Kinetic study of transformations of arsenic species during heat treatment

The combination of temperatures and pH levels applied in domestic or industrial cooking and in the sterilization of seafood might cause the transformation of certain species of arsenic into other more toxic species, which could pose a risk to the consumer. To clarify the effect of the temperatures traditionally used in cooking or sterilization on the stability of the various species of arsenic, a kinetic study was carried out, using standards of arsenobetaine (AB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), trimethylarsine oxide (TMAO), tetramethylarsonium ion (TMA(+)), and arsenocholine (AC) heated at different temperatures (85--190 degrees C) and for different treatment times. Various pH levels (4.5, 5.5, 6.5, and 8.0) were applied during the heating process. The results obtained indicated that there were no transformations of arsenic species after temperature treatments up to 120 degrees C. However, when temperatures between 150 and 190 degrees C were used, a partial decomposition of AB was achieved, producing TMAO at 150 degrees C and TMAO and TMA(+) at temperatures of 160 degrees C or above, in proportions that varied according to the temperature and duration of the heat treatment.     

Gas chromatographic method for determination of dimethylamine, trimethylamine, and trimethylamine oxide in fish-meat frankfurters

A method is described for analysis of minced fish-meat and surimi-meat frankfurters for dimethylamine (DMA), trimethylamine (TMA), and trimethylamine oxide (TMAO) using a headspace-gas chromatographic technique. After simple acid extraction and addition of NaOH, the headspace was directly injected into a gas chromatograph by a gas-tight syringe. DMA and TMA were separated on a Chromosorb 103 column and detected by a flame ionization detector. TMAO was measured as TMA after Zn reduction. Repeatability of the method for DMA, TMA, and TMAO was 6.6, 1.0, and 18.8 ppm, respectively. The method was applicable to Alaska pollock-meat and Atlantic menhaden-meat frankfurters, unwashed, and washed mince and surimi.     

Estimation of arsenic bioaccessibility in edible seaweed by an in vitro digestion method

The aim of this study was to examine the bioaccessibility (maximum soluble concentration in gastrointestinal medium) of total (AsT) and inorganic (AsI) arsenic contents and the effect on them of cooking edible seaweed, a food of great interest because of its high As content. An in vitro gastrointestinal digestion (pepsin, pH 2, and pancreatin-bile extract, pH 7) was applied to obtain the mineral soluble fraction of three seaweeds (Hizikia fusiforme, Porphyra sp., and Enteromorpha sp.). AsT was determined by dry-ashing flow injection hydride generation atomic absorption spectrometry. AsI was determined by acid digestion, solvent extraction, and flow injection hydride generation atomic absorption spectrometry. The bioaccessibility of AsI increased significantly after cooking, attaining 73% in Porphyra sp. and 88% in H. fusiforme. For cooked H. fusiforme, the AsI attained in the bioaccessible fraction was 26 microg g(-1) seaweed, a concentration that is a warning of the toxicological risk of this food.     

Organoarsenical species contents in fresh and processed seafood products

A study was carried out to determine organic species of arsenic in the main varieties of seafood consumed in the Basque country (Spain). The concentrations of arsenobetaine (AB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenocholine (AC), and tetramethylarsonium ion (TMA(+)) in 64 samples corresponding to different food items are presented. The study provides information about a possible distribution pattern of organoarsenical species in seafood products. AB was detected in all of the samples [0.3-104.1 microg g(-1) dry weight (dw)]. DMA was detected in all of the samples except squid and salted cod (0.027-1.757 microg g(-1) dw). MMA was detected only in certain fatty fish (0.004-0.028 microg g(-1) dw) and bivalves (0.031-0.047 microg g(-1) dw). AC was only present in some samples of lean fish (0.014-0.089 microg g(-1) dw), and TMA(+) was detected only in anchovy (0.039-0.169 microg g(-1) dw) and crustaceans (0.044-0.966 microg g(-1) dw).     

