Leaching of Sulfentrazone in Soils from the Sugarcane Region in the Northeast Region of Brazil

Sulfentrazone leaching potential is dependent on soil properties such as strength and type of clay, organic matter content and pH, and may result in ineffectiveness of the product and contamination of groundwater. The objective of this study was to evaluate sulfentrazone leaching in five soils of the sugarcane region in the Northeast Region of Brazil, with different physical and chemical properties, by means of bioassay and high-performance liquid chromatography (HPLC) resolution. The experiment was conducted in a split plot in a completely randomized design. The plots had PVC columns with a 10 cm diameter and being 50 cm deep, filled with five different soil classes (quartzarenic neosol, haplic cambisol, yellowish-red latosol, yellowish-red acrisol, and haplic gleysol), and subplots for 10 depths in columns, 5 cm intervals. On top of the columns, sulfentrazone application was conducted and 12 hours later there was a simulated rainfall of 60 mm. After 72 hours, the columns were horizontally placed and longitudinally open, divided into sections of 5.0 cm. In the center of each section of the columns, soil samples were collected for chromatographic analyses and sorghum sowing was carried out as an indicator plant. The bioassay method was more sensitive to detect the presence of sulfentrazone in an assessment for chromatography soil, having provided greater herbicide mobility in quartzarenic neosol and yellowish-red latosol, whose presence was detected by the indicator plant to a depth of 45 and 35 cm, respectively. In the other soils, sulfentrazone was detected up to 20 cm deep. The intense mobility of sulfentrazone in quartzarenic neosol may result in herbicide efficiency loss in the soil because the symptoms of intoxication and the amount of herbicide detected via silica were highest between 15 cm and 35 cm depth regarding the soil surface layer (0-10 cm), indicating that sulfentrazone should be avoided in soils with such characteristics.

Kaksi tietä huipulle. Media ja puoluejohtajuus Suomessa naisten noususta populismin aaltoon

