scholarly journals Effects of pH on aquatic biodegradation processes

2009 ◽  
Vol 6 (1) ◽  
pp. 491-514 ◽  
Author(s):  
R. F. Krachler ◽  
R. Krachler ◽  
A. Stojanovic ◽  
B. Wielander ◽  
A. Herzig
Keyword(s):  
Organic Matter ◽  
Lake Water ◽  
Decomposition Rate ◽  
Degradation Mechanism ◽  
Ph Dependence ◽  
Degradation Process ◽  
Plant Litter ◽  
Lake Basin ◽  
Causal Connection ◽  
Ph Values

Abstract. To date, little is known about the pH-stimulated mineralization of organic matter in aquatic environments. In this study, we investigated biodegradation processes in alkaline waters. Study site is a large shallow soda lake in Central Europe (Neusiedler See/Ferto). The decomposition rate of plant litter was measured as a function of pH by incubating air-saturated lake-water samples in contact with Phragmites litter (leaves) from the littoral vegetation. All samples showed high decomposition rates (up to 32% mass loss within 35 days) and a characteristic two-step degradation mechanism. During the degradation process, the solid plant litter was dissolved forming humic colloids. Subsequently, the humic colloids were mineralized to CO2 in the water column. The decomposition rate was linearly related to pH. Increasing pH values accelerated significantly the leaching of humic colloids as well as the final degradation process. The observed two-step mechanism controls the wetland/lake/air carbon fluxes, since large quantities of humic colloids are currently produced in the reed belt, exported through wind-driven circulations and incorporated into the open lake foodweb. At present, the lake is rapidly shrinking due to peat deposition in the littoral zone, whereas it has been resistant to silting-up processes for thousands of years. In order to investigate the cause of this abrupt change, the chemical composition of the lake-water was measured during 1995–2007. A thorough analysis of these data revealed that major lake-water discharges through the lake's artificial outlet channel led to a decline in salinity and alkalinity. According to our estimates, the lake's original salinity and alkalinity was 70–90% higher compared to the present conditions, with the consequence of substantially lower pH values in the present lake. The observed pH dependence of reed litter biodegradation rates points to a causal connection between low pH values and accumulation of peat in the lake basin. Our results suggest that the pH stimulated remineralisation of organic matter plays a major role in maintaining the long-term integrity of saline lake/wetland systems.

scholarly journals Traces of sunlight in the organic matter biogeochemistry of two shallow subarctic lakes

2021 ◽  
Author(s):  
Marttiina V. Rantala ◽  
Carsten Meyer-Jacob ◽  
E. Henriikka Kivilä ◽  
Tomi P. Luoto ◽  
Antti. E. K. Ojala ◽  
...  
Keyword(s):  
Organic Matter ◽  
Organic Carbon ◽  
Lake Sediments ◽  
Lake Water ◽  
Human Impacts ◽  
Global Environmental Change ◽  
Carbon Export ◽  
Subarctic Lakes ◽  
Carbon Regulation ◽  
In Situ Experiments

AbstractGlobal environmental change alters the production, terrestrial export, and photodegradation of organic carbon in northern lakes. Sedimentary biogeochemical records can provide a unique means to understand the nature of these changes over long time scales, where observational data fall short. We deployed in situ experiments on two shallow subarctic lakes with contrasting light regimes; a clear tundra lake and a dark woodland lake, to first investigate the photochemical transformation of carbon and nitrogen elemental (C/N ratio) and isotope (δ13C, δ15N) composition in lake water particulate organic matter (POM) for downcore inferences. We then explored elemental, isotopic, and spectral (inferred lake water total organic carbon [TOC] and sediment chlorophyll a [CHLa]) fingerprints in the lake sediments to trace changes in aquatic production, terrestrial inputs and photodegradation before and after profound human impacts on the global carbon cycle prompted by industrialization. POM pool in both lakes displayed tentative evidence of UV photoreactivity, reflected as increasing δ13C and decreasing C/N values. Through time, the tundra lake sediments traced subtle shifts in primary production, while the woodland lake carried signals of changing terrestrial contributions, indicating shifts in terrestrial carbon export but possibly also photodegradation rates. Under global human impact, both lakes irrespective of their distinct carbon regimes displayed evidence of increased productivity but no conspicuous signs of increased terrestrial influence. Overall, sediment biogeochemistry can integrate a wealth of information on carbon regulation in northern lakes, while our results also point to the importance of considering the entire spectrum of photobiogeochemical fingerprints in sedimentary studies.

