Two related techniques, based upon ion-exchange solid phase extraction, have been developed for the determination of arsenic speciation. The inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) are separated by anion-exchange and detected with graphite furnace atomic absorption spectrophotometry (GFAAS) with a nickel matrix modifier. The first separation technique, which is based on a published method, utilizes a strong anion-exchange resin in a column format. The method was refined to achieve a cleaner and more rapid separation of the As species. In the second separation technique, the recently available Empore[superscript TM] anion-extraction disks are used. In both cases, rapid separations of several samples are achieved with the use of a vacuum manifold. The simplicity of the separation techniques allows them to be applied in the field which eliminates potential problems due to sample storage. In the pH range of most natural water samples (5-9), As(III) exists as a neutral species which is not retained by the resin, while As(V) exists as a monovalent or divalent species which are subsequently retained by the resin. The two arsenic species are collected in 3 to 4 fractions with As(III) appearing in the first two fractions. The As(V) species is eluted from the resin with 0.1 M HCl and collected in the last one or two fractions. Percent recoveries for each species range from 94 to 99%. The detection limit for each species with GFAAS is 2 ��g/L. The speciation techniques were used successfully in several applications. First, the resin technique was used to monitor the oxidation of As(III) by 0���, H���0���, and ��-Mn0���. The technique was also used to monitor the reduction of As(V) by Fe(II) and in solutions containing combinations of Fe(II), Fe(III), and a scorbic acid. Second, the resin technique was used to monitor the redox behavior of arsenic in soil slurries in bio-reactor systems. Upon spiking the soil slurry to a level of 500 ��g/L As(V), 80 to 90% of the As(V) was immediately adsorbed, presumably to hydrous Fe(III) oxides. In general, as conditions became more reducing, total soluble arsenic increased as a result of either abiotic or biotic reduction of the As(V) to the more soluble As(III). Third, the disk technique was applied in the field to determine arsenic speciation in creek water at Sutter Creek, Ca., where homes are built upon a large pile of mine tailings containing arsenic. In the creek water, no As(III) was detected but As(V) was detected at a level of 8 ��g/L. Fourth and finally, the resin technique was used to determine arsenic speciation when a sample of the mine tailings was placed in a reactor and combined with a soil slurry thus simulating a flooded condition. As conditions became more reducing, up to 800 ��g/L As was detected in solution with As(III) accounting for almost 90% of total soluble species. Also presented here is an investigation of zinc amalgam as a reducing agent for Cr(III) and selected redox indicators. Zinc amalgam, in a column format, also known as the classic Jones Reductor, provides an efficient means for production of Crap and reduced forms of various redox indicators. Finally, the reduction capabilities of Ti(III) citrate and zinc amalgam were compared. / Graduation date: 1996

The properties of an element are highly dependent on its chemical form, it’s called elemental speciation. This study evaluates the arsenic species found in a range of food stuffs together with growing environments and toxicity issues. Total arsenic concentrations in fish tissue and vegetable crops were determined by ICP-MS following microwave-assisted acid digestion using nitric acid/hydrogen peroxide, trypsin and cellulase enzymatic extraction procedures. The extracted arsenic species were then quantified using HPLC-ICP-MS. A dilute nitric acid (1 % (v/v)) digestion procedure was also used to extract arsenic species from rice and the different parts (root, skin, stem, leaf and grain) of a range of plant crops. The study was extended to include the aqua-regia extractable arsenic content of the soils collected from the area where the plants had been cultivated in the Kurdistan region of Iraq. Irrigation water was also investigated, but found to contain low levels of arsenic. An anion-exchange HPLC-ICP-MS method was developed, using sulphate and phosphate, for the separation and quantification of AsB, MMA, DMA, InAsIII and InAsV. The results obtained for fish samples were in the range of 3.53-98.80 µg g-1 (dry weight) with non-toxic AsB being the predominant species. The InAsV concentration was in the range of 0.1-1.19 µg g-1 for all fish species except for the John Dory which was below the limit of detection (0.027 µg g-1). Total arsenic, arsenic species, and total multi-elements (including Ag, Al, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Si, Ti, V and Zn) were determined in rice samples from Kurdistan, Iraq and other regions of geographical origin. The transport of arsenic from the soil and irrigation water into roots, stem, leaf and subsequently into the grain or bean of the plants is important when assessing the potential health risks from food crops. For the soil sample, InAsV was found to be the major species with smaller quantities of InAsIII . After applying a full BCR sequential extraction procedure to the soils, it was found that 7.87 - 21.14 % of the total arsenic was present in an easily acid-soluble extractable form. Finally, a novel method was developed to measure total arsenic and arsenic species associated with vegetative DNA. In rice plant, it was found that InAsV incorporated within the DNA molecule in which it could replace phosphate. It was also found that the concentration of InAsV associated with DNA molecule decreased with decreasing total arsenic in the rice plant from the root to the leaf.

