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Abstract: Marine chromophoric dissolved organic matter (CDOM) imparts highly variable optical signatures in surface waters over short spatial and temporal scales, but the cause of that variability is poorly understood. A major fraction of dissolved organic matter in seawater is colloidal in size and can cycle quite rapidly, potentially contributing to the observed variability in CDOM. The relationship between marine colloids and CDOM optical variability was examined using flow field-flow fractionation (FlFFF) to partition the colloidal organic phase into a continuum of molecular sizes for optical characterization by excitation emission matrix spectroscopy (EEMS). Colloidal organic matter in surface seawater of the Damariscotta River estuary showed 2 major peaks in apparent abundance, spanning at ∼1–5 kDa and ∼15–150 kDa in size, respectively. The relative magnitude of these peaks changed systematically with the phase of phytoplankton blooms during 2003 and 2004, implying a relationship between colloid size distribution and bloom dynamics. Of the two colloidal sizes, the 1–5 kDa fraction was far more variable in apparent abundance than the larger colloidal matter. EEMS results reveal a compositional partitioning of protein-like and humic-like fluorescence between size fractions. Protein-like materials occurred primarily in the smallest colloid size fraction while humic-type materials resided mainly in the larger colloidal phase. These findings suggest that the fluorescence signature of bulk dissolved organic matter results from a collage of chromophores having optical characteristics that differ according to size of the molecular constituents. The colloidal-sized fluorescence characteristics of marine derived CDOM were contrasted with bulk CDOM to provide fundamental information on the distribution and forms of CDOM in Maine coastal waters. The findings here indicate that colloidal processes will have significant effects on the character and variability in the optical signature of surface seawaters. [Copyright &y& Elsevier]

Recent work demonstrates that the micronutrient iron may strongly influence the magnitude and character of algal production in nearshore waters due in part to the higher but variable iron requirements of neritic phytoplankton. However, ascertaining the direct effects of iron nutrition in coastal waters has been forestalled by our inability to experimentally regulate ambient iron availability independent of other factors. We present here results from size-fractionated iron uptake experiments showing that increasing concentrations of the siderophore Desferriferrioxime B (DFB) progressively decreases the biological availability of iron tracer added to natural seawater. These findings extend those of previous studies showing that high concentrations of DFB induce iron limitation of phytoplankton in coastal waters. Similar tests with two siderophores (P1P and PCC7002 No. 1) isolated from marine prokaryotes showed little or no impact on short-term iron uptake in these natural population cultures. DFB additions did not influence the short-term uptake of carbon indicating that its inhibitory effect was not due to general toxicity to the cells. Uptake rates of iron tracer in the large (>5.0 μm) phytoplankton fraction decreased linearly with increasing DFB concentrations, becoming undetectable at ≥3 nM DFB, or ∼5× over ambient dissolved iron concentrations. The decrease in iron availability with DFB addition was equally dramatic for the ultraplankton (0.2–5.0 μm), but in this case low-level tracer uptake (∼10%) persisted even at high DFB concentrations (3–500 nM). Our experimental findings are combined with a preliminary kinetic model to suggest that iron equilibration among the natural ligand classes (L1, L2) and DFB may require an adjunctive (or associative) ligand substitution mechanism to explain the very rapid effect that DFB exerts on iron uptake when added to seawater. Even so, several hours to days likely are needed for the equilibration of added iron among DFB and natural ligands when low-level (e.g., 0.5 nM) DFB concentrations are employed. Model results provide indirect support to earlier suggestions that large eukaryotic phytoplankton extract iron from the weaker class of natural ligands (Fe(III)L2). The combination of iron enrichment and DFB amendments provides a practical means for studying how iron influences algal production, carbon cycling and phytoplankton species composition in nearshore waters. [Copyright &y& Elsevier]

The chemical speciation of iron in seawater is controlled by complexation with organic ligands, the character of which likely regulates which phytoplankton groups can readily access this resource. Evidence from the IronEx II mesoscale iron enrichment experiment provides some insight to this regulation. Dissolved iron (<0.4 μm) in the enriched surface waters during IronEx II was partitioned into colloidal (>1 kDa–0.4 μm) and soluble (<1 kDa) size fractions using cross flow filtration to better delineate iron dynamics with respect to phytoplankton growth. While dissolved concentrations in the patch increased by two orders of magnitude to ∼2 nM Fe, soluble concentrations only roughly doubled to ∼35 pM Fe, and this change occurred only during the first few days of the experiment. The subsequent decrease in soluble iron to ambient levels coincided with a dramatic increase in chlorophyll a, indicating that biological demand was responsible for the disappearance of soluble iron. This decrease also coincided with preferential drawdown of silicic acid over nitrate in the patch, indicating that diatoms were experiencing iron stress even as the bloom developed. Even so, calculations of the diffusional flux and iron uptake kinetics at the cellular level reveal that the concentrations of soluble iron during the later stages of the bloom were above that required to support continued rapid growth of the long, narrow pennate diatoms. This observation implies that the bulk of the organically bound soluble and colloidal iron was unavailable to meet the diatom growth requirements, and further that the measured increase in concentrations of strong Fe(III) complexing ligands impaired iron acquisition by diatoms. These findings indicate that excess macronutrients in HNLC waters might not be fully converted into diatom biomass even with repeated infusions of iron. [Copyright &y& Elsevier]

Discusses research which invoked polymer gel theory to explain the behavior of marine colloids. Role of marine colloids in ocean life; Research by Chin et al in this issue; Importance of research; What colloids are; Colloids affecting the behavior of carbon and metals in estuaries; Results of tracer studies; Factors controlling colloid residence times in sea water; Nonspecific surface interactions in colloid cycling; Missing biological aspect in study.