Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction.

The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to study at the nano-scale. Atom probe tomography (APT) is uniquely positioned among the suite of characterization techniques, as it can provide 3D chemical information with sub-nm resolution. In this work, we have used APT to study the nano-scale coking behavior of zeolite SSZ-13 and its relation to bulk coke formation on the macro-/micro-scale studied with operando and in situ UV-vis spectroscopy and microscopy. Radial distribution function analysis (RDF) of the APT data revealed short carbon-carbon length scale affinities, consistent with the formation of larger aromatic molecules (coke species). Using nearest neighbor distribution (NND) analysis, an increase in the homogeneity of carbon was found with increasing time-on-stream. However, carbon clusters could not be isolated due to spatial noise and limited clustering. Therefore, it was found that the coke formation in zeolite SSZ-13 (CHA) is reasonably homogeneous on the nano-scale, and is rather similar to the silicoaluminophosphate analogue SAPO-34 (CHA) but different in nano-scale coking behavior compared to previously studied zeolite ZSM-5 (MFI).

Innovative process scheme for removal of organic matter, phosphorus and nitrogen from pig manure.

Disposal of pig manure often requires treatment with respect to environmental legislations. In this study different processes for reduction of the organic matter (anaerobic digestion, effluent separation by decanter centrifugation, membrane microfiltration, post-digestion in upflow anaerobic sludge blanket (UASB) reactor, partial oxidation), nitrogen (oxygen-limited autotrophic nitrification-denitrification, OLAND) and phosphorus (phosphorus removal by precipitation as struvite, PRS) from pig manure were tested. Results obtained showed that microfiltration was unsuitable for pig manure treatment. PRS treated effluent was negatively affecting the further processing of the pig manure in UASB, and was therefore not included in the final process flow scheme. In a final scheme (PIGMAN concept) combination of the following successive process steps was used: thermophilic anaerobic digestion with sequential separation by decanter centrifuge, post-digestion in UASB reactor, partial oxidation and finally OLAND process. This combination resulted in reduction of the total organic, nitrogen and phosphorus contents by 96%, 88%, and 81%, respectively.

Influence of wastewater characteristics on methane potential in food-processing industry wastewaters.

In this study, we identified the influence of wastewater characteristics on the theoretical and practical methane potential using different food industrial wastewaters as substrates. Ten composite wastewater samples from five industries were investigated. The ultimate practical methane yields (B(o)) were compared to the theoretical methane yields (B(o,th)) in order to evaluate the biodegradability of the tested wastewaters and the influence of their physico-chemical characteristics. The analytical method applied to quantify the wastewaters' organic content proved to influence the estimation of their theoretical yields. The substrate:inoculum ratio as well as the dilution factor of the wastewaters influenced the ultimate practical methane yields differently in each of the wastewaters assessed. Substrate chemical oxygen demand (COD) concentrations did not present any influence on ultimate practical methane yields; on the other hand, it was found that they were affected positively by concentrations of total inorganic carbon when wastewaters were 25% and 50% diluted and affected negatively by concentrations of total acetate when wastewaters were undiluted. Carbohydrate and protein concentrations affected negatively the maximum achieved practical methane yields.

Inactivation of ANAMMOX communities under concurrent operation of anaerobic ammonium oxidation (ANAMMOX) and denitrification.

A concurrent operation of anaerobic ammonium oxidation (ANAMMOX) and denitrification was investigated in a well known UASB reactor seeding with both ANAMMOX and anaerobic granular sludges. ANAMMOX activity was confirmed by hydroxylamine test and the hybridization of biomass using the gene probes of Amx 820 and EUB 338 mixed. Denitrification was observed through the reductions of both COD and nitrate-nitrite concentrations under anaerobic/anoxic conditions. By providing a stoichiometric ratio of nitrite to ammonium nitrogen with addition nitrate nitrogen, a gradual reduction of ANAMMOX activity was found with an increase of COD concentration in a range of 100-400 mg l(-1). This is equivalent to the COD to N ratio of 0.9-2.0. The COD concentration was found to be a control variable for process selection between ANAMMOX reaction and denitrification. A reduction of COD and nitrite-nitrate concentrations in all reactors confirmed the undergone concurrent denitrification which thrives when sufficient organic matter is available. COD concentration over 300 mg l(-1) was found to inactivate or eradicate ANAMMOX communities.

Examining the biodegradation of endocrine disrupting bisphenol A and nonylphenol in WWTPs.

