Arsen im Trinkwasser und in der Nahrung stellen regional bedeutsame Probleme dar. Die Abschätzung der Dimension und eine wissenschaftliche Klärung der Ursachen sind Voraussetzung für den Schutz von Mensch und Natur. Mit dem Speicher Altenberg wurde ein Trinkwasserspeichersystem untersucht, in dem erhöhte Arsenkonzentrationen zu beobachten sind. Ziel der Untersuchungen waren Erkenntnisse über eine mögliche Fortsetzung des bisher beobachteten Trends zu steigenden Arsenkonzentrationen. Hierzu wurde das System in Kompartimente unterteilt und diese auf ablaufende Prozesse und Dynamiken untersucht. Das System besitzt eine geringe Produktivität auf Grund von Nährstoffarmut, insbesondere einer Phosphat-Oligotrophie. Es ist, wie viele Gewässer in der nördlichen Hemisphäre, im Kontext sinkender Immissionsbelastungen wie auch des Klimawandels von hohen und zunehmenden Huminstoffeinträgen aus dem Einzugsgebiet geprägt. Hinzu kommt das Wirken von internen und externen Arsenquellen. Am Grund der Gewässer wurden arsenreiche und humose Substrate nachgewiesen. Sie sind einerseits die Folge einer lang anhaltenden Akkumulation von Sedimenten, die auf Einträge aus dem von arsenreichen Grundgesteinen und anmoorigen Böden geprägten Einzugsgebiet zurückgehen. Andererseits kommt eine Überstauung anmooriger Böden und Moore mit gespeichertem lithogenen bzw. chalkogenen Arsen am Baugrund der Speichergewässer in Frage. Die Bedeutung deponierter Flugaschen wird für das System als untergeordnet eingeschätzt. Für den im System als Vorsperre genutzten Galgenteich zeigt sich seit Beginn der Arsenmessungen im Jahre 1997 ein bis zum Jahre 2000 andauernder stetiger Anstieg der Arsenkonzentration, der statistisch signifikant mit einem Rückgang der Nitratkonzentration einhergeht. Diese ist ihrerseits Teil eines allgemeinen Trends einer ökologischen Regeneration mitteleuropäischer bewaldeter Wassereinzugsgebiete seit Ende der Achtzigerjahre in der Folge abnehmender Depositionslasten. Die wahrscheinlichste kausale Verknüpfung zwischen beiden Parametern ist eine Änderung des redoxchemischen Milieus der Gewässersedimente. Zu Zeiten der hohen Depositionen unterdrückten hohe Konzentrationen von Nitrat als sekundärem Elektronenakzeptor eine Freisetzung von Arsen aus Eisenoxid-Sorbaten. Im Zuge andauernder reduktiver Prozesse und mit dem Rückgang der Nitratkonzentration gewinnen Rücklösungsprozesse an Bedeutung. Seit der Jahrtausendwende zeigen sich reguläre zyklische Jahresverläufe der Arsenkonzentration mit Maxima im Spätsommer und Minima im Frühjahr. Eine Bilanzierung der Massenströme legt eine Quellfunktion der Gewässersedimente im Sommerhalbjahr offen, während der Rückgang der Arsenkonzentration im Winterhalbjahr hauptsächlich auf eine Auswaschung und, zu geringerem Anteil, auf eine interne Senkenfunktion zurückgeführt werden kann. Der Speicher Altenberg ist im Sommer thermisch geschichtet. Aber eine Schichtung von Arsen ist weit schwächer ausgeprägt. Ein Anstieg der Arsenkonzentration wurde sowohl im Hypo- als auch im Epilimnion nachgewiesen. Dies legt eine Arsenfreisetzung auch aus epilimnischen Sedimenten nahe, trotz oxischer Bedingungen im überstehenden Wasserkörper. Der dystrophen Natur des Gewässers entsprechend, wird die Triebkraft der zur Arsenfreisetzung führenden respirativen Prozesse dem Abbau humosen Kohlenstoffes zugeordnet. Für Sicker- und Interstitialwässer im System wurde die Mobilisation des Arsens in Zusammenhang mit der Respiration huminstoff-bürtigen Kohlenstoffes nachgewiesen. Neben der internen Arsenmobilisation ist auch die Arsennachlieferung aus dem Einzugsgebiet von Bedeutung. Die Arsenfracht befindet sich in diesen Wasserströmen vorzugsweise in Abhängigkeit von gelöstem organischen Kohlenstoff und der Abflussintensität. Daraus ergibt sich für den Arsenhaushalt des Speichersystems eine besondere Bedeutung von Starkregenereignissen mit verstärktem hypodermischen Abfluss und der Verfrachtung von Arsen in Assoziation mit wasserlöslichen Huminstoffen. Es wird eine Fallunterscheidung vorgestellt, wonach a) in trockenen Jahren mit geringen Durchflüssen sich Arsen aus der internen Rücklösung aus Sedimenten im Wasserkörper des Speichers anreichert; b) bei durchschnittlichen Durchflüssen im Speicher Verdünnungseffekte über die Anreicherung dominieren und tendenziell niedrige Arsenkonzentrationen resultieren; sowie c) in Jahren mit hohen dynamischen Durchflüssen bzw. ausgeprägten Starkregenereignissen ein verstärkter Eintrag aus dem Einzugsgebiet die Arsenkonzentrationen im Speicher ebenfalls ansteigen lässt. Eine exemplarische Analyse der chemischen Spezies des Elements hat ergeben, dass anorganisches fünfwertiges Arsen die dominante Form im