Particulate Amino Acids Research Articles

Variability of Particulate Amino Acids and Processes Responsible for Sources into the Coastal Waters of the Bay of Bengal

Variability of Particulate Amino Acids and Processes Responsible for Sources into the Coastal Waters of the Bay of Bengal

Source, composition, and reactivity of particulate organic matter along the Changjiang Estuary salinity gradient and adjacent sea

The sources, distribution, and fate of particulate organic matter (POM) in estuaries are dynamic and complex, influenced by highly intensive human activities and high productivity. In this study, water samples were collected along the Changjiang Estuary salinity gradient and adjacent sea (CEAS) in February and May 2017. Particulate organic carbon (POC), particulate nitrogen (PN), the δ13C isotope values and major biochemical constituent (total particulate amino acids, TPAA) were measured. The concentrations of POC, PN, and TPAA showed an overall decreasing trend from the river end-member to the open sea; however, their maximum always occurred around the turbidity maximum zone (TMZ). Concentrations of POC and TPAA showed a negative correlation with salinity and a positive correlation with chlorophyll a, indicating that the variation in POM concentrations and composition was mainly controlled by both terrigenous input and in situ phytoplankton production. The δ13C values gradually increased from the river mouth to the open sea in both winter and spring, in contrast to the molar C/N, reflecting the transition from terrestrial POC to phytoplankton-derived fresh POC with increasing salinity. Major biochemical indicators of TPAA/POC (%) and the degradation index (DI), showed a gradual shift towards more bioactive POM with increasing salinity in spring, although low TPAA/POC (%) values appeared within the TMZ. In spring, POC reactivity was higher than in winter. The proportions of glycine (Gly) and serine (Ser) were higher in winter, indicating that POM had suffered extensive degradation. Based on a two end-member mixing model, the contribution of marine POC in spring (53 ± 14%) was significantly greater than in winter (39 ± 19%), indicating that phytoplankton-derived POM was dominant in spring, associated with the increase in phytoplankton biomass from winter to spring. Based on mass balance, a box model showed evidence of a net POC sink over the Changjiang estuary and its adjacent East China Sea shelf in both winter and spring, with a net POC budget of 20.49 ± 7.01 and 15.87 ± 6.57 kmol s−1, respectively. Results illustrate that the spatio-temporal distribution of POM varies distinctively and will further affect the variability in its composition and reactivity in the CEAS.

What can we learn from amino acids about oceanic organic matter cycling and degradation?

Abstract. Amino acids (AAs) mainly bound in proteins are major constituents of living biomass and non-living organic material in the oceanic particulate and dissolved organic matter pool. Uptake and cycling by heterotrophic organisms lead to characteristic changes in AA composition so that AA-based biogeochemical indicators are often used to elucidate processes of organic matter cycling and degradation. We analyzed particulate AA in a large sample set collected in various oceanic regions covering sinking and suspended particles in the water column, sediment samples, and dissolved AA from water column and pore water samples. The aim of this study was to test and improve the use of AA-derived biogeochemical indicators as proxies for organic matter sources and degradation and to better understand particle dynamics and interaction between the dissolved and particulate organic matter pools. A principal component analysis (PCA) of all data delineates diverging AA compositions of sinking and suspended particles with increasing water depth. A new sinking particle and sediment degradation indicator (SDI) allows a fine-tuned classification of sinking particles and sediments with respect to the intensity of degradation, which is associated with changes of stable isotopic ratios of nitrogen (δ15N). This new indicator is furthermore sensitive to sedimentary redox conditions and can be used to detect past anoxic early diagenesis. A second indicator emerges from the AA spectra of suspended particulate matter (SPM) in the epipelagic and that of the meso- and bathypelagic ocean and is a residence time indicator (RTI). The characteristic changes in AA patterns from shallow to deep SPM are recapitulated in the AA spectra of the dissolved organic matter (DOM) pool, so that deep SPM is more similar to DOM than to any of the other organic matter pools. This implies that there is equilibration between finely dispersed SPM and DOM in the deep sea, which may be driven by microbial activity combined with annealing and fragmentation of gels. As these processes strongly depend on physico-chemical conditions in the deep ocean, changes in quality and degradability of DOM may strongly affect the relatively large pool of suspended and dissolved AA in the ocean that amounts to 15 Pg amino acid carbon (AAC) and 89 ± 29 Pg AAC, respectively.