Tässä väitöskirjassa tarkastellaan suomalaisen puoluejohtajuuden ja suuren puolueen johtajaksi nousun murroskautta 1980-luvun lopulta 2010-luvulle median ja politiikan vuorovaikutuksen näkökulmasta. Puolueiden johtaminen on myös Suomessa ollut miesten työtä, ja perinteisesti tehtävään on ollut yksi väylä: asettuminen ehdolle puheenjohtajavaalissa ja valituksi tulo puoluekokouksessa. Tarkastelujakson alkupuolella naisia oli Suomessa ensimmäistä kertaa ehdolla suurten puolueiden puheenjohtajavaaleissa. Kauden loppupuolella heitä myös valittiin tuohon tehtävään ja ensimmäiset naiset nousivat pääministeriksi. Tämä historiallinen murros päätti liki satavuotisen perinteen, jossa miehet ovat olleet Suomessa sekä suurten puolueiden että hallitustyön johtajia. Julkisessa keskustelussa kysymys tasa-arvosta jäi toissijaiseksi: naisia alettiin valita puoluejohtajiksi tilanteissa, joissa heidän valintansa nähtiin puolueille edulliseksi. Naisen valinta tulkittiin miehen valintaa merkittävämmäksi symboliseksi viestiksi, johon liitettiin ajatuksia uudistumisesta ja puolueen julkisuuskuvan parantamisesta. Merkille pantavaa on, että naisten ensimmäiset valinnat suurten puolueiden johtajiksi tapahtuivat vaiheessa, jossa puoluejohtajien valta-asema on vahvin kautta suomalaisen poliittisen historian. Tässä valossa näyttää siltä, että valta ei aina pakenekaan naisilta. Vaikka suomalainen yhteiskunta ja suomalaiset naiset ovat monessa mielessä olleet edelläkävijöitä tasa-arvon suhteen, politiikan johtopaikkoja tavoitelleet naiset ovat meilläkin kohdanneet kansainvälisessä tutkimuksessa naisten haasteeksi osoitettuja lasikattoja, pyöröovia ja liukkaita jyrkänteitä. Tutkittavan ajanjakson aikana konkretisoitui myös toinen mahdollinen, joskin poikkeuksellinen reitti suuren puolueen johtajaksi: pienen puolueen nouseminen suurten joukkoon eduskuntavaaleissa. Tämä vaihtoehto toteutui vuonna 2011 perussuomalaisten eduskuntavaalivoiton myötä. Perussuomalaisten nousu eduskunnan pienimmästä puolueesta kolmanneksi suurimmaksi mursi perinteisen kolmen suuren puolueen asetelman. Puolueen menestyksen seuraukset ovat olleet kauaskantoisemmat kuin ehkä ensin ajateltiin: perussuomalaisten vaalivoiton sosiaalidemokraateille, keskustalle, ja kokoomukselle aiheuttama järkytys heijastui myöhemmin myös niiden johtajavaihdoksiin ja -valintoihin. Sekä naisten läpimurrossa että populismin voittokulussa median rooli oli monisyisempi kuin siihen perinteisesti liitetty tiedon välittäjän ja valtaa pitävien toimia kriittisesti seuraavan neljännen valtiomahdin tehtävänkuva. Tutkittavalla jaksolla tiedotusvälineet tekivät onnistuneen intervention politiikan osapuoleksi. Toimittajat ottivat kantaa valintoihin ja ohjeistivat puolueita, ja puolueet taas mukauttivat näkyvyyden maksimoidakseen käytäntöjään median tarpeisiin. 1980-luvun lopulta 2010-luvulle ulottuvalla jaksolla suuren puolueen puoluejohtajaksi valikoitumisen kriteerit muuttuivat, samalla kun median merkitys johtajavalinnoissa ja myös puoluejohtajan käytännön työssä kasvoi. Mediasta tuli aiempaa konkreettisemmin johtajavalintojen ja valtakamppailun areena, ja siihen liittyvät näkökohdat nousivat myös keskeisiksi johtajan taitoja arvioitaessa. Kuka ehdokkaista toisi näkyvyyttä, ”pärjäisi” median paineissa ja vakuuttaisi äänestäjät? Vielä 1980- ja 1990-lukujen taitteessa johtajavalinnat olivat pitkälti puolueorganisaatioiden hallinnoimia prosesseja, joista lehdistö raportoi askeleen jäljessä kulkien. Viimeistään 2000-luvun ensimmäisellä vuosikymmenellä puolueet omaksuivat ajatuksen median hyödyllisyydestä. Tämän strategisen muutoksen myötä puolueet tulivat samalla luovuttaneeksi määriteltyvaltaa oman organisaationsa ulkopuolelle. Kokoomuksen vuoden 2014 johtajavaalissa silmiinpistävää oli pyrkimys sekä hyötyä julkisuudesta että palauttaa valtaa takaisin puolueelle. Politiikan mediajulkisuuden alttius tarttua myyviin poliitikkopersooniin, ilmiöihin, ristiriitoihin ja draamaan sekä vastaavasti populistijohtaja Timo Soinin ja perussuomalaisten kyky tarjota kaikkia näitä auttoivat puolueen suurvoittoon vuoden 2011 eduskuntavaaleissa. Organisaatioltaan pieni ja johtajaansa henkilöityvä puolue sai selvästi poliittista painoarvoaan suuremman julkisuuden, koska kiinnostavuus määritti näkyvyyden ja puolueen nousevasta kannatuksesta tuli yksi vaalien pääaiheista. Median ja politiikan suhteessa tapahtuneet muutokset olivat vauhdittamassa niin naisten nousua suurten puolueiden johtajiksi kuin populistisen johtajuuden läpimurtoa ja perussuomalaisten menestystä. Koska suurten puolueiden johtajista valikoituvat myös pääministerit, näiden muutosten vaikutus ulottuu Suomen poliittisesti vaikutusvaltaisimpaan tehtävään asti.