Wasser des Speichers Altenberg ist. Der Anteil von höher toxischem dreiwertigen Arsen ist niedrig, ebenso auch der von methylierten Spezies. Daher wird auch eine Bildung volatiler Methylspezies, d.h. eine Öffnung des Arsenhaushaltes zur Atmosphäre, als unbedeutend eingeschätzt. Im Speichersystem offenbart sich eine spezifische Verknüpfung eines an Eisen-Huminstoff-Kolloide gebundenen Antransportes von Arsen aus dem Einzugsgebiet mit einer auf Huminstoffabbau basierenden, redoxchemisch gesteuerten saisonalen Arsenfreisetzung aus den Sedimenten. Dies hat Modellcharakter für Gewässersysteme, in denen hohe Huminstoffmobilität mit geogen oder auch anthropogen bedingten Arsenvorräten zusammentrifft.:Zusammenfassung I Summary III Abbildungs- und Tabellenverzeichnis V 1 Einleitung 1 1.1 Arsen 1 1.2 Das Untersuchungsobjekt - Spezifik der Problemstellung 3 1.3 Fragestellungen 8 2 Hauptergebnisse 10 3 Schlussfolgerungen und Ausblick 17 4 Literatur 19 5 Publikationen 24 5.1 Changes in catchment conditions lead to enhanced remobilization of arsenic in a water reservoir (Publikation 1) 24 5.2 High mobilization of arsenic, metals and rare earth elements in seepage waters driven by respiration of old allochthonous organic carbon (Publikation 2) 25 5.3 Enhanced arsenic mobility in a dystrophic water reservoir system after acidification recovery (Publikation 3) 26 Erklärung zur Eigenständigkeit i Lebenslauf ii Publikationsliste iii / Arsenic in drinking water and food represent regionally significant problems. The estimation of the dimension and a scientific explanation of the causes is a prerequisite for the protection of humans and nature. The Altenberg reservoir system was investigated as a drinking water facility, where elevated arsenic concentrations are observed. The aim of the investigations was to get findings about a possible continuation of recently observed trends of increasing arsenic concentrations in the water reservoir. For this purpose, the system was divided into compartments and these were investigated for running processes and dynamics. The system has a low productivity due to a low nutrient state, in particular a phosphate oligotrophy. Like a lot of surface waters in the northern hemisphere, it is shaped by high and increasing inputs of humic matter from the catchment area in context of declining immissions as well as of climate change. Additionally, there are internal and external sources of arsenic. At the bottom of the reservoirs, sediments rich in arsenic and humic matter were found. On the one hand side, they are the result of a long-lasting accumulation of sediments which originate in inputs from the catchment area, which is shaped by arsenic-rich basic rocks and histic soils. Likewise, an inundation of gleyic and histic soils with stored lithogenic respectively chalcogenic arsenic inside the construction ground of the reservoirs is an option. The importance of deposited fly ash for the system is assessed to be subordinate. For the Galgenteich, which is operated as a predam, since the beginning of arsenic measurements in 1997 an until the 2000 lasting steady increase in the concentration of arsenic concentration was found, which is significantly associated with a decrease in nitrate concentration. The nitrate concentration decrease in turn is part of an ecological regeneration of Central European forested catchments since the late eighties as a result of decreasing deposition loads. The most likely causal linkage between both parameters is a change in the redox-chemical environment of reservoir sediments. At past times of high depositions, high concentrations of nitrat as a secondary electron acceptor suppressed a release of arsenic from iron oxide sorbates. In the course of reductive processes, and with the decrease in nitrate concentration, release processes gain importance. Since the turn of the millennium regular cyclic annual courses of the arsenic concentration emerge with maxima in the late summer and minima in spring. An accounting of the mass flows reveals a source function of reservoir sediments in the summer season, whilst the decrease of the arsenic concentration during the winter months can be mainly attributed to washout and to a lesser proportion to an internal sink function. The Altenberg reservoir is thermally stratified in summer. But a stratification of arsenic is far less pronounced. An increase in the arsenic concentration was detected in hypolimnion and in epilimnion too. This suggests an arsenic release also from epilimnetic sediments despite oxic conditions in the overlaying water body. According to the dystrophic nature of the water body, the driving force leading to arsenic release during