Solubilization Rate Research Articles

Development and characterization of stable anaerobic thermophilic methanogenic microbiomes fermenting switchgrass at decreasing residence times

BackgroundAnaerobic fermentation of lignocellulose occurs in both natural and managed environments, and is an essential part of the carbon cycle as well as a promising route to sustainable production of fuels and chemicals. Lignocellulose solubilization by mixed microbiomes is important in these contexts.ResultsHere, we report the development of stable switchgrass-fermenting enrichment cultures maintained at various residence times and moderately high (55 °C) temperatures. Anaerobic microbiomes derived from a digester inoculum were incubated at 55 °C and fed semi-continuously with medium containing 30 g/L mid-season harvested switchgrass to achieve residence times (RT) of 20, 10, 5, and 3.3 days. Stable, time-invariant cellulolytic methanogenic cultures with minimal accumulation of organic acids were achieved for all RTs. Fractional carbohydrate solubilization was 0.711, 0.654, 0.581 and 0.538 at RT = 20, 10, 5 and 3.3 days, respectively, and glucan solubilization was proportional to xylan solubilization at all RTs. The rate of solubilization was described well by the equation r = k(C − C0fr), where C represents the concentration of unutilized carbohydrate, C0 is the concentration of carbohydrate (cellulose and hemicellulose) entering the bioreactor and fr is the extrapolated fraction of entering carbohydrate that is recalcitrant at infinite residence time. The 3.3 day RT is among the shortest RT reported for stable thermophilic, methanogenic digestion of a lignocellulosic feedstock. 16S rDNA phylotyping and metagenomic analyses were conducted to characterize the effect of RT on community dynamics and to infer functional roles in the switchgrass to biogas conversion to the various microbial taxa. Firmicutes were the dominant phylum, increasing in relative abundance from 54 to 96% as RT decreased. A Clostridium clariflavum strain with genetic markers for xylose metabolism was the most abundant lignocellulose-solubilizing bacterium. A Thermotogae (Defluviitoga tunisiensis) was the most abundant bacterium in switchgrass digesters at RT = 20 days but decreased in abundance at lower RTs as did multiple Chloroflexi. Synergistetes and Euryarchaeota were present at roughly constant levels over the range of RTs examined.ConclusionsA system was developed in which stable methanogenic steady-states were readily obtained with a particulate biomass feedstock, mid-season switchgrass, at laboratory (1 L) scale. Characterization of the extent and rate of carbohydrate solubilization in combination with 16S rDNA and metagenomic sequencing provides a multi-dimensional view of performance, species composition, glycoside hydrolases, and metabolic function with varying residence time. These results provide a point of reference and guidance for future studies and organism development efforts involving defined cultures.

Treatment of petroleum oil spill sludge using the combined ultrasound and Fenton oxidation process

In this paper, advanced oxidation process (AOP) combining ultrasound (US) and Fenton’s process was proposed for the treatment of total petroleum hydrocarbons present in oil spill sludge. The effect of several parameters like pH, ultrasonic power, weight ratio of hydrogen peroxide to iron [H2O2/Fe2+], Fenton reagent dosage, addition of salts and contact time were analyzed for the reduction of Petroleum Hydrocarbons (PHCs) in terms of hydrocarbon fractions (nC7–C10, nC11-C20). Chemical characterization of oil spill sludge was analysed by gas chromatography- mass spectrum (GC–MS) Elemental analyser, Fourier Transform Infra Red (FT-IR) Analyser and particle size analyser. Experiments were conducted for identifying the wide range of hydrocarbons fractions (nC7–C10, nC11–C20 and nC21–C30). Results shown that maximum solubilisation and PHC removal rate of up to 84.25% could be achieved at a pH of 3.0, sludge/water ratio of 1:100, ultrasonic power of 100 W with 40–50% ultrasonic amplitude, a H2O2/Fe2+ weight ratio of 10:1, and an ultrasonic treatment time of 10 min. The lower and medium fractions (nC7–C10, nC11–C20) were amenable to degradation due to ultrasound treatment compared to the heavier carbon fraction (nC21–C30). The study concludes that the combined sono-Fenton (SF) process significantly enhanced the degradation of oil spill sludge as compared to ultrasound treatment and Fenton oxidation alone. The enhanced solubilisation achieved by US alone is highly beneficial when we couple this with biodegradation which will be greatly facilitated by the enhanced solubility.