Distribution of Coomassie Blue Stainable Particles in the Pearl River Estuary, China, Insight Into the Nitrogen Cycling in Estuarine System

Distributions of Coomassie Blue stainable particles (CSP), the sources and transports, as well as their implications for nitrogen biogeochemical cycles in the Pearl River estuary (PRE) were investigated during two cruises in August 2016 and January 2017. CSPcolor concentrations (CSP concentration determined spectrophotometrically) were 73.7–685.3 μg BSA eq L–1 [μg Bovine serum albumin (BSA) equivalent liter–1] in August 2016 and 100.6–396.4 μg BSA eq L–1 in January 2017, respectively. CSP concentrations were high in low-salinity waters (<5), and declined from the river to the middle estuary by 80% in the wet season and 55.6% in the dry season, respectively, then increased again in the lower estuary due to high primary production. CSP concentrations were mainly associated with chlorophyll a (Chl a) concentration except for the turbid mixing zone, suggesting that autochthonous phytoplankton production served as the primary source of CSP in the PRE. The concentrations of nitrogen (N) as CSP in the PRE were comparable to the nitrogen content of particulate hydrolysable amino acids (PHAA). Pictures of CSP taken by microscopy and the correlation between composition of PHAA and the ratio of Chl a/CSPcolor showed that CSP were relatively degraded due to delivery of old terrestrial protein to river section and extensive microbial degradation during mixing at the upper and middle parts of the estuary, whereas CSP in lower estuary appeared to be more labile due to higher fresh algal production. The contribution of CSP nitrogen (CSP-N) to the particulate nitrogen (PN) pool was 34.98% in summer and 30.8% in winter. The conservative estimate of CSP-N input flux in the Pearl River Delta was about 6 × 106 mol N d–1. These results suggested that CSP was a significant pool of organic nitrogen in the PRE. The study of CSP composition in terms of nitrogen provides new insight into the roles of CSP on nitrogen biogeochemical processes in the turbid and productive estuarine system.

Distribution and bioavailability of dissolved and particulate organic matter in different water masses of the Southern Yellow Sea and East China Sea

As the largest marginal seas, the Southern Yellow Sea (SYS) and the East China Sea (ECS) are important areas to study the biogeochemical cycles of organic matter from different sources. Seawater samples were collected from the SYS and ECS to determine the composition of organic carbon and major biochemicals (amino acids and carbohydrates) making up the dissolved (DOM) and particulate organic matter (POM). Concentrations of dissolved organic carbon (DOC) in the surface waters exhibited a latitudinal gradient, with high values appearing in the Yellow Sea Coastal Current Water (YSCCW). As the labile fraction of DOM, the concentrations of total hydrolysable amino acids (THAA) and total dissolved carbohydrates (TDCHO) were variable and tended to decrease from inshore to offshore sites. The DOC, THAA, and TDCHO concentrations were negatively correlated with salinity, suggesting that physical mixing and lateral transport played an important role in the distribution of DOM. In contrast, phytoplankton production directly affected the particulate amino acid (PAA) concentrations. High concentrations of PAA in the bottom water along a transect were probably due to resuspension by strong currents. DOC-normalized yields of THAA and TDCHO (THAA-C% and TDCHO-C%) were used to characterize the bioavailability of DOM in different water masses. Elevated THAA-C% values occurred in regions with high phytoplankton biomass, while high TDCHO-C% values were widespread in the Yellow Sea Warm Current Water (YSWCW) and the YSCCW. THAA-C% and TDCHO-C% had similar depth distributions, higher in the surface and middle layers than in the bottom layer, suggesting that organic matter undergoes diagenetic alterations as it sinks. The degradation index (DI) of DOM was lower than that of POM, which could be explained by their different sources and degradation states. The sporadic occurrence of hot spots likely represented important sites of biological activity. • Concentration, chemical composition, and bioavailability of OM were studied. • Physical mixing and lateral transport affect the distribution of DOM. • Amino acid and carbohydrate yields decreased with water depth. • Hot spots of bioavailable DOM occur sporadically in the surface water.

