The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Influence of pH on the fluorescence of dissolved organic matter

During two surveys (June, 1980 and March, 1981) the influence of the pH on the fluorescence (mFl) was studied in the Ems-Dollart estuary. In the natural pH range (7–9) the fluorescence (mFl) increased by 16.4%. To express the fluorescence (mFl) at a fixed pH, a formula was derived (see eq. 1). From the results it is concluded that an increase in fluorescence (mFl) does not necessarily include an increase in the concentration of fluorescent matter. For areas where pH changes are possible, it is premature to infer from the increase in fluorescence that the fluorescent matter is produced in situ.     

Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy

Dissolved organic matter (DOM) is a complex and poorly understood mixture of organic polymers that plays an influential role in aquatic ecosystems. In this study we have successfully characterised the fluorescent fraction of DOM in the catchment of a Danish estuary using fluorescence excitation–emission spectroscopy and parallel factor analysis (PARAFAC). PARAFAC aids the characterisation of fluorescent DOM by decomposing the fluorescence matrices into different independent fluorescent components. The results reveal that at least five different fluorescent DOM fractions present (in significant amounts) in the catchment and that the relative composition is dependent on the source (e.g. agricultural runoff, forest soil, aquatic production). Four different allochthonous fluorescent groups and one autochthonous fluorescent group were identified. The ability to trace the different fractions of the DOM pool using this relatively cheap and fast technique represents a significant advance within the fields of aquatic ecology and chemistry, and will prove to be useful for catchment management.     

Tracing dissolved organic matter cycling in the eastern boundary of the temperate North Atlantic using absorption and fluorescence spectroscopy

Apparent oxygen utilization (AOU), dissolved organic carbon (DOC), coloured dissolved organic matter (CDOM) absorption spectra, and CDOM fluorescence characteristic of aromatic amino acids (excitation/emission 280 nm/320 nm; F(280/320)) and marine-humic like substances (320 nm/410 nm; F(320/410)) were measured in full depth during a cruise in the temperate Eastern North Atlantic (ENA). An optimum multi-parameter (OMP) inverse method was run to calculate water mass proportion-weighted average (archetypal) concentrations of these chemical parameters for all water masses and samples. Archetypal concentrations retain the variability due to water mass mixing and basin scale mineralization from the water mass formation sites to the study area. Conversely, the difference between measured and archetypal concentrations, retain the variability due to dissimilarities in mineralization processes within the study area. Our analysis indicates that DOC supported 26±3% of the AOU in the dark temperate ENA and that basin scale processes occurring at and from the formation area of the water masses explained 63% of the total DOC variability. Our data also suggests that DOC remineralized at the basin scale was of lower molecular weight, and with a lower proportion of fluorescent aromatic amino acids than found within the study area. The relationship between the absorption coefficient at 254 nm (a_CDOM(254)) and AOU indicates that a_CDOM(254) was consumed during organic matter remineralization in the dark ocean, with 55% of the variability being explained by basin scale processes. The relationships of F(320/410) with AOU and DOC confirmed that marine humic-like substances are produced by microbial degradation processes, at a rate of 6.1±0.9×10⁻³ mg equivalents of QS mol AOU⁻¹. Our results also indicate that basin-scale remineralization processes account for 85% of the total variability of F(320/410), emphasizing that large scale processes control the formation of humic-like substance in the dark ENA.     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