Organoarsenical species contents in cooked seafood

The organoarsenical species arsenobetaine (AB), arsenocholine (AC), tetramethylarsonium ion (TMA+), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined in 64 cooked seafood products (fish, bivalves, squid, crustaceans) included in a Total Diet Study carried out in the Basque Country (Spain). For cooking, various treatments were employed (grilling, roasting, baking, stewing, boiling, steaming, microwaving). The results obtained show that in cooked seafood AB is the major species, followed by DMA and TMA+. AC and MMA are minor species. The results in cooked seafood were compared with the arsenic species contents obtained for the same product raw. After cooking there was an increase in DMA for sardines and bivalves and an increase or appearance of TMA+ for meagrim, anchovy, Atlantic horse mackerel, and sardine. The data provided add to the very scant information available about organoarsenical species contents in cooked seafood.     

Determination of arsenic and selenium in environmental and agricultural samples by hydride generation atomic absorption spectrometry

Agricultural and environmental samples are digested with acid, and arsenic and selenium are determined using hydride generation atomic absorption spectrometry. Interelement interferences are eliminated by high acid concentrations or cation-exchange resins. Agreement with standard reference material is excellent. The technique is also applied to actual samples.     

Effects of various cooking processes on the concentrations of arsenic, cadmium, mercury, and lead in foods

The effects of cooking processes commonly used by the population of Catalonia (Spain) on total arsenic (As), cadmium (Cd), mercury (Hg), and lead (Pb) concentrations in various foodstuffs were investigated. All food samples were randomly acquired in local markets, big supermarkets, and grocery stores of Reus (Catalonia). Foods included fish (sardine, hake, and tuna), meat (veal steak, loin of pork, breast and thigh of chicken, and steak and rib of lamb), string bean, potato, rice, and olive oil. For each food item, two composite samples were prepared for metal analyses, whose levels in raw and cooked (fried, grilled, roasted, and boiled) samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The highest concentrations of As, Hg, and Pb (raw and cooked samples) were mainly found in fish, with a clear tendency, in general, to increase metal concentrations after cooking. However, in these samples, Cd levels were very close to their detection limit. In turn, the concentrations of metals in raw and cooked meat samples were detected in all samples (As) or only in a very few samples (Cd, Hg, and Pb). A similar finding corresponded to string beans, rice, and olive oil, while in potatoes, Hg could not be detected and Pb only was detected in the raw samples. In summary, the results of the present study show that, in general terms, the cooking process is only of a very limited value as a means of reducing metal concentrations. This hypothetical reduction depends upon cooking conditions (time, temperature, and medium of cooking).     

Organic solvent-free reversed-phase ion-pairing liquid chromatography coupled to atomic fluorescence spectrometry for organoarsenic species determination in several matrices

A novel method has been developed to determine As-containing animal feed additives including roxarsone (ROX), p-arsanilic acid (p-ASA) and nitarsone (NIT), as well as other organic As species (dimethylarsonic acid (DMAA) and monomethylarsonic acid (MMAA)) by ion-pairing high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (IP-HPLC-HG-AFS). A simple isocratic reversed-phase (RP) HPLC method with a mobile phase containing citric acid and sodium hexanesulfonate (pH 2.0) was developed using a C(18) column. The use of an organic solvent free mobile phase turns this methodology into an environmentally friendly alternative. Several ion pair forming agents, such as sodium hexanesulfonate, tetrabutylammonium bisulfate and perfluoroheptanoic acid, were studied. The limits of detection for As species were calculated in standard solution and resulted to be 0.2, 0.5, 0.6, 1.6, and 1.6 μg As L(-1) for MMAA, DMAA, p-ASA, ROX and NIT, respectively. This method exhibited convenient operation, high sensitivity and good repeatability. It was applied to As speciation in different samples including arugula, dog food, dog urine and chicken liver.     

