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.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Temporal dynamics of dissolved combined neutral sugars and the quality of dissolved organic matter in the Northwestern Sargasso Sea

The dynamics of dissolved combined neutral sugars (DCNS) were assessed in the upper 250 m at the Bermuda Atlantic Time-series Study (BATS) site between 2001 and 2004. Our results reveal a regular annual pattern of DCNS accumulation with concentrations increasing at a rate of 0.009–0.012 μmol C L^?1 d^?1 in the surface 40 m from March to July and reaching maximum mean concentrations of 2.2–3.3 μmol C L^?1. Winter convective mixing (between January and March) annually exported surface-accumulated DCNS to the upper mesopelagic zone (100–250 m), as concentrations increased there by 0.3–0.6 μmol C L^?1. The exported DCNS was subsequently removed over a period of weeks following restratification of the water column. Vertical and temporal trends in DCNS yield (% of DOC) supported its use as a diagenetic indicator of DOM quality. Higher DCNS yields in surface waters suggested a portion of the DOM accumulated relatively recently compared to the more recalcitrant material of the upper mesopelagic that had comparably lower yields. DCNS yields and mol% neutral sugar content, together, indicated differences in the diagenetic state of the surface-accumulated and deep pools of DOM. Seasonally accumulated, recently produced DOM with higher DCNS yields was characterized by elevated mol% of galactose and mannose+xylose levels. Conversely, more recalcitrant DOM from depths >100 m had lower DCNS yields but higher mol% of glucose. Lower DCNS yields and elevated mol% glucose were also observed in the surface waters during winter convective mixing, indicating an entrainment of a diagenetically altered DOM pool into the upper 100 m. A multivariate statistical analysis confirms the use of DCNS as an index of shifts in DOM quality at this site.     

Limited nutritional benefit to the seagrass Halophila ovalis, in culture, following sediment organic matter enrichment

Essential nutrients for seagrass growth may be derived from benthic decomposition of organic matter. To test this idea, cores of Halophila ovalis (seagrass-vegetated) and unvegetated sediment (control) were amended with either particulate organic matter (POM) or dissolved organic matter (DOM) to test whether a positive feed-back loop exists, where increased organic matter results in increased seagrass nutrients. POM was added in the form of seagrass wrack (0, 1, 5, 12 g core⁻¹) and DOM was added with sucrose diffusion tubes at the root zone (0, 0.8, 2.4, 5.2 g core⁻¹). Cores were incubated under saturating light conditions (12 h light/12 h dark) at 18 °C, for 4 weeks. Results suggest a complex balance between positive and negative effects of organic matter enrichment. Whilst leaf molar concentrations of N and P of H. ovalis increased (by 15 and 30% respectively), plant growth declined (up to 50% relative to control) for both DOM and POM enrichments. Phosphate was removed from sediment porewater following POM addition and most likely translocated to the leaves. Stressors other than nutrient limitation (e.g. biogeochemical constraints) reduce growth and affect the nutrient dynamics of the seagrass and should be the focus of future work.     

Particulate and dissolved amino acids in the lower Mississippi and Pearl Rivers (USA)

In this study, we present seasonal changes (monthly samples from September 2001 to August 2003) in the abundance and composition of dissolved and particulate amino acids, at one station in the lower Mississippi and Pearl Rivers (LA, MS: USA). Spatial changes over a 4-day transmit from river km 390 to river mouth (Head of Passes, LA) in the Mississippi River, and a two-day downstream sampling from Jackson (MS) to Stennis Space Center (MS) were also determined. Temporal data in the lower Mississippi River showed significantly lower concentrations of dissolved combined amino acids (DCAA, 0.8 to 2.2 μM) and dissolved amino acids in high molecular weight fraction (HMW DAA, 0.2–0.4 μM) than in the Pearl River (DCAA, 1.4–4.3 μM; HMW DAA, 0.4–1.4 μM). Dissolved free amino acids (DFAA) were significantly lower than DCAA in both rivers, and displayed minimal seasonal variability. DCAA, HMW DAA, and particulate amino acids (PAA) were generally higher during high-flow periods, which may have suggested dominance in terrestrial sources. Carbon-normalized yield of PAA (%C-PAA) was generally higher during low-flow conditions and positively correlated with chlorophyll-a (chl-a), reflective of in situ sources. Downstream variability in the lower Mississippi River showed stable DCAA concentrations, a decline in PAA (from 1.06 to 0.43 μM), and a gradual increase in mole percent of non-protein amino acids (%NPAA). This likely reflected bacterial degradation of phytoplankton biomass during falling discharge. Nitrogen-normalized yield of PAA (%N-PAA) was inversely correlated with PAA (R = − 0.7, n = 48), indicative of short-term sedimentation and resuspension events. Conversely, downstream decreases in DCAA and middle-reach peaks of PAA and %N-PAA in the Pearl River, likely resulted from photochemical degradation of DOM as well as algal production during base-flow conditions. The comparisons in abundance and composition of DAA and PAA in these different river systems provides important information on in situ nitrogen and carbon cycling as related to riverine inputs of organic matter to coastal ocean.     