Tracing Nutrients and Organic Matter Changes in Eutrophic Wenchang (China) and Oligotrophic Krka (Croatia) Estuaries: A Comparative Study

Estuaries modify the concentration and composition of riverine nutrients and organic matter (OM), which eventually determine the riverine flux effect to coasts. Nutrients, organic carbon (OC), pigments, and amino acids (AAs) from the samples collected in the eutrophic Wenchang River Estuary (WRE) in China and the oligotrophic Krka River Estuary (KRE) in Croatia were analyzed in order to have a better understanding of how estuaries regulate terrestrial materials. We found a clear increase of dissolved inorganic nitrogen (DIN) concentration and its subsequent decrease due to the removal of DIN (over 100 μM) in the WRE, whereas DIN showed minor variation lengthwise in the KRE, i.e., with the salinity changes, ranging between 1.0 and 5.8 μM. The elevated algae-derived OC, dissolved organic nitrogen, and particulate AAs nitrogen suggest that the OM assimilation may explain approximately one-third of the DIN removal in the WRE, whereas in the oligotrophic KRE, such inorganic to organic transformation is not likely to be significant. Due to the prominent estuarine nitrogen removal/assimilation process, DIN/dissolved inorganic phosphorus (DIP) ratio was as high as 425 in the upper WRE under strong riverine influence, but it declined to as low as 5.4 at the mouth of WRE, that is even lower than DIN/DIP ratio at the mouth of oligotrophic KRE (12). When compared with other rivers worldwide, the Wenchang River showed high nutrients and organic carbon yields. Given the contrasting estuarine process (e.g., DIN removal) between the KRE and the WRE, apparent high nutrient yield from eutrophic rivers should be viewed with caution in ocean studies as the final impact to coastal zone could be similar to the oligotrophic rivers like the KRE.

Source, transformation and degradation of particulate organic matter and its connection to microbial processes in Jiaozhou Bay, North China

Microbial processes during the degradation and transformation of marine organic matter (OM) are thought to play an important role in controlling the strength and efficiency of carbon export and preservation in the ocean. However, the detailed relationship between the diagenetic states of OM and microbial activity and community structures remains poorly understood. In this study, particulate amino acids (PAAs), stable carbon and nitrogen isotopic signatures, heterotrophic bacterial abundance (HBA), bacterial community structure and extracellular hydrolytic enzyme activity (EEA) in particulate OM (POM) were investigated in Jiaozhou Bay (JZB), China, with the aim of investigating bacterial degradation and adaption in response to different sources and reactivity of POM in the coastal environment. The results showed that POM from different sources had distinct PAA compositions, diagenetic states, and bacterial features, such as particle attached HBA, EEA and community structure. High PAA concentrations but low contribution of bacterial carbon to particulate organic carbon (POC) and diagenetic alteration of POM were observed in regions with high in situ marine production, where high Chl-a and autochthonous δ13C and δ15N signatures were observed. In addition, high HBA and D-amino acid (D-AA) concentrations in POM were also found in the same regions, which indicated that fresh POM also induced rapid bacterial growth and reproduction. However, the lowest D-AA proportion to PAA (mol% D-AA) in those regions still indicated a more obvious supply of AAs from marine sources, which was consistent with the low bacterial carbon contribution to POC and fresh states of POM. In contrast, POM in low primary production regions was highly degraded by bacteria, as reflected by an enrichment in D-AAs and high bacterial contribution. However, high EEA probably driven by the priming effect occurred in regions where fresh planktonic POM was mixed with terrigenous POM. High relative abundances of Flavobacteriia, Alphaproteobacteria and Gammaproteobacteria were observed in fresh planktonic, terrestrial and planktonic mixture and highly degraded POM, respectively, indicating a possible bacterial adaptation strategy to their available OM. Our study has important implications for bacteria–POM interactions and provides insight into the role of bacteria in the degradation and transformation of POM of different sources in coastal systems.

Different Biochemical Compositions of Particulate Organic Matter Driven by Major Phytoplankton Communities in the Northwestern Ross Sea.

