Kõrge täpsusega gravimeetriline Winkleri meetod lahustunud hapniku määramiseks

Väitekirja elektrooniline versioon ei sisalda publikatsioone.Lahustunud hapniku sisaldus looduslikes vetes on väga oluline parameeter. Viimasel ajal on täheldatud hapnikutaseme langust maailma ookeanide mitmetes piirkondades. Protsessid, mis selleni viivad ei ole lõpuni arusaadavad ja nende lahtimõtestamiseks on väga oluline suuta hapnikusisaldusi kõrge täpsusega mõõta. Üsna laialdaselt mõõdetakse lahustunud hapniku sisaldust vees amperomeetriliste ja viimasel ajal ka optiliste hapnikuanalüsaatoritega. Need meetodid ei ole primaarmeetodid ja vajavad kalibreerimist. Stabiilse kontsentratsiooniga hapnikulahuste tegemine on hapniku keemiliste, füüsikaliste ja biololoogiliste omaduste tõttu pea võimatu. Seega, et tagada lahustunud hapniku määramisel jälgitavus SI ühikuteni, on tarvilik kõrge täpsusega primaarmeetodi olemasolu. Primaarmeetodiks lahustunud hapniku määramisel on Winkleri jodomeetriline tiitrimismeetod. Sellel meetodil on leitud rida kitsaskohti kaasa arvatud see, et klassikaliselt on tegemist mahtanalüütilise meetodiga. Kirjanduses on avaldatud terve hulk Winkleri meetodi modifikatsioone, mis peaksid selle meetodi puudusi parendama. Nende meetoditega saadud tulemuste korrektsed, kõiki olulisi allikaid arvestavad määramatuse hinnangud aga puudusid enne käesoleva töö algust kirjandusest täielikult. Enamik kirjandusallikaid on piirdunud vaid korduvuse andmetega, mõnel juhul oli eraldi hinnatud ka üksikuid muude määramatuse allikate panuseid. Erinevalt seni pakutud Winkleri meetodi modifikatsioonidest on käesolevas töös välja töötatud metoodika gravimeetriline tagades sellega madalama määramatuse. Metoodika jaoks on viidud läbi detailne mõõtemääramatuse hindamine. Selle jaoks on läbi viidud eksperimente väga erinevate mõjuallikate kindlakstegemiseks, leitud nendele vastavad parandid ja määramatuste panused. Määramatuse hindamise tulemusena saadud määramatuse koond sisaldab erinevate komponentide panuseid ning on võimas abivahend meetodi optimeerimiseks ja veelgi täpsemate tulemuste saamiseks. Seda võimalust on ka käesolevas töös kasutatud ning selle tulemusena on välja arendatud Winkleri meetodi gravimeetriline modifikatsioon, mis annab madalaima määramatusega tulemusi lahustunud hapniku määramisel vees.DO content in natural waters is a very important parameter. Recent studies show decrease in DO content in several areas of world oceans. Processes leading to this decrease are not completely understood and it is very important to be able to measure DO content very accurately for studying the dynamics of these processes. Amperometric and more recently also optical oxygen sensors are widely used in DO measurements. These sensors need calibration and therefore solutions with accurate DO concentration are necessary. Oxygen is a very unstable analyte due to its chemical, physical and biological properties. For this reason it is almost impossible to prepare oxygen solutions in ordinary way by dissolving certain amount of oxygen in water. The problem can be solved by using some primary method (i.e. method not needing calibration) that also ensures traceability to SI units. The most reliable primary DO measurement method available is the Winkler titration method. For this method several of factors limiting its accuracy were determined, including the volumetric nature of the classical Winkler method. A number of publications propose different modifications that should eliminate or compensate for these disadvantages. However, before the start of this work there were no publications available that would comprehensively review all the important uncertainty sources of the Winkler method and still a lot of room existed for improving the accuracy of the Winkler method. Most of the publications give repeatability of the results only. In some cases individual uncertainty sources were separately estimated. The method proposed in this work differs from the previously proposed method due to its gravimetric approach, which assures lower uncertainty. Detailed analysis of the uncertainty sources and comprehensive uncertainty estimation were carried out. Experiments for determining the different influence factors were carried out, corrections were determined and uncertainty contributions for accounting these influences were estimated. As a result a detailed uncertainty budget was compiled. This budget is very useful for optimizing the function for getting more accurate measurement results. The optimization was carried out and as a result of this the gravimetric Winkler method modification for determination of DO in water giving the results with lowest available uncertainty was developed

Field measurement intercomparison - Field measurements of dissolved oxygen concentration

