Terrigenous dissolved organic matter along an estuarine gradient and its flux to the coastal ocean

The contribution of terrigenous organic matter (TOM) to high molecular weight dissolved and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. Dissolved organic matter (DOM) was fractionated by ultrafiltration into 1–30 kDa (HDOM) and 30 kDa–0.2 μm (VHDOM) nominal molecular weight fractions. Thermochemolysis with tetramethylammonium hydroxide (TMAH) was used to release and quantify lipids and lignin phenols. Stable carbon isotopes, fatty acids and lignin content indicated shifts in sources with terrigenous material in the river and turbid region and a predominantly algal/planktonic signal in the lower estuary and coastal ocean. Thermochemolysis with TMAH released significant amounts of short chain fatty acids (C₉–C₁₃), not seen by traditional alkaline hydrolysis, which appear to be associated with the macromolecular matrix. Lignin phenol distributions in HDOM, VHDOM and particles followed predicted sources with higher concentrations in the river and turbid region of the estuary and lower concentrations in the coastal ocean. TOM comprised 12% of HDOM within the coastal ocean and up to 73% of HDOM within the turbid region of the estuary. In the coastal ocean, TOM from high molecular weight DOM comprised 4% of total DOC. The annual flux of TOM from the Delaware Estuary to the coastal ocean was estimated at 2.0×10¹⁰ g OC year⁻¹ and suggests that temperate estuaries such as Delaware Bay can be significant sources of TOM on a regional scale.     

Factors affecting dissolved organic matter dynamics in mixed-redox to anoxic coastal sediments

Mixed-redox (suboxic, or oscillating between oxidizing and reducing conditions) to anoxic marine sediments from the Raritan -New York Bay complex and the Inner New York Bight of the eastern U.S. were studied to investigate the factors controlling the accumulation of pore-water dissolved organic carbon (DOC). DOC increased with depth at each of four study sites, but accumulation was generally limited in the mixed-redox zone relative to the anoxic zone. Humic-like fluorescence intensity also differed between mixed-redox and anoxic zones of the sediment, such that anoxic pore waters were relatively enriched in fluorescent, humic-like compounds.A pore-water DOC model was tested for its capacity to explain these geochemical patterns. Model results for a heavily irrigated and a non-bioturbated site both suggest that, excluding the uppermost few cm of the sediment column, pore-water DOC is predominantly comprised of poorly-reactive material with estimated degradation rate constants on the order of 10⁻³ yr⁻¹. Model results are also consistent with the suggestion that DOC accumulation is suppressed in the mixed-redox compared to the anoxic zones of the sediment due to rapid oxidation of high-molecular-weight DOC, and limited production and enhanced oxidation of the less reactive polymeric low-molecular-weight component of the DOC pool. An assessment of sorptive behavior of DOC in the surface sediments of the study area suggests that sorption can influence pore-water DOC distributions under conditions of high sedimentation and low bioirrigation.     

Transport of dissolved organic carbon in streams of differing physiographic characteristics

Transport of dissolved organic carbon (DOC) in four river systems in different physiographic regions of the United States was related to link magnitude by a power function, log Y = ?0.84 + 1.24 log X. Multiple linear regression indicated that discharge, watershed area, and link magnitude explained almost all variation in DOC transport. For purposes of ecosystem comparison, link magnitude appeared superior to other classification systems, such as stream order.In two of the river systems, the largest fraction of DOC was transported in the spring. A third has a winter transport maximum; the last had bimodal spring and fall maxima.Streams transporting similar total amounts of DOC may vary widely in DOC concentration (mg. 1^?1). Particulate organic matter concentration was not simply related to that of DOC.Ranges and means of DOC concentration, mean DOC: POC ratios, annual load of transported DOC as well as annual watershed DOC output were tabulated for 45 streams and rivers, representing a broad range of stream systems and physiographic regions. Mean DOC concentration for these 45 waterways ranged from 0.7 to 28 mg. 1^?1. The very low DOC values are found in undisturbed streams; many of the higher values are associated with larger streams influenced by human activities. Most DOC outputs fell within the range 0.21–5.42 metric tons. km^?2.yr^?1; mean DOC:POC ranged between 0.09 and 70.A comparison was made among several biomes of the ratio of experted DOC to watershed gross and net primary production. DOC, while playing a major role in aquatic ecosystem organic budgets, appears to be of little significance in the nutrient balance of watersheds.     