Marine particulate organic matter (POM) largely derived from phytoplankton is a primary food source for upper trophic consumers. Their biochemical compositions are important for heterotrophs. Especially, essential amino acids (EAAs) in phytoplankton are well known to have impacts on the survival and egg productions of herbivorous zooplankton. To estimate the nutritional quality of POM, the biochemical compositions [biomolecular and amino acid (AA) compositions] of POM were investigated in the northwestern Ross Sea during the late austral summer in 2018. Carbohydrates (CHO) accounted for the highest portion among different biomolecules [CHO, proteins (PRT), and lipids (LIP)] of POM. However, the higher contribution of PRT and lower contribution of CHO were observed in the southern section of our study area compared to those in the northern section. The spatial distribution of total hydrolyzable AAs in POM was considerably influenced by phytoplankton biomass, which indicates that the main source of particulate AA was generated by phytoplankton. Our results showed that the relative contribution of EAA to the total AAs was strongly associated with EAA index (EAAI) for determining protein quality. This result indicates that higher EAA contribution in POM suggests a better protein quality in consistency with high EAAI values. In this study, variations in the biochemical compositions in POM were principally determined by two different bloom-forming taxa (diatoms and Phaeocystis antarctica). The southern region dominated majorly by diatoms was positively correlated with PRT, EAA, and EAAI indicating a good protein quality, while P. antarctica-abundant northern region with higher CHO contribution was negatively correlated with good protein quality factors. Climate-driven environmental changes could alter not only the phytoplankton community but also the physiological conditions of phytoplankton. Our findings could provide a better understanding for future climate-induced changes in the biochemical compositions of phytoplankton and consequently their potential impacts on higher trophic levels.

Ocean acidification modifies biomolecule composition in organic matter through complex interactions

The main source of marine organic carbon (OC) is autotrophic production, while heterotrophic degradation is its main sink. Increased anthropogenic CO2 release leads to ocean acidification and is expected to alter phytoplankton community composition, primary production rates and bacterial degradation processes in the coming decades with potential consequences for dissolved and particulate OC concentration and composition. Here we investigate effects of increased pCO2 on dissolved and particulate amino acids (AA) and carbohydrates (CHO), in arctic and sub-arctic planktonic communities in two large-scale mesocosm experiments. Dissolved AA concentrations responded to pCO2/pH changes during early bloom phases but did not show many changes after nutrient addition. A clear positive correlation in particulate AA was detected in post-bloom phases. Direct responses in CHO concentrations to changing pCO2/pH were lacking, suggesting that observed changes were rather indirect and dependent on the phytoplankton community composition. The relative composition of AA and CHO did not change as a direct consequence of pCO2 increase. Changes between bloom phases were associated with the prevailing nutrient status. Our results suggest that biomolecule composition will change under future ocean conditions but responses are highly complex, and seem to be dependent on many factors including bloom phase and sampling site.

Influence of Algal Production and Decomposition on the Carbon Isotope Signature of Labile Particulate Organic Matter on a Productive Continental Shelf Under the Stress of Coastal Hypoxia

To better understand the sources and recycling of labile organic matter in coastal water, we studied the carbon isotope signature of particulate organic carbon (POC) and particulate amino acids, a major group of labile organic compounds, on the shelf of the northern South China Sea. In addition, we were able to compare effects of hypoxia on labile organic matter at one station on the shelf. We found that carbon-weighted average d13C values of particulate amino acids (wAAd13C) were generally higher at more productive offshore stations than nearshore stations. This amino acid d13C distribution suggests that the labile fraction of organic matter in coastal water originated primarily from local primary production. In contrast, bulk POC d13C values showed little spatial variation on the NSCS shelf. The different patterns of wAAd13C and PO13C distributions indicate a combined effect of POM lability and physical processes on the isotopic distribution of organic materials on this productive shelf. Moreover, the amino acid d13C in coastal hypoxic water suggests local primary production as the most likely source of labile organic matter that drives hypoxia on the NSCS shelf. No clear difference was observed in particulate amino acid d13C distribution between hypoxic and oxic waters,

Amino acid and amino sugar compositional changes during in vitro degradation of algal organic matter indicate rapid bacterial re-synthesis