Transformation of organoarsenical species by the microflora of freshwater crayfish

A study of the transformation of arsenic species by the microflora of the freshwater crayfish Procambarus clarkii was carried out. The study of the degradation of AB (arsenobetaine) was performed in aerobic conditions in two culture media (tryptic soy broth and saline medium) at two temperatures (30 and 8 degrees C). The microflora transformed AB into TMAO (trimethylarsine oxide), DMA (dimethylarsinate), MA (methylarsonate), and an unidentified compound (U1). The quickest transformations were carried out by microflora from hepatopancreas incubated in saline medium at 30 degrees C. The individualized study of other arsenic species [AC (arsenocholine), TETRA (tetramethylarsonium ion), TMAO, DMA, and MA] was also performed in saline medium. The only transformation observed was of AC into AB. The bacteria possibly responsible for AB degradation were isolated, identified by phenotypic and genotypic methods, and individually assayed for AB transformation. Only isolates allocated to the species Pseudomonas putida were able to metabolize AB.     

Determination of Arsenic in Water Samples by Using a Green Hydrophobic-Hydrophilic Switchable Liquid-Solid Dispersive Microextraction Method

A simple and green preconcentration method of hydrophobic to hydrophilic switchable liquid-solid dispersive microextraction (HSL-SDM) has been first time introduced as separation method for arsenic ion in real water samples. Multiwall carbon nanotube (MWCNT) was immobilized with diethylenetriamine (DETA) and then used as solid phase adsorbent for the determination of trace level of arsenic ion by HSL-SDM method prior to analysis by hydride generation atomic absorption spectrometry. Reversibly hydrophobic-hydrophilic switchable of functionalized MWCNT can occur due to the exposing of carbon dioxide (CO₂) as anti-solvent trigger. The reversibly hydrophobic-hydrophilic switchable phenomena of immobilized MWCNT in the liquid-solid dispersive microextraction were checked by using FT-IR and SEM. The optimized analytical condition for arsenic ion analysis such as enrichment factor and limits of detection were obtained 83 and 3.05 ng L^?1, respectively. Accuracy of the developed HSL-SDM method was confirmed by the analysis of certified reference materials. Our developed HSL-SDM method was successfully applicable for measurements of arsenic ions in real water samples.     

Determination of inorganic tin in biological samples by hydride generation-atomic absorption spectrometry after silica gel cleanup

A method is described for the determination of inorganic tin in biological samples by hydride generation-atomic absorption spectrometry (HG-AAS). A sample is extracted with ethyl acetate after addition of HCl and NaCl. The concentrated extract is passed through a silica gel column. The column is washed with ethanol, water, and 0.2N HCl successively, and then inorganic tin is eluted with 2N HCl and measured by HG-AAS. Recoveries from fish muscle spiked with 0.1 micrograms/g Sn4+ are 78.9 +/- 4.2% (average +/- standard deviation, n = 5). The detection limit is 0.01 micrograms/g as Sn.     

Soil and water contamination by arsenic from A tannery waste

The pollution of soil by arsenic contained in tannery waste is reported. Over 81 years of operation, a variety of arsenical compounds including sodium arsenite were used as pesticides at the tannery, the arsenic finding its way to the site in question as liquid waste which was disposed of either by burial or spray issigation. X-ray Fluorescence Spectrometry (XRF) was used to determine the levels of arsenic in the soil. Concentrations recorded were comparable to those in soils polluted by agricultural use of arsenical pesticides or by contamination from mining activities. In contrast to arsenic pollution from other sources however, contamination extends to a considerable depth through the soil profile. Analysis of soil water by hydride generation atomic absorption spectrometry showed evidence of arsenic movement through this medium although penetration had not extended to the groundwater. Batch leaching of soil samples with distilled water confirmed the potential mobility of arsenic.     