Calculation of breed direct and maternal genetic fractions and breed specific direct and maternal heterozygosity for crossbreeding data

Teaching, research, and herd breeding applications may require calculation of breed additive contributions for direct and maternal genetic effects and fractions of heterozygosity associated with breed specific direct and maternal heterosis effects. These coefficients can be obtained from the first NB rows of a pseudo numerator relationship matrix where the first NB rows represent fractional contributions by breed to each animal or group representing a specific breed cross. The table begins with an NB x NB identity matrix representing pure breeds. Initial animals or representative crosses must be purebreds or two-breed crosses. Parents of initial purebreds are represented by the corresponding column and initial two-breed cross progeny by the two corresponding columns of the identity matrix. After that, usual rules are used to calculate the NB column entries corresponding to breeds for each animal. The NB entries are fractions of genes expected to be contributed by each of the pure breeds and correspond to the breed additive direct fractions. Entries in the column corresponding to the dam represent breed additive maternal fractions. Breed specific direct heterozygosity coefficients are entries of an NB x NB matrix formed by the outer product of the two NB by 1 columns associated with sire and dam of the animal. One minus sum of the diagonals represents total direct heterozygosity. Similarly, the NB x NB matrix formed by the outer product of columns associated with sire of dam and dam of dam contains breed specific maternal heterozygosity coefficients. These steps can be programmed to create covariates to merge with data. If X represents these coefficients for all unique breed crosses, then the reduced row echelon form function of MATLAB or SAS can be used on X to determine estimable functions of additive breed direct and maternal effects and breed specific direct and maternal heterosis effects

Prosessiautomaatio pinnankorkeusmittauksen koelaitteistoissa

Pinnankorkeuden tunteminen kiehutusvesireaktorin painesäiliössä on erittäin tärkeää sen turvallisuusvaikutusten takia. Pinnankorkeutta mitataan vesipatsaiden korkeutta havaitsevien paine-eromittausten avulla. Säteilyturvakeskuksen YVL-ohjeiden mukaan turvallisuuteen vaikuttavien mittausten täytyy noudattaa moninkertaistus- ja erilaisuusperiaatteita. Yleensä erilaisuusperiaatetta on toteutettu käyttämällä erityyppisiä paine-eromittareita, mutta erilaisella fysikaalisella toimintaperiaatteella oleva mittaus olisi parempi ja toteuttaisi paremmin erilaisuusperiaatetta. Uimurikytkin olisi tällainen fysikaalisesti eri periaatteeseen perustuva pinnankorkeuden mittauslaite. Ydinvoimalaan tarkoitettu teknologia tulee kelpoistaa riippumattoman tahon toimesta ennen käyttöönottoa. Kelpoistamiskokeita varten Lappeenrannan teknillisen yliopiston Ydinturvallisuuden tutkimusyksikköön rakennettiin vuosina 2011–2013 kaksi koelaitteistoa. Näillä koelaitteistoilla tutkittiin uimurikytkimien toimintaa ja ominaisuuksia erilaisissa kiehutusvesireaktorin käyttötilanteissa. Koelaitteistot tarvitsivat toimiakseen automaatiojärjestelmät, jotka suunniteltiin pääosin noudattamalla suunnittelun elinkaarimallia sekä automaatiosuunnittelun sisältökokonaisuuksia. Automaatiojärjestelmien suunnittelu aloitettiin määrittelemällä koejärjestelyjen asettamat vaatimukset, jonka jälkeen tehtiin teknologiavalinnat. Seuraavaksi suunniteltiin automaatiojärjestelmien logiikkaohjelmistot, joiden kuvaukseen tämä työ pääasiassa keskittyy. Logiikkaohjelmistot toteutettiin graafisella National Instruments LabView -ohjelmointikielellä. Logiikkaohjelmistojen tuli hoitaa tiedonkeruuta, käyttöautomaatiota, turvallisuustehtäviä sekä kokeisiin liittyviä erikoistehtäviä. Ohjelmistot saatiin esikokeiden aikana toimimaan halutusti, ja varsinaiset kokeet voitiin suorittaa ilman merkittäviä ongelmia.

