Origin, enzymatic response and fate of dissolved organic matter during flood and non-flood conditions in a river-floodplain system of the Danube (Austria)

Spectroscopic techniques and extracellular enzyme activity measurements were combined with assessments of bacterial secondary production (BSP) to elucidate flood-pulse-linked differences in carbon (C) sources and related microbial processes in a river-floodplain system near Vienna (Austria). Surface connection with the main channel significantly influenced the quantity and quality of dissolved organic matter (DOM) in floodplain backwaters. The highest values of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) were observed during the peak of the flood, when DOC increased from 1.36 to 4.37 mg l^?1 and CDOM from 2.94 to 14.32 m^?1. The flood introduced DOC which consisted of more allochthonously-derived, aromatic compounds. Bacterial enzymatic activity, as a proxy to track the response to changes in DOM, indicated elevated utilization of imported allochthonous material. Based on the enzyme measurements, new parameters were calculated: metabolic effort and enzymatic indices (EEA 1 and EEA 2). During connection, bacterial glucosidase and protease activity were dominant, whereas during disconnected phases a switch to lignin degradation (phenol oxidase) occurred. The enzymatic activity analysis revealed that flooding mobilized reactive DOM, which then supported bacterial metabolism. No significant differences in overall BSP between the two phases were detected, indicating that heterogeneous sources of C sufficiently support BSP. The study demonstrates that floods are important for delivering DOM, which, despite its allochthonous origin, is reactive and can be effectively utilized by aquatic bacteria in this river-floodplain systems. The presence of active floodplains, characterized by hydrological connectivity with the main channel, creates the opportunity to process allochthonous DOC. This has potential consequences for carbon flux, enhancing C sequestration and mineralization processes in this river-floodplain system.     

Characterization of Estuarine and Fluvial Dissolved Organic Matter by Thermochemolysis using Tetramethylammonium Hydroxide

Selected samples of dissolved organic matter (DOM) isolated by ultrafiltration (UDOM) have been analyzed by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). This technique cleaves ester and ether bonds of bio‐ and geological macromolecules and releases monomer subunits and methylates them in situ as their methyl ethers and methyl esters. Compared with conventional pyrolysis, TMAH thermochemolysis avoids decarboxylation of preexisting carboxylic moieties and produces aromatic acids as their methyl esters. Various phenolic derivatives, which might originate from incorporated lignin‐derived structures, from the highly aliphatic and resistant biopolymer cutan and also from proteinaceous materials, were identified among the products produced from UDOM upon thermochemolysis. The presence of lignin derivatives in UDOM indicates input of organic matter derived from terrestrial sources. Various aromatic acids, perhaps representing the final steps in the oxidation of the side‐chain during microbial oxidation of lignin, were released upon TMAH thermochemolysis, suggesting they are structural constituents of the UDOM. Different ratios of lignin‐derived materials, commonly determined using the CuO oxidation method, such as the Δ value, indicative of the amount of lignin present, the acid/aldehyde ratio (Ad/Al)_G, indicative of the extent of oxidative degradation of the lignin component, and the syringyl/guaiacyl (S/G) and p‐hydroxyphenyl/guaiacyl (P/G) ratios, indicative of the contribution for the different types of lignin, were determined.     

木质素抑制黄土湿陷性试验研究

黄土湿陷性常引发黄土地区构筑物基础发生沉降甚至破坏,给黄土地区基础设施建设造成了严重的威胁。通过改良黄土可减轻和降低湿陷性的危害,拟采用绿色可降解工业废料木质素对湿陷性黄土进行改良,发现木质素改性黄土可显著减轻黄土湿陷性的危害,并从形变机制和微结构两方面对改良机制进行解释。研究结果表明：2%木质素掺量的黄土试样,其原有的强烈湿陷性已基本消除,改良效果在4%木质素掺量达到峰值;从形变机制看,木质素的加入改变了其结构特征,原本由湿陷性导致的结构失稳在加压期间被释放,致使改良土受湿陷影响降低;从微结构角度看,木质素会使黄土颗粒之间产生新的胶结物,使颗粒之间的联结力增强,从而提升其改良效果。通过室内试验验证木质素在抑制湿陷方面的有效性,2%木质素掺量即可达到改良效果且具有量省效宏的优点,同时符合绿色施工理念并提高工业副产品木质素的利用率,为实际工程解决湿陷问题提供新参考。     

Fate of Lignin in the Process of Aerobic Biological Treatment of Paper Mill Wastewater