Bioleaching of heavy metals from pig manure with indigenous sulfur-oxidizing bacteria: effects of sulfur concentration

The purpose of this work was to study the sulfur concentration on bioleaching of heavy metals from pig manure employing indigenous sulfur-oxidizing bacteria. Also, the variations in physicochemical properties of pig manure before and after bioleaching were investigated. The results showed that sulfur concentration significantly affected the rate of acidification, sulfate production and metal solubilization during pig manure bioleaching process. A Michaelis–Menten type equation was utilized to interpret the relationships between sulfur concentration, sulfate production and metal solubilization in the bioleaching process. The rates of metal solubilization during pig manure bioleaching were well described by a first order kinetic equation related to time. After 12 days of bioleaching, 93%–97% of Zn, 96%–98% of Mn and 48%–94% of Cu were leached out from pig manure, respectively. The metals remaining in the pig manure residual were mainly existed in stable forms. In addition, elemental analysis showed that bioleaching process could significantly modify the dewaterbility and organic composition of pig manure. However, fertility analysis found that 9.0%–19.1% of nitrogen, 68.5%–71.0% of phosphorus, 76.5%–78.8% of potassium and 47.5%–49.4% of the total organic carbon (TOC) were lost from pig manure in the bioleaching process. Therefore, bioleaching process used in this study could be applied to remove heavy metals effectively from the pig manure, but more detailed studies need to be done to decrease the nutrients loss from pig manure.

Quantitative assessment of the metabolic products of iron oxide nanoparticles to be used as iron supplements in cell cultures

Iron nanoparticles (NPs) metabolism is directly associated to human health due to their use as anemia treatment and should be studied in detail in cells. Here we present a speciation strategy for the determination of the metabolic products of iron oxide nanoparticles coated by tartaric and adipic acids in enterocytes-like cell models (Caco-2 and HT-29). Such methodology is based on the use of SDS-modified reversed phase high performance liquid chromatography (HPLC) separation using inductively coupled plasma-mass spectrometry (ICP-MS) as Fe selective detector. Post-column isotope dilution analysis is used as quantification tool by adding 57Fe as isotopically enriched standard. To assess the separation capability of the method, two different iron nanostructures: iron sucrose nanoparticles -Venofer®- used as model suspension and iron tartrate/adipate-modified nanoparticles, both of about 4 nm (core size) were evaluated. The two nanostructures were injected into the system showing good peak profiles and quantitative elution recoveries (>80%) in both cases. In addition, both nanoparticulate fractions could be based-line separated from ionic iron species, which needed to be complexed with 1 mM citrate to elute from the column. Exposed cells up to 0.5 mM of iron tartrate/adipate-modified nanoparticles were specifically treated to extract the internalized NPs and the extracts examined using the proposed strategy. The obtained results revealed the presence of three different fractions corresponding to nanoparticle aggregates, dispersed nanoparticles and soluble iron respectively in a single chromatographic run. Quantitative experiments (column recoveries ranging from 60 to 80%) revealed the presence of the majority of the Fe in the nanoparticulated form (>75%) by summing up the dispersed and aggregate particles. Such experiments point out the high uptake and low solubilization rate of the tartrate/adipate NPs making these structures highly suitable as Fe supplements in oral anemia treatments.