Sources and sinks of low molecular weight organic carbonyl compounds in seawater

Results from laboratory studies indicated that low molecular weight (LMW) carbonyl compounds, especially formaldehyde, acetaldehyde, acetone and glyoxal, can be formed in seawater by photochemical processes. Once formed, these compounds appear to be readily consumed by biota. These results suggest that concentrations of LMW carbonyl compounds should undergo diurnal variations in the illuminated layer of the sea. In support of this, diurnal fluctuations of LMW carbonyl concentrations were observed in humic-rich surface waters off the west coast of Florida over a three day sampling period using a shipboard HPLC system. Fluctuations in acetaldehyde were particularly strong and reproducible, with steady night-time concentrations of 2–3 nM and day-time concentrations reaching a maximum of 20–30 nM in the early afternoon. In contrast, diurnal fluctuations in formaldehyde were less distinct, ranging from 15 to 50 nM.The laboratory and field results are discussed in terms of biotic/abiotic sources and sinks of LMW carbonyl compounds in surface seawater. It is speculated that photooxidative cleavage of biologically refractory dissolved organic matter (DOM) in seawater to yield LMW organic fragments, such as carbonyl compounds, may be important in the breakdown and geochemical cycling of DOM in the ocean.     

Origin and biochemical cycling of particulate nitrogen in the Mandovi estuary

Mandovi estuary is a tropical estuary strongly influenced by the southwest monsoon. In order to understand, sources and fate of particulate organic nitrogen, suspended particulate matter (SPM) collected from various locations, was analyzed for particulate organic carbon (POC) and particulate organic nitrogen (PON), δ¹³C_POC, total hydrolysable amino acid enantiomers (l- and d- amino acids) concentration and composition. δ¹³C_POC values were depleted (−32 to −25‰) during the monsoon and enriched (−29.6 to −21‰) in the pre-monsoon season implying that OM was derived from terrestrial and marine sources during the former and latter season, respectively. The biological indicators such as C/N ratio, d-amino acids, THAA yields and degradation indices (DI) indicate that the particulate organic matter (POM) was relatively more degraded during the monsoon season. Conversely, during the pre-monsoon, the biological indicators indicated the presence of relatively fresh and labile POM derived from autochthonous sources. Amino acids such as alanine, aspartic acid, leucine, serine, arginine, and threonine in monsoon and glutamic acid, glycine, valine, lysine, and isoleucine in pre-monsoon were relatively abundant. Presence of bacterial biomarker, d-amino acids in the SPM of the estuary during both the seasons signifies important contribution of bacteria to the estuarine detrital ON pool. Based on d-amino acid yields, bacterial OM accounted for 16-34% (23.0 ± 6.7%) of POC and 29-75% (47.9 ± 18.7%) of PON in monsoon, and 30-78% (50.0 ± 15%) of POC and 34-79% (51.2 ± 13.3%) of the PON in pre-monsoon in the estuary. Substantial contribution of bacterial-N to PON indicates nitrogen (N) enrichment on terrestrial POM during the monsoon season. Transport of terrestrial POM enriched with bacterial OM to the coastal waters is expected to influence coastal productivity and ecosystem functioning during the monsoon season.     