Arsenic (As) is a problem with rice production systems throughout the world as high As concentrations are reported in rice grains originating from several parts of the world. This characteristic is mainly due to the flooded conditions utilized in rice culture. We hypothesized that the soluble As concentrations in the rice rhizosphere can be decreased by growing rice more aerobically through intermittent flooding. Intermittent water management practices might also change microbial populations in the rice rhizosphere that might potentially impact As chemistry and bioavailability. Two field-scale experiments were conducted over two years to study the impact of intermittent and continuous flooding on As speciation and microbial populations in the rice rhizosphere. As levels and speciation in the rhizosphere soil, root-plaque and pore-water were determined using a high performance liquid chromatography-inductively coupled plasmamass spectroscopy (HPLC-ICP-MS). The microbial populations were assessed from the rhizosphere soil and root-plaque samples using quantitative polymerase chain reaction (qPCR) and 16S rRNA sequencing. Pore-water and root-plaque total-As concentrations significantly decreased in the intermittent compared to the continuous flood plots. Inorganic arsenite (iAsIII) was predominant in pore-water and inorganic arsenate (iAsV) in root-plaque and soil. Rootplaque sequestered significantly higher levels of As (almost tenfold higher) than the adjacent rhizosphere soil. Grain As concentrations also decreased by 35 to 45 percent in the intermittent compared to the continuously flooded plots. Organic As species, monomethyl and dimethyl arsenate were detected in the rhizosphere with relative increases and decreases among the treatments. Bacteria were the predominant group (91 to 94 percent and 48 to 78 percent of total community in root-plaque and rhizosphere soils, respectively). Archaea were also a major component of rhizosphere soil with their populations being higher under continuous flooding. The relative abundance of iron-reducing bacteria was around 3 to 6 percent of the total community in root-plaque and around 6 to 6 percent in soil, with significantly lower abundance in the intermittent compared to the continuously flooded plots. Results of these studies demonstrated that intermittent flooding could be a potential management option to reduce grain As in rice cultivated on fields with moderate to high As concentrations.

Arsenic (As) undergoes extensive metabolism in biological systems involving numerous metabolites with varying toxicities. It is important to obtain reliable information on arsenic speciation for understanding toxicity and relevant modes of action. Currently, popular arsenic speciation techniques, such as chromatographic/electrophoretic separation following extraction of biological samples, may induce the alternation of arsenic species during sample preparation. The present study was aimed to develop novel arsenic speciation methods for biological matrices using surface-enhanced Raman spectroscopy (SERS), which, as a rapid and non-destructive photon scattering technique. The use of silver nanoparticles with different surface coating molecules as SERS substrates permits the measurement of four common arsenicals, including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV). This speciation was successfully carried out using positively charged nanoparticles, and simultaneous detection of arsenicals was achieved. Secondly, arsenic speciation using coffee ring effect-based separation and SERS detection was explored on a silver nanofilm (AgNF), which was prepared by close packing of silver nanoparticles (AgNPs) on a glass substrate surface. Although arsenic separation using the conventional coffee ring effect is difficult because of the limited migration distance, a halo coffee ring was successfully developed through addition of surfactants, and was shown to be capable of arsenicals separation. The surfactants introduced in the sample solution reduce the surface tension of the droplet and generate strong capillary action. Consequently, solvent in the droplet migrated into the peripheral regions and the solvated arsenicals to migrated varying distances due to their differential affinity to AgNF, resulting in a separation of arsenicals in the peripheral region of the coffee ring. Finaly, a method combining experimental Raman spectra measurements and theoretical Raman spectra simulations was developed and employed to obtain Raman spectra of important and emerging arsenic metabolites. These arsenicals include monomethylarsonous acid (MMAIII), dimethylarsinous acid (DMAIII), dimethylmonothioarinic acid (DMMTAV), dimethyldithioarsinic acid (DMDTAV), S-(Dimethylarsenic) cysteine (DMAIIICys) and dimethylarsinous glutathione (DMAIIIGS). The fingerprint vibrational frequencies obtained here for various arsenicals, some of which have not reported previously, provide valuable information for future SERS detection of arsenicals.

