No description available.

Agricultural wastes; Albizia coriaria, Coffea canephora, Cyperus papyrus, Erythrina abyssinica and Musa spp were evaluated for uptake of aqueous Cd2+ and Pb2+ ions in single- and binary-component solutions. Untreated, base-treated and peroxide-treated biomasses were employed in batch studies. The optimal conditions for Cd2+ and Pb2+ ions biosorption were  pH 3.5 – 5 for contact time 3.0 – 3.5 hours and biosorbent dosage 10 – 12.5 g/L. Base-treated biosorbents showed a 10 – 17 %  sorption enhancement for Cd2+ ions and a 1.6 – 2.3 % uptake reduction for Pb2+ ions. The sorption capacities for Cd2+ and Pb2+ ions for base-treated biosorbents were between 1.738 and 1.760 mg g-1 compared to 1.415 – 1.539 mg g-1 for untreated materials. The maximum biosorption of peroxide treated materials in single component media was between 0.819 and 1.595 mg/g for Pb2+ ions and between 0.044 and 1.343 mg/g for Cd2+ ions while in binary component media it was between 0.472 and 1.303 mg/g for Pb2+ ions and between 0.008 and 0.195 mg/g for Cd2+ ions. The pseudo-second order kinetic model suitably fitted the Cd2+ and Pb2+ ions biosorption data with regression coefficients (R2); 0.892 – 1.000 for peroxide-treated materials and 0.9784 – 0.9999 for base-treated biosorbents which implied that the biosorption was mainly a chemisorption process. The base treated biosorbents had better sorption performance for Cd2+ ions than peroxide treated materials and untreated biomass whereas the order for Pb2+ ions biosorption was untreated &gt; base treated &gt; peroxide treated materials. All materials showed superior selectivity for Pb2+ ions biosorption in comparison to that of Cd2+ ions in single- and binary-component media. A. coriaria performed best of the base treated biosorbents while C. canephora performed best amongst peroxide treated materials for Cd2+ and Pb2+ ions biosorption in single-and binary-component media. In the competitive biosorption, Cd2+ ions showed higher synergistic effects than Pb2+ ions although Pb2+ ions were preferentially sequestered even when the Cd2+:Pb2+ ions ratio was increased through 3:2, 2:1, 3:1 and 5:1. Of the three isotherm models evaluated against the experimental data, the Langmuir model generally fitted the sorption data for both metals. Regression coefficients for the Langmuir model were; 0.983 ≤ R2 ≥ 1.000 for single-component and 0.939 ≤ R2 ≥ 1.000 for binary-component solutions which revealed that the biosorption was potentially monolayer. The biosorption equilibrium coefficient                          values and change in Gibbs’ free energy  values showed that Pb2+ ions biosorption was more thermodynamically favoured than that of Cd2+ ions in single-component and binary-component media. The materials studied displayed potential for use as biosorbents for remediation of aqueous Cd2+ and Pb2+ ions. / <p>QC 20140508</p>

The increasing pollution of the aquatic environment by cadmium is a potentially severe problem and techniques are needed to document the effect of the metal. To investigate the flux of this metal through a laboratory food chain, algae were grown in various cadmium concentrations for subsequent use as contaminated food for mussels. The results showed that in order to make valid deductions, more information about chemical mechanisms and background ecophysiological data is needed, otherwise accumulation reports may become misleading. It was found that the best growth and accumulation results were achieved by harvesting algae from a zinc deficient media containing 7 μmole dm-3 cadmium and at a particular life cycle phase. Two uptake mechanisms are proposed. These "contaminated" algae were fed to mussels under different accumulation regimes. The metal gain and loss were determined and compared to a "baseline" dry body weight which had been calculated from a shell length-body weight relationship. Cadmium accumulation took place in the mussels and after some initial delay, could be correlated to weight loss. Such a weight loss was due to pathological and biochemical changes in the mussels. It was shown that the toxic effect of cadmium could be determined much earlier by the presence of special proteins. The elutant profiles of the gel chromatography study showed the production of metal binding protein as well as a spill over of cadmium into the enzyme pool, caused by a higher uptake than elimination rate. Cadmium on metal binding protein and in the enzyme pool could be related to the poisoning effect of the metal and a pollution history for the mussels identified. The characteristics of the metal binding protein were found to be very similar to those reported for metallothionein and had an approximate molecular weight of 10 600 daltons.