Deconstruction of hybrid poplar to monomeric sugars and aromatics using ethanol organosolv fractionation

Acidic ethanol organosolv fractionation of hybrid poplar was investigated to determine the impact of pretreatment conditions on the resulting biomass and lignin properties and to assess the subsequent deconstruction of the cell wall biopolymers to monomeric sugars and aromatics. It was found that increasing reaction severity (i.e., time and temperature) during the organosolv fractionation increased the rate of delignification and xylan solubilization while the lignins recovered from the liquors were found to exhibit lower degrees of polymerization. Glucose hydrolysis yields > 75% at moderate enzyme loadings (30 mg/g glucan) could be obtained for the more severe pretreatment conditions. The lignins recovered from the pretreatment liquors were subjected to fractionation using a sequential extraction with solvents of increasing polarity. It was found that the low molar mass, low polydispersity lignins increased in pretreatment liquors with increasing time and temperature and were concentrated in the methanol fraction while a high molar mass fraction was extracted with the diethyl ether. We hypothesize that the extraction of the high molar mass fraction with diethyl ether is due to partial ethyl O-alkylation of lignin hydroxyl groups during pretreatment, rendering lignins more soluble in the non-polar solvent. Finally, depolymerization of unfractionated lignins by thioacidolysis resulted in mass yields of aromatic monomers ranging from 80 to 157 mg monomer per gram of lignin and that these yields exhibited strong positive correlations to the lignin β-O-4 content, molar mass, and strong negative correlations to the pretreatment temperature.

Enhancing biomethane potential of pulp and paper sludge through disperser mediated polyhydroxyalkanoates

In the present study, the extraction of polyester like polyhydroxyalkanoates (PHAs) from enzymes extracted sludge was investigated by varying extraction time and chloroform – sodium hypochlorite dosage. Maximum of 874 mg/g of PHAs was achieved at an optimum extraction time of 120 min and chloroform – sodium hypochlorite dosage of 30% v/v. The characteristics of derived PHAs were examined using Fourier transform infrared (FTIR) spectroscopy and Nuclear magnetic resonance (1H NMR) spectroscopy. Then, the effect of derived PHAs dosage on biomethane production from pulp and paper mill secondary clarifier (PPSC) sludge was studied. Higher amount of biomethane production was observed to be 174 L/(kg VS) at 35 mg of PHAs dosage when compared to other dosage. To further enhance biomethane production, disperser pretreatment method was carried out by optimization of specific energy. At optimum specific energy of 8547 kJ/kg TS, the maximum solubilization rate and suspended solids (SS) reduction were found respectively to be 19% and 15.8%. Then, biomethane assay was conducted on disperser pretreated sludge, disperser pretreated sludge with optimized PHAs dosage (35 mg) and control sludge. Among these, disperser mediated PHAs method exhibited maximal biomethane production and was observed to be 267 L/(kg VS). Hence, PHAs based sludge treatment method can be implemented in sludge management studies by retrieval of value added product and PHAs canbe used to enhance biomethane production sustainably.

Nitrite pre-treatment of dewatered sludge for microbial fuel cell application

The effect of pre-treatment of dewatered sludge using different nitrite concentrations and pH for microbial fuel cell (MFC) application was investigated. The results show that the addition of nitrite was feasible to increase the solubilization rate of the sludge and may reduce mass transfer limitation at the anode. This helped the MFC to reach higher voltage and to generate more power. The higher free nitrous acid (FNA) concentration under the acidic condition helped to increase sludge solubilization. However, under an alkaline condition, during which the FNA concentration was relatively low, the solubilization of the sludge was higher. The highest voltage and power density produced was 390 mV and 153 mW/m2, respectively, with the addition of nitrite at 100 mg-N/L and pH 9. Furthermore, it was found that elevated levels of FNA could inhibit electrogenic bacteria thus reducing power generation.

Bioleaching potential of bacterial communities in historic mine waste areas

Microbial activity has the potential to alter all cultural heritage in mining and metallurgy, due to metal mobilization by leaching. This communication shows the consequences of the bioleaching ability of two natural enrichments on copper slag samples from a historic ore smelting site in Sangerhausen (Mansfeld, Sudharz, Saxony-Anhalt, Germany). Enrichment cultures gained from mine drainage were dominated by either the iron and sulfur-oxidizing Acidithiobacillus ferrivorans, or by the iron-oxidizing Leptospirillum. During 35 days of bioleaching in media containing copper slag pulp, inoculated with these enrichments, the change in pH and solubilized metal concentrations of the systems were monitored. Both bacterial strains were completely different from each other in their pattern of pH variation and rates of metal solubilization. The maximum removal of Cu (1725 mg/l) and Zn (715 mg/l) from copper slag substrate was achieved with enrichment culture of A. ferrivorans SCUT-1. However, maximum Mn (207 mg/l), Pb (86 mg/l), and Ni (75 mg/l) removal was observed with enrichment culture of Leptospirillum strain YQP-1. Implications for metal mobilization along with alteration of artifacts from not only historic mining areas but also aspects of decontamination and remediation are discussed.

