Mineralization of particulate organic matter derived from coral-reef organisms in reef sediments of the Gulf of Aqaba

In situ and laboratory incubation experiments in a fringing reef in the Gulf of Aqaba were performed to study degradation rates of particulate organic matter in reef sediments. Coral mucus, clam eggs, and zooxanthellae were used as model particulate organic compounds for these experiments. Aerobic and anaerobic mineralization rates were calculated by dissolved inorganic carbon (DIC) and O₂ fluxes from the sediments under different particulate organic matter additions. Fast enhancement (approximately twofold) of O₂ and DIC fluxes were found with the addition of coral mucus and clam eggs compared with control incubations without addition. Most of the degradation is believed to have occurred anaerobically rather than aerobically (DIC:O₂ ratios were 4.3–28.1). Higher degradation rates of coral mucus and clam eggs were estimated in carbonate sediment than in silicate sediment (1.2–1.6-fold), which was attributed to the different physical and chemical properties of both sediments. Our study shows the significance of the reef sediment as a suitable site for microbial degradation of particulate organic material excreted from different reef community organisms. This may increase the regeneration of nutrients in the reef environment necessary to sustain high biological productivity.     

It's a dirty job but someone has to do it: The role of marine benthic macrofauna in organic matter turnover and nutrient recycling to the water column

Benthic macrofaunal populations through their feeding, bioturbation, burrow construction and sediment irrigation activities have profound influences on organic matter inputs to marine sediments (biodeposition) and on the vertical distribution of deposited organic matter within the sediment. These effects in turn influence the rates and pathways of organic matter mineralisation, and element cycles. Similarly, bioturbation, burrow construction and burrow irrigation are major determinants of sediment-water column fluxes of oxygen and nutrients.

In this review, I discuss the influences of the different benthic macrofaunal feeding (functional) groups on mineralisation processes and sediment-water column fluxes of particulate and dissolved nutrients. How these effects influence diagenic processes, the balance between aerobic and anaerobic processes, and the redox status of the surficial sediments. Finally, I discuss some of the limitations of the predominantly laboratory techniques which have been used to study “macrofaunal effects” and how this hinders the inclusion of the effects in quantitative sediment biogeochemical models.     

It's a dirty job but someone has to do it: The role of marine benthic macrofauna in organic matter turnover and nutrient recycling to the water column

Benthic macrofaunal populations through their feeding, bioturbation, burrow construction and sediment irrigation activities have profound influences on organic matter inputs to marine sediments (biodeposition) and on the vertical distribution of deposited organic matter within the sediment. These effects in turn influence the rates and pathways of organic matter mineralisation, and element cycles. Similarly, bioturbation, burrow construction and burrow irrigation are major determinants of sediment-water column fluxes of oxygen and nutrients.

In this review, I discuss the influences of the different benthic macrofaunal feeding (functional) groups on mineralisation processes and sediment-water column fluxes of particulate and dissolved nutrients. How these effects influence diagenic processes, the balance between aerobic and anaerobic processes, and the redox status of the surficial sediments. Finally, I discuss some of the limitations of the predominantly laboratory techniques which have been used to study “macrofaunal effects” and how this hinders the inclusion of the effects in quantitative sediment biogeochemical models.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Effect of tidal currents,seston, and bottom sediments on growth of Mercenaria mercenaria: results of a field experiment

Tidal currents, seston, and sediments separately influence growth of the hard clam, Mercenaria mercenaria, but it is uncertain how these factors may interact. A 3×3 factorial field experiment, carried out in Great Sound, a coastal lagoon in Southern New Jersey, USA, between May and September 1986, determined the relative effects of three sediment types and three site-specific seston/tidal current regimes on the individual growth of M. mercenaria. Analysis of variance of the change in shell length after 15 wk (differences in initial and final lengths) demonstrated a significant difference (P=0.0064) in growth among sites, but no significant differences (P=0.1331) for growth in different sediments, although trends were evident. Effects of sites were independent of sediment type (P=0.2621). Shell growth rates differed by 10.7% between the slowest and fastest sites, but only differed by 5.7% between sediment types, with fastest growth in sand and slowest in mud. Tidal current speeds and four measures of seston (chlorophyll a, particulate inorganic and organic matter, PIM and POM, and energy content) were measured >20 times in near-bottom waters at each site. Horizontal fluxes of POM exhibited higher correlation coefficients with growth rates, than did seston concentrations or current speeds alone. We attribute significant site differences to differences in horizontal seston fluxes fluxes among sites. We suggest that horizontal seston fluxes may be a major factor affecting individual growth of suspension-feeding bivalves.No. 216 of the Jackson Estuarine Laboratory Contribution Series     