scholarly journals Photocatalytic Treatment of Wastewater Containing Simultaneous Organic and Inorganic Pollution: Competition and Operating Parameters Effects

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 855
Author(s):  
Ahmed Amine Azzaz ◽  
Salah Jellali ◽  
Nasser Ben Harharah Hamed ◽  
Atef El Jery ◽  
Lotfi Khezami ◽  
...  
Keyword(s):  
Ultra Violet ◽  
Degradation Process ◽  
Molar Ratio ◽  
Experimental Conditions ◽  
Retention Capacity ◽  
Isotherm Study ◽  
Related Data ◽  
Ph Values ◽  
Pseudo Second Order ◽  
Maximum Retention

In the present study, methylene blue (MB) removal from aqueous solutions via the photocatalytic process using TiO2 as a catalyst in the presence of external ultra-violet light (UV) was investigated. The results of adsorption in the absence of UV radiation showed that adsorption reached an equilibrium state at 60 min. The experimental kinetic data were found to be well fitted by the pseudo-second-order model. Furthermore, the isotherm study suggested that dye uptake by TiO2 is a chemisorption process with a maximum retention capacity of 34.0 mg/g. The photodegradation of MB was then assessed under various experimental conditions. The related data showed that dye mineralization decreased when dye concentrations were increased and was favored at high pH values and low salt concentrations. The simultaneous presence of organic and inorganic pollution (Zinc) was also evaluated. The effect of the molar ratio Zn2+/MB+ in the solution at different pH values and NaCl concentrations was also monitored. The corresponding experimental results showed that at low values of Zn2+ in the solution (30 mg/L), the kinetic of the MB removal became faster until reaching an optimum at Zn2+/MB+ concentrations of 60/60 mg/L; it then slowed down for higher concentrations. The solutions’ carbon contents were measured during the degradation process and showed total mineralization after about 5 h for the optimal Zn2+/MB+ condition.

scholarly journals Low Temperature Illitization through Illite-Dioctahedral Vermiculite Mixed Layers in a Tropical Saline Lake Rich in Hydrothermal Fluids (Sochagota Lake, Colombia)

Minerals ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 523
Author(s):  
Gabriel Ricardo Cifuentes ◽  
Juan Jiménez-Millán ◽  
Claudia Patricia Quevedo ◽  
Fernando Nieto ◽  
Javier Cuadros ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Organic Matter ◽  
Low Temperature ◽  
High Salinity ◽  
Source Rocks ◽  
Temperate Climate ◽  
Lake Basin ◽  
X Ray ◽  
Saline Waters ◽  
Mixed Layers

In this investigation, we showed that high salinity promoted by hydrothermal inputs, reducing conditions of sediments with high content in organic matter, and the occurrence of an appropriate clay mineral precursor provide a suitable framework for low-temperature illitization processes. We studied the sedimentary illitization process that occurs in carbonaceous sediments from a lake with saline waters (Sochagota Lake, Colombia) located at a tropical latitude. Water isotopic composition suggests that high salinity was produced by hydrothermal contribution. Materials accumulated in the Sochagota Lake’s southern entrance are organic matter-poor sediments that contain detrital kaolinite and quartz. On the other hand, materials formed at the central segment and near the lake exit (north portion) are enriched in organic matter and characterized by the crystallization of Fe-sulfides. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and energy dispersive X-ray spectrometry (EDX) data allowed for the identification of illite and illite-dioctahedral vermiculite mixed layers (I-DV), which are absent in the southern sediments. High humidity and temperate climate caused the formation of small-sized metastable intermediates of I-DV particles by the weathering of the source rocks in the Sochagota Lake Basin. These particles were deposited in the low-energy lake environments (middle and north part). The interaction of these sediments enriched in organic matter with the saline waters of the lake enriched in hydrothermal K caused a reducing environment that favored Fe mobilization processes and its incorporation to I-DV mixed layers that acted as mineral precursor for fast low temperature illitization, revealing that in geothermal areas clays in lakes favor a hydrothermal K uptake.

scholarly journals pH-controlled hydrogen-bonding (Short Communication)