the respiratory processes is assigned to the use of humic carbon. For seepage and interstitial waters in the system, the mobilization of arsenic has been demonstrated in connection with the respiration of humic carbon. In addition to the internal arsenic mobilization, also a recent arsenic delivery from the catchment area is of importance. The arsenic load in these water flows preferably depends on contents of dissolved organic carbon and on runoff intensity. That implies a special meaning of heavy rainfall events with intensified hypodermic runoff and the transportation of arsenic in association with water-soluble humic matter for the arsenic budget of the reservoir system. A case distinction is presented, according to which a) in dry years with low flow rates sediment released arsenic accumulates in the reservoir water to higher concentrations; b) at average flow rates in dilution effects dominate over the enrichment with the result of low arsenic concentrations; and c) in years with high dynamic flows and strong heavy rains an increased input from the catchment area can also increase the arsenic concentration in the reservoir. An exemplary analysis of chemical species has shown that inorganic pentavalent arsenic is dominant in the water of the Altenberg reservoir. Higher toxic trivalent arsenic was found to a lesser extent as well as methylated species. Therefore, a formation volatile methyl species, i.e. an opening of the arsenic budget to atmosphere, is assessed to be insignificant. The dynamics in the reservoir system reveal a specific linkage between a catchment arsenic feed based on arsenic in iron-humic colloids and a redox-chemically controlled arsenic release from the sediments of the reservoir. This serves as a model for water systems, where high humic matter mobility coincides with geogenic or anthropogenic arsenic inventories.:Zusammenfassung I Summary III Abbildungs- und Tabellenverzeichnis V 1 Einleitung 1 1.1 Arsen 1 1.2 Das Untersuchungsobjekt - Spezifik der Problemstellung 3 1.3 Fragestellungen 8 2 Hauptergebnisse 10 3 Schlussfolgerungen und Ausblick 17 4 Literatur 19 5 Publikationen 24 5.1 Changes in catchment conditions lead to enhanced remobilization of arsenic in a water reservoir (Publikation 1) 24 5.2 High mobilization of arsenic, metals and rare earth elements in seepage waters driven by respiration of old allochthonous organic carbon (Publikation 2) 25 5.3 Enhanced arsenic mobility in a dystrophic water reservoir system after acidification recovery (Publikation 3) 26 Erklärung zur Eigenständigkeit i Lebenslauf ii Publikationsliste iii

<p>This dissertation investigates the factors which affect the removal of arsenic from groundwater by adsorption and coagulation technologies, including the interactions between As and natural organic matter (NOM). Humic acid (HA) was utilised as an NOM analogue, and was shown to be capable of both complexing and oxidising As, depending upon the prevailing conditions. The arsenic removing capabilities of three iron oxide coated sands (IOCS) were investigated, including IOCSW, a waste material from a local drinking water treatment plant generated during the removal of iron and manganese. IOCSW was highly effective at removing both As(V) and As(III) from synthetic water matrices (qmax = 78.3 &micro;g As(V)/g and 99.1 &micro;g As(III)/g). The negative effects of competitive anions (phosphates, silicates and HA) on arsenic removals were not significant enough to preclude the application of IOCSW for arsenic removal during drinking water treatment. The removals of both As and NOM by coagulation and enhanced coagulation with pH correction and preoxidation were also investigated. As(V) &nbsp;was more readily removed by coagulation than As(III), so that the most efficient coagulation treatment investigated for arsenic and NOM removal applied preozonation with subsequent combined coagulation with polyaluminium chloride and ferric chloride. Different groundwaters displayed large variations in the As and NOM removal behaviours. Response surface methodology (RSM) was therefore applied to investigate &nbsp;the interactions between As and NOM during ferric chloride coagulation and optimise their combined removals. Multiple interaction effects were observed during this investigation, highlighting the importance of utilizing RSM to optimise drinking water treatment technologies.