The aim of this work was to examine biodegradation of the endocrine disrupting chemicals bisphenol A (BPA) and nonylphenol (NP) in activated sludge. Experiments were performed in a pilot wastewater treatment plant (WWTP) in Copenhagen, Denmark. During standard operation the BPA concentration was halved whereas the NP concentration was unchanged. Step-addition experiments showed that biomass adaptation to increased BPA and NP concentrations took 10 to more than 40 days depending on temperature, hydraulic retention time, and pre-exposure of the biomass. Mass-balance experiments showed that above 99% of the dosed BPA and 90% of the dosed NP is removed by biodegradation at steady-state. Batch experiments showed that BPA biodegradation occur solely under aerobic conditions. The work is believed to add vital knowledge to our understanding of parameters and processes governing biodegradation of EDCs in WWTPs.

The Xenopus laevis homeobox gene Xgbx-2 is an early marker of anteroposterior patterning in the ectoderm.

In a search for homeobox genes expressed during early Xenopus development, we have isolated a gene which appears to be the Xenopus cognate of the mouse Gbx-2 gene. Expression of Xgbx-2 is first detectable by in situ hybridization at the midgastrula stage when it is predominantly expressed in the dorsolateral ectoderm, with a gap in expression at the dorsal midline. By the end of gastrulation and during neurulation, Xgbx-2 is expressed dorsolaterally in the neural ectoderm and laterally and ventrally in the epidermis with sharp anterior expression borders in both tissues. The anteriormost expression in the neural ectoderm persists throughout the early stages of development, and was mapped to the region of rhombomere 1, with an anterior expression border in the region of the midbrain-hindbrain boundary. Thus Xgbx-2 is expressed anterior to the Hox genes. Xgbx-2 expression is induced by retinoic acid (RA) in animal caps, and RA treatment of whole embryos expands and enhances Xgbx-2 expression in the ectoderm. We suggest a role for Xgbx-2 in establishing the midbrain-hindbrain boundary, which appears to separate early neurectodermal regions expressing genes that are positively and negatively regulated by RA.

Strategies for changing temperature from mesophilic to thermophilic conditions in anaerobic CSTR reactors treating sewage sludge.

Thermophilic anaerobic digestion presents an advantageous way for stabilization of sludge from wastewater treatment plants. Two different strategies for changing operational process temperature from mesophilic (37 degrees C) to thermophilic (55 degrees C) were tested using two continuous flow stirred tank reactors operated at constant organic loading rate of 1.38 g VS/l reactor/day and hydraulic retention time of 20 days. In reactor A, the temperature was increased step-wise: 37 degrees C-->42 degrees C-->47 degrees C-->51 degrees C-->55 degrees C. While in reactor B, the temperature was changed in one-step, from 37 degrees C to the desired temperature of 55 degrees C, The results showed that the overall adaptation of the process for the step-wise temperature increment took 70 days in total and a new change was applied when the process was stabilized as indicated by stable methane production and low volatile fatty acids concentrations. Although the one-step temperature increase caused a severe disturbance in all the process parameters, the system reached a new stable operation after only 30 days indicating that this strategy is the best in changing from mesophilic to thermophilic operation in anaerobic digestion plants.

Requesting information about and obtaining reversal after tubal sterilization: findings from the U.S. Collaborative Review of Sterilization.

OBJECTIVE: To determine the cumulative probabilities over 14 y of requesting information on sterilization reversal and of obtaining a reversal and to identify risk factors observable at sterilization for both measures of regret. DESIGN: The U.S. Collaborative Review of Sterilization, a prospective cohort study. SETTING: Fifteen medical centers in 9 cities. PATIENT(S): 11,232 women. MAIN OUTCOME MEASURE(S): Cumulative probabilities of requesting information on reversal and undergoing reversal. RESULT(S): The 14-y cumulative probability of requesting reversal information was 14.3% (95% confidence interval [CI], 12.4%-16.3%). Among women aged 18 to 24 y at sterilization, the cumulative probability was 40.4% (95% CI, 31.6%-49.2%). Women aged 18 to 24 y were almost 4 times as likely to request reversal information as were women > or = 30 years of age (adjusted rate ratio [RR], 3.5; 95% CI, 2.8-4.4). Number of living children was not associated with requesting reversal information. The overall cumulative probability of obtaining reversal was 1.1% (95% CI, 0.5-1.6). Younger women (18 to 30 y) were more likely to obtain reversal (RR, 7.6; 95% CI, 3.2-18.3). CONCLUSION(S): Women who were sterilized at a young age had a high chance of later requesting information about reversal, regardless of their number of living children.