Chromophoric dissolved organic matter (CDOM) is the light absorbing fraction of dissolved organic carbon (DOC). The optical properties of CDOM potentially permit remote sensing of DOC and CDOM, and correction for CDOM absorption is essential for remote sensing of chlorophyll a (chl a) in coastal and estuarine waters. To provide data for this purpose, we report the distributions of CDOM, DOC, and chl a from seven cruises in Chesapeake Bay in 1994–1997. We observed non-conservative distributions of chl a and DOC in half of the cruises, indicating net accumulations within the estuary; however, there were no net accumulations or losses of CDOM, measured as absorption at 355 nm or as fluorescence. Freshwater end member CDOM absorption varied from 2.2 to 4.1 m⁻¹. Coastal end member CDOM absorption was considerably lower, ranging over 0.4–1.1 m⁻¹. The fluorescence/absorption ratio was similar to those reported elsewhere for estuarine and coastal waters; however, in the lower salinity/high CDOM region of the Bay, the relationship was not constant, suggestive of the mixing of two or more CDOM sources. Chl a was not correlated with the absorption for most of the cruises nor for the data set as a whole; however, CDOM and DOC were significantly correlated, with two groups evident in the data. The first group had high CDOM concentrations per unit DOC and corresponded to the conservative DOC values observed in the transects. The second group had lower CDOM concentrations per unit DOC and corresponded to the non-conservative DOC values associated with net DOC accumulation near the chl a maximum on the salinity gradient. This indicates the production of non-chromophoric DOC in the region of the chl a maximum of Chesapeake Bay. In terms of remote sensing, these data show that (1) the retrieval of the absorption coefficient of CDOM from fluorescence measurements in the Bay must consider the variability of the fluorescence/absorption relationship, and (2) estimates of DOC acquired from CDOM absorption will underestimate DOC in regions with recent, net accumulations of DOC.     

Synchronous fluorescence spectra of natural waters: tracing sources of dissolved organic matter

The fluorescence of North Carolina river samples observed simultaneously by scanning excitation and emission wavelengths at a fixed wavelength difference of 25 nm produced synchronous spectra characteristic of each sample's dissolved organic matter. Examination of the spectra of two river samples for pH, copper, magnesium and ferric iron effects revealed that the metals affect only fluorescence intensity whereas pH alters both intensity and spectral shape. Mixtures of up to four rivers were resolved using linear regression analysis and the synchronous spectrum of each component in the mixture. A similar analysis of field samples may be useful for tracing the source, circulation and mixing of dissolved organic matter in coastal waters, lakes or estuaries.     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

北极孔斯峡湾表层沉积物中溶解有机质的来源与转化历史

在北极地区孔斯峡湾采集28个表层沉积物样品,测定了其中水溶性有机质(也称溶解有机质,DOM)的分子量分布、紫外/可见吸收光谱和三维荧光光谱特征,并利用平行因子分析(PARAFAC)模型对DOM的荧光组分和来源进行了解析。结果表明:孔斯峡湾表层沉积物中有色溶解有机质(CDOM)及其中的荧光溶解有机质(FDOM)含量均从内湾向外湾方向呈逐渐累积的趋势,但CDOM中的FDOM所占比例逐渐减小,与DOM趋于老龄化密切相关。沉积作用减弱以及长期的光化学降解和微生物降解作用对此起主要贡献,并导致腐殖质和小分子组分在沉积物DOM中所占的比例呈逐渐递增的趋势。沉积物DOM包含陆源类腐殖质、自生源类腐殖质和类蛋白等三个荧光组分,但是其组成比例空间差异很大。吸收光谱斜率比(S_R)随自生源所占百分比增加而减小,随DOM腐殖质组分中陆源与自生源的比值增加而增加;腐殖化指数(HIX)随类腐殖质与类蛋白质比值和水深的增加而增加,生物源指数(BIX)随自生源比例增加而增加。峡湾沉积物DOM的组成和来源存在着高度的空间差异,在冰川湾区由水体颗粒有机质(POM)的近期转化和迁移而来,而在峡湾中央及口门附近以较老的腐殖质为优势,主要源于水体DOM长期迁移和转化。研究表明,FDOM/CDOM,S_R,HIX和BIX等构成的CDOM光谱指纹信息可以作为揭露沉积物溶解有机质来源及迁移转化历史的工具,对探索海洋与冰川相互作用影响下的峡湾环境演变有着重要意义。     

Variation of dissolved organic matter and fluorescence characteristics before,during and after phytoplankton bloom

The variation of dissolved organic matter (DOM) and fluorescence characteristics during the phytoplankton bloom were investigated in Yashima Bay, at the eastern part of the Seto Inland Sea, Japan. We found significant accumulations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), chromophoric dissolved organic matter (CDOM) fluorescence, and UV₂₆₀ during the phytoplankton bloom period in 2005, although lower accumulations of DOC and DON and only increases of CDOM fluorescence were observed during the bloom period in 2006. Little or no correlation between DOM and phytoplankton abundance might be due to the composition of DOM, which is a complex mixture of organic materials. The 3D-EEM results revealed that the DOM produced around the phytoplankton bloom period contained tyrosine, tryptophan, and humic-like substances. Our results showed that the occurrence of phytoplankton bloom contributed to the production of DOM in coastal water but the DOM accumulation depended on the type of phytoplankton bloom, the phytoplankton species in particular. From our results, we concluded that phytoplankton have a great role in the dynamics of DOM as a producer in a coastal environment.     