Isotopic biogeochemistry of dissolved organic nitrogen: A new technique and application

We present a new technique for isolating and isotopically characterizing dissolved organic nitrogen (DON) for non-marine waters, δ¹⁵N values for DON from lacustrine samples and data suggesting that this technique will be applicable to marine samples. Our technique involves preconcentration of DON via rotary evaporation and removal of dissolved inorganic nitrogen (DIN) via dialysis using a membrane that retains material above 100 Da. Results demonstrate quantitative removal of DIN, complete recovery of DON (95% or greater) and retention of isotopic integrity (isotope effect less than 0.4‰) for a solution containing a DON standard (tripeptide) and DIN in deionized water. Reproducibility of carbon and nitrogen isotope values and elemental concentrations is demonstrated for DOM from Chefswet Basin, Lake Superior and Grand Traverse Bay, Lake Michigan. The applicability of this technique to marine samples is suggested by demonstrating 99% removal of DIN from a sample of Gulf Stream water amended with ammonium and nitrate.     

Variability in dissolved organic matter fluorescence and reduced sulfur concentration in coastal marine and estuarine environments

Fluorescence characterization of dissolved organic matter (DOM) and measurements of Cr-reducible sulfide (CRS) are presented for 72 coastal marine and estuarine water samples obtained from the USA and Canada. Each sample is identified according to source: terrigenous, autochthonous, wastewater or mixed. Fluorescence data are resolved into contributions from humic, fulvic, tyrosine and tryptophan-like fluorophores. Humic and fulvic-like fluorophores correlate well with dissolved organic C (DOC) (r² = 0.73 and 0.71, respectively) but tyrosine and tryptophan-like fluorophores show no correlation with DOC. Quality factors are identified by normalization of fluorescence contributions to DOC. Humic and fulvic components show no statistical differences between sources but the amino acid-like fluorescence quality factors show significant variations between source, with highest values for autochthonous sources (0.07 ± 0.01 arbitrary fluorescence units per mg of C) versus low values (0.015 ± 0.005) for terrigenous source waters. CRS concentrations are highly variable from 0.07 ± 0.01 to 7703 ± 98 nM and do no correlate with DOC except when terrigenous source waters (n = 13) are separated out from the total sample set (r² = 0.55). There is an open question in the literature; does DOC source matter in terms of protective effects towards metal toxicity? Here is shown that DOC molecular-level quality does vary and that this variation is mostly in terms of the contributions of amino acids to total fluorescence.     

Chemical characterization of high molecular weight dissolved organic matter in fresh and marine waters

The high molecular weight fraction of dissolved organic matter in a suite of lakes, rivers, seawater, and marine sediment interstitial water samples was collected by ultrafiltration and characterized by molecular level and spectroscopic techniques. Proton nuclear magnetic resonance spectra of all samples show a high degree of similarity, with major contributions from carbohydrates, bound acetate, and lipids. Molecular level analyses of neutral sugars show seven monosaccharides, rhamnose, fucose, arabinose, xylose, mannose, glucose, and galactose, to be abundant, and to occur in comparable relative amounts in each sample. Previous studies have emphasized the distinctive composition of dissolved humic substances in fresh and marine waters, and have attributed these differences to sources and transformations of organic matter unique to each environment. In contrast we find a large fraction of freshwater high molecular weight dissolved organic matter (HMWDOM; > 1kD) to be indistinguishable from marine HMWDOM in bulk and molecular-level chemical properties. Aquatic HMWDOM is similar in chemical composition to biologically derived acylated heteropolysaccharides isolated from marine algal cultures, suggesting a biological source for some fraction of persistent HMWDOM. High molecular weight DOC contributes 51 ± 26% of the total DOC, and monosaccharides 18 ± 8% of the total HMWDOC in our freshwater samples. These contributions are on average higher and more variable, but not significantly different than for surface seawater (30% and 16% respectively). Biogeochemical processes that produce, accumulate, and recycle DOM may therefore share important similarities and be broadly comparable across a range of environmental settings.     