</p> / <p>Ova disertacija ispituje faktore koji utiču na uklanjanje arsena iz podzemne vode primenom adsorpcija i koagulacije, uključujući i interakcije između arsena i prirodnih organskih materija (POM). Huminska kiselina (HA) je korisćena kao model za POM, a pokazano je da može i da kompleksira i da oksiduje As, u zavisnosti od eksperimentalnih uslova. Ispitivane su mogućnosti uklanjanja arsena za tri peska obložena gvožđe oksidom (IOCS), uključujući IOCSW, koji je dobijen sa postrojenja za tretman vode za piće i potiče iz procesa uklanjanja gvožđa i mangana. IOCSW se pokazao kao visoko efikasan za uklanjanje As(V) i As(III) iz sintetičkih vodenih matriksa (q_max = 78.3 &micro;g As(V)/g i 99.1 &micro;g As(III)/g). Negativni efekti kompetirajućih jona (fosfata, silikata i HA) na uklanjanje arsena nisu bili dovoljno značajni da bi se isključila primena IOCSW za uklanjanje arsena tokom tretmana vode za piće. Zajedničko uklanjanje As i POM koagulacijom i unapređenom koagulacijom uz pode&scaron;avanje pH i kombinovanje sa oksidacionim predtretmanima je takođe ispitivano. Bolje uklanjanje koagulacijom postignuto je za As(V) u odnosu na As(III), stoga se kao najefikasniji ispitivani koagulacioni tretman pokazalo uklanjanje arsena i POM primenom predozonizacije praćene kombinovanom koagulacijom sa polialuminijum hloridom i gvožđe hloridom. Ispitivanja na različitim podzemnim vodama, pokazala su velike varijacije u pona&scaron;anju As i POM tokom tretmana. Iz tog razloga je primenjena metodologija odzivne povr&scaron;ine (RSM) u cilju ispitivanja interakcija između As i POM tokom koagulacije gvožđe hloridom i optimizacije njihovog kombinovanog uklanjanja. Sagledavanje većeg broja interakcija primenom metodologije odzivne povr&scaron;ine potvrđuje važnost njegove primene pri optimizaciji tretmana vode za piće.</p>

The determination of inorganic speciations of arsenic, antimony, selenium and tellurium in natural waters demands often separation and preconcentration. Solid phase extraction is a very effective method for these purposes. In this paper the separation and preconcentration of these microelements is realised on the basis of modified silica Separon SGX C18, SGX C8, SGX CN, SGX NH2, SGX Phenyl and strongly basic anion Exchanger SGX AX. The sorption was provided in the presence of cationic surfactants such as benzyldimethyl dodecylammonium bromide (Ajatin), benzyldimethyltetradecylammonium chloride (Zephyramine), 1-ethoxycarbonylpentadecyltrimetrhylammonium bromide (Septonex) and selected complexing agents 4-(2-pyridylazo)resorcinol (PAR), 8-hydroxyquinoline-5-sulphonic acide (8-HQS), 1,2-dihydroxybenzene (PYR), amonium 1-pyrrolidinecarbodithioate (APDC), sodium diethyldithiocarbamate (DTC) or thiourea(Thur). The interactions of the formed ion associate with the sorbent shows a complicated character which has not been cleared as yet. The previous conditioning of the sorbent plays an outstanding role. Thus, the sorption efficiency was studied in the presence and absence of surfactant and of selected organic complexing agents. Moreover, the influence of pH of the sorbed solution as well as the speed and the volume of the solution running through the sorbent and the type and volume of the eluent on the resulting sorption efficiency was evaluated. The sorption was successfully carried out from 50-1000 ml of solution which allows the 100 fold increase of the preconcentration factor and the determination of the microelements in g.l-1 instead of mg.l-1 by using the common ICP-AES. The influence of macroelements occurring in waters as well as B, Be, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, Ti, V and Zn in comparable concentrations involve less than 5% error. After the quantitative elution of microelements, the organic solvents were evaporated under IR lamps prior to the determination by ICP-AES and |ICP-MS. The conditions for the direct determination of arsenic, antimony, selenium and tellurium in g.l-1 with ICP-MS were also described in detail in the absence and presence of internal standards Ge and Bi. However, even in this case the preconcentration on silica in the presence of surfactant and selected organic complexants was also tested. When the sorption was followed from 500 ml a 50 fold enrichment factor is reached and the sensitivity for the microelements is improved. The direct determination and the sorption of microelements were applied on synthetic and real waters (dirinking, surface, mineral and sea waters). Instrumental and practical detection limits for various water samples were evaluated according to IUPAC. The results from 1000 ml solution of real waters after sorption on modified silica and the final determination of microelements with ICP-AES were compared with those from ICP-MS without sorption using the method of standards addition in the presence of suitable internal standards. By comparison of results for synthetic and real water samples the error of the determination of microelements was evaluated.

