Sewer deterioration modeling with condition data lacking historical records.

Accurate predictions of future conditions of sewer systems are needed for efficient rehabilitation planning. For this purpose, a range of sewer deterioration models has been proposed which can be improved by calibration with observed sewer condition data. However, if datasets lack historical records, calibration requires a combination of deterioration and sewer rehabilitation models, as the current state of the sewer network reflects the combined effect of both processes. Otherwise, physical sewer lifespans are overestimated as pipes in poor condition that were rehabilitated are no longer represented in the dataset. We therefore propose the combination of a sewer deterioration model with a simple rehabilitation model which can be calibrated with datasets lacking historical information. We use Bayesian inference for parameter estimation due to the limited information content of the data and limited identifiability of the model parameters. A sensitivity analysis gives an insight into the model's robustness against the uncertainty of the prior. The analysis reveals that the model results are principally sensitive to the means of the priors of specific model parameters, which should therefore be elicited with care. The importance sampling technique applied for the sensitivity analysis permitted efficient implementation for regional sensitivity analysis with reasonable computational outlay. Application of the combined model with both simulated and real data shows that it effectively compensates for the bias induced by a lack of historical data. Thus, the novel approach makes it possible to calibrate sewer pipe deterioration models even when historical condition records are lacking. Since at least some prior knowledge of the model parameters is available, the strength of Bayesian inference is particularly evident in the case of small datasets.

Identifying biases in deterioration models using synthetic sewer data.

The assessment and validation of sewer deterioration models is difficult because reliable data are missing. This makes it hard to find the most suitable model for a particular application. A network condition simulator (NetCoS) is used to generate synthetic sewer data for defined test scenarios. Thereby, the deterioration and replacement of pipes, the expansion of the sewer network, and classification errors are considered. Based on such synthetic data, deterioration models are calibrated and their results compared with the predefined scenario. While this approach is not capable of proving that a model performs correctly on a real application, it highlights the strengths and weaknesses of a model. The influence of condition classification errors and the age of the sewer system is investigated for two deterioration models. The results show, that classification errors can introduce substantial biases in the parameter estimation of the Markov model while in comparison the applied cohort model is fairly robust. Young sewer systems with fewer pipes in bad condition states on the other hand, have a very strong influence on the parameter uncertainties of the cohort model while the Markov model proved to be less sensitive.

Assessing the performance of sewer rehabilitation on the reduction of infiltration and inflow.

Inflow and Infiltration (I/I) into sewer systems is generally unwanted, because, among other things, it decreases the performance of wastewater treatment plants and increases combined sewage overflows. As sewer rehabilitation to reduce I/I is very expensive, water managers not only need methods to accurately measure I/I, but also they need sound approaches to assess the actual performance of implemented rehabilitation measures. However, such performance assessment is rarely performed. On the one hand, it is challenging to adequately take into account the variability of influential factors, such as hydro-meteorological conditions. On the other hand, it is currently not clear how experimental data can indeed support robust evidence for reduced I/I. In this paper, we therefore statistically assess the performance of rehabilitation measures to reduce I/I. This is possible by using observations in a suitable reference catchment as a control group and assessing the significance of the observed effect by regression analysis, which is well established in other disciplines. We successfully demonstrate the usefulness of the approach in a case study, where rehabilitation reduced groundwater infiltration by 23.9%. A reduction of stormwater inflow of 35.7%, however, was not statistically significant. Investigations into the experimental design of monitoring campaigns confirmed that the variability of the data as well as the number of observations collected before the rehabilitation impact the detection limit of the effect. This implies that it is difficult to improve the data quality after the rehabilitation has been implemented. Therefore, future practical applications should consider a careful experimental design. Further developments could employ more sophisticated monitoring methods, such as stable environmental isotopes, to directly observe the individual infiltration components. In addition, water managers should develop strategies to effectively communicate statistically not significant I/I reduction ratios to decision makers.

Network condition simulator for benchmarking sewer deterioration models.