Transport of dissolved organic nitrogen in Mississippi River plume and Texas-Louisiana continental shelf near-surface waters

Dissolved organic nitrogen (DON) in near-surface (<20 m depth) waters of the Texas-Louisiana continental shelf is the predominant form of total dissolved nitrogen that is advected by the Mississippi-Atchafalaya River plume. Relatively high DON concentrations associated with low-salinity (<33 psu) waters throughout the year can be traced within the plume along the Texas-Louisiana inner shelf. DON concentrations throughout the shelf were significantly higher near the Mississippi-Atchafalaya outflow region relative to downstream inner Gulf shelf locations. Significant intercruise variations were also evident, with the highest concentrations during May 1992 and lower values in October 1992. At a fixed location off the Mississippi River outflow region DON concentration covaried inversely with salinity on time scales of hours to months, confirming that source water is a determining factor for variations of bulk DON concentrations in the region. Similar variations in upper water DON concentrations at different locations and seasons occurred in both plume and nonplume waters, which resembled the seasonal concentration changes of riverine nitrogen, and show that this pool is useful in tracing the influence of riverine-derived nitrogen on the overall nitrogen balance of the NW Gulf of Mexico’s continental shelf. Plume and nonplume DON concentrations deviated from mixing lines between riverine and oceanic endmembers, suggesting that plume waters may be a sink and nonplume waters may be a source of a labile fraction of DON in the region.     

洱海沉积物间隙水中溶解有机质的地球化学特性

对洱海沉积物间隙水中溶解有机质(DOM)含量、紫外可见吸收、荧光以及分子量等的垂直分布特征进行了研究。结果表明,DOC含量在沉积物水界面明显富集,随后急剧下降,6cm处达到最小值,随后呈上升趋势。DOC与吸光度值、荧光发射光谱强度之间具有一定的线性相关关系。DOM的E3/E4值范围在1～6之间,绝大多数在1～35之间。表征DOM中腐殖质来源的指标荧光指数值处于148～159之间,说明DOM以陆源输入为主。此外,洱海沉积物间隙水DOM分子量分布呈多峰分布模式,重均分子量(M_w)值在1462～1953Da之间,数均分子量(M_n)值在547～900Da之间,多分散性系数ρ值在202～305之间。随着沉积深度增大,M_w和M_n有略微的增大趋势,但变化不大。沉积物的氧化还原条件、微生物活动以及铁、锰氧化物等在沉积剖面的差异是控制间隙水中DOM各种地球化学特性的主要因素。     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

Chemical and spectroscopic characterization of marine dissolved organic matter isolated using coupled reverse osmosis-electrodialysis