1974 ◽  
Vol 143 (3) ◽  
pp. 775-777 ◽  
Author(s):  
John L. Wood
Keyword(s):  
Hydrogen Bonding ◽  
Dissociation Constant ◽  
Small Proportion ◽  
Association Constant ◽  
Short Communication ◽  
Dibasic Acid ◽  
Ph Dependence ◽  
Ph Values ◽  
Conjugate Acid ◽  
Total Base

The pH-dependence of the degree of hydrogen-bonding between a base and its conjugate acid is considered. When only a small proportion of the total base is complexed, the amount complexed is proportional to (1+coshp)−1 where p=2.303 (pKa–pH), pKa being the dissociation constant of the conjugate acid. This represents sharp pH-dependence. As the proportion complexed increases, the curve broadens, eventually becoming flat-topped, with more than half the base complexed over the range of pH values pKa±logKC, approximately. (K is the complex association constant and C is the formal base concentration, including all forms.) There are similarities to the extent of mono-protonation of a dibasic acid.

Metal contamination of urban soils in Cork, Ireland

2021 ◽  
Author(s):  
Hannah Binner ◽  
Timothy Sullivan ◽  
Maria E. Mc Namara
Keyword(s):  
Organic Matter ◽  
Soil Organic Matter ◽  
Metal Contamination ◽  
Urban Soils ◽  
Soil Samples ◽  
Ex Situ ◽  
City Centre ◽  
Metal Concentrations ◽  
Ph Values ◽  
Background Levels

<p>Soil contamination is widespread across Europe. In particular, contamination of urban soils by metals is poorly characterised. This is a major environmental concern, especially given that urban recreational amenities may be located on former industrial sites and/or may possess ex situ soils derived from industrial areas. We surveyed soils from nine urban recreational sites (15 samples per site) in Cork city in order to assess the degree of metal contamination. The results show that Pb concentrations exceed national background levels in all soil samples from all sites by a mean of 600 % and at least 140 %. Mn, Fe and Zn are enriched above background levels in all soil samples from three (Mn and Fe) to five (Zn) of the sites and, at the remaining sites, show 7 – 14 localised hotspots. Similar hotspots characterise Cu, Rb and Sr, which each exceed background levels at eight or more sampling locations at four sites. Co, Ni, As and Sn concentrations exceed background levels in at least three hotspots at each of three to six sites. Overall, metal concentrations are highest in the sites closest to the city centre, reflecting diverse sources that potentially include traffic and current and historical domestic coal burning and industry. At each urban site, the element grouping Zn and Pb recurs in 50 to 80 % of locations and enrichment in the element grouping Mn, Fe, Cu, Zn and Pb recurs in approx. 50 % of locations; Ni and As recur in approx. 10 % of the locations. At three sites, elevated concentrations of Mn, Fe, Cu, Zn and Pb are associated with high LOI (Loss-on-ignition) values – a proxy for the amount of soil organic matter present – and near-neutral pH values. Conversely, low LOI and acidic pH values are associated with lower concentrations of these elements. This indicates that soil metal concentrations are influenced by the amount of organic matter present and by pH.  Future analyses and experiments will further investigate links between soil organic matter and metal concentrations.</p>

scholarly journals Investigation of the β-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR

2016 ◽  
Author(s):  
Martin Kaminski ◽  
Hendrik Fuchs ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Theo Brauers ◽  
...  
Keyword(s):  
Degradation Mechanism ◽  
Degradation Process ◽  
Product Distribution ◽  
High Reactivity ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Emission Rates ◽  
Photochemical Degradation ◽  
Atmosphere Simulation Chamber ◽  
Simulation Chamber

Abstract. Beside isoprene, monoterpenes are the non-methane volatile organic compounds (VOC) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR. The focus of this study is on the OH budget in the degradation process. Therefore the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC beta-pinene, its main oxidation products, acetone and nopinone, and photolysis frequencies. All experiments were carried out under low NOx conditions (≤ 2 ppb) and at atmospheric beta-pinene concentrations (≤ 5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of two whereas the total OH reactivity was slightly overestimated because of the poor reproduction of the measured nopinone by the model by up to a factor of three. A new, theory-derived first-generation product distribution by Vereecken and Peeters was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2.

scholarly journals Dynamics of microbial communities during decomposition of litter from pioneering plants in initial soil ecosystems