The area of study for this project was the development of an accurate, reliable, and inexpensive method of trace analysis for copper, cadmium, and lead in foods. AT this time, the Association of Official Analytical Chemists Manual, eleventh edition, (4) has only official and recognized methods of analysis for copper (25.023), cadmium (25.018), and lead (25.041). In general, these procedures are long and tedious. The digestions involved often require many hours and are quite dangerous due to leakage of metallic and organometallic fumes from the digestion apparatus. The official methods of analysis for these elements require a very large outlay of money for special equipment and reagents. It was the purpose of this project to determine the following: (A) The feasibility of using polarographic detection for copper, cadmium, and lead in trace amounts.; (B) Fina da new method of sample decomposition to replace the present digestion methods.; (C) Study the selection media prior to polarographic detection.; (D) Develop a method of simultaneous polarographic detection of copper, cadmium, and lead.

No description available.

Östersjön har flertalet regionala miljöproblem, exempelvis övergödning samt höga halter av tungmetaller vilka beror på mänsklig påverkan. På Gotland spolas det årligen upp stora mängder släke, alger och vattenlevande växter på stränderna, som idag inte nyttjas i större utsträckning. Denna rapport syftar att bedöma lämpligheten att använda det gotländska släket för produktion av biokol. Under denna studie har ett studiebesök till Gotland, flertalet intervjuer samt en litteraturstudie genomförts vilka lagt grund för beräkningar av energi- och materialbalanser kopplat till släkesbaserad biokolsproduktion. Släket har ett kadmiuminnehåll på cirka 0,9 mg/kg och består till 80 % av vatten, där vanligt förekommande arter är bland annat bandtång och kräkel. För beräkningar av energi- och materialbalanser nyttjades två olika förbehandlingsalternativ av släket, där alternativ A var en värmebehandling och alternativ B innefattar en kompostering samt avlsutande värmebehandling. Alternativ B är mer energieffektiv sett till energiförbrukning per kilo producerat biokol vilket var 14,5 MJ/kg jämfört med 29,8 MJ/kg. Det finns både för- och nackdelar med användning av släke för biokolsproduktion. Släke är en outnyttjad resurs som kan ingå i biokolsframställning, dock är processen energikrävande på grund av det höga vatteninnehållet i biomassan. Användningen av ett kadmiumrikt biokol är även problematiskt i och med risken för utlakning av denna tungmetall. Utifrån resultatet är det därmed svårt att bedöma lämpligheten av ett släkesbaserat biokol. / The Baltic sea has multiple environmental problems, such as over-fertilization and high concentration of certain heavy metals, caused by human activity. Yearly, beach-cast is washed up on the shores of Gotland and this biomass is today not utilised to a considerable extent. This report aims to assess the suitability of producing biochar from the left over beach-cast. During this study a visit to Gotland, interviews and a literature study has been completed, which has laid the groundwork for calculations of energy and material balances regarding algae-based biochar production. The beach-cast contains approximately 0.9 mg cadmium per kg and consists of 80 % water, in which common species found are eelgrass and furcellaria, among others. For the calculations of energy- and material balances, two different pretreatment alternatives were used before the pyrolysis. Alternative A simply uses preheating and alternative B consist of a composting step before a finishing preheating session. The most energy efficient was alternative B as the power consumption per kilo produced biochar was 14,5 MJ/kg compared to 29,8 MJ/kg. The use of beach-cast for manufacturing biochar has benefits as well as disadvantages. Beach-cast is an unexploited resource that could be used for biochar production, but on the other hand the process is demanding energy-wise due to the high amount of water in the biomass. The utilisation of cadmium rich biochar is also problematic due to the risk of the heavy metal leaching. Based on the results it is therefore complicated to estimate the suitability of a beach-cast based biochar.

No description available.

No description available.