Amino acids (AA) and, more recently, amino sugars (AS) in marine or lacustrine sediments have been increasingly used as paleoproxies. In order to assess AA and AS compositional changes during simulated microbial degradation, as well as to understand the importance of amino-compound re-synthesis by microbes during early diagenesis, decomposition experiments (300 days) were performed with algal (Fragilaria crotonensis) organic matter (OM)/quartz-sand mixtures under controlled redox conditions. Despite expected greater overall degradability under oxic conditions, decomposition kinetics of the bulk algal OM, as well as the total particulate AA and AS were similar under oxic and anoxic conditions, following exponential decay kinetics consistent with the observed mobilization and transfer of large parts of the particulate organic carbon (C) and nitrogen (N) into the dissolved inorganic and organic C and N pools. Carbon-normalized AA and AS yields suggest relative enrichment of amino compounds during partial decomposition, indicating the production and accumulation of microbial biomass during early diagenesis, independent of the redox environment. Moreover, AA and AS compositional changes, such as the relative enrichment of the AA glycine and the AS muramic acid (MurA), and the decrease in the molar ratio of glucosamine and galactosamine (GlcN:GalN) during degradation in both redox systems, were consistent with significant bacterial re-synthesis and the preferential preservation of bacterial biomaterial with increasing diagenesis. Large disparities between different bacterial amino-sugar based estimates of bacterial contribution indicate that bacterial end-member compositions are not currently known well enough to make these bacterial-biomarker constraints quantitative. However, the overall trends are consistent, indicating substantial turnover of eukaryotic into bacterial OM on short time scales of weeks to months. Together these results suggest that the influence of bacterial reworking in conserving sedimentary OM via its transfer into more refractory OM pools may be substantially greater than previously appreciated. We also investigated established amino-compound based indicators of OM degradation, bacterial synthesis, and sediment reactivity. Despite discrepancies, which we attribute to different susceptibilities of the respective indicators towards degradational changes on different time-scales, the tested indices were overall consistent with past data. These results therefore confirm their value as universal indicators of OM diagenesis. Together, our data highlight the vital role of bacterial reworking on the composition of sedimentary OM, with important implications for the alteration of primary geochemical signatures during early sedimentary diagenesis and their use as proxies in paleoenvironmental studies.

Impact of Water-Sediment Regulation on Variations of Amino Acids in the Middle-Lower Yellow River, China

In order to examine the impacts of water-sediment regulation on regional carbon cycling, we collected water, particulate and sediment samples from the middle-lower Yellow River in late June and early July, 2015 and analyzed their specific amino acids (AA), DOC, POC, and bacteria abundance. Summarized by 14 specific AA, the total hydrolysable AA (THAA), particulate AA (PAA), and sediment AA (SAA) varied in ranges of 2.29–9.05 µmol L−1, 5.22–22.96 µmol L−1, and 81.7–137.19 µg g−1 dry weight. After the regulation, dissolved free AA (DFAA) decreased by 29% while DCAA increased by 72%. These variations suggested that DFAA were further degraded, while DCAA molecules were further activated. Meanwhile, PAA increased almost 4 times as many as those before regulation, and SAA increased as well. After regulation, the amounts of bioactive amino acids (Asp, Glu and Gly) increased in THAA but decreased in PAA, with little changes in SAA. The ratios of Asp/Gly in different phases increased after regulation, indicating the AA contributions were promoted by calcareous organisms rather than by siliceous organisms. Multiple correlation analysis showed that PAA was primary representatives of AA and organic carbon, followed by DCAA and POC. Moreover, bacterial reproduction played a key role in shaping the AA compositions and properties, followed by the redox condition and acid-base balance. The results of this study provided a clear evidence for the effects of water-sediment regulation on regional biogeochemistry of organic carbon in the middle-lower Yellow River.

Distribution, degradation and bioavailability of dissolved organic matter in the East China Sea

Water samples were collected from the East China Sea (ECS) in October 2015 to investigate the distribution, degradation and bioavailability of organic matter. Concentrations of dissolved organic carbon (DOC), total hydrolyzable amino acids (THAAs, including dissolved free, DFAA and combined fraction, DCAA), particulate amino acids (PAAs), and total dissolved carbohydrates (TDCHO, including monosaccharides, MCHO and polysaccharides, PCHO) were measured. DOC and TCHO concentrations exhibited similar distribution patterns with high values occurring at nearshore stations, revealing the effects of terrestrial input and similar source and removal pathways of DOC and TCHO. The distributions of THAA, DCAA, and PAA displayed declining trends from the north to south of the ECS. Elevated THAA values simultaneously occurred in the center of the transect. The onboard incubation experiments with surface seawater from one station showed that the values of degradation index based on amino acids decreased with the increase of dissolved inorganic nitrogen (DIN) concentrations, indicating the mineralization of THAA to DIN during degradation process. TCHO-C% and THAA-C% are defined as the percentages of carbohydrates and amino acids in DOC, respectively. There were 21 stations suffering P limitation, implying that PO 4 3− -P content was the key factor limiting the growth of phytoplankton. High TCHO-C% values were found at P-limited stations, indicating that phytoplankton preferentially produced carbohydrates when experiencing nutrient limitation. The difference of dissolved organic matter bioavailability between surface and bottom water were probably due to water stratification. Overall, the present study may have implications for the source, removal and bioavailability of organic mater in the ECS.

