Altistuminen PAH-yhdisteille kreosoottikyllästetyn puun käsittelyssä

Tässä työssä selvitettiin altistutaanko kreosoottikyllästetyn puun käsittelyssä polysyklisille aromaattisille hiilivedyille ja mistä työsuojelullisista syistä altistumista tapahtuu. Lisäksi työssä selvitettiin mitä altistuminen tarkoittaa työnantajan kannalta. Altistumista tarkasteltiin työturvallisuuden näkökulmasta. Lähtöaineisto koostui maastossa toteutetuista tutkimuksista. Aineisto kerättiin kesällä 2009 kolmesta Itä-Suomessa sijaitsevasta kohteesta, joissa käsiteltiin kreosootilla kyllästettyä puuta. Altistumisen todentamiseksi tutkimukseen osallistuneilta työntekijöiltä pyydettiin virtsanäytteet, joista analysoitiin yhden yleisimmän PAH-altistumista indikoivan merkkiaineen, virtsan 1-pyrenolin pitoisuuksia työntekijöillä. Altistumisen syiden selvittämiseksi työntekijöitä haastateltiin ja havainnoitiin. Tulosten perusteella työntekijät altistuvat PAH-yhdisteille työssään. PAH-altistumisen merkkiaineena olleelle virtsan 1-pyrenolille ei toimenpiderajaa tällä hetkellä ole, mutta se on Työterveyslaitoksella suunnitteilla. Lainsäädäntö velvoittaa erinäisin toimenpitein työnantajaa minimoimaan työntekijöiden altistumisen syöpäsairauden vaaraa aiheuttaville aineille, kuten PAH-yhdisteille. Tulosten perusteella työsuojelutoimenpiteitä on syytä tehostaa altistumisen minimoimiseksi ja etenkin ihon suojaamiseen on syytä kiinnittää erityistä huomiota.

Application of electrokinetic Fenton process for the remediation of soil contaminated with HCB

Electrokinetic remediation coupled with Fenton oxidation, widely called as Electrokinetic Fenton process is a potential soil remediation technique used for low permeable soil. The applicability of the process has been proved with soil contaminated with a wide range of organic compounds from phenol to the most recalcitrant ones such as PAHs and POPs. This thesis summarizes the major findings observed during an Electrokinetic Fenton Process study conducted for the remediation of low permeable soil contaminated with HCB, a typical hydrophobic organic contaminant. Model low permeable soil, kaolin, was artificially contaminated with HCB and subjected to Electrokinetic Fenton treatments in a series of laboratory scale batch experiments. The use of cyclodextrins as an enhancement agent to mobilize the sorbed contaminant through the system was investigated. Major process hindrances such as the oxidant availability and treatment duration were also addressed. The HCB degradation along with other parameters like soil pH, redox and cumulative catholyte flow were analyzed and monitored. The results of the experiments strengthen the existing knowledge on electrokinetic Fenton process as a promising technology for the treatment of soil contaminated with hydrophobic organic compounds. It has been demonstrated that HCB sorbed to kaolin can be degraded by the use of high concentrations of hydrogen peroxide during such processes. The overall system performances were observed to be influenced by the point and mode of oxidant delivery. Furthermore, the study contributes to new knowledge in shortening the treatment duration by adopting an electrode polarity reversal during the process.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).