An accurate description of aging and deterioration of urban drainage systems is necessary for optimal investment and rehabilitation planning. Due to a general lack of suitable datasets, network condition models are rarely validated, and if so with varying levels of success. We therefore propose a novel network condition simulator (NetCoS) that produces a synthetic population of sewer sections with a given condition-class distribution. NetCoS can be used to benchmark deterioration models and guide utilities in the selection of appropriate models and data management strategies. The underlying probabilistic model considers three main processes: a) deterioration, b) replacement policy, and c) expansions of the sewer network. The deterioration model features a semi-Markov chain that uses transition probabilities based on user-defined survival functions. The replacement policy is approximated with a condition-class dependent probability of replacing a sewer pipe. The model then simulates the course of the sewer sections from the installation of the first line to the present, adding new pipes based on the defined replacement and expansion program. We demonstrate the usefulness of NetCoS in two examples where we quantify the influence of incomplete data and inspection frequency on the parameter estimation of a cohort survival model and a Markov deterioration model. Our results show that typical available sewer inventory data with discarded historical data overestimate the average life expectancy by up to 200 years. Although NetCoS cannot prove the validity of a particular deterioration model, it is useful to reveal its possible limitations and shortcomings and quantifies the effects of missing or uncertain data. Future developments should include additional processes, for example to investigate the long-term effect of pipe rehabilitation measures, such as inliners.

Co speciation in hardened cement paste: a macro- and micro-spectroscopic investigation.

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill and liner materials) of repositories for radioactive waste. In this study, Co uptake by hardened cement paste (HCP) has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray-absorption spectroscopy (XAS) on powder material (bulk-XAS) was used to determine the local environment of Co in cement systems. Bulk-XAS investigations were complemented with micro-beam investigations to probe the inherent microscale heterogeneity of cement by using micro-X-ray-fluorescence (micro-XRF) and micro-XAS. Micro-XRF was used to gain information on the spatial heterogeneity of the Co distribution, whereas micro-XAS was employed to determine the speciation of Co on the microscale. The Co-doped HCP samples hydrated for time-scales from 1 hour up to 1 year were prepared under normal atmosphere, to simulate similar conditions as for waste packages. To investigate the role of oxygen, further samples were prepared in the absence of oxygen. The study showed that, for the samples prepared in air, Co(II) is oxidized to Co(III) after 1 hour of hydration time. Moreover, the relative amount of Co(III) increases with increasing hydration time. The study further revealed that Co(II) is predominately present as a Co-hydroxide-like phase and/or Co-phyllosilicates, whereas Co(III) tends to be incorporated into a CoOOH-like phase and/or Co-phyllomanganates. In contrast to samples prepared in air, XAS experiments with samples prepared in the absence of oxygen revealed solely the presence of Co(II). This finding indicates that oxygen plays an important role for Co oxidation in cement. Furthermore, the study suggests that Co(III) species or Co(III)-containing phases should be taken into account for an overall assessment of the Co release from Co-containing cement-stabilized waste under oxidizing conditions.

Spectroscopic investigation of Ni speciation in hardened cement paste.

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill, and liner materials) of repositories for radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray absorption spectroscopy (XAS) coupled with diffuse reflectance spectroscopy (DRS) techniques were used to determine the local environment of Ni in cement systems. The Ni-doped samples were prepared at two different water/cement ratios (0.4, 1.3) and different hydration times (1 hour to 1 year) using a sulfate-resisting Portland cement. The metal loadings and the metal salts added to the system were varied (50 up to 5000 mg/kg; NO3(-), SO4(2-), Cl-). The XAS study showed that for all investigated systems Ni(ll) is predominantly immobilized in a layered double hydroxide (LDH) phase, which was corroborated by DRS measurements. Only a minor extent of Ni(ll) precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). This finding suggests that Ni-Al LDH, rather than Ni-hydroxides, is the solubility-limiting phase in the Ni-doped cement system.

The use of (micro)-X-ray absorption spectroscopy in cement research.