Collecting amino acids in the Enceladus plume

AbstractWe numerically model the dynamics of the Enceladus plume ice grains and define our nominal plume model as having a particle size distributionn(R) ~R−qwithq= 4 and a total particulate mass rate of 16 kg s−1. This mass rate is based on average plume brightness observed by Cassini across a range of orbital positions. The model predicts sample volumes of ~1600 µg for a 1 m2collector on a spacecraft making flybys at 20–60 km altitudes above the Enceladus surface. We develop two scenarios to predict the concentration of amino acids in the plume based on these assumed sample volumes. We specifically consider Glycine, Serine, α-Alanine, α-Aminoisobutyric acid and Isovaline. The first ‘abiotic’ model assumes that Enceladus has the composition of a comet and finds abundances between 2 × 10−6to 0.003 µg for dissolved free amino acids and 2 × 10−5to 0.3 µg for particulate amino acids. The second ‘biotic’ model assumes that the water of Enceladus's ocean has the same amino acid composition as the deep ocean water on Earth. We compute the expected captured mass of amino acids such as Glycine, Serine, and α-Alanine in the ‘biotic’ model to be between 1 × 10−5to 2 × 10−5µg for dissolved free amino acids and dissolved combined amino acids and about 0.0002 µg for particulate amino acids. Both models consider enhancements due to bubble bursting. Expected captured mass of amino acids is calculated for a 1 m2collector on a spacecraft making flybys with a closest approach of 20 km during mean plume activity for the given nominal particle size distribution.

Characteristics of amino acids during the process of algae-originated particles decomposition in Lake Taihu

在实验条件下研究了高浓度蓝藻堆积后水体中的藻源性颗粒物中氨基酸的分解速率、分解量和氨基酸态氮形态的变化情况.在自然光照组中，颗粒态氨基酸（PAA）的浓度从实验前的0.46 mmol/L降至实验后的0.30 mmol/L；而在无光分解组中PAA从0.44 mmol/L降至0.06 mmol/L.两种处理下PAA的降解速率常数分别为0.03916和0.17424 d^-1.溶解态氨基酸（DAA）在分解过程中浓度比较低，随时间的变化表现出先增大后减小的趋势，在两种不同的处理下，最大值分别为10.94和7.94 μmol/L，21 d后减小到与实验开始时持平，甚至低于初始值.实验初期，PAA所占比例高达74%~80%，但迅速被分解转化为DAA和铵态氮（NH₄⁺-N），随着实验的进行NH₄⁺-N又逐渐转化为硝态氮，其中无光分解组中的分解更为彻底，而自然光照组中PAA分解量小于无光分解组.实验结果表明，氨基酸作为水体中浮游植物的潜在氮源，可以被分解为水华过程中藻类所需的NH₄⁺-N，对水华的维持具有一定的促进作用.;The characteristics of decomposition rate and quantity of amino acids, as well as the change of nitrogen forms, were explored during the process of decomposition of high-density cyanobacterial particles in this study. The results showed that the initial concentrations of particulate amino acids (PAA) were 0.46 mmol/L in natural light group and 0.44 mmol/L in the aphotic group. At the end of the experiment, the PAA was much stable with a concentration of 0.30 mmol/L in natural light group, while decreased dramatically to 0.06 mmol/L in the aphotic group. The degradation rate constants were 0.03916 and 0.17424 d^-1, respectively. The concentration of dissolved amino acids (DAA) was much lower in comparison to PAA in the process of decomposition. In detail, the DAA increased gradually and peaked at 10.94 and 7.94 μmol/L for the two groups, respectively, and then declined to around the initial value in the end of the 21st day. At the beginning of the experiment, PAA accounted for 74%-80% of the total amino acids, then PAA was transformed to DAA and ammonia (NH₄⁺-N) quickly, and finally the NH₄⁺-N was transformed gradually to NO₃^--N by nitrification. Compared with the natural light group, the decomposition of particles in aphotic group was more complete. Algal photosynthesis inhibited the decomposition of cyanobacterial particles in the natural group. Our results demonstrated that amino acids are potential nitrogen sources of phytoplankton and could be demineralized to NH₄⁺-N to support phytoplankton growth during cyanobacterial blooms. Therefore, the decomposition of high-density algal particles plays a key role in the maintenance of cyanobacterial blooms.