Although lignin is known to be not readily biodegradable the concentration of dissolved lignin decreased during aerobic biological treatment of paper mill wastewater performed in sequencing batch reactors (SBR). Systematic lab scale batch tests were conducted to clarify whether the observed removal of lignin was the result of biodegradation or adsorption onto the activated sludge. For the batch tests, sludge samples were taken from sequencing batch reactors operated at solid retention times (SRT) of 10, 15, 20, 30, and 40 days, respectively. The amount of lignin present in the bulk liquid and in the sludge samples was quantified by an analytical procedure comprising pyrolysis, gas chromatography and mass spectrometry (py‐GC/MS analysis). It was found that lignin adsorbs onto the activated sludge by up to 30%[TH]w/w. This demonstrates the sludge excellent adsorption properties. The ultimate removal of lignin is achieved by sludge wasting. The highest overall removal rate was found when sludge was used from the SBR run at SRT of 20 days.     

Separation of Vanillin from Oil Palm Empty Fruit Bunch Lignin

The separation of vanillin from the lignin of empty fruit bunch oil palm is presented in this study. The lignin was extracted from soda black liquor derived from oil palm empty fruit bunches (EFB) using 20% sulfuric acid. Nitrobenzene oxidation was carried out by adding 50 mg of dry EFB lignin into a mixture of 7 mL of 2 M NaOH and 4 mL of nitrobenzene in a 15 mL steel autoclave. The autoclave was sealed tightly with a screw cap fitted with a Teflon gasket and heated to 165°C for 3 h in a preheated thermostatic oil bath. High performance liquid chromatography (HPLC) was used to determine the concentration of each compound present in the lignin. There were eight compounds detected in the HPLC chromatogram. The crystallization process was then used as a method to separate vanillin from other compounds. Based on the solubility of vanillin in acetone, 15 mL of acetone was added to the residue of the oxidized products and heated to 60°C for 10 min. A yield of 1.6% vanillin was isolated from a 50 mg lignin sample. The isolated compound was analyzed with HPLC, Fourier transform infrared spectrophotometry (FT‐IR) and nuclear magnetic resonance (¹³C‐NMR) for structural verification. The results of the characterization studies proved that the isolated compound is vanillin.     

不同制样方法对木质素改良黄土力学特性影响

利用加水湿拌和泥浆搅拌2种方法对木质素改良黄土试样先进行均匀混合,后利用静压法在50mm×100mm圆柱形模具中两端压实制备试样,基于三轴仪对不同制样方法下改良土试样进行无侧限抗压强度试验和固结不排水三轴试验。试验结果表明:泥浆制样法获得改良土试样无侧限抗压强度值和固结不排水剪切强度值均高于加水湿拌法获得改良土试样强度值。结合扫描电镜试验对不同制样方法下改良土试样细观结构进行分析,发现对于木质素改良土,泥浆搅拌法获得的试样中木质素与黄土颗粒形成了新的胶结物和团聚物;而加水湿拌法获得试样中,木质素在土颗粒中仅起到加筋作用,未出现新的胶结物。该结果从微结构角度揭示了2种制样法制备试样的本质差异。     

Copper(II) Biosorption on Soda Lignin From Oil Palm Empty Fruit Bunches (EFB)

The adsorption of Cu(II) ions from aqueous solutions by soda lignin as an absorbent using a batch adsorption system is presented in this paper. The soda lignin used in this study was extracted from black liquor derived from oil palm empty fruit bunches (EFB) using 20% v/v sulfuric acid. The effects of varying experimental parameters such as pH value, adsorbent dosage, different concentrations of Cu(II) ions, and agitation period were investigated. The results revealed that the optimum adsorption of Cu(II) onto soda lignin was recorded at a pH of 5.0 at an adsorbent dosage of 0.5 g soda lignin and an agitation period of 40 min. The adsorption capacities and rates of Cu(II) ions onto soda lignin was evaluated. The Langmuir and Freundlich adsorption models were applied to calculate the isotherm constants. It was found that the adsorption isothermal data could be well interpreted by the Freundlich model. The kinetic experimental data properly correlated with the pseudo‐second‐order kinetic model, which implies that chemical sorption is the rate‐limiting step.     