In the framework of the European Metrology Research Programme (EMRP) project ENV05 OCEAN (Metrology for ocean salinity and acidity), the dissolved oxygen field (in situ) intercomparison (FieldOxy 2014) test was organized onboard R/V Aranda on April 23, 2014 in the Gulf of Finland. The aim of the intercomparison was to enable the participants to assess their performance in measuring dissolved oxygen concentration in seawater under field conditions. The intercomparison measurement was organized jointly by the Finnish Environment Institute (Proftest SYKE. Envical SYKE) and University of Tartu. Total of 21 participants from 10 institutes in Finland, Estonia, France, Germany and Sweden participated in the intercomparison. Totally, 13-18 oxygen sensors were tested depending of the test depth. Additionally, six Winkler titrimetric setups participated in the intercomparison. The metrologically traceable Winkler titration result (the assigned value) was measured by the Winkler setup of University of Tartu onboard R/V Aranda. In total, 88 % of the results were satisfactory when total deviation of 8 % from the assigned values were accepted. Only three results were questionable and five results were unsatisfactory. A possible reason for several of the unsatisfactory results might be problems with calibration of electrochemical oxygen sensors. The movement of the water during the PT may have been insufficient for the electrochemical sensors, which may have resulted biased measurement results. Overall the share of satisfactory results was very good

Measurement Uncertainty Estimation in Amperometric Sensors: A Tutorial Review

This tutorial focuses on measurement uncertainty estimation in amperometric sensors (both for liquid and gas-phase measurements). The main uncertainty sources are reviewed and their contributions are discussed with relation to the principles of operation of the sensors, measurement conditions and properties of the measured samples. The discussion is illustrated by case studies based on the two major approaches for uncertainty evaluation–the ISO GUM modeling approach and the Nordtest approach. This tutorial is expected to be of interest to workers in different fields of science who use measurements with amperometric sensors and need to evaluate the uncertainty of the obtained results but are new to the concept of measurement uncertainty. The tutorial is also expected to be educative in order to make measurement results more accurate

HIV Testing and Diagnosis Rates in Kiev, Ukraine: April 2013-March 2014

Data from Ukraine on risk factors for HIV acquisition are limited. We describe the characteristics of individuals testing for HIV in the main testing centres of the Ukrainian capital Kiev, including HIV risk factors, testing rates, and positivity rates. As part of a larger study to estimate HIV incidence within Kiev City, we included questions on possible risk factors for HIV acquisition and testing history to existing systems in 4 infectious disease clinics. Data were provided by the person requesting an HIV test using a handheld electronic tablet. All persons (≥16 yrs) presenting for an HIV test April 2013-March 2014 were included. Rates per 100,000 were calculated using region-specific denominators for Kiev. During the study period 6370 individuals tested for HIV, equivalent to a testing rate of 293.2 per 100,000. Of these, 467 (7.8%) were HIV-positive, with the highest proportion positive among 31-35 year olds (11.2%), males (9.4%), people who inject drugs (PWID) (17.9%) and men who have sex with men (MSM) (24.1%). Using published population size estimates of MSM, diagnosis rates for MSM ranged from 490.6 to 1548.3/100,000. A higher proportion of heterosexual women compared to heterosexual men reported contact with PWID, (16% vs. 4.7%) suggesting a bridging in risk between PWID and their sexual partners. Collection of HIV risk factor information in Kiev, essential for the purposes of developing effective HIV prevention and response tools, is feasible. The high percentage of MSM among those testing positive for HIV, may indicate a significant level of undisclosed sex between men in national figures

A Phylogenetic Analysis of Human Immunodeficiency Virus Type 1 Sequences in Kiev: Findings Among Key Populations

Background: The human immunodeficiency virus (HIV) epidemic in Ukraine has been driven by a rapid rise among people who inject drugs, but recent studies have shown an increase through sexual transmission. Methods: Protease and reverse transcriptase sequences from 876 new HIV diagnoses (April 2013–March 2015) in Kiev were linked to demographic data. We constructed phylogenetic trees for 794 subtype A1 and 64 subtype B sequences and identified factors associated with transmission clustering. Clusters were defined as ≥2 sequences, ≥80% local branch support, and maximum genetic distance of all sequence pairs in the cluster ≤2.5%. Recent infection was determined through the limiting antigen avidity enzyme immunoassay. Sequences were analyzed for transmitted drug resistance mutations. Results Thirty percent of subtype A1 and 66% of subtype B sequences clustered. Large clusters (maximum 11 sequences) contained mixed risk groups. In univariate analysis, clustering was significantly associated with subtype B compared to A1 (odds ratio [OR], 4.38 [95% confidence interval {CI}, 2.56–7.50]); risk group (OR, 5.65 [95% CI, 3.27–9.75]) for men who have sex with men compared to heterosexual males; recent, compared to long-standing, infection (OR, 2.72 [95% CI, 1.64–4.52]); reported sex work contact (OR, 1.93 [95% CI, 1.07–3.47]); and younger age groups compared with age ≥36 years (OR, 1.83 [95% CI, 1.10–3.05] for age ≤25 years). Females were associated with lower odds of clustering than heterosexual males (OR, 0.49 [95% CI, .31–.77]). In multivariate analysis, risk group, subtype, and age group were independently associated with clustering (P < .001, P = .007, and P = .033, respectively). Eighteen sequences (2.1%) indicated evidence of transmitted drug resistance. Conclusions Our findings suggest high levels of transmission and bridging between risk groups