Coral mucus stable isotope composition and labeling: experimental evidence for mucus uptake by epizoic acoelomorph worms

Mucus released by scleractinian corals can act as an important energy and nutrient carrier in coral reef ecosystems, and a distinct isotopic signature would allow following the fate of this material. This study investigates the natural C and N stable isotopic signatures of mucus released by four scleractinian coral genera (Acropora, Fungia, Pocillopora and Stylophora) in comparison with those of suspended particulate organic matter (POM) in seawater of a Northern Red Sea fringing coral reef near Aqaba, Jordan. The natural δ¹³C and δ¹⁵N signatures of coral mucus differed significantly from seawater POM for the majority of seasonal comparisons, but were inappropriate for explicit tracing of mucus in the coral reef food web. Thus, a labeling technique using stable isotope tracers (¹³C and ¹⁵N) was developed that produced δ¹³C values of up to 122 ± 5‰ (mean ± SE) and δ¹⁵N of up to 2,100 ± 151‰ in mucus exuded by Fungia corals. ¹³C and ¹⁵N-enriched compounds were rapidly (within 3 h) and light-dependently transferred from the endosymbiotic zooxanthellae to the mucus-producing coral host. The traceability of ¹⁵N-labeled mucus was examined by evaluating its uptake and potential utilization by epizoic acoelomorph Waminoa worms naturally occurring on a range of scleractinian coral taxa. This tracer experiment resulted in uptake of coral mucus by the coral-associated acoelomorphs and further demonstrated the possibility to trace stable isotope-labeled coral mucus by revealing a new trophic pathway in coral reef ecosystems.     

Exponential Collapse of Benthic Depurative Capacity in A Eutrophic Tropical Marine Ecosystem: A Threshold Response to Organic Nitrogen Loading

Microbial decomposition of particulate organic matter in sediments can substantially modulate eutrophication of nearshore marine environments. Flux budgets for nitrogen compounds and quantification of rates of microbial transformation can provide important information on the process of eutrophication. This survey documents sediment nitrogen budgets for a eutrophic nearshore marine environment at La Parguera on southwest coast of Puerto Rico, including consideration of the organic fraction in addition to microbial transformations.

Sediments of the inshore channel at La Parguera denote the input of heavy organic loads with low redox potentials and high ammonium contents. Benthic fluxes of dissolved organic nitrogen are below those recorded for ammonium. These observations suggest that nearshore tropical sediments subject to heavy nitrogen loads act as a sink for organic nitrogen and that ammonification is a key process in the release of nitrogen from sediments to the water column. Nitrification and denitrification rates are low overall and inversely related to the redox potential. Depuration of excess nitrogen through denitrification is ineffective in these sediments. in contrast to more robust temperate environments, our work demonstrates that tropical marine systems are particularly susceptible to eutrophication given their limited capacity for depuration of excess nitrogen.     

Exponential Collapse of Benthic Depurative Capacity in A Eutrophic Tropical Marine Ecosystem: A Threshold Response to Organic Nitrogen Loading

Microbial decomposition of particulate organic matter in sediments can substantially modulate eutrophication of nearshore marine environments. Flux budgets for nitrogen compounds and quantification of rates of microbial transformation can provide important information on the process of eutrophication. This survey documents sediment nitrogen budgets for a eutrophic nearshore marine environment at La Parguera on southwest coast of Puerto Rico, including consideration of the organic fraction in addition to microbial transformations.

