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.     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.     

Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

Correlation of the absorption coefficient with a reduction in mean mass for dissolved organic matter in southwest Florida river plumes

Results are presented from an investigation of the relationship between molecular mass distribution and optical properties for colored dissolved organic matter (CDOM); a complex assembly of organic macromolecules of marine and freshwater origin found throughout the surface ocean. Unique data are derived from the application of a new technique, a combination of a hydrophilic–lipophilic copolymer-based solid phase extraction (SPE) with electrospray ionization (ESI) continuous flowing ion trap mass spectrometry (cf-MS), for the direct determination of CDOM mass distribution. An evaluation of this copolymer-based extraction technique for the analysis of Suwannee River Natural Organic Matter (SRNOM) reference material revealed that the current method compares favorably with C₁₈ modified silica or XAD resin-based extraction methods reported in the literature when considering extraction efficiency or low extraction bias for CDOM. The mass distribution of CDOM in several freshwater to marine transition zones along coastal southwestern Florida has been determined with this technique. All rivers in the study region had a bimodal distribution of masses. A case study of the Caloosahatchee River outflow CDOM mass distribution data are presented as an example of the modification in mass distributions. The lower mass mode of the bimodal distribution was observed to have a relatively stable mean throughout the study region at 406±9 Da, while decreasing in concentration in a non-conservative manner with salinity. In contrast, the upper mass mode of the bimodal distribution was observed to have a variable mean, reaching 1408 Da in the least saline waters and decreasing by 174 Da through the transect toward higher salinity coastal waters. Coinciding with this reduction in mean mass for the upper distribution is a non-conservative reduction in concentration when compared with salinity. We define apparent organic carbon (AOC) as a function of the cf-MS determined total integrated area and use this value to determine concentration of the total extracted CDOM. Unique correlations between the CDOM fluorescence (350-nm excitation/450-nm emission) and the AOC for these coastal samples have been observed for each of three rivers in the study region. The steepest slope and highest correlation between optical and mass spectral properties are observed in rivers with strongly absorbing waters originating in the Florida Everglades and lowest in rivers draining clearer waters from widely variable and anthropogenic influenced regions. The trends in molecular mass distribution and corresponding optical properties support the theory that CDOM in coastal zones is environmentally processed material from terrestrial sources. Probable cause of the reduction in mean mass and suggestions for further investigation of sources and transformations of CDOM are discussed.     

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.     

Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.     

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.     

Seasonal dynamics in colored dissolved organic matter in the Mediterranean Sea: Patterns and drivers

Two autonomous profiling “Bio-Argo” floats were deployed in the northwestern and eastern sub-basins of the Mediterranean Sea in 2008. They recorded at high vertical (1 m) and temporal (5 day) resolution, the vertical distribution and seasonal variation of colored dissolved organic matter (CDOM), as well as of chlorophyll-a concentration and hydrological variables. The CDOM standing stock presented a clear seasonal dynamics with the progressive summer formation and winter destruction of subsurface CDOM maxima (YSM, for Yellow Substance Maximum). It was argued that subsurface CDOM is a by-product of phytoplankton, based on two main characteristics, (1) the YSM was located at the same depth than the deep chlorophyll maximum (DCM) and (2) the CDOM increased in summer parallels the decline in chlorophyll-a. These observations suggested an indirect but tight coupling between subsurface CDOM and phytoplankton via microbial activity or planktonic foodweb interactions. Moreover, the surface CDOM variations observed both by floats and MODIS displayed different seasonal dynamics from what recorded at subsurface one. This implies that CDOM standing stock can be hardly detected by satellite. It is worthnoting that surface CDOM was found to be more related to the sea surface temperature (SST) than chlorophyll-a concentration, suggesting its physical origin, in contrast to the biological origin of YSM and subsurface standing stocks.     

Photoreactivity of chromophoric dissolved organic matter transported by the Mackenzie River to the Beaufort Sea