Temporal and spatial variations of particulate and dissolved amino acids in the East China Sea

Concentrations of amino acids in dissolved and particulate pools in the East China Sea (ECS) were determined during two cruises (October–November 2013 and May–June 2014). The spatial distributions of total hydrolyzed amino acids (THAA), dissolved combined amino acids (DCAA), dissolved free amino acids (DFAA), and particulate amino acids (PAA) in the study area were considerably influenced by phytoplankton biomass and circulations. In addition, in situ phytoplankton production and terrestrial input are the major sources of amino acids in the ECS. The %C-PAA and %N-PAA positively correlated with chlorophyll a (Chl-a), thus reflecting their phytoplankton sources. The concentrations of amino acids were higher in coastal waters than in open sea, revealing the effects of terrestrial input on amino acid concentrations. Moreover, the vertical distributions of THAA, DCAA, DFAA, and PAA exhibited similar patterns, i.e., decreasing trends from the surface water to the bottom water. Our study indicated that the deposition of phytoplankton biodetritus may affect the vertical distributions of amino acids. The major constituents of THAA were glycine, serine, and glutamic acid, whereas the major constituents of PAA are glycine, glutamic acid, and alanine. The diel variation of THAA presented a certain hysteresis, following the variation of Chl-a. Particle sorption had a contribution in describing the particulate pool and dissolved pool in the Changjiang River.

Seasonal dynamics of particulate organic matter in the Changjiang Estuary and adjacent coastal waters illustrated by amino acid enantiomers

Total suspended matter (TSM) was collected in the Changjiang Estuary and adjacent areas of the East China Sea in July, August, and November 2011, to study the composition and fate of particulate organic nitrogen (PON) during an August typhoon event and bottom trawling activities. Concentrations of particulate organic carbon (POC), particulate nitrogen (PN), and hydrolyzable particulate amino acids (PAA, D- and L-enantiomers) were higher during July and August than during November; however, D-arginine and alanine levels were significantly higher in November. Seasonal trends in the composition of PAAs indicate that in situ production is a key factor in their temporal distribution. No significant increase in TSM or decrease in labile organic matter was observed during the transit period following a typhoon event in August. In contrast, higher primary production was observed at this time as a result of the penetration of Changjiang Diluted Water caused by the typhoon event. Trawling effects were studied by comparing the calm season (July) with the bottom-trawling period (November) at similar sampling sites. The effect of trawling on the composition of bottom organic matter was studied by comparing D-amino acids concentrations and C/N ratios in the calm season (July) with the bottom-trawling period (November). A substantial contribution of microbial organic matter during the November cruise was indicated by a decrease in glutamic acid, an increase in TSM and D-alanine, and a lower carbon/nitrogen (C/N) ratio. In shallow coastal regions, anthropogenic activities (bottom trawling) may enhance the transfer of low-nutritional-value particulate organic matter into the benthic food chain.

Sources, transformation and fate of particulate amino acids and hexosamines under varying hydrological regimes in the tropical Wenchang/Wenjiao Rivers and Estuary, Hainan, China

