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Smithsonian at the Poles: Contributions to International Polar

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330 SMITHSONIAN AT THE POLES / KIEBER, TOOLE, AND KIENE<br />

our low SR results would suggest th<strong>at</strong> <strong>the</strong> Ross Sea samples<br />

contained a rel<strong>at</strong>ively high proportion of HMW DOM<br />

compared <strong>to</strong> wh<strong>at</strong> is observed in oligotrophic w<strong>at</strong>ers. The<br />

rel<strong>at</strong>ively higher molecular weight DOM and low SR in <strong>the</strong><br />

Ross Sea may be rel<strong>at</strong>ed <strong>to</strong> <strong>the</strong> lower pho<strong>to</strong>bleaching r<strong>at</strong>es<br />

th<strong>at</strong> are observed in <strong>the</strong> Antarctic, since pho<strong>to</strong>bleaching<br />

is <strong>the</strong> main mechanism <strong>to</strong> increase SR and remove HMW<br />

DOM (Helms et al., 2008).<br />

CDOM SOURCE<br />

The CDOM present in coastal areas near rivers and in<br />

estuaries in subtropical-temper<strong>at</strong>e and nor<strong>the</strong>rn boreal l<strong>at</strong>itudes<br />

is predominantly of terrestrial origin (e.g., Blough et<br />

al., 1993; Blough and Del Vecchio, 2002; Rochelle-Newall<br />

and Fisher, 2002a), but in <strong>the</strong> open ocean, as in <strong>the</strong> Antarctic,<br />

terrigenous CDOM is only a minor component of<br />

<strong>the</strong> <strong>to</strong>tal DOM pool (Opsahl and Benner, 1997; Nelson<br />

and Siegel, 2002).<br />

Phy<strong>to</strong>plank<strong>to</strong>n are expected <strong>to</strong> be <strong>the</strong> main source of<br />

CDOM in <strong>the</strong> open ocean, although <strong>the</strong>y are not thought<br />

<strong>to</strong> be directly responsible for CDOM production (Bricaud<br />

et al., 1981; Carder et al., 1989; Del Castillo et al.,<br />

2000; Nelson et al., 1998, 2004; Rochelle-Newall and<br />

Fisher 2002b; Ferenac, 2006). Our results are consistent<br />

with this fi nding (Figure 7). With no substantial grazing<br />

pressure (Rose and Caron, 2007, and as noted by our<br />

colleagues D. Caron and R. Gast during our cruise <strong>to</strong> <strong>the</strong><br />

Ross Sea in early November 2005) and very low bacterial<br />

activity (Ducklow et al., 2001; Del Valle et al., in press),<br />

it is not surprising th<strong>at</strong> CDOM a300 and a340 changed<br />

very little during <strong>the</strong> bloom. In fact, a300 did not apparently<br />

increase even during <strong>the</strong> l<strong>at</strong>ter stages of <strong>the</strong> Ross<br />

Sea Phaeocystis antarctica bloom when <strong>the</strong> microbial activity<br />

was higher (Kieber et al., 2007: fi g. 5). This fi nding<br />

is r<strong>at</strong>her remarkable since DOC is known <strong>to</strong> increase<br />

by �50% during <strong>the</strong> Phaeocystis antarctica bloom from<br />

�42 <strong>to</strong> �60 �M in <strong>the</strong> Ross Sea (Carlson et al., 1998).<br />

We also observed a DOC increase during our cruise from<br />

background levels (�43 �M <strong>at</strong> 130 m) <strong>to</strong> 53-�M DOC<br />

near <strong>the</strong> surface (based on one DOC profi le obtained <strong>at</strong><br />

our last st<strong>at</strong>ion, R14F, on 30 November 2005). This difference<br />

suggests th<strong>at</strong> <strong>the</strong> DOC increase was due <strong>to</strong> <strong>the</strong><br />

release of nonchromophoric m<strong>at</strong>erial by Phaeocystis antarctica.<br />

Field results support this supposition, showing<br />

th<strong>at</strong> <strong>the</strong> main DOC produced by Phaeocystis antarctica<br />

is carbohydr<strong>at</strong>es (M<strong>at</strong>hot et al., 2000).<br />

The temporal and sp<strong>at</strong>ial decoupling between DOC<br />

and CDOM cycles in <strong>the</strong> Ross Sea photic zone indic<strong>at</strong>e<br />

th<strong>at</strong> CDOM was produced l<strong>at</strong>er in <strong>the</strong> season or elsewhere<br />

in <strong>the</strong> w<strong>at</strong>er column. Since evidence from Kieber et al.<br />