The coupled reverse osmosis-electrodialysis (RO/ED) method was used to isolate dissolved organic matter (DOM) from 16 seawater samples. The average yield of organic carbon was 75 ± 12%, which is consistently greater than the yields of organic carbon that have been commonly achieved using XAD resins, C₁₈ adsorbents, and cross-flow ultrafiltration. UV-visible absorbance spectra and molar C/N ratios of isolated samples were consistent with the corresponding properties of DOM in the original seawater samples, indicating that DOM samples can be isolated using the coupled RO/ED method without any bias for/against these two properties. Five of the samples were desalted sufficiently that reliable measurements of their ¹³C and ¹HNMR spectra and their Fourier transform ion cyclotron resonance (FTICR) mass spectra could be obtained. The ¹³C and ¹HNMR spectra of RO/ED samples differed distinctly from those of samples that have been isolated in much lower yields by other methods. In particular, RO/ED samples contained a relatively lower proportion of carbohydrate carbon and a relatively greater proportion of alkyl carbon than samples that have been isolated using cross-flow ultrafiltration. From the FTICR mass spectra of RO/ED samples, samples from the open ocean contained a much lower proportion of unsaturated compounds and a much higher proportion of fatty acids than coastal samples.     

Optical characteristics and solar photodegradation of dissolved organic matter in Arkansas River, USA

Dissolved organic matter （DOM）, a mixture of numerous organic compounds of 30 to 300000 D, exists in all natural water resources including rivers, lakes and oceans, and plays a very important role in global carbon cycle and ecology. The DOM molecules absorb UV light strongly in short wavelengths and prevent microorganisms from being damaged by solar UV irradiation. Meanwhile, the large DOM molecules are then photodegraded into inorganic carbon and smaller organic molecules which are easier for bacterioplankton to digest. The Arkansas River is one of the largest rivers in the US, and a major input of organic materials to the Mississippi River and Gulf of Mexico. However, the photochemical properties of the DOM in the river water have not been investigated. To study this photodegradation process of the Arkansas River, water samples from the river were collected, filtered, sealed into quartz flasks, and exposed to sunlight for up to 15 hours. Some samples were retrieved from the flasks at certain time intervals. The intensity of the sunlight was measured during the exposure process at 30 min to 1 hr intervals. UV-vis absorption, fluorescence emission, 3D fluorescence spectra and DOM concentrations were determined for all retrieved samples. It was found that the total DOM concentration decreased while the dissolved inorganic carbon （DIC） concentration increased in the samples. UV absorption and fluorescence intensity of DOM decreased exponentially. The disappearance rate of UV absorption varied with wavelength. The loss of integral fluorescence was about 2.6 times that of the UV absorption at the excitation wavelength. In addition, the quantum yields also decreased, and the peak position of 3D fluorescence scan shifted to shorter wavelength.     

Characteristics of dissolved organic nitrogen (DON) in the surface water of Beijing Olympic Forest Park

The characteristics of dissolved organic nitrogen (DON) in surface water from Beijing Olympic Forest Park (BOFP) were investigated in this study. Nanofiltration (NF) pretreatment procedure using two NF membranes (NF90 and NF270) was applied to increase the accuracy and precision of DON measurements in surface water samples with high dissolved inorganic nitrogen/total dissolved nitrogen (DIN/TDN) ratios. Compared to NF90, NF270 showed better performance in lowering the DIN/TDN ratio and retaining DOC in both the synthetic water and raw water samples. DON concentrations ranged from 0.01 to 0.83 mg N L^?1 in water samples collected over four different months and showed a seasonal variation. The DON increased in summer due to the higher activity of decomposers on recent litterfall or because of a higher production of biomass in the surface water body. The molecular weight (MW) fractions of <3 kDa accounted for more than 50 % of the total DOC concentration and the fractions of <3 kDa contributed to more than 48 % of the total DON concentration. It could be concluded that most of the DON present in surface water of BOFP was composed of small molecules, which were mainly composed of monomers such as amino acids and urea, readily available for the uptake by phytoplankton and heterotrophic bacteria.     

Optical characteristics of the colored dissolved organic matter on the East Siberian shelf

This work is based on the results of a cruise of the R/V Akademik Lavrent’ev in September 2011 in the Laptev and East Siberian seas. The optical characteristics of one of the most characteristic components of the river runoff colored dissolved organic matter (CDOM), which intensely absorbs solar radiation in the short-wave spectrum range are analyzed. On the basis of experimental data, the possibility to use spectral characteristic not only for quantitative estimations but also for determination of the DOM composition in the waters of the East Siberian shelf is shown.     