The small tropical Wenchang and Wenjiao Rivers on the island of Hainan, tropical China, are affected by effluents from municipal sewage, aquaculture and agriculture, and by contrasting hydrological regimes related to monsoon and tropical storms. In order to obtain information on the sources, transformation and fate of organic matter (OM) we investigated the amount and composition of amino acids and hexosamines as well as the carbon isotope composition in suspended particulate matter (SPM) from the Wenchang/Wenjiao Estuary. SPM was collected along the salinity gradient starting from the river sites, along the lagoon-shaped Bamen Bay to coastal waters during four sampling campaigns between 2006 and 2009. SPM concentrations ranged between 4.7 and 58.2mgL−1. Apart from highest values after heavy rain events in spring and summer, SPM showed little seasonal variation, but increased with salinity. From SPM POC% (1.2–20.9%), C/N (4.9–16.5) and δ13Corg (−31.5 to −19.5‰), the molar composition and content of amino acids and hexosamines (8.2–156.2mgg−1 dry weight) and by comparison with sediments, mangroves, soils and plants we are able to show that soil-derived material, freshwater and marine plankton were the major sources of suspended OM. High POC and amino acid contents were related to primary production sustained by dissolved nutrients to a large extent stemming from municipal and aquaculture effluents. Factor analysis showed that the suite of biogeochemical parameters measured clearly depict the terrestrial vs. marine origin and the freshness/reactivity of OM. The four groups of samples resulting from cluster analysis were basically related to varying hydrological regimes. With respect to the sources, degradation and fate of particulate OM the major factors were: (i) the year round input of labile, amino acid rich riverine OM matter at the freshwater dominated sites, (ii) high input of degraded soil OM after heavy rains with dispersal throughout the estuary and export to the adjacent coastal area, (iii) significant production of labile marine OM especially during summer inside the bay and the (iv) dominance of refractory marine OM during winter and spring season and in the offshore region. While a major part of the fresh OM fuelled by anthropogenic nutrients appears to be stored or recycled inside the bay, periodic torrential rainfalls can lead to a pulsed export of this OM to the coastal area where it may adversely affect seagrass meadows and coral reefs.

Investigating the effect of ballasting by CaCO3 in Emiliania huxleyi, II: Decomposition of particulate organic matter

The quantitative relationship between organic carbon and mineral contents of particles sinking below 1800 m in the ocean indicates that organisms with mineral shells such as coccolithophores are of special importance for transporting carbon into the deep sea. Several hypotheses about the mechanism behind this relationship between minerals and organic matter have been raised, such as mineral protection of organic matter or enhanced sinking rates through ballast addition. We examined organic matter decomposition of calcifying and non-calcifying Emiliania huxleyi cultures in an experiment that allowed aggregation and settling in rotating tanks. Biogenic components such as particulate carbon, particulate nitrogen, particulate volume, pigments, transparent exopolymer particles (TEP), and particulate amino acids in suspended particles and aggregates were followed over a period of 30 d. The overall pattern of decrease in organic matter, the amount of recalcitrant organic matter left after 30 d, and the compositional changes within particulate organic matter indicated that cells without a shell are more subject to loss than calcified cells. It is suggested that biogenic calcite helps in the preservation of particulate organic matter (POM) by offering structural support for organic molecules. Over the course of the experiment, half the particulate organic carbon in both calcifying and non-calcifying cultures was partitioned into aggregates and remained so until the end of the experiment. The partial protection of particulate organic matter from solubilization by biominerals and by aggregation that was observed in our experiment may help explain the robustness of the relationship between organic and mineral matter fluxes in the deep ocean.

The coupling of surface seawater organic nitrogen and the marine aerosol as inferred from enantiomer-specific amino acid analysis

Atmospheric deposition is now well recognised as a major source of both inorganic and organic nitrogen for many aquatic ecosystems. In the present study HPLC was used to determine d and l amino acids in remote Atlantic aerosol samples and surface seawater particulate material. This work provides molecular evidence for both microbial and phytoplankton contributions to the organic nitrogen content of the atmospheric aerosol. Samples of aerosol and surface water particulate material were collected from the Atlantic Ocean during the Atlantic Meridional Transect AMT 12 cruise. Samples were leached with water and the extracts analysed for free amino acids (DFAA) and hydrolysable amino acids (DHAA). The residual (non-leachable) particulate amino acids (PAA) were also determined in each sample. The peptidoglycan derived d-enantiomers of aspartic acid ( d-Asp), glutamic acid ( d-Glu), serine ( d-Ser), and alanine ( d-Ala) were found in significant amounts in all dissolved and suspended surface water and aerosol samples. Plant derived d-enantiomers of leucine ( d-Leu) and isoleucine ( d-Ile) were found mainly in the surface water samples. It is estimated that in the aerosol samples ∼60% of particulate amino acids, ∼55% of leachable combined amino acids and ∼8% of leachable free amino acids derive from bacterial sources. The bacterial contribution to the amino acid inventory of surface water particulate material ranged between 15 and 30% of the different fractions studied. Similarities between the composition of surface particulate material and marine aerosol provide evidence that these systems are coupled and that consequently the concepts of ‘new’ and ‘recycled’ nitrogen may apply across the air–sea interface as well as within ocean waters.