Anaerobic biodegradation of spent sulphite liquor in a UASB reactor.

Anaerobic biodegradation of fermented spent sulphite liquor, SSL, which is produced during the manufacture of sulphite pulp, was investigated. SSL contains a high concentration of lignin products in addition to hemicellulose and has a very high COD load (173 g COD l(-1)). Batch experiments with diluted SSL and pretreated SSL indicated a potential of 12-22 l methane per litre SSL, which corresponds to 0.13-0.22 l methane (g VS)(-1) and COD removal of up to 37%. COD removal in a mesophilic upflow anaerobic sludge blanket, UASB. reactor ranged from 10% to 31% at an organic loading rate, OLR, of 10-51 g (1 d)(-1) and hydraulic retention time from 3.7 to 1.5 days. The biogas productivity was 3 1 (l(reactor d)(-1), with a yield of 0.05 l gas (g VS)(-1). These results suggest that anaerobic digestion in UASB reactors may provide a new alternative for the treatment of SSL to other treatment strategies such as incineration. Although the total COD reduction achieved is limited, bioenergy is produced and readily biodegradable matter is removed causing less load on post-treatment installations.

The EUVAC-NET survey: national measles surveillance systems in the EU, Switzerland, Norway, and Iceland.

The EUVAC-NET network undertook a questionnaire study on measles surveillance systems in EU member countries, Switzerland, Norway and Iceland. All questionnaires were completed. Surveillance systems for measles are implemented in 16 of the 18 countries. Most countries have some case based data and in all countries the shift is towards case based surveillance for measles, though there are differences between countries concerning case definitions and classifications. A two-dose MMR vaccination schedule is implemented in all the EUVAC-NET countries but methods used for estimation of vaccination coverage are diverse.

The EUVAC-NET survey: national pertussis surveillance systems in the European Union, Switzerland, Norway, and Iceland.

A questionnaire was mailed out to member states of the European Union (EU) plus Switzerland, Norway, and Iceland, to inquire about the type of information routinely recorded in national pertussis surveillance systems. Information was requested on surveillance methods, type of information recorded for cases of pertussis, vaccination schedule, type of vaccine used, and methods for estimating vaccination coverage. Local surveillance methods, vaccination strategies, and methods to estimate vaccination coverage were found to differ widely across the participating countries. The results of the questionnaire survey show, however, that there are comparable subsets of variables common to many countries. Future activities of the EUVAC-NET project will include defining the homogeneous elements in national systems and to group appropriately those countries with common surveillance features.

Improved nitrogen removal in upflow anaerobic sludge blanket (UASB) reactors by incorporation of Anammox bacteria into the granular sludge.

Upflow anaerobic sludge blanket reactors may offer a number of advantages over conventional mixed-tank, SBR, and biofilm reactors, including high space-loading, low footprint, and resistance to shocks and toxins. In this study, we assessed the use of upflow anaerobic sludge blanket (UASB) reactor technology as applied to anaerobic ammonia removal, or Anammox. Four 200 ml UASB reactors were inoculated with 50% (by volume) anaerobic granular sludge and 50% flocular sludge from different sources (all with the potential for containing Anammox organisms). Tools used to assess the reactors included basic analyses, fluorescent in-situ hybridisation, and mathematical modelling, with statistical non-linear parameter estimation. Two of the reactors showed statistically identical Anammox activity (i.e., identical kinetic parameters), with good ammonia and nitrite removal (0.14 kgNHx m(-3) reactor day(-1), with 99% ammonia removal). The third reactor also demonstrated significant Anammox activity, but with poor identifiability of parameters. The fourth reactor had no statistical Anammox activity. Modelling indicated that poor identifiability and performance in the third and fourth reactors were related to an excess of reduced carbon, probably originating in the inoculum. Accumulation of Anammox organisms was confirmed both by a volume loading much lower than the growth rate, and response to a probe specific for organisms previously reported to mediate Anammox processes. Overall, the UASB reactors were effective as Anammox systems, and identifiability of the systems was good, and repeatable (even compared to a previous study in a rotating biological contactor). This indicates that operation, design, and analysis of Anammox UASB reactors specifically, and Anammox systems in general, are reliable and portable, and that UASB systems are an appropriate technology for this process.

Use of an anaerobic sequencing batch reactor for parameter estimation in modelling of anaerobic digestion.