Long-term predictions on the mobility and the fate of radionuclides and contaminants in cementitious waste repositories require a molecular-level understanding of the geochemical immobilization processes involved. In this study, the use of X-ray absorption spectroscopy (XAS) for chemical speciation of trace elements in cementitious materials will be outlined presenting two examples relevant for nuclear waste management. The first example addresses the use of XAS on powdered cementitious materials to determine the local coordination environment of Sn(IV) bound to calcium silicate hydrates (C-S-H). Sn K-edge XAS data of Sn(IV) doped C-S-H can be rationalized by corner sharing binding of Sn octahedra to Si tetrahedra of the C-S-H structure. XAS was further applied to determine the binding mechanism of Sn(IV) in the complex cement matrix. The second example illustrates the potential of emerging synchrotron-based X-ray micro-probe techniques for elucidating the spatial distribution and the speciation of contaminants in highly heterogeneous cementitious materials at the micro-scale. Micro X-ray fluorescence (XRF) and micro-XAS investigations were carried out on Co(II) doped hardened cement paste. These preliminary investigations reveal a highly heterogeneous spatial Co distribution. The presence of a Co(II)-hydroxide-like phase Co(OH)2 and/or Co-Al layered double hydroxide (Co-Al LDH) or Co-phyllosilicate was observed. Surprisingly, some of the initial Co(II) was partially oxidized and incorporated into a Co(III)O(OH)-like phase or a Co-phyllomanganate.

Microscale investigations of Ni uptake by cement using a combination of scanning electron microscopy and synchrotron-based techniques.

Cement is used to condition waste materials and for the construction and backfilling of repositories for low-and intermediate-level radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of Ni(ll) in cement on the microscale. Information on the cement microstructure, Ni distribution, Ni concentration, and speciation of the Ni phases formed in the cement system and their association with specific cement minerals has been gained by using scanning electron microscopy (SEM) and synchrotron-based micro-X-ray fluorescence (micro-XRF) and micro-X-ray absorption spectroscopy (micro-XAS). The Ni-doped samples were prepared at a water/cement ratio of 0.4 using a sulfate-resisting Portland cement and were hydrated for 30 days. The metal loadings of the system were varied from 50 up to 5000 mg/kg. SEM investigations show that for all metal loadings the Ni phases form rims around inner-calcium silicate hydrates, suggesting a direct association with this cement phase. The micro-XAS measurements further reveal that a mixture of Ni phases form at Ni-enriched regions. Data analysis indicates that Ni(ll) is predominantly immobilized in a layered double hydroxide-type phase (Ni-Al LDH) and only to a minor extent precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). At 50 mg/kg Ni loading, however, the p-XAS measurements suggest the presence of an additional Ni species. In the latter system Ni-Al LDH is found in Ni-rich regions, whereas at Ni-poor regions an unknown species is formed.

Ni clay neoformation on montmorillonite surface.

Polarized extended X-ray absorption fine structure spectroscopy (P-EXAFS) was used to study the sorption mechanism of Ni on the aluminous hydrous silicate montmorillonite at high ionic strength (0.3 M NaClO4), pH 8 and a Ni concentration of 0.66 mM. Highly textured self-supporting clay films were obtained by slowly filtrating a clay suspension after a reaction time of 14 days. P-EXAFS results indicate that sorbed Ni has a Ni clay-like structural environment with the same crystallographic orientation as montmorillonite layers.

Ni phases formed in cement and cement systems under highly alkaline conditions: an XAFS study.

X-ray absorption fine structure (XAFS) spectroscopy was applied to assess the solubility-limiting phase of Ni in cement and cement minerals. The study reveals the formation Ni and Al containing hydrotalcite-like layered double hydroxides (Ni-Al LDHs) when cement material (a complex mixture of CaO, SiO2, Al2O3, Fe2O3 and SO3) was treated with Ni in artificial cement pore water under highly alkaline conditions (pH = 13.3). This finding indicates that Ni-Al LDHs and not Ni-hydroxides determine the solubility of Ni in cement materials.

Sorption mechanisms of zinc to calcium silicate hydrate: X-ray absorption fine structure (XAFS) investigation.

In this study, X-ray absorption fine structure (XAFS) spectroscopy has been used to further elucidate the binding mechanisms of Zn(II) to calcium silicate hydrate (C-S-H), the quantitatively most important cement mineral. Such knowledge is essential for the assessment of the longterm behavior of cement-stabilized waste materials. XAFS spectra of the Zn(II) equilibrated with C-S-H(I) for up to 28 days are best modeled by tetrahedral coordination of Zn(II) by four O atoms in the first atomic shell. Beyond the first coordination shell, data analysis of more highly concentrated samples suggests the presence of two distinct Zn distances and possibly the presence of an Si shell. On the basis of the comparison with a set of reference compounds, this coordination environment can be reasonably related to the structure of hemimorphite, a naturally occurring zinc silicate, and/or the presence of gamma-Zn(OH)2. At the lowest Zn uptake, the above fitting approach failed and data could be described best with a Zn-Si and a Zn-Ca shell. Previous work has been able to show that Zn(II) diffuses into the C-S-H(I) particles and does not form discrete precipitates, so the findings appear to confirm the incorporation of Zn(II) in the interlayer of C-S-H(I).

