Early diagenesis of organic matter in Peru continental margin sediments: Phosphorite precipitation

Pore water chemistry (total dissolved CO₂, NH₄, NO₃, NO₂, PO₄, Si(OH)₄, Ca, Mg, Fe, Mn, SO₄, H₂S and F, and titration alkalinity), solid phase chemistry (C_org, P_org, C_TOT, N_TOT, F, Si_OPAL and S_II), and sediment characteristics (porosity, dry bulk density and formation factors) were determined on a centimeter-scale spacing in the upper 20–40 cm of sediments under intense upwelling areas on the Peru continental shelf. These data demonstrate that carbonate fluorapatite (CFA) is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content (up to 20% C_org), very high porosity ( > 0.96 ml cm⁻³) and very low dry bulk density (< 0.1 g cm⁻³). Dissolved phosphate concentrations at the sediment-water interface range from 20 to 100 μM, orders of magnitude higher than bottom-water concentrations, and much higher than predicted from regeneration of organic matter. The mechanism of this interfacial phosphate release is unclear, but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments. Fluoride is incorporated into CFA by diffusion from the overlying seawater, and carbonate ions are provided from pore-water alkalinity. Magnesium concentrations in this reaction zone are not significantly different from those of seawater, suggesting that magnesium depletion is not a necessary prerequisite for CFA precipitation.

The environment of precipitation is interface-linked rather than driven by organic diagenesis of phosphorus deeper in the sediment. Most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region, but almost all show the precipitation signature near the interface. This interface-linked early diagenetic porewater environment for the precipitation of CFA explains many of the geochemical characteristics of phosphorites and provides a “testable” model to compare the modern phosphogenic analog with ancient phosphorite deposits. Two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites.     

珠江口外近海沉积有机质化学及稳定同位素组成的早期成岩改变

理解早期成岩过程中有机质的化学和同位素分馏对于研究海洋和湖泊环境中的生物地球化学过程是很重要的。将珠江口外近海生物成因有机质分为可水解氨基酸、碳水化合物、脂类和酸不溶四个部分,分析了有机质的化学和同位素组成(δ13C,δ15N),借以讨论沉积有机质在埋藏的早期成岩过程中所发生的化学和同位素改变,结果表明,从浮游生物→悬浮颗粒物→表层沉积物→沉积柱内部,易降解组分可水解氨基酸、碳水化合物、脂类占样品总有机碳的份额依次降低。沉积物及四个有机部分的稳定碳同位素组成在纵向上随深度保持相对恒定,而在不同有机部分之间差异明显。不同类型有机物的分解速率差异在改变有机质化学成分的同时,导致其δ13C发生小幅度负向漂移;细菌有机质的形成和分解对有机质化学成分和同位素组成演化也有重要贡献,并且在一定程度上抵消了上述δ13C的负向漂移,其结果导致沉积有机质的δ13C略低于浮游生物;另一方面,由于异养菌生长过程中的氮同位素分馏系数与可利用氮源的特征和培养基的性质等多种因素有关,导致沉积物的δ15N变化范围增大。在这里δ13C可以可靠地指示该海域沉积有机质的来源,而δ15N变化范围较大且规律不明显,难以用作沉积有机质来源的指示。     

Degradation rates of organic matter in the sediment of Mikawa Bay

Sedimentary core samples were collected from Mikawa Bay and analyzed for organic C, N and P, carbohydrate and protein including amino acids. Sedimentation rates for each of the core samples were found to lie in the range of 0.21–0.24 g cm^–2yr^–1 by the²¹⁰Pb method. Degradation rate constants of organic C, N and P, carbohydrate and protein including amino acids had ranges of 3.8–5.5, 4.7–5.9, 6.3–7.4, 5.7–6.8 and 3.9–6.8×10^–2yr^–1, respectively. The rate of degradation of organic matter in the sediment was also calculated and is discussed in relation to the flux of particulate organic matter to the surface of the sediment.     