Comparative material balances and preliminary technical analysis of the pilot scale sugarcane bagasse alkaline pretreatment to 2G ethanol production

Material balance and preliminary technical analyses of pilot scale sugarcane bagasse alkaline pretreatment, using sodium hydroxide with and without anthraquinone (AQ) addition were analyzed and compared to elucidate the carbohydrates and phenolic components flux in the streams.The lowest carbohydrates solubilization rates (9% wt for cellulose and 41% wt for hemicelluloses) were reached for the condition at 130 °C with AQ addition, however the highest lignin solubilization (87% wt) was accomplished for the condition using 170 °C with AQ addition. Preliminary technical analysis was carried out to evaluate the performance of the best pretreatment condition when integrated to a first and second generation ethanol plant, in a biorefinery concept, showing that 83.03 m3/h of ethanol can be produced by this process. Ethanol production (in L/ton biomass) for proposed process is 8.1% lower than the expected for short terms technologies concluding that upgrades on the process, as higher solids concentrations and lignin energy use or, principally, lignin valorization must be performed to allow viability of the process.

Developing new synthetic biomimetic nanocomposite adhesives: Synthesis and evaluation of bond strength and solubilization

Complex coacervate adhesive analog of the glue secreted by a marine polychaete (Phragmatopoma California) was studied for gluing a wet bone. The aim of this in-vitro study is to investigate bond strength and solubilization of a complex, coacervate adhesive. A complex coacervate adhesive was synthesized by mixing aminated gelatin and polyphosphodopamid. Polyphosphodopamide (Poly (DMA-co-MOEP)) was synthesized by free radical polymerization of 2-(methacryloyloxy) ethyl phosphate (MOEP) and dopamine methacrylamide (DMA) (in the three ratios of MOEP to DMA: 11, 7, and 3) initiated with Azobisisobutyronitrile (AIBN) in MeOH at 60 °C for 24 h. The structure of polymers was characterized by IR and 1H NMR spectra. The surface charges of aminated gelatin were positive, and its average zeta potential was about 31.08 mV: this shows gelatin was slightly aminated. For obtaining the optimum condition of adhesive, at first we changed the amount of the cross-linkable groups, dopamine (DOPA) sidechains in DMA, and then we investigated bond strength and solubilization behaviors. After obtaining the optimal amount of DOPA sidechains in the adhesive, we added 10% Wt human bone nanopowder (HBN) to the adhesive as filler and surveyed that behavior again. Results showed that with increase in DOPA sidechains in the adhesive, bond strength increased and solubilization rate decreased. Also, by adding bone nanopowder to the adhesive, bond strength and solubilization rate increased. The SEM images of this complex coacervate adhesive show a porous structure where in most of the porosities are in the range of 10–50 μm. Cytotoxicity effect of the adhesive and the nanocomposite adhesive were investigated on bone marrow mesenchymal primer cells: the results demonstrated cell growth and proliferation. This study shows that complex coacervate nanocomposite adhesive is a good candidate to act as a bone adhesive for sternal closure.

Charged Residues in the C-Terminal Domain of Apolipoprotein A-I Modulate Oligomerization