Interhemispheric connections between primary visual areas: beyond the midline rule

In the last five years, a number of detailed anatomical, electrophysiological, optical imaging and simulation studies performed in a variety of non-human species have revealed that the functional organization of callosal connections between primary visual areas is more elaborate than previously thought. Callosal cell bodies and terminals are clustered in columns whose correspondence to features mapped in the visual cortex, such as orientation and ocularity, are starting to be understood. Callosal connections are not restricted to the vertical midline representation nor do they establish merely point-to-point retinotopic correspondences across the hemispheres, as traditionally believed. In addition, anatomical studies have revealed the existence of an ipsilateral component of callosal axons. The aim of this short review is to propose how these new data can be integrated into an updated scheme of the circuits responsible for assembling the primary visual field map.

Visual maps in the adult primate cerebral cortex: some implications for brain development and evolution

In this paper, the topology of cortical visuotopic maps in adult primates is reviewed, with emphasis on recent studies. The observed visuotopic organisation can be summarised with reference to two basic rules. First, adjacent radial columns in the cortex represent partially overlapping regions of the visual field, irrespective of whether these columns are part of the same or different cortical areas. This primary rule is seldom, if ever, violated. Second, adjacent regions of the visual field tend to be represented in adjacent radial columns of a same area. This rule is not as rigid as the first, as many cortical areas form discontinuous, second-order representations of the visual field. A developmental model based on these physiological observations, and on comparative studies of cortical organisation, is then proposed, in order to explain how a combination of molecular specification steps and activity-driven processes can generate the variety of visuotopic organisations observed in adult cortex.

Anatomical connections of the periaqueductal gray: specific neural substrates for different kinds of fear

The periaqueductal gray (PAG) has been traditionally considered to be an exit relay for defensive responses. Functional mapping of its subdivisions has advanced our knowledge of this structure, but synthesis remains difficult mainly because results from lesion and stimulation studies have not correlated perfectly. After using a strategy that combined both techniques and a reevaluation of the available literature on PAG function and connections, we propose here that freezing could be mediated by different PAG subdivisions depending on the presence of immediate danger or exposure to related signaling cues. These subdivisions are separate functional entities with distinct descending and ascending connections that are likely to play a role in different defensive responses. The existence of ascending connections also suggests that the PAG is not simply a final common path for defensive responses. For example, the possibility that indirect ascending connections to the cingulate cortex could play a role in the expression of freezing evoked by activation of the neural substrate of fear in the dorsal PAG has been considered.

In situ enzyme immunoassay for titration of a Brazilian hepatitis A virus strain (HAF-203)

Hepatitis A virus (HAV) replicates relatively slowly in cell culture without a cytopathic effect, a fact that limits the use of tissue culture assays. The radioimmunofocus assay is the standard method for HAV titration, although it is labor intensive and requires the use of radioisotopes. A simple, rapid and objective infectivity assay based on an in situ enzyme immunoassay (EIA) is described here for a Brazilian cell culture-adapted HAV strain (HAF-203). The assay uses a peroxidase-labeled polyclonal antibody to fixed monolayers as an indicator of infection. EIA may be completed within 7 days using serial 5-fold dilutions of the virus, yielding a titer of 5.024 log 50% tissue culture infective dose (TCID50)/ml for HAF-203. This technique had a detection limit of 1.1 log TCID50/ml and the specificity was demonstrated by detecting no reaction on the columns of uninfected wells. The reproducibility (with intra- and inter-assay coefficients of variation ranging from 1.9 to 3.8% and from 3.5 to 9.9%, respectively) and quantitation of the assay were demonstrated by close agreement in virus infectivity titers among different assays of the same amount of virus and between assays of different amounts of virus. Furthermore, this assay does not require the use of radiolabeled antibodies. We describe here an efficient EIA that is highly reproducible and that could be used to monitor HAV growth in cell culture and to determine the quantity of HAV antigen needed for diagnostic assays. This is the first report of the infectious titer of the Brazilian cell culture-adapted HAV strain (HAF-203).

