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Arsenic in Porewaters of the Unsaturated Zone of an Argentinean Watershed: Adsorption and Competition with Carbonate as Important Processes that Regulate its Concentration

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Abstract

The arsenic (As) concentration in porewaters of the unsaturated (vadose) zone of a watershed located in the Chaco-Pampean Plain of Argentina was investigated. A water displacement method using carbon tetrachloride was applied to the sediments in order to obtain the water samples, which could not be obtained by a simple high-speed centrifugation method. The CD-MUSIC surface complexation model was applied to calculate arsenate adsorption on sediments, arsenate concentration in porewaters in contact with the sediments and effects of carbonate. Ferrihydrite was considered to represent the active adsorbing material in the sediments. Therefore, proton adsorption (surface charge) data and arsenate adsorption isotherms obtained with a synthetic ferrihydrite were used to calibrate the CD-MUSIC model. Arsenate and carbonate concentrations in the studied porewaters were positively correlated. The model was able to predict As concentration within a factor of two in most samples. Carbonate affects As concentration by competing with arsenate species for adsorption sites on the mineral surface. As it occurs with groundwater samples of the saturated zone in many aquifers, this article shows for the first time that adsorption–desorption processes also seem to control As concentration in oxic porewaters of the unsaturated zone.

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Acknowledgments

This work was financed by CONICET, SECyT-Argentina and SECyT-UNS. Olga Pieroni is thanked for her help with infrared measurement. MA and FL are members of CONICET.

Author information

Authors and Affiliations

  1. Departamento de Química, INQUISUR-CONICET, Universidad Nacional del Sur, Av. Alem 1253, 8000, Bahía Blanca, Argentina

    Virginia Puccia & Marcelo Avena

  2. Departamento de Ciencias Agronómicas, CERZOS-CONICET, Universidad Nacional del Sur, Bahía Blanca, Argentina

    Fabiana Limbozzi

Authors
  1. Virginia Puccia
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  2. Fabiana Limbozzi
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  3. Marcelo Avena
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Corresponding author

Correspondence to Marcelo Avena.

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Supplementary material 1 (DOC 87 kb)

Appendix

Appendix

[Hexahidrita170910.MDI]

SCAN: 20.0/79.976/0.024/1(sec), Cu, I(max) = 41.0, 09/17/10 12:18p

PEAK: 27-pts/Parabolic filter, Threshold = 3.0, Cutoff = 0.1 %, BG = 3/1.0, Peak-top = Summit

Intensity = Counts, 2T(0) = 0.0(deg), Wavelength to computed-spacing = 1.54059A (Cu/K-alpha1)

#

2-Theta

d(Å)

Height

Height %

Phase ID

d(Å)

I %

(hkl)

2-Theta

Delta

Peak ID report

1

21.104

4.2063

34.5

85.9

      

2

25.737

3.4587

31.3

77.8

      

3

33.032

2.7096

39.3

97.8

      

4

33.776

2.6516

39.0

96.9

      

5

34.856

2.5719

40.2

100.0

      

6

35.912

2.4986

38.1

94.7

Fe5O7(OH)4H2…

2.5000

100.0

(110)

35.892

−0.020

7

36.752

2.4434

34.9

86.9

      

8

40.136

2.2449

21.8

54.2

      

9

40.474

2.2269

22.1

55.0

      

10

41.072

2.1958

22.3

55.5

Fe5O7(OH)4H2…

2.2100

80.0

(200)

40.797

−0.275

11

46.399

1.9554

19.6

48.7

Fe5O7(OH)4H2…

1.9600

80.0

(113)

46.284

−0.115

12

50.600

1.8025

17.0

42.3

      

13

51.776

1.7642

15.6

38.8

      

14

54.128

1.6930

18.2

45.2

      

15

55.353

1.6584

19.7

49.0

      

16

57.268

1.6074

20.0

49.8

      

17

59.048

1.5631

20.9

52.0

      

18

61.160

1.5141

22.8

56.6

Fe5O7(OH)4H2…

1.5100

70.0

(115)

61.345

0.185

19

61.832

1.4993

24.1

60.0

      

20

62.959

1.4751

25.9

64.5

Fe5O7(OH)4H2…

1.4800

80.0

(106)

62.728

−0.231

21

63.945

1.4547

23.7

58.9

      

22

65.168

1.4304

18.9

47.1

      

23

65.504

1.4238

16.3

40.6

      

24

67.088

1.3940

14.3

35.5

      

25

68.312

1.3720

12.0

29.9

      

26

69.200

1.3565

14.5

36.1

      

27

69.992

1.3431

11.5

28.5

      

28

71.576

1.3172

12.0

29.9

      

29

73.208

1.2918

11.0

27.4

      

30

73.734

1.2839

14.4

35.8

      

31

75.152

1.2632

10.6

26.3

      

32

76.544

1.2436

10.7

26.6

      
 

Line shifts of individual phases:

00-029-0712 > Ferrihydrite–Fe5O7(OH)4H2O < 2T(0) = 0.0, d/d(0) = 1.0>

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Puccia, V., Limbozzi, F. & Avena, M. Arsenic in Porewaters of the Unsaturated Zone of an Argentinean Watershed: Adsorption and Competition with Carbonate as Important Processes that Regulate its Concentration. Aquat Geochem 21, 513–534 (2015). https://doi.org/10.1007/s10498-015-9271-1

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