Charged residues of the C-terminal domain of human apolipoprotein A-I (apoA-I) were targeted by site-directed mutagenesis. A series of mutant proteins was engineered in which lysine residues (Lys 195, 206, 208, 226, 238, and 239) or glutamate residues (Glu 234 and 235) were replaced by glutamine. The amino acid substitutions did not result in changes in secondary structure content or protein stability. Cross-linking and size-exclusion chromatography showed that the mutations resulted in reduced self-association, generating a predominantly monomeric apoA-I when five or six lysine residues were substituted. The rate of phosphatidylcholine vesicle solubilization was enhanced for all variants, with approximately a threefold rate enhancement for apoA-I lacking Lys 206, 208, 238, and 239, or Glu 234 and 235. Single or double mutations did not change the ability to protect lipolyzed low density lipoprotein from aggregation, but variants lacking >4 lysine residues were less effective in preventing lipoprotein aggregation. ApoA-I mediated cellular lipid efflux from wild-type mice macrophage foam cells was decreased for the variant with five lysine mutations. However, this protein was more effective in releasing cellular phosphatidylcholine and sphingomyelin from Abca1-null mice macrophage foam cells. This suggests that the mutations caused changes in the interaction with ABCA1 transporters and that membrane microsolubilization was primarily responsible for lipid efflux in cells lacking ABCA1. Taken together, this study indicates that ionic interactions in the C-terminal domain of apoA-I favor self-association and that monomeric apoA-I is more active in solubilizing phospholipid bilayers.

Solubilization kinetics determines the pulsatory dynamics of lipid vesicles exposed to surfactant

We establish a biophysical model for the dynamics of lipid vesicles exposed to surfactants. The solubilization of the lipid membrane due to the insertion of surfactant molecules induces a reduction of membrane surface area at almost constant vesicle volume. This results in a rate-dependent increase of membrane tension and leads to the opening of a micron-sized pore. We show that solubilization kinetics due to surfactants can determine the regime of pore dynamics: either the pores open and reseal within a second (short-lived pore), or the pore stays open up to a few minutes (long-lived pore). First, we validate our model with previously published experimental measurements of pore dynamics. Then, we investigate how the solubilization kinetics and membrane properties affect the dynamics of the pore and construct a phase diagram for short and long-lived pores. Finally, we examine the dynamics of sequential pore openings and show that cyclic short-lived pores occur with a period inversely proportional to the solubilization rate. By deriving a theoretical expression for the cycle period, we provide an analytical tool to estimate the solubilization rate of lipid vesicles by surfactants. Our findings shed light on some fundamental biophysical mechanisms that allow simple cell-like structures to sustain their integrity against environmental stresses, and have the potential to aid the design of vesicle-based drug delivery systems. This article is part of a Special Issue entitled: Emergence of Complex Behavior in Biomembranes edited by Marjorie Longo.

A non-toxic microbial surfactant from Marinobacter hydrocarbonoclasticus SdK644 for crude oil solubilization enhancement

This study aims to investigate the ability of a biosurfactant produced by Marinobacter hydrocarbonoclasticus strain SdK644 isolated from hydrocarbon contaminated sediment to enhance the solubilization rate of crude oil contaminated seawater. Phylogenetic analysis shows that strain SdK644 was very closely related to M. hydrocarbonoclasticus with 16S rRNA gene sequence similarity of 97.44%. Using waste frying oil as inducer carbon source, the producing biosurfactant by strain SdK644 was applied to improve crude oil solubilization in seawater. The preliminary characterization of the produced biosurfactant by FT-IR analysis indicates its possible classification in a glycolipids group. Results from crude oil solubilization assay showed that SdK644 strain biosurfactant was 2-fold greater than Tween 80 surfactant in crude oil solubilization and 12-fold higher than seawater control, as shown by GC-MS analysis of aliphatic compounds. Furthermore, this bioactive compound was shown to be nontoxic against Artemia larvae in short-term acute toxicity bioassay. Generally, the results showed the possible use of M. hydrocarbonoclasticus strain SdK644 biosurfactant in bioremediation processes of the marine environments.

Mathematical modelling of waste activated sludge thermal disintegration

Chemical Oxygen Demand (COD) solubilisation was used to evaluate the impact of thermal pretreatment on the transfer of sewage sludge from particulate to soluble phase. It was gathering the experimental data needed for building of empirical mathematical model describing the relation between applied temperature and time and rate of COD solubilisation and degradation. In view of repeated measurements, in order to describe the relationship between changes in the fraction of dissolved COD and the time and temperature, mixed models have been adopted where by fixed factor measurement conditions have been adopted: time and temperature, while the random factor changes the characteristics of waste activated sludge. Linear and logistic nonlinear mixed models were analyzed. The tests demonstrated that all variables are statistically significant in assessing their impact on the efficiency of liquefaction of sludge. On the basis of the estimated model, the temperature rise of 10°C increases degree of disintegration 1.7% above the average treatment time for 0.5h, by 2.6% for 1 hour, and by 3.9% for 2h. COD values decrease between 3 to 23% at temperatures in the range of 55 to 115°C. At higher temperatures COD was reduced in the range of 32 to 44%. Disintegration time did not have the significant impact on the degradation effect.