Composition of dissolved organic matter in groundwater

Groundwater constitutes a globally important source of freshwater for drinking water and other agricultural and industrial purposes, and is a prominent source of freshwater flowing into the coastal ocean. Therefore, understanding the chemical components of groundwater is relevant to both coastal and inland communities. We used electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to examine dissolved organic compounds in groundwater prior to and after passage through a sediment-filled column containing microorganisms. The data revealed that an unexpectedly high proportion of organic compounds contained nitrogen and sulfur, possibly due to transport of surface waters from septic systems and rain events. We matched 292 chemical features, based on measured mass:charge (m/z) values, to compounds stored in the Kyoto Encyclopedia of Genes and Genomes (KEGG). A subset of these compounds (88) had only one structural isomer in KEGG, thus supporting tentative identification. Most identified elemental formulas were linked with metabolic pathways that produce polyketides or with secondary metabolites produced by plants. The presence of polyketides in groundwater is notable because of their anti-bacterial and anti-cancer properties. However, their relative abundance must be quantified with appropriate analyses to assess any implications for public health.     

Global patterns of dissolved inorganic and particulate nitrogen inputs to coastal systems: Recent conditions and future projections

We examine the global distribution of dissolved inorganic nitrogen (DIN) and particulate nitrogen (PN) export to coastal systems and the effect of human activities and natural processes on that export. The analysis is based on DIN and PN models that were combined with spatially explicit global databases. The model results indicate the widely uneven geographic distribution of human activities and rates of nitrogen input to coastal systems at the watershed, latitudinal, and regional-continental scales. Future projections in a business-as-usual scenario indicate that DIN export rates increase from approximately 21 Tg N yr⁻¹ in 1990 to 47 Tg N yr⁻¹ by 2050. Increased DIN inputs to coastal systems in most world regions are predicted by 2050. The largest increases are predicted for Southern and Eastern Asia, associated with predicted large increases in population, increased fertilizer use to grow food to meet the dietary demands of that population, and increased industrialization. Results of an alternative scenario for North America and Europe in 2050 indicate that reductions in the human consumption of animal protein could reduce fertilizer use and result in substantial decreases in DIN export rates by rivers. In another scenario for 2050, future air pollution control in Europe that would reduce atmospheric deposition of nitrogen oxides in watersheds is predicted to decrease DIN export by rivers, particularly from Baltic and North Atlantic watersheds. Results of a newly developed global PN river export model indicate that total global PN and DIN export by rivers in 1990 are similar, even though the global distribution of the two differ considerably.     

The relationship between primary production and the vertical export of particulate organic matter in a river-impacted coastal ecosystem

As part of the National Oceanic and Atmospheric Administration’s (NOAA) Nutrient Enhanced Coastal Ocean Productivity program, we have conducted four research cruises, July–August 1990, March 1991, September 1991, and May 1992, in the Mississippi River plume and adjacent shelf regions. Over this time period, photic-zone-integrated primary production varied significantly in both the river plume and shelf study regions, with greatest variability observed in the river plume region. In the river plume and the adjacent shelf, highest production occurred during July–August 1990 (8.17 g C m^?2 d^?1 for the plume and 1.89–3.02 g C m^?2 d^?1 for the shelf) and the lowest during March 1991 (0.40–0.69 g C m^?2 d^?1 for the plume and 0.12–0.45 g C m^?2 d^?1 for the shelf). The vertical export of POC from the euphotic zone, determined with free-floating MULTITRAP sediment trap systems, also varied temporally in both study regions, with highest values occurring in May 1992 (1.80±0.04 g C m^?2 d^?1 for the plume and 0.40±0.02 g C m^?2 d^?1 for the shelf) and the lowest values occurring during July–August 1990 (0.29±0.02 g C m^?2 d^?1 for the plume and 0.18±0.01 g C m^?2 d^?1 for the shelf). The fraction of production exported out of the photic zone was highly variable and was dependent, in part, on phytoplankton species composition and on the grazing activities of microzooplankton and mesozooplankton. The lowest ratio of export to production coincided with the time when production was greated and the highest ratios occurred when production was the lowest.     