广州市蔬菜和菜地土壤砷含量及其健康风险研究

测定了广州市郊区菜地土壤(n=120)、菜地蔬菜(n=109)和市售蔬菜(n=237)中砷含量,结合广州居民蔬菜消费情况,分析了砷对广州居民的健康风险影响.结果表明:不同类型菜地土壤砷含量不同,为菜园土(12.94±9.78)mg/kg>水稻土(8.67±10.24)mg/kg>赤红壤(4.17±3.70)mg/kg,土壤质量主要属于二级标准以内;菜地蔬菜砷含量范围为ND～0.179 mg/kg,均值为(0.017±0.024)mg/kg;市售蔬菜砷含量范围为ND-0.314 mg/kg,含量变化为豆类(0.038±0.047)mg/kg)>根茎类(0.027±0.031)mg/kg>茄类(0.025±0.030)mg/kg>叶菜类(0.024±0.022)mg/kg>葱蒜类(0.019±0.025)mg/kg>瓜类(0.017±0.020)mg/kg,所有蔬菜均没有超过我国食品中砷的限量卫生标准(GB-4810-94).广州市居民从蔬菜中摄入的砷为0.045 mg/d,叶菜类和根茎类蔬菜是主要的贡献者.     

Quantitation of toxic arsenic species and arsenobetaine in Pacific oysters using an off-line process with hydride generation-atomic absorption spectroscopy

An off-line process-based speciation technique was devised here to quantitatively determine toxic inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), and the dominant, albeit virtually nontoxic, arsenobetaine (AB) in Pacific oysters (Crassostrea gigas). Oysters were extracted with fresh methanol-water (8+2), and this was replicated three times. They were then evaporated to near dryness and subsequently redissolved in pure water; defatting was then performed with a C18 cartridge. The trace hydride active arsenic species, that is, iAs, MA, and DMA, in the defatted solutions were determined with a sensitive hydride generation-packed coldfinger trap-atomic absorption spectrometric (HG-PCFT-AAS) coupled system. The arsenicals that were desorbed from the cation-exchange resin (Dowex 50W-X8) in the washings of 4 M NH3 were categorized on the basis of AB + DMA. The total quantity of arsenic in the recovered AB + DMA was determined with a commercial hydride generation-atomic absorption spectrometric (HG-AAS) system, and finally, AB was calculated from (AB + DMA) - DMA. The average concentrations of iAs, MA, DMA, AB, and total arsenic (TAs) in the oysters collected from six aquacultural sites along the west coast of Taiwan were, respectively, 0.15, 0.06, 0.64, 6.93, and 13.74 mg kg(-1) of dry weight. AB was the major species, whereas iAs (arsenite + arsenate) were the most toxic species, although the iAs made up only approximately 1% of the TAs in the oysters. The lifetime target cancer risk, as determined by the concentration of iAs on a fresh weight basis in the oysters, was well below the ordinary health protection criteria (10(-6)).     

Determination of water-soluble arsenic compounds in commercial edible seaweed by LC-ICPMS

This paper reports arsenic speciation in edible seaweed (from the Galician coast, northwestern Spain) produced for human consumption. Chondrus crispus , Porphyra purpurea , Ulva rigida , Laminaria ochroleuca , Laminaria saccharina , and Undaria pinnatifida were analyzed. The study focused on arsenosugars, the most frequently occurring arsenic species in algae. As(III) and As(V) were also determined in aqueous extracts. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). For arsenic speciation, a water extraction especially suitable for arsenosugars was used, and the arsenic species were analyzed by liquid chromatography with both anionic and cationic exchange and ICPMS detection (LC-ICPMS). The total arsenic content of the alga samples ranged from 5.8 to 56.8 mg As kg(-1). The mass budgets obtained in the extracts (column recovery × extraction efficiency) ranged from 38 to 92% except for U. pinnatifida (4%). The following compounds were detected in the extracts: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO(3)-sug), phosphate sugar (PO(4)-sug), arsenobetaine (AB), and glycerol sugar (Gly-sug). The highest concentrations corresponded to the arsenosugars.     