A novel technique for waste sludge solubilization using a combined magnetic field and CO2 injection as a pretreatment prior anaerobic digestion

In this study, the effect of combined magnetic field and CO2 microbubble technology on the solubilization rate and performance of municipal waste activated sludge (WAS) was investigated. Four numerical variables (CO2 injection, initial pH, magnetic field, and retention time) were selected to analyze and optimize the process. The region of exploration for the process was taken as the area enclosed by CO2 flow rate (0–1 L/min), initial pH (3–11), magnetic field (0–40 mT) and retention time (20–180 min) boundaries. In order to analyze the process, three dependent parameters as the process responses were studied. The results showed that the disintegration performance of WAS was effectively improved in the presence of magnetic field and CO2 microbubble. The sCOD, sTKN and PO43− concentrations in sludge supernatant increased to 48%, 40% and 47% respectively, with increasing CO2 flow rate from 0 to 1 L/min and magnetic field from 0 to 40 mT. This study showed that the initial pH was a key factor affecting the process performance, cell lysis and disintegration. The result showed that acid and base range of pH caused an increase in the WAS degradation. It was also observed that the sludge settleability was improved about 43% and oxygen uptake rate decreased by 30%. In conclusion, the combined magnetic field and CO2 microbubble pretreatment is an effective method to disintegrate the waste activated sludge.

Complexes of lutein with bovine and caprine caseins and their impact on lutein chemical stability in emulsion systems: Effect of arabinogalactan

Lutein is an important xanthophyll carotenoid with many benefits to human health. Factors affecting the application of lutein as a functional ingredient in low-fat dairy-like beverages (pH 6.0-7.0) are not well understood. The interactions of bovine and caprine caseins with hydrophobic lutein were studied using UV/visible spectroscopy as well as fluorescence. Our studies confirmed that the aqueous solubility of lutein is improved after binding with bovine and caprine caseins. The rates of lutein solubilization by the binding to bovine and caprine caseins were as follows: caprine αS1-II-casein 34%, caprine αS1-I-casein 10%, and bovine casein 7% at 100 μM lutein. Fluorescence of the protein was quenched on binding supporting complex formation. The fluorescence experiments showed that the binding involves tryptophan residues and some nonspecific interactions. Scatchard plots of lutein binding to the caseins demonstrated competitive binding between the caseins and their sites of interaction with lutein. Competition experiments suggest that caprine αS1-II casein will bind a larger number of lutein molecules with higher affinity than other caseins. The chemical stability of lutein was largely dependent on casein type and significant increases occurred in the chemical stability of lutein with the following pattern: caprine αS1-II-casein > caprine αS1-I-casein > bovine casein. Addition of arabinogalactan to lutein-enriched emulsions increases the chemical stability of lutein-casein complexes during storage under accelerated photo-oxidation conditions at 25°C. Therefore, caprine αS1-II-casein alone and in combination with arabinogalactan can have important applications in the beverage industry as carrier of this xanthophyll carotenoid (lutein).