Hydrography of chromophoric dissolved organic matter in the North Atlantic

The distribution and optical absorption characteristics of chromophoric dissolved organic matter (CDOM) were systematically investigated along three meridional transects in the North Atlantic Ocean and Caribbean Sea conducted as part of the 2003 US CLIVAR/CO₂ Repeat Hydrography survey. Hydrographic transects covered in aggregate a latitudinal range of 5° to 62° north along longitudes 20°W (line A16N, Leg 1), 52°W (A20), and 66°W (A22). Absorption spectra of filtered seawater samples were collected and analyzed for depths ranging from the surface to ∼6000 m, sampling all the ocean water masses in the western basin of the subtropical North Atlantic and several stations on the North and South American continental slopes. The lowest surface abundances of CDOM (< 0.1 m⁻¹ absorption coefficient at 325 nm) were found in the central subtropical gyres while the highest surface abundances (∼0.7 m⁻¹) were found along the continental shelves and within the subpolar gyre, confirming recent satellite-based assessments of surface CDOM distribution. Within the ocean interior, CDOM abundances were relatively high (0.1–0.2 m⁻¹ absorption coefficient at 325 nm) except in the subtropical mode water, where a local minimum exists due to the subduction of low CDOM surface waters during mode water formation. In the subthermocline water masses of the western basin, changes in CDOM abundance are not correlated with increasing ventilation age as assessed using chlorofluorocarbon (CFC) concentrations and the atmospheric CFC history. But dissolved organic carbon (DOC) mass-specific absorption coefficients of CDOM increase with increasing ventilation age in the deep sea, indicating that CDOM is a refractory component of the DOC pool. The overall CDOM distribution in the North Atlantic reflects the rapid advection and mixing processes of the basin and demonstrates that remineralization in the ocean interior is not a significant sink for CDOM. This supports the potential of CDOM as a tracer of ocean circulation processes for subducted water masses.     

Characterization of dissolved organic matter fluorescence in the South Atlantic Bight with use of PARAFAC model: Interannual variability

Systematic water sampling for characterization of chromophoric dissolved organic matter (CDOM) in the coastal South Atlantic Bight, was conducted as part of the long term Coastal Ocean Research and Monitoring Program (CORMP). Water samples were collected during a 3.5 year period, from October 2001 until March 2005, in the vicinity of the Cape Fear River (CFR) outlet and in adjacent Onslow Bay (OB). During this study there were two divergent hydrological and meteorological conditions in the CFR drainage area: a severe drought in 2002, followed by the very wet year of 2003. CDOM was characterized optically by the absorption coefficient at 350 nm, the spectral slope coefficient (S), and by Excitation Emission Matrix (EEM) fluorescence. Parallel Factor Analysis (PARAFAC) was used to assess CDOM composition from EEM spectra and six components were identified: three terrestrial humic-like components, one marine humic-like component and two protein-like components. Terrestrial humic-like components contributed most to dissolved organic matter (DOM) fluorescence in the low salinity plume of the CFR. The contribution of terrestrial humic-like components to DOM fluorescence in OB was much smaller than in the CFR plume area. Protein-like components contributed significantly to DOM fluorescence in the coastal ocean of OB and they dominated DOM fluorescence in the Gulf Stream waters. Hydrological conditions during the observation period significantly impacted both concentration and composition of CDOM found in the estuary and coastal ocean. In the CFR plume, there was an order of magnitude difference in CDOM absorption and fluorescence intensity between samples collected during the drought compared to the wet period. During the drought, CDOM in the CFR plume was composed of equal proportions of terrestrial humic-like components (ca. 60% of the total fluorescence intensity) with a significant contribution of proteinaceous substances (ca. 20% of the total fluorescence). During high river flow, CDOM was composed mostly of humic substances (nearly 75% of total fluorescence) with minor contributions by proteinaceous substances. The impact of changes in fresh water discharge patterns on CDOM concentration and composition was also observed in OB, though to a lesser degree.     