Sediments of the inshore channel at La Parguera denote the input of heavy organic loads with low redox potentials and high ammonium contents. Benthic fluxes of dissolved organic nitrogen are below those recorded for ammonium. These observations suggest that nearshore tropical sediments subject to heavy nitrogen loads act as a sink for organic nitrogen and that ammonification is a key process in the release of nitrogen from sediments to the water column. Nitrification and denitrification rates are low overall and inversely related to the redox potential. Depuration of excess nitrogen through denitrification is ineffective in these sediments. in contrast to more robust temperate environments, our work demonstrates that tropical marine systems are particularly susceptible to eutrophication given their limited capacity for depuration of excess nitrogen.     

The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

Physico-chemical and microbial characteristics of the coral reef environment of the Gulf of Mannar marine biosphere reserve, India

Investigation on physico-chemical parameters and bacteial characteristics of the coral reef environs of the Gulf of Mannar biosphere reserve was studied. The study found the influence of different physico-chemical parameters on one another and also on the distribution of the total heterotrophic bacteria (THB) in the coral reef areas. Nutrients exhibited considerable seasonal and spatial variations with influence on the bacterial population. Coral reef areas recorded higher bacterial population density both in water (3.5 to 18 x 10(5) CFU ml(-1)) and sediment (1 to 14 x 10(7) CFU g(-1)) samples than the non coral reef areas (3.4 to 10.5 x 10(4) CFU ml(-1) in water and 0.9 to 7 x 10(6) CFU g(-1)). The study also found the dominance of gram negative groups at all the three stations (64.73, 63,5 and 72.59%) with Pseudomonas contributing maximum number of strains in all the samples. In addition Vibrio, Aeromonas, Flavobacterium, Cytophaga, Enterobacter and Alcaligenes were also recorded. The gram positive group was represented by Bacillus, Micrococcus, Arthrobacter and Corynebacterium. The genetic composition of THB isolated from the coral mucus revealed the presence of Vibrio and Micrococcus in all the coral mucus.     

Nitrogen excretion by some demersal macrozooplankton in Heron and One Tree Reefs,Great Barrier Reef,Australia

Nitrogen excretion rates of demersal macrozooplankton were measured together with nitrogen concentrations in the water column and sediments in lagoons of Heron Reef and One Tree Reef, Great Barrier Reef, Australia, during August and November 1991. Excretion rates increased with body weight, and weight-specific excretion rates of the demersal macrozooplankton were comparable to those of pelagic zooplankton and meiofauna in the Great Barrier Reef. Values of demersal macrozooplankton abundance from previous studies and excretion rates from this study were combined to estimate fluxes of ammonium from demersal macrozooplankton in coral reef lagoons. The estimated fluxes in the water column and sediments were 12 M NH₄ m^-2 d^-1 and 34 M NH₄ m^-2d^-1, respectively. These fluxes were compared with reported fluxes of ammonium in coral reef lagoons in the Great Barrier Reef, Australia. The estimated flux from the demersal macrozooplankton in the water column was 29 and 9% of those reported for microheterotroph regeneration and phytoplankton utilization, respectively. It was 10% of the reported advective flux during periods of low advection and 13% of the maximum efflux from sediments computed from diffusion models. The estimated flux from the demersal macrozooplankton in the sediments exceeded those reported for meiofauna, and was 5 to 32% and 2 to 13% of those reported for ammonification and utilization in sediments, respectively. The potential importance of demersal macrozooplankton in mediating sediment-water column exchanges in the absence of diffusive effluxes and when they swarm is discussed.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Inventories and Distribution of Radiocaesium in Arctic Marine Sediments: Influence of Biological and Physical Processes