Algal activity of dissolved organic nitrogen (DON) in the sediments of Lake Taihu,Eastern China

Understanding the contents and reactivity of dissolved organic nitrogen (DON) is important for illustrating its productivity contribution in aquatic ecosystem. The primary objective of this study was to investigate the characteristics and algal activity of DON in the sediments of Lake Taihu. A series of experiments were carried out to evaluate the algal bioavailability of DON fractions in the sediments of Lake Taihu, Eastern China. DON extracted in the lake sediments was separated into hydrophilic and hydrophobic forms by DAX-8 resin, and ammonia nitrogen in raw sample and hydrophilic fraction was removed by cation exchange resin. 77.42–109.18% DON recovery rates were obtained after DON fractionation at ZSW and DPG stations. The hydrophilic DON was the main DON form contributing 62.74–76.33% of total DON concentrations. Selenastrum capricornutum was incubated for 15 days with different nitrogen forms (raw sample, hydrophilic and hydrophobic fractions). Approximately 33.69–79.23% DON of the three fractions was available for algal uptake in the incubation. The order of DON bioavailability was ranked as follows: raw sample > hydrophilic fraction > hydrophobic fraction, indicating that hydrophilic fractions and raw samples exhibited higher DON bioavailability for algae. Parallel factor analysis resulted in identification of tryptophan-like proteins, tyrosine-like proteins and humic acid (HA)-like substances during the incubation periods. During the growth phase, the relative fluorescent intensities of tryptophan-like proteins, tyrosine-like substance and HA-like substance accumulated greatly with 24.84–26.38, 27.82–62.73 and 0–28.92%, respectively.     

Benthic nutrient remineralization in a coastal lagoon ecosystem

In situ measurements of the exchange of ammonia, nitrate plus nitrite, phosphate, and dissolved organic phosphorus between sediments and the overlying water column were made in a shallow coastal lagoon on the ocean coast of Rhode Island, U.S.A. The release of ammonia from mud sediments in the dark (20–440 μmol per m² per h) averaged ten times higher than from a sandy tidal flat (0–60 μmol per m² per h), and while mud sediments also released nitrate and phosphate, sandy sediments took up these nutrients. Fluxes of nutrients from mud sediments, but not from sandy areas, markedly increased with temperature. Ammonia release rates for mud sediments in the light (0–350 μmol per m² per h) were lower than those in the dark and it is estimated that some 25% of the ammonia released to the water column on an annual basis may be intercepted by the benthic microfloral community. Estimates of the annual net exchange of nutrients across the sediment-water interface, weighted by sediment type for the lagoon as a whole, showed a release of 450 mmol per m² of ammonia, 5 mmol per m² of phosphate, 5 mmol per m² of dissolved organic phosphorus, and an uptake of 80 mmol per m² of nitrate. Although rates of ammonia and nitrate exchange were comparable to those described for the deeper heterotrophic bottom communities of nearby Narragansett Bay, rates of benthic phosphate release were significantly lower. On an annual basis the Bay benthos released approximately 20 times more inorganic phosphate per unit area than did the lagoon benthos. As a result., the N/P ratio for the flux from the sediments was 74∶1 in the lagoon, compared with 16∶1 in “average” marine plankton and 8∶1 for the benthic flux from Narragansett Bay. The lack of remineralized phosphate in the lagoon, is reflected in water, column phosphate concentrations (always <1 μm) and water column N/P ratios (annual N/P=27) and suggests that the lagoon may show phosphate limitation rather than the nitrogen limitation commonly associated with marine systems.