial mass DOP isotherm for the Ap, EB and Bt horizons after 24 hours of reaction. Left: pH 7, right: pH5. Each data point represents the average of two replicates.

Initial mass isotherm:

RE: Amount of substance sorbed or released .

Xi: Initial amount of substance added to the soil water

system.m: Affinity measure related to the distribution coefficient,

Kd.

b: The amount of substance released or removed from system.

bmXRE i

Ap horizon pH 5

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 0.1 0.2 0.3 0.4

EB horizon pH 5

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 0.1 0.2 0.3 0.4

EB horizon pH 7

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 0.1 0.2 0.3 0.4S

orb

ed D

OP

[m

mole

/ k

g s

oil]

Ap horizon pH 7

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 0.1 0.2 0.3 0.4

Sorb

ed D

OP

[m

mole

/ k

g s

oil]

Bt horizon pH 5

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 0.1 0.2 0.3 0.4

Initial DOP concentration [mmole/kg]

Bt horizon pH 7

-0.25-0.2

-0.15-0.1

-0.050

0.05

0.10.15

0.20.25

0 0.1 0.2 0.3 0.4

Initial DOP concentration [mmole/kg]

Sorb

ed D

OP

[m

mole

/ k

g s

oil]

CONCLUSION AND PERSPECTIVE

In general

•Sorption isotherms of DOC and DOP had convex shapes •Sorption increased with time of reaction. •Sorption processes achieving equilibrium within a couple of days.

Estimating the mobility of DOC and DOP in agricultural soil, the initial mass isotherm could be a future tool in modeling sorption of DOC and DOP. However, factors as pH are important factors concerning mobility of DOC and DOP that should be taken into account.

pH exerts a strong control on the mobility of DOC

DOC sorption is much lower at pH 7 than at pH 5. In fact, at pH 7 DOC is de-sorbed from the Ap horizon no matter how much DOC is applied to the solution. At pH 5 desorption of DOC occurred only when zero or very small amounts of DOC is applied.

Equal or preferential DOC and DOP sorption?

DOP is sorbed as anions in soil, however, whether the negatively charged P ester group or the carboxylic acids determine this behavior has not been determined. Analysis of relationship between dissolved molar DOC:DOP ratios as functions of dissolved DOC concentration for the two pH values, showed increasing solute DOC:DOP ratios at increased DOC (or DOP). This indicates that at high concentration levels DOP is sorbed preferentially in relation to DOC, which may indicate that the negatively charged P ester group is the reactive site.

Initial mass isotherm

Initial mass isotherm could describe DOC and DOP sorption to agricultural soil with correlation coefficient in the range of 0.81-0.99. In general, the parameter m is higher at pH 5 than at pH 7 for both DOC and DOP, except for the EB horizon. For DOC the affinity are higher for the subsoil than for the topsoil

pH 7

0

50

100

150

200

250

300

0 2 4 6

DOC concentration [mmole / L]

pH 5

0

50

100

150

200

250

300

0 2 4 6DOC concentration [mmole / L]

Dis

solv

ed m

olar

DO

C /

DO

P-

ratio

[ ]

A-horizon

E-horizon

B-horizon

ONGOING ACTIVITIES

DHI Water & Environment • Agern Allé 11 • DK-2970 Hørsholm • Tel: +45 4516 9200 • dhi@dhi.dk

The Royal Veterinary and Agricultural University • Bülowsvej 17 • DK-1870 Frederiksberg C

DOC sorption dynamic

•pH exerts a strong control on the mobility of DOC•Much higher sorption of DOC at pH 5 than at pH 7•Extensive desorption at pH 7 especially for the topsoil

DOP sorption dynamic

Similar sorption patterns were observed for DOP, but they were not as pronounced as for DOC and pH exerted a minor control of the mobility of DOP in subsoil horizons.

Archived at http://orgprints.org/5391