Extensive surveys of sediment burdens of radiocaesium, specifically ¹³⁷Cs, and other radioactive contaminants in the Arctic during the 1990's, indicate that almost all anthropogenic radionuclides buried on continental shelves adjacent to Alaska are derived from global bomb fallout. the ¹³⁷Cs (half-life: 30.2y) activities observed in surface (0-4 cm) marine sediments however, vary widely, albeit much less than the expected current inventory resulting from bomb fallout at this latitude (∼100mBq cm^-2). This observed geographical variation provided the opportunity to evaluate physical and biological mechanisms that may affect caesium biogeochemistry on Arctic continental shelves. We investigated whether high biological productivity in portions of the Bering and Chukchi Seas is effective in removing dissolved radiocaesium from the water column, and whether biological production in overlying water affects total radiocaesium inventories in sediments. Based upon C/N ratios in the organic fraction of shallow sediments, we found no evidence that higher inventories or surface activities of radiocaesium are present in areas with higher deposition of particulate organic matter. Based upon stable carbon isotope ratios of organic matter in sediments, we found no evidence that terrestrial runoff contributes proportionally to higher surface activities, although terrestrial runoff may affect total inventories of the radionuclide. Radiocaesium content of surface sediments was significantly correlated with total organic carbon content of sediments and the proportion of sediments in the finest sediment fractions. Because high current flow can also be expected to influence distributions of those sedimentary parameters, we conclude that re-distribution of     

Is atmospheric oxidation capacity better in indicating tropospheric O3 formation?

● This study summarizes and evaluates different approaches that indicate O₃ formation. ● Isopleth and sensitivity methods are useful but have many prerequisites. ● AOC is a better indicator of photochemical reactions leading to O₃ formation. Tropospheric ozone (O₃) concentration is increasing in China along with dramatic changes in precursor emissions and meteorological conditions, adversely affecting human health and ecosystems. O₃ is formed from the complex nonlinear photochemical reactions from nitrogen oxides (NO_x = NO + NO₂) and volatile organic compounds (VOCs). Although the mechanism of O₃ formation is rather clear, describing and analyzing its changes and formation potential at fine spatial and temporal resolution is still a challenge today. In this study, we briefly summarized and evaluated different approaches that indicate O₃ formation regimes. We identify that atmospheric oxidation capacity (AOC) is a better indicator of photochemical reactions leading to the formation of O₃ and other secondary pollutants. Results show that AOC has a prominent positive relationship to O₃ in the major city clusters in China, with a goodness of fit (R²) up to 0.6. This outcome provides a novel perspective in characterizing O₃ formation and has significant implications for formulating control strategies of secondary pollutants.     

Benthic Fluxes and Pore Water Profiles in the Tigullio Gulf

Diffusive fluxes of elements (NO^-₂, NO^-₃, NH⁺₄, SiO₂, PO^3-₄, Cl^-, SO^2-₄, Fe, Mn) have been measured by applying the Fick's first law in two stations of the Tigullio Gulf: the first one characterized by sandy sediments rich in vegetal detritus and the second one, located to within the tourist harbour, characterized by a silty-clay sediments.

Benthic fluxes were measured only in the second station by means of benthic chamber experiments. Although the significant presence of dissolved oxygen in the surface sediments, and the evidence of processes usually occurring in oxidised sediments such as nitrification, both stations also presented characteristics of anoxic sediments such as high oxygen consumption rate and high pore water concentrations of ion, manganese and N-ammonia and reactive orthophosphate.

In both stations, sediments seemed to represent a potential source for most of the chemical species studied, although fluxes were not confirmed for ion, manganese and reactive orthophosphate in benthic chamber experiments.

Diffusive fluxes presented a general agreement for both stations, with higher fluxes of N-nitrate and N-nitrite at the first station were oxidative processes of N-ammonia in the upper layer of the sediments seemed to be more active. the comparison between diffusive and benthic fluxes showed a possible contribution of bioturbation.     