Tracing terrigenous dissolved organic matter and its photochemical decay in the ocean by using liquid chromatography/mass spectrometry

Reversed-phase liquid chromatography/mass spectrometry (LC/MS) is introduced as a new molecular fingerprinting technique for tracing terrigenous dissolved organic matter (DOM) and its photochemical decay in the ocean. DOM along a transect from the mangrove-fringed coast in Northern Brazil to the shelf edge was compared with mangrove-derived porewater DOM exposed to natural sunlight for 2–10 days in a photodegradation experiment. DOM was isolated from all samples via solid-phase extraction (C18) for LC/MS analysis. DOM in the estuary and ocean showed a bimodal mass distribution with two distinct maxima in the lower m/z range from 400 to 1000 Da (intensity-weighted average of 895 Da). Terrigenous porewater DOM from the mangroves was characterized by a broad molecular mass distribution over the detected range from 150 to 2000 Da (intensity-weighted average of 1130 Da). Polar compounds, i.e., those that eluted early in the reversed-phase chromatography, absorbed more UV light and had on average smaller molecular masses than the more apolar compounds.     

Lipid and 13C signatures of submicron and suspended particulate organic matter in the Eastern Tropical North Pacific: Implications for the contribution of Bacteria

The contribution of bacterial biomass to total particulate organic matter (POM) in the ocean, including exported material, is poorly constrained. To examine potential signatures for the presence and export of bacterioplankton and their detrital remains, here we provide a detailed compound-specific ¹³C characterization of fatty acids from membrane polar lipids obtained from a water column profile in the Eastern Tropical North Pacific. POM of submicron size (0.2–0.7 μm; “X-POM”) was sampled and analyzed separately from the size class typically collected as “suspended” POM (0.7–53 μm; “L-POM”). The distributions of polar head group classes, specific fatty acid side chains, and natural ¹³C contents all vary, both between particle size classes and with depth in the water column. In general, the polar lipids in submicron material – and by inference, lipids of bacterial origin – have higher ¹³C content than polar lipids from larger POM and are equally abundant. Lipid signatures from the photic zone appear to be partially conserved in the suspended pool during transit down the water column. However, bacterial heterotrophy and possibly chemoautotrophy partially overprint these surface signatures. In addition, active metabolisms in the oxygen minimum zone (OMZ) appear to mediate the disaggregation of POM transported from the surface, thus adding complexity to the pathways of mid-water carbon flux and providing additional organic substrates to the OMZ and below. This “substrate injection” may provide important fuel for the denitrification and anammox reactions. Finally, examination of ¹³C content in polar lipids provides a basis for new interpretation of depth-related variations in δ¹³C values of bulk suspended POM.     

Degradation of phytoplankton-derived organic matter: Implications for carbon and nitrogen biogeochemistry in coastal ecosystems

Experiments were conducted using seawater from the Oregon continental shelf to determine: (1) rates of phytoplankton-derived particulate organic matter (POM) and dissolved organic matter (DOM) degradation by natural microbial communities, and (2) whether inorganic nutrients or flagellate grazing limit the bacterial response to, and subsequent degradation of, the DOM. In the initial seawater samples, nutrients were depleted and organic matter concentrations were elevated above concentrations found in upwelled water, indicative of recent bloom conditions. In whole water treatments incubated for 3 d, an average of 24% of the total organic C and 33% of the POC was degraded, with some portion of the POC being converted to DOC. In treatments incubated after POM was removed by filtration, DOC degradation was initially rapid and then proceeded at a slower rate. After 3 d, an average of 41% of the DOC was degraded. Selective degradation of the C-component of both the POM and DOM relative to the N-component was observed. Reductions in flagellate grazing resulted in increases in bacterial abundance and enhanced DOC degradation, while inorganic nutrient amendments had little effect. Overall, these results suggest that a fraction of the phytoplankton-derived POM and DOM can be rapidly degraded, contributing to oxygen consumption on the continental shelf. The long degradation time of a less labile DOC fraction relative to potential offshelf transport mechanisms suggests that Oregon's coastal waters may be a source of DOC to adjacent offshore waters of the North Pacific.     