(2007) suggests th<strong>at</strong> additional CDOM did not accumul<strong>at</strong>e<br />

l<strong>at</strong>er in <strong>the</strong> season, it was likely produced elsewhere.<br />

Previous studies have shown th<strong>at</strong> sea ice is a rich source of<br />

CDOM (Scully and Miller, 2000; Xie and Gosselin, 2005).<br />

It is <strong>the</strong>refore possible th<strong>at</strong> <strong>the</strong> pack ice along <strong>the</strong> edges<br />

of <strong>the</strong> Polynya was an important source of CDOM in <strong>the</strong><br />

photic zone, especially <strong>the</strong> bot<strong>to</strong>m of <strong>the</strong> ice, which was<br />

visibly light brown with ice algae. It is also possible th<strong>at</strong><br />

CDOM was produced below <strong>the</strong> photic zone and reached<br />

<strong>the</strong> photic layer via vertical mixing. Several lines of evidence<br />

indic<strong>at</strong>e th<strong>at</strong> Ross Sea Phaeocystis antarctica may<br />

be exported out of <strong>the</strong> photic zone (DiTullio et al., 2000;<br />

Rellinger et al., in press) and perhaps reach <strong>the</strong> ocean fl oor<br />

(�900 m) (DiTullio et al., 2000), as seen in <strong>the</strong> Arctic.<br />

Arctic algal blooms often occur in <strong>the</strong> early spring when<br />

<strong>the</strong> w<strong>at</strong>er is still <strong>to</strong>o cold for signifi cant zooplank<strong>to</strong>n grazing<br />

and bacterial growth (Overland and Stabeno, 2004).<br />

As a consequence, <strong>the</strong> algae sink out of <strong>the</strong> photic zone<br />

and settle <strong>to</strong> <strong>the</strong> ocean fl oor r<strong>at</strong>her than being consumed,<br />

<strong>the</strong>reby providing a DOM source for long-term CDOM<br />

production in dark bot<strong>to</strong>m w<strong>at</strong>ers. A similar phenomenon<br />

may occur in <strong>the</strong> Ross Sea. The possibility th<strong>at</strong> CDOM<br />

may be gener<strong>at</strong>ed in deep w<strong>at</strong>ers, with no pho<strong>to</strong>bleaching,<br />

might explain <strong>the</strong> high pho<strong>to</strong>sensitizing capacity of<br />

this CDOM for important reactions like DMS pho<strong>to</strong>lysis<br />

(Toole et al., 2004).<br />

Deepw<strong>at</strong>er production of CDOM in <strong>the</strong> Ross Sea<br />

would explain why our a325 values are comparable <strong>to</strong><br />

those observed by Nelson et al. (2007: fi gs. 8– 9) in deep<br />

w<strong>at</strong>er (�0.1– 0.2 m �1 ) and nearly <strong>the</strong> same as would be<br />

predicted on <strong>the</strong> basis of values in Antarctic Bot<strong>to</strong>m W<strong>at</strong>er<br />

and Antarctic Intermedi<strong>at</strong>e W<strong>at</strong>er (average of �0.13– 0.14<br />

m �1 ). Although specul<strong>at</strong>ive, it is possible th<strong>at</strong> CDOM<br />

is exported from <strong>the</strong> Sou<strong>the</strong>rn Ocean <strong>to</strong> deep w<strong>at</strong>ers <strong>at</strong><br />

temper<strong>at</strong>e- subtropical l<strong>at</strong>itudes, which would be consistent<br />

with CDOM as a tracer of oceanic circul<strong>at</strong>ion ( Nelson<br />

et al., 2007).<br />

CONCLUSIONS<br />

Despite <strong>the</strong> necessity of understanding <strong>the</strong> sp<strong>at</strong>ial<br />

and temporal distributions of CDOM for remote sensing,<br />

pho<strong>to</strong>chemical, and biogeochemical applic<strong>at</strong>ions, few<br />

measurements have been made in <strong>the</strong> Sou<strong>the</strong>rn Ocean.<br />

Our results indic<strong>at</strong>e th<strong>at</strong> Antarctic CDOM shows spectral<br />

properties th<strong>at</strong> are intermedi<strong>at</strong>e between wh<strong>at</strong> is observed

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