(EN) The presented dissertation is devoted to hydride generation from arsenic species and its application for speciation analysis based on atomic fluorescence detection. Hydride generation from toxicologically relevant arsenic species was optimized in order to achieve a 100% efficiency. The resulted experimental setup was subsequently used for speciation analysis of arsenic in human urine by high performance liquid chromatography with detection by atomic fluorescence spectrometry. The accuracy of the developed method was verified by comparative analyses of human urine samples collected from five individuals with an independent reference method. The cleavage of As-C bond during the reaction of methylated arsenic species with tetrahydridoborate(1-) (THB) in acidic media was studied in detail. Pronounced demethylation of methylated arsenic species was found during the reaction of THB with HCl, H2SO4, and HClO4 while hydride generation from CH3COOH or TRIS buffer after prereduction with L- cysteine resulted in the exclusive formation of the corresponding hydrides. Firstly, this phenomenon can endanger the accuracy of arsenic speciation which is based on hydride generation of substituted arsanes. Secondly, the more complex arsenic species can be converted to the hydride. That was demonstrated on hydride...

The aim of this work was to determine chemical species of arsenic in sea originating certified reference materials. Measurements were done using method of hydride generation. Hydrides were preconcentrated in liquid nitrogen cooled tube and detected using inductively coupled plasma mass spectrometry. During the testing of the method, mutual conversion of arsenic species was observed for inorganic arsenic, monomethyl arsenic and dimethylarsenic. Further study revealed that with presence of matrix and hydrogen peroxide, demethylation occured only in hydride generation phase, not during extraction. Dissociation of hydrogen peroxide in extracts was verified using catalase. End of the demethylation process was proved using measurement with addition of arsenic species standards. The newly invented procedure was used to determine arsenic species in reference materials with sufficient accuracy. Final results are compatible with results from different method, and already published results as well. Key words: speciation analysis, arsenic, hydride generation, seafood, inductively coupled plasma mass spectrometry

Excessive arsenic and boron concentrations determined in natural waters within the Department of Tacna in southern Peru are associated with active Andean volcanism, being further exacerbated by the ongoing mining activity in the area. Both arsenic and boron concentrations at five investigated sites significantly exceed the maximum permissible limits determined by the World Health Organisation and the Peruvian legislation for drinking water, thus affecting the health and wellbeing of the local population. Due to the remoteness of the area of interest, which lacks infrastructure, skilled human resources as well as capital, Photon Water Technology s.r.o. has come up with a solution based on the use of small water treatment plants operating on the principle of reverse osmosis in combination with a commercial remediation product Katalox Light® . This product enables the formation of alkaline conditions needed for proper complexation of boron into B(OH)4 - (aq), which is better remediated by the proposed technology. Reverse osmosis can remediate arsenic, although the efficiency of As removal depends on the chemical composition of natural waters at the investigated sites. Laboratory experiments have been focused to prove the viability of Katalox Light® for enhancing the rate of boron removal within the designed...

The filtration and ultrafiltration experiment was applied on the stream water at the Mokrsko gold deposit and the results revealed that most of the elements were in the dissolved form and the 0,45 or 0,1 m filters could be used. During two 24-h field experiments, water samples were collected at 1-h intervals in order to prove the diel changes in the concentration and speciation of several trace elements. The determination of sorption processes at the surface of or within the veneer of biofilm has been determined by collecting natural and artificial priphyton. The results showed regular diel changes of As, Sb and Mo with highest concentrations occurring after the moon and the lowest concentrations in the early morning. The dissolved concentrations of other elements are conservative or their values were closed to their detection limits. The diel cycles are caused by changes in adsorption/desorption equilibria induced by diel cycles of temperature. The samples of biofilm revealed increased concentrations of the elements under the study and their diel variation were significant (approximatelly 35-96%); however, biofilm-controlled diel cycles of dissolved concentrations have not been proved.