Neutral aldoses as source indicators for marine snow

The chemical characteristics of aggregating material in the marine environment are largely unknown. We investigated neutral aldose (NA) abundance and composition in aggregation of marine snow and other organic matter (OM) size fractions in the field. Four sample sets were fractionated using membrane filtration and ultrafiltration into the following size fractions: particulate material, high-molecular-weight (HMW) material, and low-molecular-weight (LMW) material. We also collected three sample sets of marine-snow aggregates. Each sample set contained small, medium, and large aggregate size fractions and each size fraction consisted of 25–50 aggregates. For 7 marine-snow samples and for each water-sample size fraction, we determined monomeric and polymeric NA concentration, NA yield (amount of NA-C normalized to organic carbon), and composition; total organic carbon (TOC) concentration; transparent exopolymer particles (TEP) concentration, and TEP propensity (TEP concentration after inducing TEP formation in filtered samples). This is the first study to include compound-specific NA determinations on these four marine OM size fractions.The mass balances of organic carbon and NA indicated that there were no serious contamination or loss problems. Concentrations, yields, and NA mol fractions in water samples were similar to results from other studies. Glucose and galactose had the highest relative abundance in all size fractions. The NA yield increased with increasing molecular weight or particle size for all fractions except marine snow. The NA yield increased in the order: LMW< marine snow< HMW< particles. Marine snow had a higher average NA yield than the LMW fraction, but lower than particle and HMW-fractions. This indicates that OM in marine snow could have been diagenetically derived from particulate and HMW-fractions, that is, marine snow may include material from the particulate and the colloidal phase.TEP concentration or TEP propensity was positively correlated with concentrations of all individual NAs as well as the sum NA concentrations, indicating that TEP contains neutral sugars in addition to the acidic polysaccharides stained in the determination of TEP concentrations.Despite the relatively low NA yield in marine snow, marine snow was enriched in NA when compared with seawater, with enrichment factors of 34–225 (average 125). By combining data from this study with data from other studies, we estimate that < 10% of carbohydrates in marine snow comprise NAs.There was no clear correlation between marine-snow aggregate size and NA yield, that is, there appears to be no general age difference between small and large marine-snow aggregates. NA composition was similar among different marine-snow size fracions collected during the same day, indicating that aggregation/disaggregation reactions resulted in homogenizing NA composition in marine-snow aggregates of all sizes. The NA composition of marine snow was different from that of other OM size fractions, indicating either that bacterial degradation has modified the composition of marine snow to a larger extent than other OM size fractions or that marine snow is formed through the aggregation of selected subcomponents of OM.     

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.     

Stocks and dynamics of dissolved and particulate organic matter in the southern Ross Sea, Antarctica

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 μM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 μM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO₃ concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DIC_equiv). The fraction of DIC_equiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DIC_equiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as “semi-labile” DOM. The “semi-labile” pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.     

Biogeochemistry of Mangrove Soil Organic Matter: a Comparison BetweenRhizophoraandAvicenniaSoils in South-eastern Brazil

Soil core samples fromRhizophora mangleL. andAvicennia schauerianaStapf & Leech forests from south-eastern Brazil were analysed for their total organic matter content and their sugars, amino acid and amino sugars composition. Organic carbon and nitrogen contents were higher inAvicenniathan inRhizophorasoils. The contribution of sugars and amino acids to the total organic carbon pool was constant with depth inRhizophorasoils whereas inAvicenniasoils it increased. Spectral distribution of sugars and amino acids showed a dominance of Ca-affine monomers, particularly acidic amino acids, and the sugar arabinose. Biogeochemical indicators derived from ratios of individual sugar and amino acid monomers confirm previous studies which showed that organic matter in both soils is mainly of mangrove origin. The results further suggest accumulation of organic matter inRhizophorasoils and a continuing degradation of organic matter inAvicenniasoils. The latter may thus release more nutrients to adjacent ecosystems thanRhizophorasoils.     

Distribution and alteration of amino acids in bulk DOM along a transect from bay to oceanic waters

A systematic survey of the concentrations and composition of total hydrolyzable amino acids (THAA) in bulk dissolved organic matter (DOM) was conducted at 11 stations along the 137°E transect from bay to oceanic areas in the northwestern Pacific. Concentrations of THAA and their contributions to dissolved organic carbon were high in the bay and coastal areas, declined toward the oceanic area and decreased with depth in the water columns. From the distribution patterns of the relative abundances of amino acids along the transect, individual amino acids were divided into four groups. One group included tyrosine, valine, isoleucine, phenylalanine, leucine and tryptophan, and was considered to represent easily degradable THAA, while glycine and alanine belonged to a more biorefractory group of THAA. Principal components analysis (PCA) was conducted to quantitatively differentiate patterns of amino acid composition. Amino acid groups based on PCA agreed with the groups classified by distribution patterns, indicating that first principal component scores reflected the degree of degradation of THAA in DOM, and were defined as a degradation index (DI). Two amino acids, glycine and alanine, increased in relative abundance with increasing DI, while valine, isoleucine, phenylalanine and leucine decreased with decreasing DI. The agreement indicated that the degradation process was the key factor controlling the quantity and quality of THAA in bulk DOM.     