The global soil resources are significantly threatened by pollution. In addition to the existing burden of contaminants in agricultural soils, the increasing anthropogenic input of metal(loid)s, further referred to as trace elements (TE), presents a major public health concern, since it endangers the food security of a rising human population. However, the growing demand for agricultural commodities will increase the pressure on fertile soils. In this context, steering the needed agricultural extensification towards arable TE-contaminated soils (TECS) could protect highly biodiverse or carbon stock land and, thereby, help reach global sustainability targets. The sustainable crop production on TECS requires effective and non-destructive measures to control relevant pollutant linkages. These are offered by gentle remediation options (GRO), the practical adoption of which is scarce across Europe as yet. This study provides different approaches of GRO applied to an agricultural soil in a characteristic post-mining region (Freiberg, Saxony (Germany)) in practical adoption (chapter 2) and under semi-controlled conditions (chapters 3 and 4). Due to severe topsoil contamination by metals (Cd, Pb, and Zn) and As, the pollutant linkages of concern at the study site are food-chain transfer, leaching to the groundwater, and tilling-related dust emissions. The overall aim was to find best management practices for coupling soil remediation with the production of marketable biomass. This was attempted via (i) in situ stabilization, alone (chapter 4.1) or combined with phytoexclusion (chapter 2), (ii) labile TE phytoextraction (chapter 3), and (iii) (aided) phytostabilization (chapter 4.2). Soil remediation by GRO was assessed with scientifically established (DGT, soil solution; chapter 4.1) and/or legally relevant chemical soil extractions (NH4NO3-solution; chapters 2 to 4) and pH measurements. Additionally, earthworms served as ecotoxicological endpoints (chapter 4.1). Initial soils, earthworms, vegetative and generative biomass produced from each approach, as well as the investigated soil additives, including fertilizers, were microwave-assisted chemically digested (HNO3, H2O2, aqua regia) prior to analysis. All environmental samples were analyzed for TE by inductively coupled plasma mass spectrometry (ICP-MS). Nutrient concentrations in soil additives and selected plant samples were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES). The measured TE concentrations were evaluated against applicable European and/or national thresholds. At field (chapter 2), the repeated fertilization with superphosphate and/or lime marl basically attenuated the chemical TE availability over a three years crop rotation of Brassica napus, Triticum aestivum, and Hordeum vulgare. In turn, the simultaneous phytoexclusion by low-accumulating cultivars (LAC) effectively decreased the Cd concentrations in cereal grains (by averagely 21 % in wheat and 39 % in barley). However, straw metals´ accumulation or grain As uptake partly revealed opposing trends among LAC and high-accumulating cultivars (HAC). As investigated under semi-controlled conditions (chapter 3), a sunflower (Helianthus annuus L. mutant inbred line M7 (R3B-F-U/R13M10A; test series R13F-MP)), modified towards enhanced labile TE phytoextraction by chemical mutagenesis, proved less advantageous as pre-crop for winter wheat (Triticum aestivum L. cv. Tiger) than the regionally common winter oilseed rape (Brassica napus L. cv. Lorenz). This resulted from soil alkalinization by rape, whereas sunflower mobilized more TE than it depleted from the rhizosphere. Within in situ stabilization approaches under semi-controlled conditions, a Fe- /Al-rich drinking water treatment residue (WTR), soil-applied at a rate of 1 % (m/m) prior to cultivation of wheat (Triticum aestivum L. cv. Tiger; chapter 4.1) or Szarvasi-1 (Elymus elongatus subsp. ponticus cv. Szarvasi-1; chapter 4.2), decreased the chemical availability of As, Cd, and Pb by up to 77 % , 46 %, and 61 %, respectively. Thereby, it immobilized these hazardous TE increasingly effective over time and better than a Mn-rich WTR or lime marl. The bioassays with wheat and earthworms (Dendrobaena veneta L.) showed, however, that the habitat function for biocenoses benefited more from the Fe-/Al-rich WTR when it was applied at a lower application rate (0.5 % m/m). This resulted from dose-dependent P fixation and TE entries induced by the WTR, to which Szarvasi-1 appeared insensitive. Unlike As, the availability of Cd and Zn to biota in amended soils could not be predicted by any of the applied chemical methods due to endpoint-specific binding of competing cations to the biotic ligand (plant roots, earthworm tissue), and a preferential translocation of Zn over Cd in planta. Among all studied plants, the perennials Szarvasi-1 and cup plant (Silphium