Readout architectures for hybrid pixel detector readout chips

The original contribution of this thesis to knowledge are novel digital readout architectures for hybrid pixel readout chips. The thesis presents asynchronous bus-based architecture, a data-node based column architecture and a network-based pixel matrix architecture for data transportation. It is shown that the data-node architecture achieves readout efficiency 99% with half the output rate as a bus-based system. The network-based solution avoids “broken” columns due to some manufacturing errors, and it distributes internal data traffic more evenly across the pixel matrix than column-based architectures. An improvement of > 10% to the efficiency is achieved with uniform and non-uniform hit occupancies. Architectural design has been done using transaction level modeling (TLM) and sequential high-level design techniques for reducing the design and simulation time. It has been possible to simulate tens of column and full chip architectures using the high-level techniques. A decrease of > 10 in run-time is observed using these techniques compared to register transfer level (RTL) design technique. Reduction of 50% for lines-of-code (LoC) for the high-level models compared to the RTL description has been achieved. Two architectures are then demonstrated in two hybrid pixel readout chips. The first chip, Timepix3 has been designed for the Medipix3 collaboration. According to the measurements, it consumes < 1 W/cm^2. It also delivers up to 40 Mhits/s/cm^2 with 10-bit time-over-threshold (ToT) and 18-bit time-of-arrival (ToA) of 1.5625 ns. The chip uses a token-arbitrated, asynchronous two-phase handshake column bus for internal data transfer. It has also been successfully used in a multi-chip particle tracking telescope. The second chip, VeloPix, is a readout chip being designed for the upgrade of Vertex Locator (VELO) of the LHCb experiment at CERN. Based on the simulations, it consumes < 1.5 W/cm^2 while delivering up to 320 Mpackets/s/cm^2, each packet containing up to 8 pixels. VeloPix uses a node-based data fabric for achieving throughput of 13.3 Mpackets/s from the column to the EoC. By combining Monte Carlo physics data with high-level simulations, it has been demonstrated that the architecture meets requirements of the VELO (260 Mpackets/s/cm^2 with efficiency of 99%).

Functional changes of dendritic cells in hypersensivity reactions to amoxicillin

A better understanding of dendritic cell (DC) involvement in responses to haptenic drugs is needed, because it represents a possible approach to the development of an in vitro test, which could identify patients prone to drug allergies. There are two main DC subsets: plasmacytoid DC (pDC) and myeloid DC (mDC). β-lactams form hapten-carrier conjugates and may provide a suitable model to study DC behavior in drug allergy reactions. It has been demonstrated that drugs interact differently with DC in drug allergic and non-allergic patients, but there are no studies regarding these subsets. Our aim was to assess the functional changes of mDC and pDC harvested from an amoxicillin-hypersensitive 32-year-old woman who experienced a severe maculopapular exanthema as reflected in interleukin-6 (IL-6) production after stimulation with this drug and penicillin. We also aim to demonstrate, for the first time, the feasibility of this method for dendritic cell isolation followed by in vitro stimulation for studies of drug allergy physiopathology. DC were harvested using a double Percoll density gradient, which generates a basophil-depleted cell (BDC) suspension. Further, pDC were isolated by blood DC antigen 4-positive magnetic selection and gravity filtration through magnetized columns. After stimulation with amoxicillin, penicillin and positive and negative controls, IL-6 production was measured by ELISA. A positive dose-response curve for IL-6 after stimulation with amoxicillin and penicillin was observed for pDC, but not for mDC or BDC suspension. These preliminary results demonstrate the feasibility of this methodology to expand the knowledge of the effect of dendritic cell activation by drug allergens.