2013 ◽  
Vol 10 (7) ◽  
pp. 5115-5124 ◽  
Author(s):  
J. Esperschütz ◽  
C. Zimmermann ◽  
A. Dümig ◽  
G. Welzl ◽  
F. Buegger ◽  
...  
Keyword(s):  
Microbial Community ◽  
Food Web ◽  
Microbial Communities ◽  
Litter Quality ◽  
Degradation Process ◽  
Mining Area ◽  
Plant Litter ◽  
Litter Addition ◽  
Fungal Abundance ◽  
Soil Ecosystems

Abstract. In initial ecosystems, concentrations of all macro- and micronutrients can be considered as extremely low. Plant litter therefore strongly influences the development of a degrader's food web and is an important source for C and N input into soil in such ecosystems. In the present study, a 13C litter decomposition field experiment was performed for 30 weeks in initial soils from a post-mining area near the city of Cottbus (Germany). Two of this region's dominant but contrasting pioneering plant species (Lotus corniculatus L. and Calamagrostis epigejos L.) were chosen to investigate the effects of litter quality on the litter decomposing microbial food web in initially nutrient-poor substrates. The results clearly indicate the importance of litter quality, as indicated by its N content, its bioavailability for the degradation process and the development of microbial communities in the detritusphere and soil. The degradation of the L. corniculatus litter, which had a low C / N ratio, was fast and showed pronounced changes in the microbial community structure 1–4 weeks after litter addition. The degradation of the C. epigejos litter material was slow and microbial community changes mainly occurred between 4 and 30 weeks after litter addition to the soil. However, for both litter materials a clear indication of the importance of fungi for the degradation process was observed both in terms of fungal abundance and activity (13C incorporation activity)

Increased atmospheric CO2 and litter quality

1998 ◽  
Vol 6 (1) ◽  
pp. 1-12 ◽  
Author(s):  
M Francesca Cotrufo ◽  
Björn Berg ◽  
Werner Kratz
Keyword(s):  
Chemical Composition ◽  
Leaf Litter ◽  
Decomposition Rate ◽  
Litter Quality ◽  
Castanea Sativa ◽  
Plant Litter ◽  
Decomposition Rates ◽  
Chemical Changes ◽  
Substrate Quality ◽  
N Concentration

There is evidence that N concentration in hardwood leaf litter is reduced when plants are raised in an elevated CO2 atmosphere. Reductions in the N concentration of leaf litter have been found for tree species raised under elevated CO2, with reduction in N concentration ranging from ca. 50% for sweet chestnut (Castanea sativa) to 19% for sycamore (Acer platanoides). However, the effects of elevated CO2 on the chemical composition of litter has been investigated only for a limited number of species. There is also little information on the effects of increased CO2 on the quality of root tissues. If we consider, for example, two important European forest ecosystem types, the dominant species investigated for chemical changes are just a few. Thus, there are whole terrestrial ecosystems in which not a single species has been investigated, meaning that the observed effects of a raised CO2 level on plant litter actually has a large error source. Few reports present data on the effects of elevated CO2 on litter nutrients other than N, which limits our ability to predict the effects of elevated CO2 on litter quality and thus on its decomposability. In litter decomposition three separate steps are seen: (i) the initial stages, (ii) the later stages, and (iii) the final stages. The concept of "substrate quality," translated into chemical composition, will thus change between early stages of decomposition and later ones, with a balanced proportion of nutrients (e.g., N, P, S) being required in the early decomposition phase. In the later stages decomposition rates are ruled by lignin degradation and that process is regulated by the availability of certain nutrients (e.g., N, Mn), which act as signals to the lignin-degrading soil microflora. In the final stages the decomposition comes to a stop or may reach an extremely low decomposition rate, so low that asymptotic decomposition values may be estimated and negatively related to N concentrations. Studies on the effects of changes in chemical composition on the decomposability of litter have mainly been made during the early decomposition stages and they generally report decreased litter quality (e.g., increased C/N ratio), resulting in lower decomposition rates for litter raised under elevated CO2 as compared with control litter. No reports are found relating chemical changes induced by elevated CO2 to litter mass-loss rates in late stages. By most definitions, at these stages litter has turned into humus, and many studies demonstrated that a raising of the N level may suppress humus decomposition rate. It is thus reasonable to speculate that a decrease in N levels in humus would accelerate decomposition and allow it to proceed further. There are no experimental data on the long-term effect of elevated CO2 levels, and a decrease in the storage of humus and nutrients could be predicted, at least in temperate and boreal forest systems. Future works on the effects of elevated CO2 on litter quality need to include studies of a larger number of nutrients and chemical components, and to cover different stages of decomposition. Additionally, the response of plant litter quality to elevated CO2 needs to be investigated under field conditions and at the community level, where possible shifts in community composition (i.e., C3 versus C4 ; N2 fixers versus nonfixers) predicted under elevated CO2 are taken into account.Key words: climate change, substrate quality, carbon dioxide, plant litter, chemical composition, decomposition.