The photoreactivity of chromophoric dissolved organic matter (CDOM) transported to Arctic shelf environments by rivers has only recently been studied and its quantitative role in Arctic shelf biogeochemistry has received little attention. Sunlight exposure experiments were performed on CDOM collected over a three year period (2002 to 2004) from river, estuary, shelf, and gulf regions of the Western Canadian Arctic. Decreases in CDOM absorption, synchronous fluorescence (SF), and dissolved organic carbon (DOC) concentration were followed after 3 days of exposure, and in two experiments, six optical cutoff filters were used to incrementally remove ultraviolet radiation incident on the samples. Apparent quantum yields for CDOM photobleaching (AQY_ble) and for DOC photomineralization (AQY_min) were computed, as were two AQY spectra (_ble and _min) for the Mackenzie River and a sample from the Mackenzie Shelf. The photoreactivity of Mackenzie River CDOM was highest after break-up and peak discharge and lowest in late summer. The half-lives of CDOM and DOC were estimated at 3.7 days and 4.8 days, respectively, when Mackenzie River water was exposed to full sunlight. Photobleaching of Mackenzie River CDOM fluorescence after most UV-B wavelengths were removed increased the correlation between the river and offshore waters in the Beaufort Sea. When light attenuation from particle- and CDOM-rich river water was considered for the Mackenzie Shelf, our photodegradation models estimated around 10% loss of absorption and < 1% DOC loss, suggesting that sunlight exposure does not substantially degrade CDOM on Arctic shelves.     

Analysis of lignin-derived phenols in standard reference materials and ocean dissolved organic matter by gas chromatography/tandem mass spectrometry

A series of reference materials are proposed for intercomparison and quality control purposes during the quantification of lignin oxidation products (LOP) from diverse environmental matrices. These materials are all easily accessible and certified for diverse organic constituents (NIST and IHSS). They represent a suite of natural environmental matrices (from solids to aqueous) and are characterized by a wide range of organic carbon and lignin concentrations with abundant proportions of all major LOP. The variability of LOP concentrations and signatures for all these materials averages 3–5% and does not exceed 10%. Using these standards, a new quantification method was developed and validated for the determination of low-level CuO oxidation products using capillary gas chromatography–tandem mass spectrometry (GC/MS–MS). Tandem mass spectrometry provides both the high sensitivity and selectivity required for the identification and quantification of trace levels of dissolved lignin. The method is particularly useful for removing interference from co-eluting isotopes generated from the DOM matrix and during glucose amendment procedures of low-carbon samples. Such glucose amendment is not necessary, however, when the CuO to organic carbon weight-to-weight ratio can be kept at a value < 200–300.     

Marine proteomics: generation of sequence tags for dissolved proteins in seawater using tandem mass spectrometry

Dissolved proteins in seawater samples from the Gulf of Mexico were concentrated using tangential flow ultrafiltration and methanol/chloroform/water precipitation. Following concentration and purification, two different separation methods were employed. In one method, intact proteins were separated by SDS–PAGE and digested enzymatically in-gel. In the second method, the peptides resulting from a solution proteolytic digest of the whole protein pellet mixture were separated by capillary HPLC. In both methods, the final chromatographic separation was coupled on-line with a mass spectrometer using an electrospray interface, and peptide CID spectra were collected using tandem mass spectrometry (MS). De novo sequencing of the peptide tandem mass spectra generated short amino acid sequences (peptide tags) that were used to search databases for protein class and source information. Trends of conserved sequences for two specific classes of proteins were observed: membrane/envelope proteins and enzymes. Similarity searching of peptide tags produced identification of conserved sequences from several protein homologues originating from many different species, including: long chain fatty acyl CoA synthetase, anthranilate synthase, ribulose bisphosphate carboxylase, and luminal binding protein. These results provide new insight into the sources and production mechanisms for dissolved organic matter (DOM), as there is direct evidence for dissolved proteins other than the bacterial outer membrane proteins reported by Tanoue et al. Furthermore, the data presented herein support the idea that physical protection and selective preservation are not mutually exclusive survival mechanisms, but rather these two models are dependent upon one another for explaining the survival of refractory dissolved proteins in seawater.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Seasonal trends in the abundance, composition and bioavailability of particulate and dissolved organic matter in the Chukchi/Beaufort Seas and western Canada Basin