The Impact of Dummy Gate Processing on Si-Cap-Free SiGe Passivation: A Physical Characterization Study on Strained SiGe 25% and 45%

High mobility channel materials like SiGe, Ge and IIIV receive lots of interest in order to enable the continuation of Moore’s path during the upcoming technology nodes. Recently Si-cap-free SiGe passivation with the number of interface states (NIT) down to 2 1011 cm-2 have been demonstrated. [1-3] A clear correlation was established between Ge-content in the SiGe-oxide and NIT. Unfortunately no process information has been provided on how the Ge-oxide-free interlayers were obtained. In a separate study the impact of HF, HCl and SC1 cleaning solution on the SiGe surface and oxide composition was reported. [4] A comparison of SiGe Gate-All-Around (GAA) and FinFET devices using a Si-cap-free SiGe 25% passivation scheme in a replacement metal gate (RMG) integration indicate the device performance is improved by a TMAH (aq) treatment prior to SiGe interlayer formation and high-k deposition. [5] Here the formation of a SiGe wet chemical oxide will be presented. The impact of dummy gate processing on the interlayer composition is reported. Also the impact of a TMAH (aq) treatment prior to chemical oxide formation has been analyzed and will be reported. Blanket strained SiGe 25% and 45% were grown by epitaxy. The SiGe-substrate and -oxide composition were measured by angle-resolved XPS using the Si2p and Ge3d peaks. The Ge3d peak is fitted with three different compounds: elemental Ge, GeO2 and Ge-suboxide. The angle dependence lets us estimate the distribution of the different components with respect to the sample top surface. An concentration increase with increasing angle (relative to the surface normal) indicates the compound is located closer to the sample surface. And reversely a concentration increase with increasing angle indicates the compound is located deeper into the sample. A native oxide was grown on SiGe 25 and 45% by exposing the wafers to the cleanroom air for approx. 1 week. The native oxide was found to be stoichiometric or nearly stoichiometric with a uniform Ge content throughout the oxide for SiGe 25 and 45% respectively. A wet chemical oxide was grown using an ‘imec clean’ [6] having a final O3/HCl (aq) rinse. The wet chemical oxide is Ge-poor compared to the SiGe substrate. No or only a small variation in Ge content of the SiGe-oxide is seen with ARXPS. However the fraction Ge-suboxide decreases with increasing angle, indicating the Ge-suboxide are located deeper within the sample, so closer to the SiGe-oxide/SiGe-substrate interface. The Ge-content of the SiGe-substrate after wet chemical oxidation shows a weak incident-angle-dependence, indicative a limited Ge enrichment of the SiGe substrate towards the SiGe-oxide/-substrate interface. The low Ge content of the SiGe-oxide is attributed to the water solubility of GeO2. The increase in Ge-content towards the SiGe-oxide/-substrate can be (at least partially) attributed to the poor water solubility of Ge-suboxide. The small increase in Ge content of the SiGe substrate can be attributed to the thermodynamically preferred oxidation of Si over Ge. The combined impact of dummy gate deposition, spike anneal and dummy gate removal prior to SiGe interlayer formation was investigated by AR-XPS and SIMS. The temperature used during spike anneal was found to have a significant impact on the Ge-content of the SiGe-oxide formed during an O3-last imec clean. The results will be reported in detail at the conference. The impact of TMAH (aq) on the chemical oxide composition and surface roughness will also be reported. TMAH (aq) was found to improve SiGe device performance. [5] Also the interaction with the subsequent HfO2 deposition will be reported. In summary SiGe is found to behave as a non-linear combination of Si and Ge. In HF-free aqueous solutions, the SiGe oxide composition is a combination of (1) thermodynamically preferred oxidation of Si versus Ge; (2) poor water-solubility of SiO2 and/or its low solubilization rate; and (3) fast dissolution of GeO2 but slow dissolution of Ge-suboxides. [1] CH Lee et al. VLSI 2016. [2] S. Siddiqui et al. presented MRS Spring Meeting 2016. [3] CH Lee et al. IEDM 2016. [4] S.L. Heslop et al. ECS Trans 69 (2015) 287. [5] H. Mertens et al VLSI 2015. [6] M. Meuris et al. Solid State Phenom, July 1995, p. 109. Figure 1

Characterization of potential liquid fertilizers obtained by hydrothermal treatment of chicken feathers