Nutrient gradients in the western North Atlantic Ocean: Relationship to microbial community structure and comparison to patterns in the Pacific Ocean

Studies of nitrogen and phosphorus dynamics in the oligotrophic surface waters of the western North Atlantic Ocean have been constrained because ambient concentrations are typically at or below the detection limits of standard colorometric methods, except during periods of deep vertical mixing. Here we report the application of high-sensitivity analytical methods—determinations of nitrate plus nitrite (N+N) by chemiluminescence and soluble reactive phosphorus (SRP) by the magnesium induced co-precipitation (MAGIC) protocol—to surface waters along a transect from the Sargasso Sea at 26°N through the Gulf Stream at 37°N, including sampling at the JGOFS Bermuda Atlantic Time-series Study (BATS) station. The results were compared with data from the BATS program, and the HOT station in the Pacific Ocean, permitting cross-ecosystem comparisons. Microbial populations were analyzed along the transect, and an attempt was made to interpret their distributions in the context of the measured nutrient concentrations.Surface concentrations of N+N and SRP during the March 1998 transect separated into 3 distinct regions, with the boundaries corresponding roughly to the locations of the BATS station (∼31°N) and the Gulf Stream (∼37°N). Although N+N and SRP co-varied, the [N+N] : [SRP] molar ratios increased systematically from ∼1 to 10 in the southern segment, remained relatively constant at ∼40–50 between 31°N and 37°N, then decreased again systematically to ratios <10 north of the Gulf Stream. Dissolved organic N (DON) and P (DOP) dominated (⩾90%) the total dissolved N (TDN) and P (TDP) pools except in the northern portion of the transect. The [DON] : [DOP] molar ratios were relatively invariant (∼30–60) across the entire transect.Heterotrophic prokaryotes (operationally defined as “bacteria”), Prochlorococcus, Synechococcus, ultra- and nanophytoplankton, cryptophytes, and coccolithophores were enumerated by flow cytometry. The abundance of bacteria was well correlated with the concentration of SRP, and that of the ultra- and nanophytoplankton was well correlated with the concentration of N+N. The only group whose concentration was correlated with temperature was Prochlorococcus, and its abundance was unrelated to the concentrations of nutrients measured at the surface.We combined our transect results with time-series measurements from the BATS site and data from select depth profiles, and contrasted these North Atlantic data sets with time-series of N and P nutrient measurements from a station in the North Pacific subtropical gyre near Hawaii [Hawaii Ocean Time-series (HOT) site]. Two prominent differences are readily observed from this comparison. The [N+N] : [SRP] molar ratios are much less than 16 : 1 during stratified periods in surface waters at the BATS site, as is the case at the HOT site year round. However, following deep winter mixing, this ratio is much higher than 16 : 1 at BATS. Also, SRP concentrations in the upper 100 m at BATS fall in the range 1–10 nM during stratified periods, which is at least one order of magnitude lower than at the HOT site. That two ecosystems with comparable rates of primary and export production would differ so dramatically in their nutrient dynamics is intriguing, and highlights the need for detailed cross ecosystem comparisons.     

Chemical forms and dynamics of amino acid-containing particulate organic matter in Pacific surface waters

Particulate combined amino acids (PCAA) are the most abundant identified constituents of particulate organic matter (POM) in Pacific Ocean surface waters, but their chemical forms are unclear. In the present study, chemical characterization of amino acid-containing materials in surface POM from subarctic to subtropical waters along 165 °E in the Pacific was carried out by one- and two-dimensional gel electrophoresis. At least four chemical forms of amino acid-containing POM were distinguished: proteins, acidic materials containing peptides, protein/peptide-specific dye-stainable low-molecular-mass materials (stainable materials) and non-stainable materials, all of which were considered to be major components of detrital POM. Seventeen distinct protein containing components were distinguished in samples across the transect. A majority of stainable materials was estimated to comprise 6–8 amino acid residues, while less than six amino acid residues made up the non-stainable materials. Among the four chemical forms, acidic materials and non-stainable materials were major components, accounting for 31–42% and 49–63% of PCAA, respectively, along the transect. Proteins were common, but they were quantitatively less than 2% of PCAA. Stainable materials were regionally variable and more abundant in subarctic waters than in subtropical waters. The mechanistic processes by which such amino acid-containing POM occurs as detrital POM are discussed.     