Accumulation of beach cast biomass on coastal zones around Gotland is an increasing problem that reduce the recreational value of beaches and cause environmental degradation of coastal environments. Beach cast was once regularly harvested on Gotland, as it was considered a valued biofertilizer, but as it seized to be used in combination with the eutrophication of the Baltic sea, beach cast accumulation has increased in scale. The use of beach cast as a resource for bioenergy and agriculture does not only provide important services that can replace the use of greenhouse gases and finite resources but can also mitigate eutrophication and increase the quality of coastal zones as nutrients are retrieved from the water. Macroalgae and seaweeds are hyperaccumulators of heavy metals which pose a challenge for the utilization of beach cast as a fertilizer. Especially cadmium, a heavy metal that is harmful for human consumption, is strictly regulated and limits the amount of beach cast that can be used for agriculture. This thesis has analysed the potential benefit of beach cast harvesting and three potential utilization strategies of beach cast; fertilizer to food crops, fertilizer to fast growing energy forest (Salix) and biogas production with digestate utilization. The result indicate that all strategies are possible and viable utilization strategies under certain conditions. Because of the complex and site specific factors that affect beach cast utilization, adapting strategies depending on the conditions and needs of the local coastal zones is required. Cadmium uptake is affected by a range of factors that can be controlled so that beach cast can provide nutrients and improve soil structure without contaminating the soil. Especially promising is the prospect of fertilizing Salix with beach cast as the cadmium absorption and growth rate of Salix enables large amounts of beach cast to be spread without risk for it accumulating in the soil. The cadmium contained within the Salix can later be removed from the environment entirely as it is collected from the ash when Salix is converted to bioenergy. Recent studies also indicate that food crops can be safely fertilized with beach cast without cadmium being transferred if specific crops are chosen. Cadmium uptake to crops can also be limited if specific beach cast with low cadmium content are used and if the beach cast is pre-composted with other substrates. Both for Salix and food crops its instead legal restraints on cadmium spreading that limits the use of beach cast. When abiding by the set cadmium restrictions, beach cast can only marginally supply the macronutrient requirement of the average food crop on Gotland. Biogas production and digestate utilization from beach cast provides many environmental benefits as clean renewable energy is generated that can replace fossil fuels and the nutrients contained in the digestate can be spread on arable land. From the conducted energy balance of the system on Gotland it was found that beach cast has theoretically good conditions to ferment beach cast. However, beach cast isn’t practically viable on Gotland because the substrate can’t compete financially with other available substrates and it requires costly pre-treatments. Regardless of which beach cast utilization strategy chosen, harvesting is concluded to have a positive effect on mitigating coastal eutrophication and beach and water quality. Although it cannot on its own mitigate a net nutrient loading to coastal zones in Gotland, harvesting easily available beach cast can reduce the nutrient loading to coastal zones on Gotland with up to 27 % and 4,5 % phosphorus and nitrogen respectively.