The model structure in anaerobic digestion has been clarified following publication of the IWA Anaerobic Digestion Model No. 1 (ADM1). However, parameter values are not well known, and uncertainty and variability in the parameter values given is almost unknown. Additionally, platforms for identification of parameters, namely continuous-flow laboratory digesters, and batch tests suffer from disadvantages such as long run times, and difficulty in defining initial conditions, respectively. Anaerobic sequencing batch reactors (ASBRs) are sequenced into fill-react-settle-decant phases, and offer promising possibilities for estimation of parameters, as they are by nature, dynamic in behaviour, and allow repeatable behaviour to establish initial conditions, and evaluate parameters. In this study, we estimated parameters describing winery wastewater (most COD as ethanol) degradation using data from sequencing operation, and validated these parameters using unsequenced pulses of ethanol and acetate. The model used was the ADM1, with an extension for ethanol degradation. Parameter confidence spaces were found by non-linear, correlated analysis of the two main Monod parameters; maximum uptake rate (k(m)), and half saturation concentration (K(S)). These parameters could be estimated together using only the measured acetate concentration (20 points per cycle). From interpolating the single cycle acetate data to multiple cycles, we estimate that a practical "optimal" identifiability could be achieved after two cycles for the acetate parameters, and three cycles for the ethanol parameters. The parameters found performed well in the short term, and represented the pulses of acetate and ethanol (within 4 days of the winery-fed cycles) very well. The main discrepancy was poor prediction of pH dynamics, which could be due to an unidentified buffer with an overall influence the same as a weak base (possibly CaCO3). Based on this work, ASBR systems are effective for parameter estimation, especially for comparative wastewater characterisation. The main disadvantages are heavy computational requirements for multiple cycles, and difficulty in establishing the correct biomass concentration in the reactor, though the last is also a disadvantage for continuous fixed film reactors, and especially, batch tests.

Anaerobic bioprocessing of sewage sludge, focusing on degradation of linear alkylbenzene sulfonates (LAS).

Anaerobic degradation of sludge amended with linear alkylbenzene sulfonates (LAS) was tested in a one stage continuous stirred tank reactor (CSTR) and a two stage reactor system consisting of a CSTR as first step and upflow anaerobic sludge bed (UASB) reactor as the second step. Anaerobic removal of LAS was only observed at the second step but not at the first step. Removal of LAS in the UASB reactors was approx. 80% where half was due to absorption and the other half was apparently due to biological removal as shown from the LAS mass balance. At the end of the experiment the reactors were spiked with 14C-LAS which resulted in 5.6% 14CO2 in the produced gas. Total mass balance of the radioactivity was however not achieved. In batch experiments it was found that LAS at concentrations higher than 50 mg/l is inhibitory for most microbial groups of the anaerobic process. Therefore, low initial LAS concentration is a prerequisite for successful LAS degradation. The results from the present study suggest that anaerobic degradation of LAS is possible in UASB reactors when the concentration of LAS is low enough to avoid inhibition of microorganisms active in the anaerobic process.

Anaerobic digestion of olive oil mill effluents together with swine manure in UASB reactors.

Combined anaerobic digestion of olive oil mill effluent (OME) with swine manure, was investigated. In batch experiments was shown that for anaerobic degradation of OME alone nitrogen addition was needed. A COD:N ratio in the range of 65:1 to 126:1 was necessary for the optimal degradation process. Furthermore, it was found that methane productions rates during digestion of either swine manure alone or OME alone were much lower than the rates achieved when OME and manure were digested together. Admixing OME with manure at a concentration of 5 to 10% OME resulted in the highest methane production rates. Using upflow anaerobic sludge blanket (UASB) reactors, it was shown that codigestion of OME with swine manure (up to 50% OME) was successful with a COD reduction up to 75%. The process was adapted for degradation of OME with stepwise increase of the OME load to the UASB reactor. The results showed that the high content of ammonia in swine manure, together with content of other nutrients, make it possible to degrade OME without addition of external alkalinity and without addition of external nitrogen source. Anaerobic treatment of OME in UASB reactors resulted in reduction of simple phenolic compounds such as mequinol, phenyl ethyl alcohol and ethyl methyl phenol. After anaerobic treatment the concentration of these compounds was reduced between 75 and 100%. However, the concentration of some degradation products such as methyl phenol and ethyl phenol were detected in significantly higher concentrations after treatment, indicating that the process has to be further optimised to achieve satisfactory removal of all xenobiotic compounds.

Removal of polycyclic aromatic hydrocarbons (PAHs) from sewage sludge by anaerobic degradation.