Metaproteomic characterization of dissolved organic matter in coastal seawater

We performed a comprehensive metaproteomic analysis of the dissolved organic matter (DOM) in Japanese coastal waters using liquid chromatography–tandem mass spectrometry and demonstrated that these proteomes were characterized by proteins with various functions, including metabolic enzymes, membranes, and photosynthetic proteins. The protein sources included cyanobacteria, heterotrophic bacteria, and eukaryotic phytoplankton. Most of the components were similar among samples and also similar to pelagic components. We also observed differences in the compositions of the microbial communities of origin among the different dissolved protein samples and differences in the relative abundance of specific dissolved protein types (e.g., cytoskeletal proteins), possibly indicating potential dynamics in the coastal DOM pool.     

红树林间隙水溶解态陆源有机质的光降解和生物降解行为分析

红树林输送的溶解态陆源有机质是海洋中陆源有机质的主要来源之一,对其光降解和生物降解过程的研究有助于进一步了解红树林生态系统输出的有机质在近岸的归宿以及对近岸水体生物地球化学过程的影响,因此于2010年4月在海南省清澜港红树林采集间隙水,并进行了光降解和生物降解培养实验。分析了光培养(光降解)和暗培养过程(生物降解)中溶解态有机碳(DOC)、细菌以及溶解态木质素等的变化。结果显示经历128 d的暗培养后,DOC由初始的2 216 μmol/L下降至718 μmol/L,表明红树林间隙水的生物可利用性约为70%左右;经历11 d的自然光照后,DOC下降至800 μmol/L。木质素在光降解过程中的移除速率(-0.132 d-1)远高于生物降解过程(-0.008 d-1)。光培养中,木质素的下降速率高于总体DOC。不同系列溶解态木质素的下降速率不同,随着培养的进行,紫丁香基酚类(S)与香草基酚类(V)的比值(S/V)呈下降趋势,而V系列的酸醛比值((Ad/Al)v)呈上升的趋势。对比光培养和暗培养过程中DOC和木质素的变化可以得出生物消耗是引起红树林间隙水DOC从水体中移除的主要因素;而光照则是陆源有机质从水体中移除的主要因素;光培养和暗培养过程中细菌变化的差异表明光照可以促进细菌对溶解态有机碳的利用。与其他地区比较发现,海南红树林间隙水的光降解速率与热带河流(刚果河)相近,高于温带密西西比河流,降解过程中各参数的变化[S/V和(Ad/Al)v]与其他区域接近。     

Binding of monomeric organic compounds to marcomolecular dissolved organic matter in seawater

Several monomeric organic compounds, including amino acids, sugars, and fatty acids, were found to bind abiologically to dissolved macromolecular materials in particle-free seawater at natural substrate concentrations. The binding primarily occurred in ocean surface waters, at rates slower than in situ biological utilization rates of most of the compounds. Seasonal patterns of binding in Gulf of Maine waters may have been related to seasonal variations in macroalgal exudation of polyphenolic materials. Enhanced reactivity of relatively hydrophobic monomers implicated hydrophobic effects as potentially important in marine organic condensations. The resultant condensates showed high particle reactivity, consistent with low concentrations of dissolved condensed materials in seawater.     