The bis(2-pyridylthio)methyl ligand, [Bptm], offers a synthetically convenient alternative to a variety of multidentate ligands, including most notably [Tptm] (tris(2-pyridylthio)methyl) and [BptmSTol] (bis(2-pyridylthio)(p-tolylthio)methyl), and, in contrast with [Tptm], necessarily coordinates to metal centers in a κ³ fashion. As such, numerous [Bptm] complexes of zinc have been synthesized and structurally characterized. In Chapter 1, we describe the reaction of the protonated ligand [Bptm]H with the homoleptic zinc compounds Me₂Zn and Zn[N(SiMe₃)₂]₂ to afford, respectively, [Bptm]ZnMe and [Bptm]ZnN(SiMe₃)₂; the latter has been used as a starting point for a wide range of reactivity.Most notably, the terminal zinc hydride, [Bptm]ZnH, can be accessed via either (i) metathesis of the zinc siloxide, [Bptm]ZnOSiPh₃, with either PhSiH₃ or HBpin, or (ii) direct metathesis of the zinc amide [Bptm]ZnN(SiMe₃)₂ with HBpin; the latter reactivity is not precedented and offers a novel approach for the synthesis of molecular zinc hydrides. Both [Bptm]ZnN(SiMe₃)2 and [Bptm]ZnH provide access to a variety of monomeric derivatives, including the zinc halides [Bptm]ZnX (X = Cl, Br, I) and the zinc isocyanate [Bptm]ZnNCO; the latter can be accessed directly via (i) metathesis of [Bptm]ZnH with Me₃SiNCO or (ii) a multistep reaction of [Bptm]ZnN(SiMe₃)₂ with CO₂. [Bptm]ZnH also undergoes insertion of CO₂ into its Zn—H bond to afford the zinc formate, [Bptm]ZnO₂CH, in which the formate moiety exhibits a monodentate binding mode in the solid state. This reactivity enables it to serve as a catalyst for the hydrofunctionalization of CO₂; specifically, [Bptm]ZnH catalyzes the hydrosilylation of CO₂ by (RO)₃SiH (R = Me, Et) at elevated temperatures to afford the respective silyl formates (RO)3SiO₂CH, as well as the hydroboration of CO₂ by HBpin at room temperature to afford the boryl formate HCO₂Bpin. In the absence of CO₂, [Bptm]ZnH also catalyzes the reduction of HCO₂Bpin to the methanol level, MeOBpin. Similarly, [Bptm]ZnH serves as an effective catalyst for the hydrosilylation and hydroboration of a variety of ketones and aldehydes. In all cases, hydroboration is more facile than the corresponding hydrosilylation. The [Bptm]Zn system has been investigated computationally, and the kinetics of insertion of CO₂ into the Zn—H bond of [Bptm]ZnH as well as the thermodynamics of the catalytic cycle have been examined. Further mechanistic studies examine two noteworthy spectroscopic features of the system, namely rapid exchange (i) between the zinc and boryl formates [Bptm]ZnO₂CH and HCO₂Bpin, as well as (ii) between [Bptm]ZnH and [Bptm]ZnO₂CH. Both of these exchange processes have been investigated with variable-temperature NMR spectroscopy; in particular, the former exchange resolves at low temperatures and can be confirmed by exchange spectroscopy. In addition to the aforementioned monomeric zinc halides [Bptm]ZnX (X = Cl, Br, I), the dimeric bridging zinc fluoride {[Bptm]Zn(μ-F)}₂ has been synthesized via reaction of Me3SnF with either [Bptm]ZnN(SiMe₃)₂ or [Bptm]ZnH, as outlined in Chapter 2. The dimeric nature of the fluoride in contrast with the other monomeric halides can be attributed to the significant polarity of the Zn—F bond. {[Bptm]Zn(μ-F)}2 also reacts with Me₃SiCF₃ to afford an unusual instance of a structurally characterized zinc trifluoromethyl complex, [Bptm]ZnCF₃. Chapter 3 discusses cadmium analogues to the [Bptm]Zn system, which provide a comparison and a contrast both with their zinc counterparts as well as with previously reported [Tptm]Cd complexes. While the cadmium amide [Bptm]CdN(SiMe₃)2 may be synthesized in a manner corresponding to that for its zinc analogue, the siloxides {[Bptm]Zn(μ-OSiR₃)}₂ (R = Me, Ph) form dimers that are distinct from the monomeric [Bptm]ZnOSiPh₃ and [Tptm]CdOSiPh₃, although similar to {[Tptm]Cd(μ-OSiMe₃)}₂. The distinctions between the [Bptm]Zn and [Bptm]Cd siloxides have been investigated computationally, indicating that the cadmium species show a thermodynamic preference for dimer formation, which can be attributed to the larger atomic radius of cadmium relative to zinc. Attempts to synthesize a cadmium hydride are interrupted by a Schlenk-type equilibrium giving way to the bis(ligand) complex [Bptm]2Cd and CdH₂, which in turn decomposes to Cd and H2. However, spectroscopic studies indicate that under CO₂, [Bptm]CdN(SiMe₃)₂ and HBpin react to trap a cadmium hydride species as the bridging formate derivative, [Bptm]Cd(μ-O₂CH)₂Bpin. The interaction of nitrogen-rich ligands with main group metals is further probed in Chapter 4, which describes the investigation of the coordination of 2,2’:6,2”-terpyridine (terpy) to magnesium compounds. Most prominently, unsubsituted terpy forms an adduct, terpyMg[N(SiMe₃)₂]₂, with the monomeric form of the magnesium amide {Mg[N(SiMe₃)₂]₂}₂. The adduct reacts with halide donors to form a series of mixed amide-halide complexes, terpyMg[N(SiMe₃)]X (X = Cl, Br, I), as well as a mixed amide-azide complex, terpyMg[N(SiMe₃)₂]N₃. These complexes represent the first instances of neutral monomeric terpyMg compounds that feature unsubstituted terpyridine. Structural comparisons of these complexes with one another as well as with comparable compounds are undertaken. Complexes of terpy with cadmium and zinc analogues, terpyCd[N(SiMe₃)₂]₂ and terpyZn [N(SiMe₃)₂]₂, are explored further, and DFT calculations are used to explore the strength of the interactions between the ligand and the metals in each case. Finally, in Chapter 5, attention is given to the recently reported zinc bromide complex featuring a zwitterionic carboxylate ligand, (Cbp)2ZnBr₂. The structure reported for this complex features several anomalous features, including abnormally long Zn—Br and Zn—O bonds, unusually small atomic displacement parameters for Zn, and a high R-value. This information led us to synthesize and investigate the cadmium counterpart, (Cbp)₂CdBr₂; we find that the cadmium complex possesses nearly identical structural parameters to the reported zinc complex, and when the cadmium is refined as zinc, the displacement parameter problems are reproduced. Therefore, we conclude that the reported structure is in fact that of (Cbp)₂CdBr₂, and report a revised structure for (Cbp)₂ZnBr₂.