Dissolved Oxygen Concentration Interlaboratory Comparison: What Can We Learn?

wate

Time to virological failure, treatment change and interruption for individuals treated within 12 months of HIV seroconversion and in chronic infection.

BACKGROUND Estimates of treatment failure, change and interruption are lacking for individuals treated in early HIV infection. METHODS Using CASCADE data, we compared the effect of treatment in early infection (within 12 months of seroconversion) with that seen in chronic infection on risk of virological failure, change and interruption. Failure was defined as two subsequent measures of HIV RNA>1,000 copies/ml following suppression (500 copies/ml 6 months following initiation. Treatment change and interruption were defined as modification or interruption lasting >1 week. In multivariable competing risks proportional subdistribution hazards models, we adjusted for combination antiretroviral therapy (cART) class, sex, risk group, age, CD4(+) T-cell count, HIV RNA and calendar period at treatment initiation. RESULTS Of 1,627 individuals initiating cART early (median 1.8 months from seroconversion), 159, 395 and 692 failed, changed and interrupted therapy, respectively. For 2,710 individuals initiating cART in chronic infection (median 35.9 months from seroconversion), the corresponding values were 266, 569 and 597. Adjusted hazard ratios (HRs; 95% CIs) for treatment failure and change were similar between the two treatment groups (0.93 [0.72, 1.20] and 1.06 [0.91, 1.24], respectively). There was an increasing trend in rates of interruption over calendar time for those treated early, and a decreasing trend for those starting treatment in chronic infection. Consequently, compared with chronic infection, treatment interruption was similar for early starters in the early cART period, but the relative hazard increased over calendar time (1.54 [1.33, 1.79] in 2000). CONCLUSIONS Individuals initiating treatment in early HIV infection are more likely to interrupt treatment than those initiating later. However, rates of failure and treatment change were similar between the two groups

Symptomatic illness and low CD4 cell count at HIV seroconversion as markers of severe primary HIV infection

The risk/benefit of initiating ART in primary HIV infection (PHI) is unclear. The benefits are more likely to outweigh the risks in patients with severe PHI. An accepted definition of severe PHI is, however, lacking

Immune reconstitution and risk of Kaposi sarcoma and non-Hodgkin lymphoma in HIV-infected adults.

OBJECTIVE: Given the well documented occurrence of immune reconstitution inflammatory syndrome (IRIS) in HIV-infected patients who recently started combination antiretroviral therapy (cART), we examined whether cART initiation increased the risk of Kaposi sarcoma and non-Hodgkin lymphoma (NHL) using data from the Concerted Action on SeroConversion to AIDS and Death in Europe (CASCADE) collaboration. DESIGN: A nested matched case-control study design was used to assess the effects of individual CD4 cell trajectories and exposure to cART close to the time of cancer diagnosis. METHODS: Cases were patients diagnosed with either cancer during follow-up with a minimum of two consecutive CD4 cell readings within the year preceding diagnosis. For each case, up to 10 controls, matched by sex and cohort, were selected by random sampling. Changes in CD4 cell count, calculated by simple and piecewise linear regression, and recent exposure to cART were compared within matched case-control sets using conditional logistic regression. RESULTS: Using data on 689 cases and 4588 controls, we found that an initially low and decreasing CD4 cell count during the year prior to cancer diagnosis is predictive of both Kaposi sarcoma and NHL. Most of this cancer risk is explained by the immunodeficiency characteristic of the period before cART initiation; however, an increased cancer risk was seen in patients who initiated cART in the previous 3 months (odds ratio 2.31; 95% confidence interval 1.33, 4.00). CONCLUSION: Although IRIS may transiently increase the risk of Kaposi sarcoma or NHL in HIV-infected patients, the timely initiation of cART remains the best strategy to avoid the development of these malignancies