perfoliatum L.; chapter 4.2) best excluded the present mixture of TE in shoots, whereby the latter exhibited growth depression. However, only grain biomass of barley and rape, and partly of low-accumulating wheat, produced at the study site presented legally compliant animal feed based on European limit values for Cd and As. Given the investigated measures´ restricted efficacy to assure forage safety, a land-use change e.g. towards the perennial Szarvasi-1, which provides a continuous plant cover at low tillage and input requirements, possibly accompanied by the monitored reuse of an Fe- /Al-rich WTR, could most promisingly control all above-stated pollutant linkages. Revenues could be generated from energy conversion or valorization in the fibrous material sector. The waste recycling of WTR in TECS, though promising, requires proper characterization, eventual process optimization, and further studies regarding long-term stability to ensure legal compliance and environmental safety. Future research and breeding efforts regarding low Cd cultivars in particular could greatly contribute to safe food or forage production at the majority of moderately contaminated sites.:Table of contents Danksagung VI Abstract VII Zusammenfassung X List of Figures XIV List of Tables XVIII Abbreviations XXII 1 Introduction 1 1.1 The contamination of agricultural soils with trace elements - a global challenge to be tackled at local scale 1 1.2 The study site 5 1.3 Objectives 7 1.4 Structure of the thesis 8 2 Field assessment of conventional fertilizers and cultivars of annual plants 11 2.1 Management of trace element-contaminated agricultural land by in situ stabilization combined with phytoexclusion over a three years crop rotation 11 3 Exploring pre-crop effects of annual oilseeds 37 3.1 Trace elements bioavailability to winter wheat (Triticum aestivum L.) grown subsequent to high biomass plants in a greenhouse study 37 4 The potentials of drinking water treatment residues and/or perennialplants 53 4.1 Trace elements bioavailability to Triticum aestivum and Dendrobaena veneta in a multielement-contaminated agricultural soil amended with drinking water treatment residues 53 4.2 (Aided) phytostabilization of trace elements using cup plant (Silphium perfoliatum L.), or tall wheatgrass (Elymus elongatus subsp. ponticus cv. Szarvasi-1) and soilapplied drinking water treatment residues 77 5 Synthesis 91 5.1 The potential of crop management practices to mitigate food chain transfer of trace elements 91 5.2 The in situ stabilization efficacy under differential experimental conditions 96 6 Future perspectives 101 References 104 List of publications 121 Erklärung 123

Arsenic (As) contaminated groundwater has been a major concern due to the negative impacts to exposed people. This research was conducted to assess and compare the removal efficiency of As from groundwater by laterite, sand, and ash. The experiment was carried out in 14 days in a household scale in Son Dong commune, Hoai Duc district, Ha Noi. Groundwater was pumped directly from a well and flowed through 20 cm (diameter) x 80 cm (length) columns. The initial As concentration in groundwater was 526 μg/L decreasing to an average of 189, 192 and 154 μg/L after being filtrated using sand, ash, and laterite, respectively. Average removal efficiency of sand, ash and laterite during the experiment was 63.3, 63.9, and 70.5%, respectively. Laterite had higher As removal efficiency may be due to higher content of goethite and kaolinite in this sorbent which resulted in better adsorption of As. The concentrations of As in the outflow water were higher than the allowable limit set by the national technical regulation on drinking water quality (QCVN 01:2009/BYT). Therefore, it requires higher volume of sorbents or additional treatment technologies for removal of As from groundwater. / Ô nhiễm asen (As) trong nước ngầm hiện nay là một vấn đề cấp bách đối với xã hội bởi những rủi ro tiềm ẩn với sức khoẻ con người. Nghiên cứu được thực hiện nhằm đánh giá và so sánh khả năng hấp phụ As trong nước ngầm của đá ong, cát và tro. Thí nghiệm được tiến hành trong vòng 14 ngày đặt tại một hộ gia đình có nguồn nước ngầm bị ô nhiễm As thuộc xã Sơn Đồng, huyện Hoài Đức, Hà Nội. Nước ngầm được bơm từ giếng và chảy qua các cột đựng vật liệu có đường kính và chiều dài lần lượt là 20 cm và 80 cm. Nồng độ As ban đầu là 526 μg/L đã giảm xuống còn 189, 192 và 154 μg/L sau khi lọc bằng cát, tro và đá ong. Hiệu suất xử lý As trung bình của cát, tro và đá ong lần lượt là 63,3, 63,9 và 70,5 μg/L. Đá ong xử lý As tốt hơn có thể do hàm lượng goethit và kaolinit cao hơn trong vật liệu hấp phụ này dẫn đến khả năng hấp phụ As tốt hơn. Tuy nhiên hàm lượng As trong nước đầu ra vẫn chưa đạt quy chuẩn cho nước uống (QCVN 01:2009/BYT). Do đó, cần tăng thêm lượng vật liệu hoặc kết hợp với các phương pháp khác để xử lý As hiệu quả hơn.