Groundwater vulnerability at the Solzanskii area of sludge-lignin accumulation ponds at the Baikal pulp-and-paper plant

The article presents the results of a hydrogeological survey aimed to substantiate the engineering recultivation of accumulation ponds of lignin mud by inwashing it with coal ash. The ash bed causes compression consolidation of lignin bed, leading to an increase in the pond seal margin. The mass exchange between the ash and the lignin mud is accompanied by changes in the hydrogeochemical conditions: the mineralization of the liquid phase of technogenic soils increases by a factor of up to 8, and the concentration of microcomplex increases to very high values. The analysis of the qualitative state of groundwater showed it to be tolerant to the effect of accumulation ponds. The moderate deviation from the local natural background is due to other pollution sources. The applied recultivation technology is effective and environmentally safe, though it needs modernization. The alternative technology, proposed by OOO VEB-Inzhiniiring, i.e., grouting the pond content, is extremely hazardous, and the implementation of the project involves considerable environmental risk because of the possible loss of pond containment.     

Development and Characterization of Lignin‐Based Hydrogel for Use in Agricultural Soils: Preliminary Evidence

In arid and semi‐arid regions of the world, agricultural production is greatly limited by water scarcity and inefficient water use. Water‐absorbent hydrogels are a technological solution that can retain soil water for plants. A lignin‐based hydrogel as a natural plant‐based water absorbent is prepared from lignin alkali polymers and poly(ethylene glycol) diglycidyl ether (PEGDGE) in adjusted alkali (NaOH) solution. The maximum swelling capacity of the hydrogel is achieved in 1.5 m NaOH with 0.5 mmol PEGDGE g ${}_{\mathrm{lignin}}^{?1}$. Water swelling capacity is 34 g g ${}_{\mathrm{Hydrogel}}^{?1}$ dry weight of hydrogel in distilled water, which is reduced to 53% and 64% in 0.1 m NaCl and 0.1 m CaCl₂ solution, respectively. Biodegradability and phytotoxicity tests show that 6.5% of the sample mass decomposed after 40 days of incubation in soil solution media and the hydrogel is not phytotoxic to wheat seeds. These findings support the use of the lignin‐based hydrogel as an environmentally friendly additive to promote water retention in dry, saline soils. Due to the limitations of this study, further assessments are needed in order to understand the efficiency of lignin‐based hydrogel application in different soils with different biota.     

Anwendung einer enzymatischen Methode zur Charakterisierung von Huminstoffen Enzymatic Characterization of Humic Substances

A method is described for the specific hydrolysis of amino acids from humic substances by using the proteolytic enzyme “Pronase E”. The amino acids are analyzed by a fluorescence detector after precolumn derivatization and HPLC-separation. The pattern and the concentration of amino acids after the enzymatic hydrolysis are set up for humic substances of different origin. Due to the results the enzymatic hydrolysis is suitable for the characterization of humic substances with a nitrogen content higher than 3%. As shown in a kinetic study of the hydrolysis of a fulvic acid the influence of humic substances on the enzyme activity increases in case of lower nitrogen content. Due to the specificity of the proteolytic enzyme the operationally defined method is limited as shown by a protein of a known amino acid content. The amino acids leucine, valine, tyrosine and histidine are released to the highest extent. The determined total extent for the hydrolysis of Insulin B is 26.34% and for Casein 38.37%. By comparison of the enzymatic hydrolysis with the classic acid hydrolysis the advantages of the biochemical method are the simple experimental handling and the mild reaction conditions. Amino acids which are very unstable like glutamine and asparagine can only be analyzed by the enzymatic hydrolysis.     

制样拌和方法对木质素纤维改良黄土强度的影响

为减小室内试验中得到的木质素纤维改良黄土试样试验数据的离散程度,对采用稀释拌和法与直接拌和法制备的改良黄土试样分别进行了无侧限抗压强度试验。通过对比两种拌和方法所制备试样的干密度变化率和无侧限抗压强度的离散性,分析了拌和方法对试样强度产生的影响。结果表明:稀释拌和法所制备的改良黄土试样养护前后干密度变化更相近,同一掺量试样的干密度变化率离散程度均小于直接拌和法所制备试样;稀释拌和法与直接拌和法所制备试样均能反应改良黄土无侧限抗压强度受掺量影响的基本趋势,但稀释拌和法所制备试样的无侧限抗压强度试验结果更加稳定,能更好的反映出木质素纤维掺量变化对改良黄土试样强度的影响。     

Modeling the biodegradation of multicomponent organic matter in an aquatic environment: 2. Analysis of the structural organization of lignin

A model is developed to describe the degradation kinetics of an organic substance with chaotic structure of macromolecules. The model is based on the results of analysis of lignin structure and its degradation mechanisms described in previous papers of this series. Model postulates are formulated and their chemical substantiation is given. Degradation regimes corresponding to different molecular size distributions are studied. The decrease in organic carbon concentration at the asymptotic stage of the process is shown to obey the power law. Theoretical results were checked against some empirical data taken from the literature.     