[Ambulatory surgery clinic in a public general hospital. Organization and results]. / Tagesklinik an einem öffentlichen Spital der Grundversorgung. Organisation und Resultate.

In surgery a day care clinic is defined as an institution in which patients undergo elective operations the day of their admission and are discharged within 24 h after surgery. An important goal of day care surgery is to avoid unnecessary hospitalisations however providing the patient with the same quality of treatment and personal satisfaction. This presentation describes the patients selection, information and follow-up, the organization of the day care system, the computerized quality control and the medical outcome. Our experience is based on a 2-year period of day care surgery in a general community hospital. The results of 581 consecutively operated, not selected, patients are presented. Quality control was performed for all patients during their stay at the day care unit, and for 98.5% as follow-up control by the General Practitioners. The most frequent operations were: arthroscopies, meniscectomies, removals of implants after osteosynthesis, decompressions of peripheral nerves, large excisions of skin-tumors, bursectomies, reconstructions of torn ligaments, hernial repairs, strippings of varicose veins, hemorrhoidectomies and operations of the anal and genital region. We present the patients age, the type of anesthesia, the type of operation, eventual complications (in clinic, 24 hours after discharge and at the end of the treatment), the medical results as well as the costs of the after-treatment.

A Novel Class of Herbicides (Specific Inhibitors of Imidazoleglycerol Phosphate Dehydratase).

A new mode of herbicidal action was established by finding specific inhibitors of imidazoleglycerol phosphate dehydratase, an enzyme of histidine (His) biosynthesis. Three triazole phosphonates inhibited the reaction of the enzyme with Ki values of 40 [plus or minus] 6.5, 10 [plus or minus] 1.6, and 8.5 [plus or minus] 1.4 nM, respectively, and were highly cytotoxic to cultured plant cells. This effect was completely reversed by the addition of His, proving that the cytotoxicity was primarily caused by the inhibition of His biosynthesis. These inhibitors showed wide-spectrum, postemergent herbicidal activity at application rates ranging from 0.05 to 2 kg/ha.

Isolation and characterization of cDNAs encoding imidazoleglycerolphosphate dehydratase from Arabidopsis thaliana.

cDNA clones encoding imidazoleglycerolphosphate dehydratase (IGPD; EC 4.2.1.19) from Arabidopsis thaliana were isolated by complementation of a bacterial auxotroph. The predicted primary translation product shared significant identity with the corresponding sequences from bacteria and fungi. As in yeast, the plant enzyme is monofunctional, lacking the histidinol phosphatase activity present in the Escherichia coli protein. IGPD mRNA was present in major organs at all developmental stages assayed. The Arabidopsis genome appears to contain two genes encoding this enzyme, based on DNA gel blot and polymerase chain reaction analysis.

Mass movements in Hilly areas (with examples from Nigeria)

In mountaimous areas of great relief, mass movements occur regularly as the result of the normal cyclic landscape development process. However, mass movements also occur in areas of lower relief, i.e. in areas of less geomorphic activity. An extreme case of this type has been found in the development of cracks in a flat savannah area of Nigeria which has generally been ascribed to purely hydrological causes. Nevertheless, it can be shown that the development of the cracks occurs along the shear lines of the neotectonic stress field, so that geotectonic processes represent the "ultimate" cause of the mass movements here as well.(AU)

Purification and Properties of a Monofunctional Imidazoleglycerol-Phosphate Dehydratase from Wheat.