<p>Doktorska disertacija &ldquo;Model procene kvaliteta podzemne vode sa<br />povećanim sadržajem arsena primenom fazi logike&rdquo; urađena je kao rezultat<br />potrebe za istraživanjem mogućnosti primene fazi logike u savremenom<br />pristupu procene kvaliteta podzemnih voda. Imajući u vidu da ova tematika<br />nije dovoljno istražena u na&scaron;em okruženju i da joj nije dat odgovarajući<br />akcenat i težina, osnovni cilj disertacije je da se razrade optimalni modeli za<br />procenu kvaliteta podzemnih voda sa povećanim sadržajem arsena.<br />Disertacija pored teorijske dimenzije prezentuje i primenu evaluiranih fazi<br />modela na primeru eksperimenatlno odabranog lokaliteta grada Zrenjanina.<br />Razvijene modele je moguće transponovati na urbanim i ruralnim područjima<br />uz odgovarajuće iteracije.</p> / <p>PhD Thesis &ldquo;Model assessment for groundwater quality with elevated arsenic<br />content with application of fuzzy logic&rdquo; was elaborated as a result of the need<br />to explore the possibilities of application of fuzzy logic in the modern<br />approach of assessing the groundwater quality. Because this issue has not<br />been sufficiently explored and it was not given proper emphasis and weight,<br />the main aim of the dissertation is to develop optimal models for assessing<br />the groundwater quality with elevated arsenic content. Dissertation, besides<br />theoretical dimensions, presente and evaluate the implementation of the<br />created models to the experimentaly selected locality of the city of Zrenjanin.<br />The developed models can be transposed to the urban and rural areas with<br />appropriate iteration.</p>

Die Studie bestätigt, dass regional höhere Arsenverbindungen in sächsischen Böden über das Futter in die Nahrungskette gelangen können. Im Einzelnen zeigte sich, dass weder durch Zusatz von synthetischen As-Verbindungen bis 50 mg je kg TM noch durch Beimischung einer As-haltigen Erde bis 23 mg As je kg TM die mikrobielle Aktivität in den Vormägen der Wiederkäuer beeinträchtigt wird. Ein Versuch mit Mutterschafen zeigt, dass bei einer As-Zulage übers Futter größere As-Mengen über das Blut in alle Gewebe transportiert und dort eingelagert werden. Erhöhte As-Konzentrationen in den Plazenten und dem Blut neugeborener Lämmer lassen vermuten, dass ein plazentaler Übertritt von As in den Fötus stattfindet. Die As-Absorption der Lämmer und As-Einlagerung in die Gewebe aus der Milch war demgegenüber gering. Die Akkumulation im tierischen Gewebe war trotz 10-facher Grenzwertüberschreitung jedoch minimal (Homöostase).

Durch die Untersuchungen mittels der RP-HPLC hinsichtlich der Bildung der gemischten Moleküle in den Systemen P4S3/P4Se3 und P4S3/As4S3 in Abhängigkeit von der Temperatur und der Zeit konten die k-Werte unddie Reaktionsordungen für die Bildung dieser Moleküle bestimmt werden. Dabei konnte im System P4S3/P4Se3 eine Reaktion zweiter Ordnung festgestellt und das Vorliegen einer Festkörperreaktion bestätigt werden. Auch im System P4S3/As4S3 konnte so eine Parallelreaktion zweiter Ordnung festgestellt werden, hierbei wird das symmetrische Molekül PapAs3S3 bevorzugt gebildet. Bei der Bestimmung von Phosphor - Arsen - Schwefel - Schmelzen konnte durch den Einsatz der Untersuchungsmethode GC-MS P3AsS7, P3AsS8, P2As2S5, P2As2S6, sowie PAs3S5 und PAs3S6 bestimmt werden. Durch vergleichende Versuche mit der 31P-NMR-Spektroskopie konnte die Annahme, dass die Verbindungen durch den Zerfall höherer gemischter Verbindungen im GC-MS entstehen, wiederlegt werden. Die Untersuchungen im Phosphor - Schwefel - System erbrachten ein Phasendiagramm, das in verschiedenen Bereichen von den bekannten Diagrammen abweicht. Neben der Temperatur von 124°C für das Eutektikum bei 55 Mol% P, konnte auch die Liquiduskurve im Bereich P4S7 - P4S3 neu bestimmt werden. Die Abweichungen konnten durch die Verwendung von HPLC und Röntgenfilmuntersuchungen, sowie einer mathematischen Bestimmung, belegt werden. Für die Verbindung P4S7 konnte die Kristallstruktur erfeinert werden. Desweiteren konnte die Struktur der Verbindung [EnH2][TeS3] mittels Einkristallröntgenanalyse bestimmt werden. Die Versuche mit verschiedenen Templaten zeigten, dass bei größerer Variation der Template, der Templatkonzentrationen und der eingesetzten Verbindungen weitere Strukturen mit einem TeS32- - Ion möglich sind.