Plants might contain heavy metals from the surrounding polluted environment. Medicinal herb and plants, commonly used in Vietnam, may pose a risk to public health when polluted with heavy metals such as Pb, Cd and As. This study aims to investigate the content of Pb, Cd, and As in five selected herb plants (Phyllanthus urinaria L., Plantago asiatica L., Eleusine indica L., Wedelia chinensis (Osbeck) Merr, and Artemisia vulgaris L.). The samples were collected from natural sites in some provinces in northern Vietnam. The concentrations of Pb, Cd, and As were determined by the Inductively coupled plasma mass spectrometry (ICP-MS) method. The content of Pb, Cd and As was 0.247 ÷ 32.080 mg kg-1, 0.000 ÷ 1.099 mg kg-1, 0.000 ÷ 2.261 mg kg-1, respectively. A total of 50 out of the 58 investigated samples had concentrations of Pb, Cd, As lower than the permissible values of the World Health Organization (WHO). The remaining samples had contents of Pb or Cd or As significantly higher than the permissible limit defined by WHO. / Thực vật có thể bị ô nhiễm do hấp thụ kim loại nặng từ môi trường ô nhiễm xung quanh. Các loại cây thảo dược được sử dụng phổ biến làm thuốc chữa bệnh ở Việt Nam. Chúng có thể gây nguy hiểm cho sức khỏe cộng đồng khi bị ô nhiễm kim loại nặng (Pb, Cd…vv.). Nghiên cứu này nhằm điều tra hàm lượng Pb, Cd và As trong năm loại cây thảo dược (cây Diệp Hạ Châu, cây Mã Đề, cây Cỏ Mần Trầu, cây Sài Đất và cây Ngải Cứu). Các mẫu cây này được lấy từ các địa điểm mọc tự nhiên ở một số tỉnh khác nhau thuộc khu vực miền bắc Việt Nam. Hàm lượng của Pb, Cd, và As được xác định bằng phương pháp ICP-MS. Hàm lượng Pb, Cd và As trong các mẫu phân tích lần lượt nằm trong khoảng là 0.247 ÷ 32.080 mg. Kg-1, 0.000 ÷ 1.099 mg. Kg-1, 0.000 ÷ 2.261 mg. Kg-1. 50 trên 58 mẫu phân tích có hàm lượng Pb, Cd, As thấp hơn giới hạn cho phép do tổ chức y tế thế giới (WHO) quy định. Có 8 trên 58 mẫu cây phân tích có hàm lượng Pb hoặc, Cd hoặc As cao hơn tiêu chuẩn giới hạn của WHO.

More and more attention has been paid to the research on phytoremediation and hyperaccumulators. Arsenic (As) uptake by hyperaccumulator plant species depends on many different environmental factors. Fertilizer is one of the most important factors because the plant growth needs nutrients. In this study, the pot experiments were conducted in 12 weeks to understand the effect of different fertilizer on As removal capacity of Pityrogramma calomelanos and Pteris vittata. The results showed that, Arsenic concentration in the frond is higher than that in the root of the fern. As removal efficiency of the ferns from the soil amended with both inorganic and organic fertilizer is highest. The ferns removed As content in soil up to 7.4 and 12.6 mg As per kg DW soil, respectively. For the control experiments without adding fertilizers, As removal ability of the ferns from the soil is lowest that was only 2.1 mg As per kg DW soil. / Trên thế giới đã và đang có nhiều nghiên cứu, ứng dụng phương pháp sử dụng thực vật để xử lýônhiễm, đặc biệt là các loài thực vật siêu tích tụ kim loại nặng. Sự tích lũy Asen (As) trong các loài thực vật siêu tích lũy phụ thuộc vào rất nhiều yếu tố môi trường và dinh dưỡng khác nhau. Phân bón là một trong những yếu tố quan trọng nhất vì sự phát triển cây rất cần chất dinh dưỡng. Trong nghiên cứu này, các thí nghiệm được tiến hành trong 12 tuần để đánh giá về ảnh hưởng của các loại phân bón khác nhau đến khả năng xử lý ô nhiễm As trong đất của dương xỉ. Kết quả thu được cho thấy, nồng độ As tích lũy trong phần thân của dương xỉ cao hơn rất nhiều so với phần rễ của cây. Hiệu quả loại bỏ As ra khỏi đất của dương xỉ trong các thí nghiệm bổ sung cả phân bón vô cơ và phân bón hữu cơ là cao nhất. Pityrogramma calomelanos và Pteris vittata có thể loại bỏ hàm lượng As trong 1 kg trọng lượng khô đất tương ứng lên đến 7,4 và 12,6 mg. Các công thức thínghiệm đối chứng không bổ sung phân bón thì cho hiệu quả loại bỏ As ra khỏi đất là thấp nhất chỉ 2,1 mg As trên 1 kg trọng lượng khô đất.