Imidazoleglycerol-phosphate dehydratase (EC 4.2.1.19) activity was detected in extracts of several monocotyledonous and dicotyledonous plants using a newly developed assay method. The enzyme was purified 114,000-fold (to apparent homogeneity) from wheat germ by five chromatographic steps. Its native relative molecular weight (Mr) was determined to be 600,000 to 670,000, and it consists of identical subunits of Mr 25,500. In wheat germ, the dehydratase, unlike those of prokaryotic origin, is not associated with histidinol phosphatase activity. The reaction product was identified as imidazoleacetol phosphate (IAP) by comparing it with synthetic IAP as an authentic reference. The Km value for imidazoleglycerol phosphate was 0.36 mM at the optimal pH of 6.6. The enzyme required a reducing agent, such as 2-mercaptoethanol or dithiothreitol, and Mn2+ for maximal activity. 3-Amino-1,2,4-triazole competitively inhibited the activity with a Ki value of 46 [mu]M. The purification of imidazoleglycerol-phosphate dehydratase from wheat germ and histidinol dehydrogenase from cabbage (A. Nagai, A. Scheidegger [1991] Arch Biochem Biophys 284: 127-132) suggests that at least the second half of the histidine biosynthesis in plants is identical to that in microorganisms.

Overexpression of plant histidinol dehydrogenase using a baculovirus expression vector system.

A cDNA encoding cabbage histidinol dehydrogenase, including the chloroplast transit peptide sequence, was overexpressed using a baculovirus expression vector system. The maximum level of the expression of histidinol dehydrogenase was reached 5 days after infection of the insect cells. Two forms of recombinant histidinol dehydrogenase with molecular masses of 53 and 52 kDa, respectively, were obtained by a one-step purification from the cell homogenate. Compared with the 52-kDa form, the 53-kDa form contained 10 additional amino acids at the N-terminus derived from the transit peptide. By incubating the cell homogenate for 2 h at 30 degrees C, the 53-kDa form could be completely converted to the 52-kDa form. This conversion was blocked by leupeptin. Eighty percent of the converted 52-kDa form had Cys at position 31 at the N-terminal amino acid and the rest had Met 33. Kinetic properties of the recombinant enzyme were virtually identical to those of histidinol dehydrogenase isolated from cabbage plants. The overexpression of recombinant cabbage histidinol dehydrogenase in insect cells, the proteolytic processing of the preprotein next to the N-terminus (compared to the mature cabbage enzyme), and its easy purification allow the preparation of large amounts of the active enzyme for structural and functional studies.

Structural and functional conservation of histidinol dehydrogenase between plants and microbes.

The partial amino acid sequence of histidinol dehydrogenase (L-histidinol:NAD+ oxidoreductase, EC 1.1.1.23) from cabbage was determined from peptide fragments of the purified protein. The relative positions of these peptides were deduced by aligning their sequences with the sequence of the HIS4C gene product of Saccharomyces cerevisiae. cDNA encoding histidinol dehydrogenase was then amplified from a library using a polymerase chain reaction primed with degenerate oligonucleotide pools of known position and orientation. By using this amplified fragment as a probe, an apparently full-length cDNA clone was isolated that is predicted to encode a proenzyme having a putative 31-amino acid chloroplast transit peptide and a mature molecular mass of 47.5 kDa. The predicted protein sequence was 51% identical to the yeast enzyme and 49% identical to the Escherichia coli enzyme. Expression of the cDNA clone in an E. coli his operon deletion strain rendered the mutant able to grow in the presence of histidinol.

Purification and characterization of histidinol dehydrogenase from cabbage.

Histidinol dehydrogenase (EC 1.1.1.23) activity was determined in several plant species and in cultured plant cell lines. The enzyme was purified from cabbage (Brassica oleracea) to apparent homogeneity. To render complete purification, a new, specific histidinol-Sepharose 4B affinity chromatography was developed. The apparent molecular mass of the protein is 103 kDa. On sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the protein migrated as a single band with a molecular mass of 52 kDa, giving evidence for a dimeric quaternary structure. By isoelectric focusing, the enzyme was separated into six protein bands, five of which possessed the dehydrogenase activity when examined by an activity staining method. The Km values for L-histidinol and NAD+ were 15.5 and 42 microM, respectively. Enzyme activity was stimulated by addition of Mn2+, but was inhibited in the presence of Ba2+, Mg2+, Ni2+, Ca2+, Zn2+, or Cu2+. Histidinol dehydrogenase is the first histidine enzyme that has been purified to homogeneity and characterized from plants. This plant enzyme catalyzes the NAD-linked four-electron dehydrogenase reaction leading from histidinol to His. The results indicate a similar pathway of His in plants and show furthermore the last two reaction steps to be identical to those in microorganisms.