Ochratoxin A in Brazilian green coffee

Ochratoxin A is a nephrotoxic, teratogenic and imunotoxic compound produced by Aspergillus and Penicillium spp. It is a suspected carcinogen to humans and it is carcinogenic to rats. Recently it has drawn attention because it has been found in coffee and it has been the object of regulation by coffee importing countries. Brazil is the largest coffee producing country and its largest consumer. In order to conduct an initial assessment of the situation of the coffee produced in the country and offered to its population, one hundred and thirty two samples of Brazilian green coffee from 5 producing states (Minas Gerais, Paraná, São Paulo, Espírito Santo and Bahia) and destined for the home market, were collected at sales points at the cities of Londrina and Santos, Brazil, and analyzed for ochratoxin A. The toxin was isolated in immunoaffinity columns and quantified by HPLC with florescence detection. The limit of detection was 0.7ng/g and the average RSD for duplicates of the samples was 11%. Twenty seven samples were found contaminated with the toxin and the average concentration for the contaminated samples was 7.1ng/g ochratoxin A. Neither the total number of defects nor the number of specific defects according to the Brazilian coffee classification system (black, partly -- black, sour, stinkers-black, stinkers-green, pod beans) showed any relation to the contamination of the samples with ochratoxin A.

Turkic Manuscript in Kazakh-Chaghatai (MS Or.49)

A coverless notebook, written in two columns in ink in various colours. Rhymed verse, written by an author from the Temir-Bolat clan. He mentions the following names: Samarkand, Bukhara, Urgench, Tashkent, Kokand, the Karakalpaks, and the Turkmens. It the opening notes there are names of persons.

Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

Studies on oxamyl : analytical method development and investigation of fate in peach seedlings and corn seeds

A high performance liquid chromatographic method employing two columns connected in series and separated~y·a.switching valve has been developed for the analysis of the insecticide/ nematicide oxamyl (methyl-N' ,N'-dimethyl-N-[(methylcarbamoyl) oxy]-l-thiooxarnimidate) and two of its metabolites. A variation of this method involving two reverse phase columns was employed to monitor the persistence and translocation of oxamyl in treated peach seedlings. It was possible to simultaneously analyse for oxamyl and its corresponding oxime (methyl-N',N'-dimethyl-N-hydroxy-l-thiooxamimidate}, a major metabolite of oxamyl in plants, without prior cleanup of the samples. The method allowed detection of 0.058 pg oxamyl and 0.035 p.g oxime. On treated peach leaves oxamyl was found to dissipate rapidly during the first two-week period, followed by a period of slow decomposition. Movement of oxamyl or its oxime did not occur in detectable quantities to untreated leaves or to the root or soil. A second variation of the method which employed a size exclusion column as·the first column and a reverse phase column as the second was used to monitor the degradation of oxamyl in treated, planted corn seeds and was suitable for simultaneous analysis of oxamyl, its oxime and dimethylcyanoformamide (DMCF), a metabolite of oxamyl. The method allowed detection of 0.02 pg oxamyl, 0.02 p.g oxime and 0.005 pg DMCF. Oxamyl was found to persist for a period of 5 - 6 weeks, which is long enough to permit oxamyl seedtreatment to be considered as a potential means of protecting young corn plants from nematode attack. Decomposition was found to be more rapid in unsterilized soil than in sterililized soil. DMCF was found to have a nematostatic effect at high concentrations ( 2,OOOpprn), but at lower concentrations no effect on nematode mobility was observed. Oxamyl, on the other hand, was found to reduce the mobility of nematodes at concentrations down to 4 ppm.