Zur Klärung welche Reaktionswege im Cu-As-S-System vorherrschen, wurden die kongruent schmelzende Verbindung Cu3AsS4 und die peritektisch zerfallende Verbindung CuAsS aus verschiedenen Kombinationen (Reaktionsgemische) der Elemente und/oder der sechs gän-gigsten Verbindungen der Randsysteme synthetisiert und die dabei ablaufenden Reaktionen in-situ thermoanalytisch (b = 10 °C/min) und in-situ röntgenographisch (b = 10 °C/h) verfolgt. Bei Verwendung der gleichen Komponenten laufen in den Reaktionsgemischen unabhängig von der Zusammensetzung zunächst die gleichen Reaktionen ab, bis sie sich bei fortschreitendem Umsatz gemäß der zu synthetisierenden Verbindung diversifizieren. Bei der Synthese einer Verbindung aus unterschiedlichen Komponenten bilden sich im mittleren Temperaturbereich bevorzugt die gleichen Zwischenprodukte, wobei zuerst binäre und dann ternäre Verbindungen entstehen. Dieses sind bei Cu3AsS4 schwefelreiche Arsensulfide, CuS und Cu6As4S9 und bei CuAsS arsenreiche Arsensulfide, Cu2-xS, Cu6As4S9 und Cu12+xAs4+yS13. Die DTA-Kurven der Reaktionsgemische lassen sich in Gruppen mit ähnlichen Komponenten einteilen, wenn die Hauptkomponenten für stark exotherme Reaktionen verantwortlich sind. Bei der Bildung von Cu2S aus den Elementen wurde der Einfluss zahlreicher Parameter auf den Reaktionsverlauf ermittelt. Neben dem Partikeldurchmesser und der Aufheizgeschwindigkeit spielen Probenform (Tablette, Pulver, in Schwefel eingebettete Kupferfolie), Herkunft und Reinigung des Kupferpulvers (Sauerstoffgehalt), mechanische Behandlung und Alterung (unter Schutzgas oder im Vakuum) des Reaktionsgemisches eine bedeutende Rolle. Bei der Reaktion von Cu3-xAs mit Schwefel zu Cu3AsS4 wurden ähnliche Einflussparameter untersucht wie bei der Bildung von Cu2S. Allgemein hat sich gezeigt, dass das Präparieren von Proben in Tablettenform bezüglich einer schnellen und vollständigen Reaktion bei niedriger Temperatur gegenüber dem Arbeiten mit Pulvern keine Vorteile bietet.

Iron oxide is a good and inexpensive adsorbent for arsenic (As) compounds and other heavy metals in water (Fe, Cu, Cd, Pb, Ni, Zn). Waste sludge from water treatment plant, which is highly in iron content, can be considered as a great adsorbent. Utilizing this waste as material for water treatment would get benefits on not only environment but also energy, resources and social economy. This study describes experiments to produce arsenic adsorbent material from waste sludge taken from Ha Dinh water treatment plant by using glass water, Fe(NO3)3 and heat to modify and enrich iron content. This process aims to make a good material for filtration and sorption of As. Other effects of pH, time, adsorbent mass, and adsorbate concentration are also considered. The processes are successful in removing Arsenic ion clearly. Initial As sample of 1000μg/L, contact time 4 hours, material 1 g/L, the efficiency is 99.64%. Treated water is under national technical regulation on domestic water quality (QCVN 02:2009/BYT column I) –, where column I is applicable to water provision units. Research also starts to make material particles, which are more favorable to practical application. These adsorbent productions after modification are beneficial with low-cost and environmentfriendly advantages. / Oxít sắt là một chất hấp phụ tốt và rẻ trong việc loại bỏ các hợp chất asen (As) và một số kim loại nặng khác trong nước (Fe, Cu, Cd, Pb, Ni, Zn). Trong khi đó, bùn thải từ các nhà máy xử lí nước giàu thành phần sắt, có thể xem là một vật liệu hấp phụ tốt. Việc tận dụng bùn thải này làm vật liệu xử lý ô nhiễm không chỉ đem lại những lợi ích cho môi trường mà còn về mặt tài nguyên, năng lượng và kinh tế xã hội. Báo cáo này trình bày cách chế tạo vật liệu từ bùn thải của nhà máy xử lý nước cấp Hạ Đình thành vật liệu xử lý ô nhiễm asen bằng cách sử dụng thủy tinh lỏng, Fe(NO3)3 và nhiệt để biến tính làm tăng hàm lượng sắt trong bùn thải, tạo vật liệu tốt cho quá trình lọc và hấp phụ As. Các nhân tố ảnh hưởng tới hiệu suất hấp phụ như pH, thời gian, khối lượng chất hấp phụ, và nồng độ As cũng được đưa ra đánh giá. Việc loại bỏ As đạt hiệu quả rõ rệt. Với nồng độ As ban đầu là 1000 μg/L, thời gian xử lý 4 giờ, vật liệu sử dụng là 1g/L thì hiệu suất xử lý đạt 99,64%. Nồng độ As sau xử lý đạt tiêu chuẩn QCVN 02:2009/BYT, cột I – Quy chuẩn kỹ thuật quốc gia về chất lượng nước sinh hoạt, cột I áp dụng đối với các cơ sở cung cấp nước. Nghiên cứu cũng bước đầu thử nghiệm chế tạo thành viên vật liệu để thuận lợi hơn trong việc ứng dụng trong thực tiễn. Vật liệu bùn thải sau biến tính có lợi thế về chi phí thấp và thân thiện với môi trường