Due to the hydrophobic nature of the polyaromatic hydrocarbons (PAHs) they are mostly bound to the sludge and escape aerobic treatment in a wastewater treatment plant. They therefore proceed directly to the anaerobic post treatment, terminate in the sludge, and can be released to the environment if land spreading is used. PAH degradation in anaerobic methanogenic systems has only recently been shown to occur. In this study we have assessed several factors of anaerobic PAH degradation by evaluating thermodynamic feasibility of degradation, assessing degradation at different temperatures, and investigating the enriched cultures using fluorescent in-situ hybridization (FISH). Thermodynamic calculations indicated that PAH degradation was possible under methanogenic conditions, in the presence of hydrogen utilizing methanogens. Removal of naphthalene and 1-methyl naphthalene depended both on temperature and the initial inoculum. Inocula sourced from contaminated land sites were the most effective. The enrichments were all a mixture of Bacteria, and Archaea, and the Archaea were generally identified as Methanobacteriales, using an order-specific probe. The bacteria were not specifically identified. The results indicate a syntrophic culture, with the bacteria oxidizing the naphthalene, and the Archaea converting the hydrogen produced by oxidation, to methane.

Chemical characteristics and methane potentials of source-separated and pre-treated organic municipal solid waste.

A research project has investigated the biogas potential of pre-screened source-separated organic waste. Wastes from five Danish cities have been pre-treated by three methods: screw press; disc screen; and shredder and magnet. This paper outlines the sampling procedure used, the chemical composition of the wastes and the estimated methane potentials.

[A survey of forensic psychiatric resources. Trends in the flow of patients to a new unit of forensic psychiatry, Sygehus Fyn, December 31, 1985 to December 31, 1995]. / En retspsykiatrisk ressourceopgørelse. Udviklingen i patientbelastningen i en nyetableret retspsykiatrisk afdeling, Sygehus Fyn, Middelfart, 31.12.1985-31.12.1995.

The study covered 163 patients sentenced to special measures. All of them were from the county of Funen, which is a representative part of Denmark regarding forensic psychiatry. On the cross-sectional date 31st December each year the total number of patients treated in the unit was the recorded. The number of patients sectioned to psychiatric treatment in hospital increased by 150% during the observation period. The recorded rise covered both offenders sentenced according to the section 16 and section 69 of the Danish penal code and reflected an increasing number of schizophrenic patients and to lesser-extent patients with personality disorder. The increasing number of beds occupied by forensic patients was in accordance with the development in the total number of patients treated in the unit.

[Psychiatric observations 1986-1993. Sygehus Fyn, Middelfart, the unit of forensic psychiatry]. / Mentalobservationer 1986-1993. Sygehus Fyn, Middelfart, retspsykiatrisk afdeling.

Two hundred and sixty psychiatric reports for law courts conducted between 1986-1993 at the Unit of Forensic Psychiatry, Middelfart were reviewed. The aim was to record a number of essential characteristics with special focus on the number of reports, demographic data, diagnosis and type of criminal act. All the offenders were inhabitants of the county of Funen, where about 50-60 reports for law courts were carried out each year during the period of investigation. Serious crimes (homicide, attempted suicide, violence, arson and rape), were mainly (74%) committed by offenders with personality disorder, of whom few were sentenced to special measures. However, a higher percentage than expected of individuals charged with arson were psychotic (30%) and mentally retarded (10%). Schizophrenics and individuals with other types of non-affective psychosis covered a higher percentage of persons charged with violence compared to manic-depressive individuals. Fifty percent of the offenders were chronic drug abusers.

Magnetic interactions in exchange-coupled yet unbiased IrMn/NiCu bilayers.

This paper reports experimental and model magnetization results obtained on exchange-coupled ferromagnet/antiferromagnet (FM/AF) bilayers that show zero net bias. The coercivity of the films, either irradiated with He or implanted with Ge ions at 40 keV, varies significantly with the fluence used. We employed the remanence plots technique in order to estimate the nature of the interactions present and check if there exists a correlation between their type and the coercivity variations. The analysis of the remanence plots through numerical simulations based on the Landau-Lifshitz-Gilbert equation demonstrated that outcomes of interactions within the FM layer could be distinguished from those coming from coupling at the FM/AF interface and that demagnetizing interaction effects could be achieved without the presence of dipolar interactions. Our findings indicate that such experiments could give selective information on modifications caused by a post-deposition treatment in each layer of the film.