The objectives of this study were to investigate the seasonality, abundance, sources and bioreactivity of organic matter in the water column of the western Arctic Ocean. The concentrations of particulate and dissolved amino acids and amino sugars, as well as bulk properties of particulate and dissolved organic matter (DOM), were measured in shelf, slope and basin waters collected during the spring and summer of 2002. Particulate organic matter concentrations in shelf waters increased by a factor of 10 between spring and summer. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations exhibited only minor seasonal variations, whereas dissolved amino acid concentrations doubled between spring and summer, and dissolved amino sugars increased by 31% in shelf waters of the Chukchi and Beaufort Seas. Concentrations of DOC did not exhibit a significant seasonal change in surface waters of the Canada Basin, but dissolved amino acid concentrations increased by 45% between spring and summer. No significant seasonal differences were detected in the concentration or composition of DOM in waters below 100 m in depth. Concentrations of particulate and dissolved amino acids and amino sugars were strongly correlated with chlorophyll-a, indicating a plankton source of freshly produced organic matter. The amino acid and amino sugar compositions of freshly produced DOM indicated that a large portion of this material is bioavailable. While freshly produced DOM was found to be relatively bioreactive, preformed DOM in the Arctic appears to be less bioreactive but similar in degradation state to average DOM in the Atlantic and Pacific. These data demonstrate substantial summer production of POM and DOM on the Chukchi and Beaufort shelves that is available for utilization in shelf waters and export to the Canada Basin.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

2011年夏季胶州湾表层溶解有机物荧光特征的时空变化

利用三维荧光光谱技术(EEMs)结合平行因子分析(PARAFAC)的方法,对2011年8月至9月胶州湾表层海水溶解有机物荧光特征的时间与空间变化进行了研究。PARAFAC模型共鉴别出四个荧光组分:类蛋白质荧光组分(C1),陆源类腐殖质荧光组分(C2,C4)和海源类腐殖质荧光组分(C3)。类蛋白组分在调查期间的荧光强度最强(0.14±0.06),其余三个组分荧光强度相近(0.07±0.02,0.09±0.02,0.05±0.02)。这四种组分在8月下旬多雨期和9月上旬受径流影响的时期荧光强度较高,在9月下旬雨季影响消退后荧光强度显著降低。研究表明各组分荧光强度总体上与叶绿素a浓度显著正相关,与盐度负相关,说明胶州湾夏季FDOM浓度主要受降雨引发的生物活动影响。     

An optical model for the remote sensing of coloured dissolved organic matter in coastal/ocean waters

An optical model is developed for the remote sensing of coloured dissolved organic matter (CDOM) in a wide range of waters within coastal and open ocean environments. The absorption of CDOM (denoted as a_g) is generally considered as an exponential form model, which has two important parameters – the slope S and absorption of CDOM at a reference wavelength a_g(λ₀). The empirical relationships for deriving these two parameters are established using in-situ bio-optical datasets. These relationships use the spectral remote sensing reflectance (R_rs) ratio at two wavelengths R_rs(670)/R_rs(490), which avoids the known atmospheric correction problems and is sensitive to CDOM absorption and chlorophyll in coastal/ocean waters. This ratio has tight relationships with a_g(412) and a_g(443) yielding correlation coefficients between 0.77 and 0.78. The new model, with the above parameterization applied to independent datasets (NOMAD SeaWiFS match-ups and Carder datasets), shows good retrievals of the a_g(λ) with regression slopes close to unity, little bias and low mean relative and root mean square errors. These statistical estimates improve significantly over other inversion models (e.g., Linear Matrix-LM and Garver-Siegel-Maritorena-GSM semi-analytical models) when applied to the same datasets. These results demonstrate a good performance of the proposed model in both coastal and open ocean waters, which has the potential to improve our knowledge of the biogeochemical cycles and processes in these domains.     

莱州湾荧光溶解有机物的时空分布

利用三维荧光光谱-平行因子分析法(EEMs-PARAFAC)技术结合多元统计方法研究了莱州湾海域春季(2020年5月)和秋季(2020年10月)荧光溶解有机物(FDOM)的来源及时空分布特征。结果显示莱州湾海域FDOM由2类共4个荧光组分组成:C1、C4为类蛋白质组分,分别为色氨酸和酪氨酸; C2、C3为类腐殖质组分。并对各组分的来源及分布特征分析:春季FDOM分布主要受到陆源输入的影响,其中表层C1、C2、C3也受微生物活动影响。秋季表层C1、C2、C3分布受到陆源输入和浮游植物生产共同影响,秋季表层C4主要受生物现场生产影响,秋季底层C1、C2、C3主要受陆源输入影响,C4受陆源输入和浮游植物生产共同影响。各荧光组分在表层的季节性差异主要是由于春季部分FDOM经陆源输入后受偏南风作用,在莱州湾西部及南部海域扩散。FDOM在底层的季节性差异主要由于受到沉积物再悬浮的影响。HIX高值分布表明莱州湾西部和南部FDOM受陆源输入影响显著,BIX高值分布表明莱州湾远海FDOM受生物活动影响程度较高。总体上,陆源输入影响莱州湾FDOM分布的主要因素。