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25th International Meeting on Organic Geochemistry IMOG 2011

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P-139<br />

Role and nature of organic matter in the mobilisati<strong>on</strong> of arsenic<br />

in shallow reducing aquifers<br />

Wafa. M. Al Lawati 1 , Jiin-Shuh Jean 2 , Ming-Kuo Lee 3 , Thomas. R. Kulp 4 , Michael Berg 5 ,<br />

Elisabeth Eiche 6 , Athanasios Rizoulis 1 , J<strong>on</strong> Lloyd 1 , David Polya 1 , Bart. E. van D<strong>on</strong>gen 1<br />

1 School of Earth, Atmospheric and Envir<strong>on</strong>mental Sciences, The University of Manchester, Manchester,<br />

United Kingdom, 2 Department of Earth Sciences, Nati<strong>on</strong>al Cheng Kung University, Tainan, Taiwan (Province<br />

of China), 3 Department of Geology and Geography, Auburn University, Auburn, United States of America,<br />

4 U.S. Geological Survey, Water Resources Divisi<strong>on</strong>, Menlo Park, United States of America, 5 Eawag, Swiss<br />

Federal Institute of Aquatic Science and Technology, Dubendorf, Switzerland, 6 Institute of Mineralogy and<br />

<strong>Geochemistry</strong>, Universitat Karlsruhe, Karlsruhe, Germany (corresp<strong>on</strong>ding<br />

author:Wafa.AlLawati@postgrad.manchester.ac.uk)<br />

Over a hundred milli<strong>on</strong> people across the globe are<br />

chr<strong>on</strong>ically exposed to high c<strong>on</strong>centrati<strong>on</strong>s (>10 ppb)<br />

of the geogenic pois<strong>on</strong>, As, in shallow reducing<br />

groundwaters utilised as drinking water. The detailed<br />

mechanisms by which As is mobilized into the waters<br />

of these aquifers is still a matter of debate. However,<br />

it is generally believed that microbes play a key role<br />

through the reductive dissoluti<strong>on</strong> of As-bearing Fe(III)<br />

hydrated oxides and/or the reducti<strong>on</strong> of sorbed As(V).<br />

Electr<strong>on</strong> d<strong>on</strong>ors such as organic matter (OM) are<br />

required to drive this process, yet As release rates are<br />

often poorly correlated to total OM – this may in part<br />

reflect the varying bioavailabilities of different types of<br />

OM [1,2], the importance of other electr<strong>on</strong> d<strong>on</strong>ors or<br />

the c<strong>on</strong>founding influence of other, notably<br />

mineralogical or microbiological, processes. The role<br />

and nature of OM in As mobilisati<strong>on</strong> therefore remains<br />

rather unambiguous, perhaps in part due to the<br />

limited number of studies to date. An improvement in<br />

understanding of this link is required to better inform<br />

theories of l<strong>on</strong>g-term anthropogenically driven secular<br />

increases in groundwater As in these aquifers [3].<br />

In this project, we further investigate the correlati<strong>on</strong><br />

between As release from aquifers and the OM<br />

present. To date, all aquifer sediments analysed,<br />

including new sediments from well known As hotspots<br />

in Vietnam, West Bengal and Taiwan, revealed inputs<br />

from comparable multiple sources including<br />

c<strong>on</strong>tributi<strong>on</strong>s from naturally occurring petroleum<br />

seeping into the shallow aquifer sediments from<br />

deeper thermally mature source rocks. However,<br />

comparis<strong>on</strong> between core-sites with c<strong>on</strong>trasting As<br />

c<strong>on</strong>centrati<strong>on</strong>s (e.g. < 10 ppb and up to 600 ppb) in<br />

the groundwater indicated no noticeable differences in<br />

biomarker distributi<strong>on</strong> patterns, suggesting that As<br />

mobilisati<strong>on</strong> is not associated with a specific organic<br />

source at these sites.<br />

Microcosm experiments were used to determine the<br />

correlati<strong>on</strong> between different sources of OM and As<br />

mobilisati<strong>on</strong>. No correlati<strong>on</strong> between any OM source<br />

and the amounts of As(III) released could be<br />

observed (Fig.1). This suggests that As mobilisati<strong>on</strong><br />

might not be exclusively associated with a specific<br />

type of OM but could be different from site to site.<br />

Further more, microcosms using OM-lean aquifer<br />

sediments (TOC < 0.02%) showed that As can even<br />

be mobilised in the absence of substantial amounts of<br />

bioavailable organics [4] suggesting that other<br />

electr<strong>on</strong> d<strong>on</strong>ors need to be c<strong>on</strong>sidered as well.<br />

Combined, these studies show that the precise<br />

mechanism of As mobilisati<strong>on</strong> in a variety of<br />

sediments is still unknown but at best, a complex<br />

interplay between microbiology, mineralogy and<br />

geochemistry at the nano-scale should be expected.<br />

Fig.1. Correlati<strong>on</strong>s between (a)TOC, HMW (b)nalkanes,<br />

(c)n-alkanoic acids and (d)n-alkanols and the<br />

% As(III) released in microcosm experiments using<br />

sediments from a Taiwanese As hot spot aquifer.<br />

References:<br />

[1] Rowland, H.A.L. et al. J. Envir<strong>on</strong>. Qual. 38, 1598-<br />

1607 (2009)<br />

[2] van D<strong>on</strong>gen, B.E. et al. Appl. Geochem. 23, 3047-<br />

3058 (2008)<br />

[3] Polya, D.A. and Charlet, L. Nature Geosc. 2, 383-<br />

384 (2009)<br />

[4] Hery, M. et al. Geobiol. 8, 155-168 (2010)<br />

280

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