Characterization of chromophoric dissolved organic matter (CDOM) in the Baltic Sea by excitation emission matrix fluorescence spectroscopy

Chromophoric dissolved organic matter (CDOM) is the major light absorber in the Baltic Sea. In this study, excitation emission matrix (EEM) fluorescence spectra and UV–visible absorption spectra of CDOM are reported as a function of salinity. Samples from different locations and over different seasons were collected during four cruises in 2002 and 2003 in the Baltic Sea in both Pomeranian Bay and the Gulf of Gdansk. Absorption by CDOM decreased with increased distance from the riverine source and reached a relatively stable absorption background in the open sea. Regression analysis showed that fluorescence intensity was linearly related to absorption by CDOM at 375 nm and a_CDOM(375) absorption coefficients were inversely related to salinity. Analysis of CDOM-EEM spectra indicated that a change in composition of CDOM occurred along the salinity gradient in the Baltic Sea. Analysis of percent contribution of respective fluorophore groups to the total intensity of EEM spectra indicated that the fluorescence peaks associated with terrestrial humic components of the CDOM and total integrated fluorescence decreased with decreasing CDOM absorption. In contrast, the protein-like fraction of CDOM decreased to a lesser degree than the others. Analysis of the percent contribution of fluorescence peak intensities to the total fluorescence along the salinity gradient showed that the contribution of protein-like fluorophores increased from 2.6% to 5.1% in the high-salinity region of the transect. Fluorescence and absorption changes observed in the Baltic Sea were similar to those observed in similar transects that have been sampled elsewhere, e.g. in European estuaries, Gulf of Mexico, Mid-Atlantic Bight and the Cape Fear River plume in the South Atlantic Bight, although the changes in the Baltic Sea occurred over a much smaller salinity gradient.     

Impact of halides on the photobleaching of dissolved organic matter

Understanding absorbance photobleaching of marine dissolved organic matter (DOM) is important because DOM chromophores impact oceanic primary productivity by affecting the depth of the photic zone, absorb UV radiation and affect ocean color used in remote sensing. However, the fundamental mechanisms which account for this bleaching are largely unknown. Controlled laboratory studies demonstrated that the presence of seawater concentrations of chloride and bromide ions enhanced absorbance photobleaching reaction rates by ~ 40%, regardless of DOM source or the presence or absence of carbonate ions. In contrast, halide ions generally did not affect fluorescence bleaching rates. Variations in ionic strength did not alter the enhancement in absorbance photobleaching by halide ions. Accordingly, the enhancement in absorbance photobleaching was specific to halide ions, rather than a generalized salinity effect. We confirmed the formation of hydroxyl radical (HO^•) in illuminated samples, and its significant scavenging in the presence of halide salts. Gamma-radiolysis experiments and associated modeling indicated that a small component (~ 12%) of the photobleaching enhancement by halides was consistent with the hypothesis that halide scavenging of HO^• will form reactive halogen radicals that target electron-rich chromophores within DOM more selectively than HO^•. The mechanism responsible for the major component of absorbance photobleaching rate enhancement by halides remains unresolved.     

Production of chromophoric dissolved organic matter fluorescence in marine and estuarine environments: an investigation into the role of phytoplankton

We tested whether phytoplankton are a direct source of chromophoric dissolved organic matter (CDOM) fluorescence in a series of experiments. In the first experiment, sonication of 11 dense algal cultures from several algal classes revealed no immediate release of CDOM fluorescence. In a second experiment, using nutrient addition bioassays from a range of sites in the mid-Atlantic region, we found no increase in CDOM fluorescence when nutrient limitation was alleviated despite large increases in chlorophyll a over 3–5 days. In a third experiment, the change in CDOM fluorescence over a 28-day period in five non-axenic algal batch cultures was measured. There was little or no increase in CDOM fluorescence until the cultures entered the stationary phase, whereupon an exponential increase in CDOM fluorescence was observed. In a fourth set of experiments, the production of CDOM fluorescence was examined in a series of cultures of Skeletonema costatum and Prorocentrum minimum. In the dark, in the absence of autotrophic growth, we observed slow rates of CDOM fluorescence production (0.02–0.05 NFlU day⁻¹). Rates were much higher in parallel lighted cultures (0.1–0.2 NFlU day⁻¹) but were more related to bacterial counts than to algal biomass. In a third phase of this experiment, when illuminated, stationary phase cultures were filtered through 1-μm pore size filters and incubated in the dark, CDOM fluorescence production continued unchanged. These results are consistent with the hypothesis that phytoplankton are not a direct source of CDOM fluorescence in marine and estuarine environments and that CDOM fluorescence is produced by bacteria using non-fluorescent organic matter derived from phytoplankton.