River or mangrove? Tracing major organic matter sources in tropical Brazilian coastal waters

The influence of mangrove-fringed tropical estuaries on coastal carbon budgets has been widely recognised. However, a quantitative differentiation between riverine and mangrove-derived inputs to the dissolved (DOM) and microparticulate organic matter (POM) pool of these environments has been hitherto not possible. Based on lignin-derived phenols and stable carbon isotopes a chemical signature for mangrove, terrestrial and marine-derived organic matter was established for a mangrove estuary in North Brazil. A mixing model was applied to calculate the contribution of each of the three sources to the DOM and POM pool in the estuary throughout 18 tidal cycles in the course of one year. Best source assignment for POM was reached with the yield of lignin phenols and δ¹³C as paired indicators, while the origin of DOM was best identified by the yield of lignin phenols and the acid to aldehyde ratio of vanillyl phenols. Although only about 6% of the fluvial catchment area is covered by mangroves, their contribution to the estuarine DOM and POM pool generally exceeded several times the terrigenic input from the hinterland. This outwelling of mangrove-derived organic matter was enhanced during the rainy season. DOM and POM were exported from the mangrove to the estuary in similar proportions. Most mangrove-POM was rapidly removed from the water column, while mangrove-DOM behaved conservatively. In contrast, terrestrial DOM was almost entirely removed in the outer part of the estuary, which was accompanied by a concomitant increase in terrestrial POM. This seems to be the result of a geochemical barrier zone for this type of DOM in the estuary. Generally, a high proportion of mangrove-DOM was present in the outer part of the estuary, even at high tide. This indicates DOM outwelling from mangroves in adjacent bays or estuaries and points to similar driving forces controlling this process on a regional scale. Mangroves probably play a more important role than rivers for marine carbon budgets along the North Brazilian coast south of the Amazon estuary.     

Tracing suspended organic nitrogen from the Yangtze River catchment into the East China Sea

Total suspended matter was collected along the Yangtze River (Changjiang) and in the East China Sea in April to May and in September 2003, respectively, to study origin and fate of particulate organic nitrogen. Concentrations of particulate organic carbon (POC), nitrogen (PN) and hydrolyzable particulate amino acids (PAA; d- and l-enantiomers) were higher in the Yangtze Estuary than in the river and decreased offshore towards the shelf edge. In the coastal area, higher values of PAA were observed in the surface layer than in the bottom water. Stable carbon isotope ratios (δ¹³C) of POC increased from − 24.4‰ in the river to values around − 21‰ on the East China Sea Shelf. Dominant amino acids were aspartic acid + aspartine (Asx), glutamic acid + glutamine (Glx), glycine, alanine and serine. The proportions of Asx, Glx and isoleucine were higher in the marine than in the riverine samples contrary to the distributions of glycine, alanine, threonine and arginine. The proportions of d-amino acids were highest in the riverine suspended organic matter (6% of PAA) decreasing towards the shelf edge (1.5% of PAA). d-arginine, not reported in natural aquatic samples so far, was the most abundant d-amino acid in the river. The amino acid composition of the particulate organic matter (POM) in the Yangtze River indicates an advanced stage of degradation of POM. Highly degraded organic matter from soils is probably a main source of POM in the Yangtze River, but the relatively high δ¹³C values and low C/N ratios (7.7 ± 1.6) also indicate contribution from anthropogenic sources. The degraded riverine material was a dominant organic matter source in the estuary, where aquatic primary production had only a small overall contribution. In the East China Sea, gradual settling of riverine organic matter and the addition of fresher phytoplankton impacted the amino acid composition and δ¹³C values, and on the outer shelf relatively fresh phytoplankton-derived organic matter dominated.