Modeling the biodegradation of multicomponent organic matter in an aquatic environment: 4. Degradation kinetics model

A model is developed to describe the degradation kinetics of an organic substance with chaotic structure of macromolecules. The model is based on the results of analysis of lignin structure and its degradation mechanisms described in previous papers of this series. Model postulates are formulated and their chemical substantiation is given. Degradation regimes corresponding to different molecular size distributions are studied. The decrease in organic carbon concentration at the asymptotic stage of the process is shown to obey the power law. Theoretical results were checked against some empirical data taken from the literature.     

Composition and flux of suspended organic matter in the middle and lower reaches of the Changjiang (Yangtze River) — impact of the Three Gorges Dam and the role of tributaries and channel erosion

To investigate the sources of particulate organic matter (POM) and the impact of Three Gorges Dam (TGD), two large lakes and erosion processes on determining the composition and flux of POM in low water discharge periods along the middle and lower Changjiang, suspended particulate samples were collected along the middle and lower reaches of the Changjiang (Yangtze River) in January 2008. Organic geochemistry of bulk sediment (particulate organic carbon, organic carbon to nitrogen molar ratio (C/N), stable carbon isotope (δ¹³C) and grain size) and biomarker of bulk sediment (lignin phenols) were measured to trace the sources of POM. The range of C/N ratios (6.4–8.9), δ¹³C (?24.3‰ – ?26.2‰) and lignin phenols concentration Λ8 (0.45 mg/100 mg OC‐2.00 mg/100 mg OC) of POM suggested that POM originated from the mixture of soil, plant tissue and autochthonous organic matter (OM) during the dry season. POM from lakes contained a higher portion of terrestrial OM than the mainstream, which was related to sand mining and hydropower erosion processes. A three end‐member model based on δ¹³C and Λ8 was performed. The results indicated that soil contributed approximately 50% of OM to the POM, which is the dominant OM source in most stations. POM composition was affected by total suspended matter (TSM) and grain size composition, and the direct OM input from two lakes and channel erosion induced OM. The lower TSM concentration in January 2008 was mainly caused by seasonal variations; the impact from the TGD in the dry season was relatively small. A box model indicated that more than 90% of the terrestrial OM transported by the Changjiang in January 2008 was from the middle and lower drainage basins. Channel erosion induced OM, and contributions from Poyang Lake were the major terrestrial OM sources in the dry season. Copyright © 2012 John Wiley & Sons, Ltd.     

Low-decomposition rates of riparian litter in a North Patagonian ultraoligotrophic lake

Littoral zones of lakes are important for carbon and nutrient recycling because of the accumulation and decomposition of organic matter (OM) coming from terrestrial and aquatic plants. Here, we aimed to study OM decomposition from the most abundant riparian trees (Nothofagus dombeyi and Myrceugenia exsucca), and an emergent macrophyte (Schoenoplectus californicus), in the littoral zone of an ultraoligotrophic North-Patagonian Andean lake. We analysed the initial 2-days leaching, and litter mass loss and litter nutrient changes after one year of decomposition in a litter-bag experiment. The three studied species had very slow decay rates (k < 0.005 day⁻¹), and initial nutrient release by leaching was not related to differences in decomposition rates. However, differences in leaf traits (lignin content) were related to interspecific variation in decomposition rates. The highest decomposition rates were observed for the macrophyte S. californicus, the species with the lower lignin content, while the opposite was observed in the Myrtaceae M. exsucca. In the three studied species, nitrogen content increased during decomposition. Our results indicated that in the shore of ultra-oligotrophic lakes, litter remains for long periods with net nutrient immobilization, thus OM of the riparian vegetation represents a carbon and nutrient sink.     