Bio‐based fertilizers are currently gaining interest as a method for reducing the use of chemical fertilizers and as a means for safe disposal of biomass waste. Feathers, which are an abundantly available biomass and have a high N content, are a potential source of fertilizer nutrients. In this study, chicken feathers were subjected to hydrothermal treatment (HTT) with lime addition in the temperature range of 140–200°C to obtain a high N containing liquid product that can be used as a liquid fertilizer. The objective of this study was to examine the effect of HTT conditions on the feather solubilization rate and the properties of the liquid products. The results showed that HTT with a reaction temperature of 180°C, a reaction time of 30 min, feather‐water ratio of 1:5, and lime addition is sufficient to solubilize as high as 83% of the chicken feather protein. The produced liquid contained nitrogen of up to 3.4% and total amino acid content of 13.6%. These results indicate the potential utilization of soluble hydrolyzed feather obtained from the HTT process for liquid N fertilizer. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 375–382, 2018

Mechanistic understanding of low methylmercury bioaccessibility from crayfish (Procambarus clarkii) muscle tissue

Recent research indicates that dietary exposure to mercury and other metals from crayfish consumption poses a human health concern, particularly in regions with high crayfish-consuming populations. To better understand consumption risk from methylmercury (MeHg), we quantified MeHg bioaccessibility in edible tail muscle of cooked red swamp crayfish (Procambarus clarkii, collected from seven cities in China), versus cooked fillet tissue of two finfish species: yellow croaker (Larimichthys polyactis) and snakehead (Channa argus). Results indicated that digestive solubilization rate (DSR) of MeHg in crayfish (7.8±3.9% for restaurant-crayfish and 9.8±0.8% for market-crayfish) was lower than the rate in yellow croaker (25.8±2.7%) and snakehead (26.2±4.7%) tissue, suggesting that relatively low MeHg bioaccessibility in crayfish may reduce dietary exposure to humans. Three possible mechanisms for the reduced MeHg DSR in crayfish tissue were examined: MeHg-Se interactions, MeHg subcellular fractionation, and Hg-amino acid binding. Selenium concentrations were comparable among the examined species, and no significant relationship was observed between tissue Se and MeHg DSR. Similarly, observed differences in subcellular fractionation of MeHg could not explain the species-specific MeHg DSR. Therefore, MeHg-Se interactions and MeHg subcellular fractionation do not explain the relatively low MeHg bioaccessibility in crayfish. Significantly higher cysteine and arginine content was found in crayfish than in the finfish. We suspect that the lower MeHg bioaccessibility of crayfish tail muscle may be attributed to the higher cysteine concentrations, and thus, stronger MeHg-protein binding in crayfish. These results support the interpretation that bioaccessibility differences will alter risk interpretations for MeHg, especially when comparing hazard across aquatic food types.

Diminished capacity of opsonization and immune complex solubilization, and detection of anti-C1q antibodies in sera from patients with hereditary angioedema

BackgroundHereditary angioedema (HAE) is an autosomal dominant disease caused by deficiency of C1 esterase inhibitor. Symptoms of HAE include edema, which can potentially cause suffocation. Some patients with HAE exhibit immunological abnormalities, which could prevent an accurate diagnosis. Low levels of complement components are characteristic of HAE and in other settings are thought to reduce elimination of apoptotic cells and immune complex (IC). Thus, we aimed to experimentally clarify the mechanism of immunological abnormalities using sera from HAE patients. MethodsSerum samples from 18 patients with HAE were collected when free from angioedema attack and compared with normal human pooled sera (NHPS) from 20 healthy volunteers. Opsonization was measured as the rate of phagocytosis of apoptotic Jurkat cells by macrophages differentiated from THP-1 cells incubated with serum. IC solubilization in serum was analyzed by quantifying peroxidase released from a synthetic IC composed of peroxidase and anti-peroxidase antibodies. Anti-C1q antibody levels were detected using an enzyme-linked immunosorbent assay. ResultsSerological immunological abnormalities were detected in 12 patients. Opsonization in serum samples from each patient with HAE was lower than that in NHPS (∼20% versus 70%, respectively). The rate of IC solubilization was lower in serum from HAE patients than NHPS. Some patients had high serum anti-C1q antibody levels with increased serum IC levels. ConclusionsSera from patients with HAE exhibit anti-C1q antibodies, with a lower capacity for opsonization and IC solubilization. This may be associated with immunological abnormalities and should be investigated further to facilitate accurate diagnosis of HAE.