Biogeochemistry of organic matter in the Laurentian Trough, II. Bulk composition of the sediments and relative reactivity of major components during early diagenesis

The organic carbon of 280–320 m deep Laurentian Trough sediments at landward and seaward sites (13–24 mgN/g) consisted of carbohydrates (15–22%), hydrolysable amino acids (7–13%), lipids (1–5%), labile proteins (0.3–1%) and a non-characterized fraction (62–74%). Amino acids, proteins and uncharacterized compounds accounted for 21–43, 0.9–4 and 51–78%, respectively, of total nitrogen (1.2–2.2 mgN/g). A clear reactivity trend (pheopigments ? lipids > proteins > amino acids ≈ nitrogen > carbon > carbohydrates) was deduced from the concentration decreases between settling particles and surficial sediments. This was confirmed by one-year inventories in the top cm, burial rates at 35 cm depth, and one-G model calculations. Lipids were a dominant substrate near the sediment-water interface whereas carbohydrates and amino acids constituted the principal energy sources deeper in the sediment. In the porewaters, DOC levels were low (2–6 mg/l) in the top 4 cm, indicating rapid removal (i.e. consumption, irrigation, diffusion), and increased with depth (8–12 mg/l), reflecting the buildup of refractory products. There were also clear compositional changes of DOC with depth. Geographical differences in water column fluxes were recorded in the sediments. The organic contents and ratios were higher at the landward site due to higher rates of sedimentation, bioturbation and terrestrial and total organic inputs. At the seaward station, the lower rates of these processes and stronger marine influence resulted in lower ratios and a more complete decay of organic matter within the top 35 cm sediments.     

太平洋东部ES0103柱状样品中可溶有机质的组成变化及其早期成岩作用

利用2001年采自太平洋东部ES0103站位的多管沉积物柱状样品,采用GC/MS对沉积物中的可溶有机质(氯仿沥青"A")及其族组成(饱和烃、芳烃、非烃和沥青质)、正构烷烃、类异戊二烯烃和萜类化合物进行了定量分析,结果表明:(1)氯仿沥青"A"中的非烃较饱和烃和芳烃的含量高,反映出该海区沉积物中有机质的演化程度较低.(2)正构烷烃的碳分子数范围多为nC14～nC34,CPI值略显奇偶优势,轻重烃比值(nC23-/nC24 )较低;类异戊二烯烃的Pr/Ph值较低,显示出该海区沉积物中的烃类是在较强的还原环境下形成的低成熟烃类,其母质来源主要为大型低等水生生物.(3)总有机碳与显晶蜡产率、氯仿沥青"A"均呈明显正相关关系,表明有机质相对富集层位所处的沉积环境也有利于高蜡烃的形成,成烃演化与成岩作用阶段有较好的对应关系.而萜类化合物的Ts/Tm值在表层和深部差别不大,显示出典型的低成熟烃类的特征.由此可见, ES0103柱状样品所处海区的沉积物为在较强还原环境中形成的,其有机质演化程度较低,为早期成岩作用阶段的产物.     

Transport and diagenesis of trace metals and organic matter in Palos Verdes shelf sediments affected by a wastewater outfall

Particles from the Whites Point/JWPCP outfalls operated by the Los Angeles County Sanitation District (LACSD) have been discharged onto the Palos Verdes (PV) shelf, Southern California, since the late 1930s. Since the early 1950s, they have made a significant contribution to the sedimentary deposits on the shelf. In order to study the transport and diagenesis of organic carbon (OC) and associated trace metals, replicate sediment cores were collected during 1996 and 1997 at four different sites at the ∼60 m isobath on the PV shelf, and analyzed for OC, Ag, Al, Cd, Cr, Cu, Mn, Ni, Pb, and Zn. We conclude from these results that a significant fraction of OC and associated heavy metals were transported laterally on silt particles from shallower environments. Cross-shelf transport of sediments caused multiple peaks in measured profiles of OC and trace metals at site 6C, 2 km away from the outfall. The same mechanism is likely to contribute to a concentration decrease that is smaller than that expected from decreases from the Whites Point outfall emissions. Based on Pb/OC ratios in sediments, deposited in 1971, and comparisons to the outfall from the same year, we estimate that 50±10% of the OC deposited in the early 1970s, now buried at 30–50 cm depth, had oxidized since that time, implying a half-life of about 26 years for the outfall-OC, as an upper limit. The average OC oxidation rate at peak depth (about 2 mg C cm⁻² year⁻¹) is, however, only about 10% of the present-day OC accumulation rate (20 mg C cm⁻² year⁻¹), which itself is adding not much more than 1% per year to the post-1950s OC inventory (∼1500 mg cm⁻²). We furthermore estimate that the OC inventory in PV shelf sediments in 1971 was equivalent to about 35% of that emitted by the outfall. OC and trace metal inventories did not decrease in the period 1981 to 1997, contrary to those of other contaminants such as DDTs and PCBs.     