pH Effects in trypsin catalysis

1969 ◽  
Vol 47 (21) ◽  
pp. 4021-4029 ◽  
Author(s):  
H. P. Kasserra ◽  
K. J. Laidler
Keyword(s):  
Complex Formation ◽  
Ph Dependence ◽  
Specific Rotation ◽  
Ph Effects ◽  
Ph Values ◽  
A Value ◽  
Available Information ◽  
Hydrolysis Of ◽  
Substrate Concentrations ◽  
Covalent Complex

A kinetic study has been made of the trypsin-catalyzed hydrolysis of N-benzoyl-L-alanine methyl ester, at pH values ranging from 6 to 10. The substrate concentrations varied from 1.7 × 10−3 to 4.3 × 10−2 M. From the rates were calculated, at each pH, values of [Formula: see text] (corresponding to [Formula: see text]), [Formula: see text] (corresponding to [Formula: see text]) and [Formula: see text] The specific levorotation of trypsin was measured and found to vary with pH in the pH region 5–11, the change in specific rotation following the ionization of a single group with pK(app) of 9.4. At pH 11 the specific rotation of trypsin, its zymogen, and its phosphorylated derivative were approximately the same, suggesting similar conformations for all three forms of the protein.The kinetic results on the acid side were very similar to those obtained by other investigators for chymotrypsin; they imply that there is a group of [Formula: see text] in the free enzyme, presumably the imidazole function of a histidine residue, and that this group is involved in acylation and deacylation, which can only occur if it is unprotonated. The behavior on the basic side was found to be different from that with chymotrypsin revealing a decrease in [Formula: see text] at high pH corresponding to a value of [Formula: see text] whereas [Formula: see text] showed sigmoid pH-dependence. An interpretation of these results that is consistent with all available information is that a group of [Formula: see text] (presumably the —NH3+ function of the terminal isoleucine) controls the conformation and thereby the activity of the enzyme at different stages of complex formation. In contrast to chymotrypsin, the pK of this ionizing group appears to be generally lowered by covalent complex formation between trypsin and its substrates.

scholarly journals Site-selective Protonation of the One-electron Reduced Cofactor in [FeFe]-Hydrogenase

2020 ◽  
Author(s):  
Konstantin Laun ◽  
Iuliia Baranova ◽  
Jifu Duan ◽  
Leonie Kertess ◽  
Florian Wittkamp ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Active Site ◽  
Catalytic Mechanism ◽  
Ph Dependence ◽  
H2 Evolution ◽  
Proton Reduction ◽  
Ph Values ◽  
Site Selective ◽  
H2 Oxidation ◽  
Diiron Site

Hydrogenases are microbial redox enzymes that catalyze H2 oxidation and proton reduction (H2 evolution). While all hydrogenases show high oxidation activities, the majority of [FeFe]-hydrogenases are excellent H2 evolution catalysts as well. Their active site cofactor comprises a [4Fe-4S] cluster covalently linked to a diiron site equipped with carbon monoxide and cyanide ligands that facilitate catalysis at low overpotential. Distinct proton transfer pathways connect the active site niche with the solvent, resulting in a non-trivial dependence of hydrogen turnover and bulk pH. To analyze the catalytic mechanism of [FeFe]-hydrogenase, we employ in situ infrared spectroscopy and infrared spectro-electrochemistry. Titrating the pH under H2 oxidation or H2 evolution conditions reveals the influence of site-selective protonation on the equilibrium of reduced cofactor states. Governed by pKa differences across the active site niche and proton transfer pathways, we find that individual electrons are stabilized either at the [4Fe-4S] cluster (alkaline pH values) or at the diiron site (acidic pH values). This observation is discussed in the context of the natural pH dependence of hydrogen turnover as catalyzed by [FeFe]-hydrogenase.<br>

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