This thesis describes the syntheses, the crystal structures, and the physical properties of some new ternary and quaternary rare-earth coinage metal arsenides, selenides and oxides. All ternary compounds LnCu1+[delta]As2 (Ln = Y, La, Ce, Nd, Sm, Gd - Lu), LnAg1+[delta]As2 (Ln = La - Nd, Sm), and LnAuAs2 (Ln = Pr, Sm, Gd, Tb) adopt structures closely related to the HfCuSi2 type consisting of PbO-like layers of T and As atoms, square layers of As atoms and layers of Ln atoms separating the former two building units. All copper compounds of this series contain regular square nets of As atoms, whereas the respective nets in the silver and gold compounds are distorted. Two principally different patterns of distortion have been found: [As] zigzag chains in LnAgAs2 (Ln = Pr, Nd, Sm) and [As] cis-trans chains in LaAg1.01(1)As2, CeAgAs2, and PrAuAs2. Both patterns can undergo a further reduction of symmetry to end up with a pattern of As2 dumb-bells as can be seen in SmAuAs2, GdAuAs2, and TbAuAs2. Stoichiometric samples LnCuAs2 (Ln = Y, Pr, Nd, Sm, Gd, Tb, Dy, Er) have been used for measurements of the conductivity [rho], magnetic susceptibility [chi] and heat capacity cp. All investigated compounds exhibit metallic conductivity and, except for Y, order antiferromagnetically at temperatures below 10 K. In contrast to LnCuAs2 compounds, the silver compound CeAgAs2 shows semiconducting behavior throughout the temperature range from 4 to 350 K, whereas in PrAgAs2 metallic conductivity is preserved. The crystal structure of Sm2CuAs3O contains two different PbO-like layers formed either by Sm and O or Cu and As atoms. Both PbO-type layers are separated by sheets of Sm and distorted square nets of As atoms. The As atoms are arranged in planar zigzag chains, like those found in NdAgAs2. Sm2CuAs3O is thus the first quaternary rare-earth pnictide oxide with a distorted As net. The quaternary potassium rare-earth copper selenides KGd2CuSe4, KLn2Cu3Se5 (Ln = Ho, Er, Tm), and K2Ln4Cu4Se9 (Ln = Dy, Y) extend three series of previously described sulfide and selenide compounds. All three series adopt a three-dimensional tunnel structure built up by [LnSe6] octahedra and [CuSe4] tetrahedra. The K atoms reside in the tunnels with a bicapped trigonal prismatic coordination of eight Se atoms for KGd2CuSe4 and KLn2Cu3Se5 (Ln = Ho, Er, Tm), while for K2Ln4Cu4Se9 (Ln = Dy, Y), the K atoms are coordinated by seven Se atoms in monocappped trigonal prisms.