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.     

Input and early diagenesis of chlorophylls in a temperate intertidal sediment

This paper reports the initial steps in the degradation of chlorophyll-a in a temperate, sandy intertidal sediment from a low-energy coastline at Corner Inlet, SE. Victoria. The chlorophyll-a is shown to be derived primarily from diatom input into the surface layers and it is possible to show that in this environment, relative stabilities are: chlorophyll-a > chlorophyllide-C₂ > chlorophyllide-C₁. Traces only of chlorophyll-b are present, and little or no degradation of this pigment with depth was observed. Bacteriochlorophyll-a, bacteriopheophytin-a concentrations are inversely proportional to one another in the upper sedimentary layers and the depth profile suggests a stabilised environment. A depth profile of a range of chlorophyll-a derivatives, including pheophytin-a, provides no basis for accepting that they are intermediates on the direct degradative pathway of chlorophyll-a in this environment. Rather, the evidence favours the view that chlorophyll-a degrades primarily to colourless compounds.     

筼筜湖绿潮期间颗粒有机物及沉积有机物的来源研究

以原子碳氮比C_at/N_at、TOC/Chl a、δ13C和δ15N等为指标,分析了筼筜湖绿潮爆发期间悬浮颗粒有机物(POM)和沉积有机物(SOM)的来源。结果显示,筼筜湖的POM主要以外源输入为主。在靠近海水入口的引水渠,POM主要来自厦门西海域的陆源有机碎屑;位于筼筜湖上游的干渠,生活污水及餐饮业废水的有机质是其POM的主要贡献者;内、外湖POM的C_at/N_at(6.94~7.08)与浮游植物接近,但它们并不以浮游植物为主,而主要来自引水渠和干渠有机质的输入。以内湖为例,它们对内湖POM的联合贡献高达54%~97%。筼筜湖SOM的潜在来源多样,但不同湖区差异显著:在大型海藻覆盖区,主要以大型海藻和POM为主,而在无海藻覆盖的区域,则主要来自POM的自然沉降或与底栖微藻的联合贡献。结果表明,在来源复杂的潟湖系统,有机物的化学组成并不能很好的指示有机物的来源和成因,它在有机质的示踪方面并不如稳定同位素来得有效可靠。不过,基于多种指标的分析结果可能更准确。     

Vertical and seasonal differences in biogenic silica dissolution in natural seawater in Suruga Bay, Japan: Effects of temperature and organic matter

Vertical and seasonal characteristics of biogenic silica (BSi) dissolution in seawater were investigated by multiple dissolution experiments using seawater collected from surface and mesopelagic layers in Suruga Bay during the period 2002–2004. The dissolution rate coefficients calculated based on temporal changes of BSi concentration varied with the season of sample collection. They ranged from 0.023–0.057 day^− 1 for surface samples and 0.0018–0.0025 day^− 1 for mesopelagic samples for temperatures approaching in situ conditions. Experiments at various temperatures confirmed that BSi dissolution depends on temperature in natural seawater. Dissolution rate coefficient (day^− 1) of BSi correlated significantly with temperature (°C), and Q₁₀ was 2.6. Addition of bioavailable organic matter to low-bioactivity seawater enhanced the protease activity and abundance of bacteria, and increased BSi dissolution rate by a factor of 1.4–2.0. There is clear evidence that BSi dissolution is accelerated by bacterial activity and potentially limited by bioavailable organic matter in natural seawater. Dissolution rates and total decreases of BSi concentration were lower during experiments using mesopelagic samples than in those using surface samples. This suggests that dissolution of BSi varies with depth and that BSi in the mesopelagic water is more resistant to the dissolution than that in the surface water. This lower dissolution rate was caused by lower temperature and lower bacterial activity due to less bioavailable organic matter in mesopelagic water. Our results provide a mechanistic understanding of variations in silica cycling within the seasonally and vertically differing marine environment.     