Phosphate enrichment in the northern Gulf of Aqaba: Regulation by carbonate sediments and impact on nitrogen elevation

The effect of carbonate sediment in regulating phosphate concentrations in sea water was investigated by laboratory incubation experiments using different sediment types. Incubation experiments were made with two types of sediments: uncontaminated sediment from a marine reserve and contaminated sediment with deposited phosphate powders. Fluxes of inorganic nitrogen and phosphate were estimated from linear regressions of solute concentrations over incubation periods. Ammonium and phosphate fluxes were about twofold higher in the uncontaminated sediment that had significantly lower organic carbon and total phosphate concentrations than in the phosphate-contaminated sediment. To test the effect of dissolved phosphate on increasing nitrogen fixation, additional incubation experiments were carried out using treated carbonate and silicate sediments with added dissolved phosphate (20 μM). Incubations were made under sterile conditions with HgCl₂ added to distinguish between biologically enhanced processes and pure physicochemical processes. The adsorption rate of phosphate onto carbonate sediment was about twice that onto silicate sediments. No nitrogen elevation either as ammonium or as nitrate was observed in the soluble phosphate enrichment incubations. In conclusion, this study demonstrates the importance of the regulation of soluble phosphate concentrations in carbonate sediment environments where the carbonate sediment acts as a buffering system keeping soluble phosphate concentrations at certain steady-state levels. The study also demonstrates the lack of evidence on enhancement of nitrogen concentrations due to the increase phosphate concentrations.     

Productivity of bacteria and microalgae and the effect of grazing by holothurians in sediments on a coral reef flat

Bacterial productivity in sandy sediments on reef flats at Lizard Island, Great Barrier Reef was determined from the rate of incorporation of tritiated thymidine into DNA. The study was conducted during January 1982 and July 1983. A small diurnal increase occurred in sediments having a dense population of microalgae. Bacterial production was 120 to 370 mg C m^-2 d^-1 in summer on reef flats, which was equivalent to 30–40% of primary production by benthic microalgae. In winter, rates of primary production by benthic microalgae and secondary production by bacteria were about one-half to one-fifth of those in summer. There was much variation in production, due to patchiness in the distribution of benthic microbes, especially microalgae. Doubling times for the bacteria in surface sediment were 1 to 2 d in summer and 4 to 16 d in winter on the reef flats. These high productivity values for bacteria indicated that a net input of organic matter to the sediment was needed to support the growth of bacteria. Sediment bacteria thus have a very important role in transforming organic matter on the reef flats. Grazing by Holothuria atra depressed both primary production and bacterial production. It was estimated that these holothurians ate about 10 to 40% of bacterial carbon produced each day in summer, and thus have an important role in the carbon cycle. Harpacticoid copepods were numerically important components of the benthic meiofaunal community and probably had a significant impact on bacterial density as grazers.     

Origin and Distribution of Suspended Organic Matter As Inferred From Carbon Isotope Composition in A Mediterranean Semi-Enclosed Marine System

The origin and distribution of suspended organic matter, the trophic features and the stable carbon isotopic composition of particulate organic carbon (POC) were studied monthly in a Western Mediterranean semi-enclosed basin. Sampling stations were selected as a function of wind-exposure and the degree of vegetation cover and then compared with an adjacent unvegetated site. the predominant vegetation was seagrass (Posidonia oceanica and Cymodocea nodosa) and Caulerpa prolifera. Water samples were analyzed for total suspended matter (inorganic and organic fractions), photosynthetic pigments (chlorophyll-a and phaeopigments), dissolved organic carbon, particulate organic carbon and their isotopic composition. Temperature and salinity were also measured at the same sampling sites within range of Mediterranean limits. the suspended organic matter concentration was 1.77 ± 1.55 mg l^-1; the chlorophyll-a concentration was low (0.35 ± 0.24 μg l^-1); the disolved organic carbon concentration was 2,140 ± 2,010 μg l^-1; the particulate organic carbon concentration was 212 ± 106 μg l^-1 and the isotopic composition was 18.77 ± 2.51%_°. There were significant temporal differences except for phaeopigments, POC and its POC isotopic composition, and there were no spatial differences other than for δ¹³C. This picture highlighted a general seasonal trend and trophical features similar to adjacent sea.

Spatial differences in δ¹³C showed that the source of suspended organic matter was different between stations as that between sources and wind-hydrodynamic constraints. In     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.