The subject of this thesis was creating of teaching material for an interactive whiteboard using ActivInspire program. The material was created in a form of interactive presentations designed to be used in chemistry lessons at secondary schools. The theme of these presentations was the 15th group of the periodic table of elements. The thesis also includes a description of the way the presentations were made and instructions for teachers how to work with them.

ii SUMMARY This master thesis deals with selectivity assessment of an arsenic sequential extraction procedure for evaluating mobility in mine wastes. A modified sequential extraction procedure was designed on the basis of preliminary tests of extraction efficiency and selectivity for the synthetic As mineral phases (scorodite, amorphous iron arsenate, schwertmannite, goethite, jarosite) and five natural samples (Kaňk, Dlouhá Ves, Giftkies, Roudný) that were previously characterized for As concentration and speciation. The modified sequential extraction has five steps. The first leaching step was performed in nitrogen-purged deionized H2O for 10 hours; next step involved 0.01M NH4H2PO4 leaching for 16 hours. Phases in the third step were dissolved with 0.2M Tamm`s reagent in darkness for 2 hours. The fourth step was represented by 0.2M of Tamm`s reagent heated in water bath at 80řC for 4 hours. Strong acid solutions HCl/KClO3/HNO3 were used to leach sulphide phases in the last step. The testing of the sequential extraction procedure using model mixtures showed a good discrimination of several fractions: adsorbed arsenic, arsenic associated with poorly crystalline oxyhydroxide, hydroxosulfate and arsenate phases (amorphous iron arsenate, schwertmannite, ferrihydrite), arsenic associated with crystalline...

Nanopartikel basierte colorimetrische Assays bieten vielfältige Anwendungsmöglichkeiten vom Nachweis ionischer oder molekularer Spezies bis hin zu komplexen Strukturen, wie zum Beispiel Zellen oder Bakterien. Trotz der großen Anzahl von Anwendungsbeispielen in der Literatur gibt es nur sehr wenige Beispiele für den Fall, wenn Analyt und Sensorpartikel etwa gleich groß sind. Jedoch nimmt das Interesse an dem Nachweis solcher Analyten, wie zum Beispiel von Viren, in der Bioverfahrenstechnik, der Umwelttechnik und Medizin stetig zu. In der Dissertation wird anhand von drei unterschiedlichen Anwendungsbeispielen die lückenlose Anwendbarkeit des Nanopartikel basierten colorimetrischen Sensorprinzips für verschiedene Analyten aus dem gesamten interessierenden Größenspektrum nachgewiesen. Für die Detektion von Ionen bzw. Ionenkomplexen ist mit der Funktionalisierung der Goldnanopartikel mit bakteriellen Zellhüllenproteinen ein spezifisches Nachweisverfahren für spezielle Ionenkomplexe entwickelt worden. Erste Ergebnisse zum Nachweis von toxischen Arsen(V)-Komplexen in wässriger Lösung belegen das enorme Potential. Als Nachweisgrenze konnten Werte im Bereich herkömmlicher sensitiver Messverfahren ermittelt werden. Durch Untersuchung der Wechselwirkung von Au- und AuxAg1-x–Nanopartikeln mit dendritischen Polymerstrukturen mit Abmessungen im Größenbereich zwischen 2 und 5 nm konnten tiefere Einblicke in das Aggregationsverhalten der Partikel bei der Ausbildung größerer komplexer Strukturen erzielt werden, die eine sensorische Umsetzung ermöglichen. Derartige Betrachtungen existieren bisher nur für Ionen oder kleinere molekulare Spezies. Der Nachweis von Analyten mit zu den Nanopartikeln vergleichbarer Größe wird am Beispiel zweier unterschiedlicher viraler Proben, dem Rinder-Coronavirus (BCV) und einem humanen Influenzavirus (H3N2) in grundlegenden Experimenten demonstriert. Die Durchführung dieser Arbeiten mit prozessnahem Virusprobenmaterial ist mit besonderen Herausforderungen an die Signalgewinnung und Interpretation verbunden. Aufbauend auf diesen experimentellen Ergebnissen konnte in einer skalenübergreifenden Betrachtung für Analytgrößen vom Subnanometerbereich bis hin zu einigen hundert Nanometern die lückenlose, universelle Anwendbarkeit des colorimetrischen Sensorprinzips demonstriert werden. Diese Betrachtungen ermöglichen generelle Aussagen zur Lage des Farbumschlagbereiches sowohl in Abhängigkeit von der Analytgröße als auch der Funktionalisierung, der Konzentration und der Größe der Nanopartikel.