珠江三角洲全新世沉积物磁性特征及早期成岩作用分析

磁性矿物的早期成岩作用是沉积物埋藏后的重要过程,辨别早期成岩作用,才能更好地解释地层的矿物磁性变化。本研究对珠江三角洲顺德平原全新世钻孔MZ孔进行沉积相和室温磁性分析,并辅以热磁分析鉴定磁性矿物,以探讨钻孔不同深度和沉积相的早期成岩作用阶段。结果表明,MZ孔全新世地层自下而上包括感潮河道、河口湾和三角洲相。室温磁性特征与沉积相缺乏明显关联,表现出强烈的早期成岩作用。此外,全新世晚期岩芯磁性特征还受人类活动影响。该孔早期成岩作用以磁性矿物溶解和形成自生黄铁矿为主。在三角洲前缘相的上部和河口湾相底部保存了硫复铁矿。根据矿物组合推测以4.51～4.56 m和30.4～30.5 m两个深度为代表的硫复铁矿形成机制不同,即三角洲前缘相中硫复铁矿可能形成于早期成岩作用的硫酸盐还原阶段,而河口湾相的硫复铁矿形成于甲烷厌氧氧化阶段,后者的含量随着深度增加逐渐增多。上述现象说明,沉积环境可以通过影响有机质和硫酸根离子的供应量,决定磁性矿物所达到的早期成岩作用阶段。     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

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

Evaluation of acetylcholinesterase activity in several zooplanktonic crustaceans

Zooplankton are an essential component of the marine and estuarine food chains. The ecotoxicological risk to zooplanktonic communities, estimated through the use of the biomarkers, can be used as an early warning signal of a potential alteration of the ecosystem health. The aim of this project was to evaluate the potential use of several biomarkers (esterases, mixed function oxidases, porphyrins) in zooplanktonic organisms. The acetylcholinesterase activity (AChE) was determined in homogenates of whole organisms of 10 different zooplanktonic crustaceans. Mean activity of AChE was 10.05 micromol/min/g for Acartia margalefi; 3.30 for Acartia latisetosa; 79.70 for Siriella clausi; 49.97 for Diamysis bahirensis; 7.48 for Siriella armata; 14.20 for Mysidopsis gibbosa; 4.49 for Euphausia crystallorophias; 1.66 for Euphausia superba; 2.74 for Streetsia challengeri; 13.26 for Meganycthiphanes norvegica. The species moreover showed a linear increase in enzyme activity in relation to the increase in sample concentration. The key result of this study concerns the different AChE activity basal values of the crustaceans' different species.     

Surface associations of enzymes and of organic matter: Consequences for hydrolytic activity and organic matter remineralization in marine systems

The extent to which marine organic matter is associated with surfaces and the consequences of such associations for organic matter remineralization are the focus of considerable attention. Since extracellular enzymes operating outside microbial cells are required to hydrolyze organic macromolecules to sizes sufficiently small for substrate uptake, the effects of surface interactions–on enzymes as well as on substrates–for hydrolytic activity also require investigation. We used a simplified laboratory system consisting of a free (dissolved) polysaccharide (pullulan) and the same polysaccharide tethered to agarose beads to restrict mobility, plus the corresponding free enzyme (pullulanase) and the same enzyme sorbed to montmorillonite (Mte), to investigate systematically the consequences of surface associations of enzymes and of substrates on hydrolytic activity. Changes in substrate molecular weight were monitored with time to measure the course of enzymatic hydrolysis. Although hydrolysis of free substrate was nearly complete after 2 min incubation with the free enzymes, the sorbed enzymes also effectively hydrolyzed free substrate, and the data suggest that they retained activity longer in solution compared to the free enzymes. Sorbed enzymes progressively hydrolyzed the free substrate from > 50 kD to lower molecular weights during a 24 h incubation, with a final product distribution on average showing only 1.4% and 10.3% of substrate still in the > 50 kD and 10 kD size classes, while 46.6%, 29.3%, and 12.5% of substrate was in the 4 kD, monomer, and free tag size classes, respectively. This product distribution was very similar to that of the free substrate/free enzyme experiment. Tethering the substrate to agarose beads led to lower substrate release (2–3% of total substrate after 98 h incubation) into solution compared to the free substrate case. For tethered substrates, the state of the enzyme (free or sorbed) measurably affected the molecular weight distribution of the hydrolysis products, with free enzymes producing a higher fraction of high molecular weight hydrolysis products (28.7 ± 5.4% of substrate > 50 kD at the end of the incubation) compared to sorbed enzymes (11.6 ± 2.8% of substrate > 50 kD at the end of the incubation.) Tethered substrates were also hydrolyzed in a sediment slurry from surface sediments from Cape Lookout Bight, North Carolina; 0.1% of total substrate was released by enzymes naturally present in 1 cm³ of sediment after 144 h incubation, demonstrating that the enzymes naturally present in marine sediments are also capable of accessing tethered substrates. These investigations suggest that surface associations of enzymes in marine systems may extend the active lifetime of such enzymes, providing an opportunity for hydrolysis over longer periods of time and producing a different size spectrum of hydrolysis products relative to free enzymes. Furthermore, in well-mixed systems, surface-associated enzymes can hydrolyze substrates whose mobility is restricted, highlighting the importance of processes such as resuspension and bioturbation on organic matter remineralization.     