ABSTRACT ARSENIC SPECIATION IN FISH BY HPLC-ICP-MS &Ouml / ZCAN, Sefika Eroglu M.S., Department of Chemistry Supervisor: Prof. Dr. O. Yavuz ATAMAN September 2010, 103 pages Arsenic speciation in fish samples on the market was performed using isocratic elution with cation exchange column high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) detection. Total As concentrations were found by ICP-MS using samples digested by nitric acid-hydrogen peroxide solution using microwave oven digestion / the results were in the range of 1.15-12.6 &micro / g/g. Separation of organic arsenicals, namely arsenobetaine (AB), dimethylarsinic acid (DMA) and monomethylarsonic acid (MA), have been achieved in 12 minutes. Freeze-dried samples were extracted by deionized water with a shaker system / the concentrations of AB and DMA in the extract was then determined using HPLC-ICP-MS. The accuracy of the method for determining AB concentration was confirmed using certified reference material (CRM), DOLT 4 (dog fish liver) / for this CRM only preliminary data are available for AB. The arsenic compounds in 6 fish muscle samples were investigated. The predominant arsenic compound found in extracts was AB / the concentrations were in the range of 0.86-12.0 &micro / g/g. DMA concentration was 0.40&plusmn / 0.03 &micro / g/g in one of the samples / in the others it was below the limit of quantation (0.21 &micro / g/g).

Several biologically important arsenic compounds including methylarsonate, trimethylarsine oxide, tetramethylarsonium ion, arsenobetaine and arsenocholine were prepared, in good yields, from sodium arsenite, or dimethylarsinic acid. These organoarsenic compounds together with arsenite, arsenate and dimethylarsinic acid were used as standards for the development of analytical methods for determining the levels of individual arsenic compounds (arsenic speciation) present in natural matrices. / Arsenobetaine, arsenocholine and tetramethylarsonium ion were separated by high performance liquid chromatography (HPLC) with on-line detection by thermochemical hydride generation (THG)-AAS. The analytes were eluted from the cyanopropyl bonded phase HPLC column with a 1% acetic acid methanolic mobile phase which also contained diethyl ether triethylamine, and trimethylsulfonium iodide or picrylsulfonic acid. A surface response methodology and a univariate optimization procedure were used to determine the optimum concentration of solvent modifiers in the methanolic mobile phase. Limits of detection in the range 4-5 ng (as As) were obtained for the arsonium analytes under optimum chromatographic conditions. / A simple phenol extraction procedure was developed to isolate arsonium analytes from edible marine tissues (lobster tail muscle, peeled and deveined shrimp, and cod fillet), cod liver oil and human urine. The crude extracts were separated on the cyanopropyl column using a methanolic mobile phase and detected on-line by THG-AAS. Recoveries from tissues or from urine which had been spiked at 0.1-3.4 $ mu$g of As cation/g of fresh weight were 80% or greater for each of five sample types. / An improved HPLC-AAS interface which was compatible with either aqueous or organic mobile phases was also developed. The interface provided approximately equivalent responses to different arsenic oxidation states which resulted in low to subnanogram chromatographic limits of detection for arsenic oxyanions and arsonium cations in an aqueous or methanolic mobile phase. Nascent As anions and As cations were conveniently coextracted from aqueous solution or from fish muscle by phenol extraction and quantified in the same chromatographic run. This method has been applied to a standard reference sample of dogfish muscle (DORM-1), a marine reference sediment sample (PACS-1) and to sediment porewaters (SAG-15) from the Saguenay Fjord.

Arsenic transfers and toxicology are important topics of research and a public health concern because arsenicosis affects millions of people worldwide every year. One of the most significant sources of arsenic in the environment is industrial wastes, such as by-products of mining operation. In Yellowknife, Northwest Territories, Canada, there were two large gold mines—Giant Mine and Con Mine, along with dozens of small-scale mines. The combined by-product of emission from these roasters might have contributed to high concentrations of arsenic found in the city. This thesis presents the results of two related studies to address the environmental health concern: (1) to investigate the arsenic transfers and arsenic species accumulation in freshwater food webs near large legacy mining operations in Yellowknife, and (2) to assess the long-term health risk of inorganic arsenic exposure from the consumption of fish in Yellowknife among the general residents and the Yellowknives Dene First Nation. We found that inorganic arsenic is biominified in food webs (i.e. inorganic arsenic concentrations diminish at higher trophic positions relative to lower trophic positions). Higher-trophic organisms have low inorganic arsenic concentrations in tissue due to biotransformation of inorganic arsenic to non-toxic organic arsenobetaine, and effective elimination of arsenic from their tissue. The trophic positions of freshwater organisms can be used to predict the range of arsenic concentrations and its species composition, accounting for more than 80% of variance. Dietary study results show that the Yellowknives Dene First Nation consumed significantly more fish in their diets (adults: 19 g/day, children: 9 g/day) compared to the general residents of Yellowknife (adults: 9 g/day, children: 5 g/day). Our probabilistic risk assessments showed no significant long-term non-carcinogenic and carcinogenic health risks of inorganic arsenic exposure from fish consumption for the majority of Yellowknife residents, but elevated cancer risks among the adult heavy fish consumers in Yellowknife. However, our data suggested that the residents of Yellowknife were not exposed to higher cancer risks from inorganic exposure compared to the general population in Canada. Therefore, due to fish health benefits and the values associated with its consumption, fish should continue to be a major source of sustenance in Yellowknife.

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