Contamination of an Unconfined Sand Aquifer by Waste Pulp Liquor: A Case Study

A zone of contaminated ground water has been identified in an unconfined sand aquifer adjacent to a pit into which spent pulp liquor was intermittently discharged from 1970 to 1979. A network of multilevel sampling, bundle-type piezometers was installed. Up to seven depthspecific sampling points were incorporated into each piezometer providing a cost-effective means for three-dimensional mapping of hydraulic head and water quality in the unconfined sand aquifer. Ground-water samples retrieved from this network showed an area of contamination 900 m long, 400 m wide, and more than 25 m deep. This plume is dispersed about the ground-water flow lines passing beneath the waste disposal pit, and it terminates at a vigorous ground-water discharge area located 800 m from the pit. The contaminated ground water is characterized by elevated concentrations of sodium (3,000 mg/1), chloride (590 mg/1), alkalinity (2,700 mg/1), total organic carbon (2,000 mg/1), chemical oxygen demand (10,800 mg/1), biological oxygen demand (2,000 mg/1), tannin and lignin (780 mg/1), and lower sulphate (1 mg/1) compared to background ground waters in the area. The apparent rate of sodium migration is more than 50 m/yr and is close to the average linear ground-water velocity. Removal of some organic matter by biological transformation has produced the increased alkalinity in the contaminated ground water and somewhat reduced pH. Tannin and lignin are relatively inert compared to other organic compounds found in the waste liquor. Extremely low sulphate levels occurring in the highly contaminated ground waters indicate the existence of conditions favorable for microbially-mediated sulphate reduction.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels,Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels, Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Nutrient enrichment does not affect diet selection by a tropical shredder species in a mesocosm experiment

The decomposition of plant litter is a fundamental ecological process in small forest streams. Litter decomposition is mostly controlled by litter characteristics and environmental conditions, with shredders playing a critical role. The aim of this study was to evaluate the effect of leaf species (Maprounea guianensis and Inga laurina, which have contrasting physical and chemical characteristics) and water nutrient enrichment (three levels) on leaf litter chemical characteristics and fungal biomass, and subsequent litter preference and consumption by Phylloicus sp. (a typical shredder in tropical streams). Maprounea guianensis leaves had lower lignin and nitrogen (N) concentrations, higher polyphenols concentration and lower lignin:N ratio than I. laurina leaves. Phosphorus concentrations were higher for both leaf species incubated at the highest water nutrient level. Fungal biomass was higher on M. guianensis than on I. laurina leaves, but it did not differ among nutrient levels. Relative consumption rates were higher when shredders fed on M. guianensis than on I. laurina leaves, due to the lower lignin:N ratio and higher fungal biomass of M. guianensis. Consumption rates on M. guianensis leaves were higher for those exposed to low water nutrient levels than for those exposed to moderate water nutrient levels. Feeding preferences by shredders were not affected by leaf species or nutrient level. The low carbon quality on I. laurina leaves makes it a less attractive substrate for microbial decomposers and a less palatable resource for shredders. Changes in litter input characteristics may be more important than short-term nutrient enrichment of stream water on shredder performance and ecosystem functioning.     

The replacement of native plants by exotic species may affect the colonization and reproduction of aquatic hyphomycetes

The tropical riparian zone has a high diversity of plant species that produce a wide variety of chemical compounds, which may be released into streams. However, in recent decades there has been an extensive replacement of tropical native vegetation by Eucalyptus monocultures. Our objective was to compare fungal colonization of Eucalyptus camaldulensis leaves with fungal colonization of native plant species from riparian zones in Brazilian Cerrado (savannah) streams. The fungal colonization and enzymatic activity significantly influenced leaf litter decomposition. Fungal sporulation rates from leaf litter varied significantly with leaf species, with E. camaldulensis showing the highest sporulation rate (1226 conidia mg⁻¹AFDM day⁻¹) and leaf mass loss (23.2 ± 0.9%). This species has the lowest lignin content and highest N concentration among the studied species. Among the studied native species, we observed the highest sporulation rate for Protium spruceanum (271 conidia mg⁻¹AFDM day⁻¹), Maprounea guianensis (268 conidia mg⁻¹AFDM day⁻¹) and Copaifera langsdorffii (196 conidia mg⁻¹AFDM day⁻¹). Overall, native plant species of the Brazilian Cerrado exhibited recalcitrant characteristics and a higher lignin:N ratio. Therefore, variations in the physical and chemical characteristics of the leaf litter could explain the higher decay rate and reproductive activity observed for E. camaldulensis. However, the detritus of this species were colonized almost exclusively by Anguillospora filiformis (99.6 ± 0.4%) and exhibited a reduction in aquatic hyphomycetes species diversity. Our results suggest that the disturbance in the composition of riparian vegetation and consequently, in the diversity of leaf litter input into streams, could change the patterns and rates of leaf litter utilization by microbial decomposers. These changes may have important consequences in the processing of organic matter and, consequently, in the functioning of freshwater ecosystems.