Aliphatic biomarker signatures of early Oligocene-early Miocene source rocks in the central Qiongdongnan Basin: Source analyses of organic matter

The geochemical signatures of fifty-four rock samples and three supplementary drill stem test(DST) oils from the Yacheng-Sanya formations in the central Qiongdongnan Basin(CQB) were analysed. Reconstruction of the early Oligocene-early Miocene(36–16 Ma) palaeovegetation and source analyses of organic matter(OM) were conducted using aliphatic biomarkers in ancient sediments and DST oils. Both the interpreted aquatic and terrigenous OM contributed to the CQB source rocks(SRs) but had varying relat...     

High resolution profiles of vertical particulate organic matter export off Cape Blanc,Mauritania: Degradation processes and ballasting effects

Vertical carbon fluxes between the surface and 2500 m depth were estimated from in situ profiles of particle size distributions and abundances me/asured off Cape Blanc (Mauritania) related to deep ocean sediment traps. Vertical mass fluxes off Cape Blanc were significantly higher than recent global estimates in the open ocean. The aggregates off Cape Blanc contained high amounts of ballast material due to the presence of coccoliths and fine-grained dust from the Sahara desert, leading to a dominance of small and fast-settling aggregates. The largest changes in vertical fluxes were observed in the surface waters (<250 m), and, thus, showing this site to be the most important zone for aggregate formation and degradation. The degradation length scale (L), i.e. the fractional degradation of aggregates per meter settled, was estimated from vertical fluxes derived from the particle size distribution through the water column. This was compared with fractional remineralization rate of aggregates per meter settled derived from direct ship-board measurements of sinking velocity and small-scale O₂ fluxes to aggregates measured by micro-sensors. Microbial respiration by attached bacteria alone could not explain the degradation of organic matter in the upper ocean. Instead, flux feeding from zooplankton organisms was indicated as the dominant degradation process of aggregated carbon in the surface ocean. Below the surface ocean, microbes became more important for the degradation as zooplankton was rare at these depths.     

High molecular weight organic matter in seawater

The presence and nature of high molecular weight organic matter in seawater was critically reviewed and its biogeochemical cycle was discussed.Organic matter that passes through a filter of 0.5–1 μm pore size is called dissolved and that which does not pass through such a filter is defined as particulate. The size of colloidal particles ranges from 0.001 to 1 μm, and therefore, they are included in the dissolved fraction having high molecular weight.High molecular weight organic matter greater than 100,000 molecular weight was found in the seawater of Tokyo Bay. The values ranged from 0.1 to 1.5 mgC/l, and accounted for 8–45% of the total dissolved organic matter.Decomposition experiments on dissolved organic matter showed that macromolecular organic matter is refractory to bacterial attack. However, macromolecular organic materials tend to aggregate or adsorb on small particles to a sufficient size for precipitation. Organic aggregates thus formed sink to the bottom of the sea and bioelements included in them are removed from water column. High molecular weight organic materials are, therefore, considered to play an important role in transportation and distribution of matter in seawater.In order to elucidate the chemical and biological properties of macromolecular organic matter, concentration and isolation of this material are important, using methods such as adsorption on organic adsorbents or ultrafiltration.     

Luminescence quenching of dissolved organic matter in seawater

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

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

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