Liquid chromatographic-atomic absorption spectrophotometric method for determination of methyl mercury in seafood: collaborative study

A previously developed method that uses a simplified sample preparation procedure and atomic absorption detection of liquid chromatographic eluates for the determination of methyl mercury in seafood has been collaboratively studied. The unique feature of the method involves the use of a specially designed interface for the generation of mercury vapor. Methyl mercury is isolated from the blended sample by chloroform elution from a diatomaceous earth-hydrochloric acid column. The organomercury compound is then extracted into a small volume of 0.01M sodium thiosulfate solution. An aliquot of this solution is injected onto a Zorbax ODS column and eluted with methanol-ammonium acetate solution (3 + 2), pH 5.7, containing 0.01% mercaptoethanol. Mercury is detected by flameless atomic absorption spectrophotometry using the interface. The samples analyzed in the study were unspiked swordfish, unspiked and spiked lobster, and unspiked and spiked tuna. The spiked samples contained methyl mercury both above and below the U.S. Food and Drug Administration guideline level of 1 microgram Hg/g. Reproducibility relative standard deviations ranged from 10.5% at 1 microgram Hg/g to 18.2% at about 0.1 microgram Hg/g. Accuracy, measured by comparison to reference values obtained by the Associate Referee, ranged from 94.4 to 99.6%. The method has been adopted official first action.     

Source of arsenic in licorice confectionery products

Spanish legislation sets a maximum level for total arsenic (As) in confectionery products at 0.1 microg g(-)(1). The U.S. Food and Drug Administration limitations for glycyrrhizic acid in hard and soft candies are 160 and 31 mg g(-)(1), respectively. Arsenic and glycyrrhizic acid were determined in 22 different confectionery products: 9 throat pearls, 4 hard candies, and 9 soft candies. Arsenic and glycyrrhizic acid were quantified by atomic absorption spectrometry with hydride generation and high-performance liquid chromatography, respectively. Levels of glycyrrhizic acid were always below the maximum limits established by the U.S. FDA; however, the As concentration in seven of nine throat pearls (0.55 +/- 0.15 microg g(-)(1)) were above the Spanish maximum limit. A clear empirical relationship between the arsenic and glycyrrhizic acid concentrations was observed (R (2) = 0.9357), implying that to avoid high levels of potentially toxic arsenic in licorice confections high-quality licorice extract should be used.     

Effects of cooking on the cell walls (dietary fiber) of 'Scarlet Warren' winter squash ( Cucurbita maxima ) studied by polysaccharide linkage analysis and solid-state (13)C NMR

Cell wall polysaccharides of 'Scarlet Warren' winter squash ( Cucurbita maxima ) were investigated before and after thermal processing. Linkage analysis of polysaccharides was done by gas chromatography coupled to mass spectrometry (GC-MS). The linkage analysis showed the cell wall polysaccharide compositions of raw and cooked squash were similar. The total pectic polysaccharides (galacturonan, rhamnogalacturonan, arabinan, and arabinogalactan) contents of the cell walls of both raw and cooked squash were 39 mol %. The amounts of pectic polysaccharides and xyloglucan in the cell walls of squash showed little alteration on heating. The cellulose content of the raw and cooked cell walls was relatively high at 47 mol %, whereas the xyloglucan content was low at 4 mol %. Solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy techniques were used to examine the molecular motion of the polysaccharides in the cell walls. The mobility of highly flexible galactan depends on the water content of the sample, but no difference was seen between raw and cooked samples. Likewise, the mobility of semimobile pectic polysaccharides was apparently unaltered by cooking. No change was detected in the rigid cellulose microfibrils on cooking.     

Effects of raw materials,ingredients, and production lines on arsenic and copper concentrations in confectionery products

The Spaniard legislation sets up maximum levels for total arsenic (As) and copper (Cu) in confectionery products at 0.1 and 5.0 microg g(-)(1), respectively. Concentrations of these two trace elements were determined in four confectionery products: chewing gum, two licorice items, and soft candy. The effects of raw materials quality and production lines were studied. Arsenic and copper were quantified by atomic absorption spectrometry with hydride generation and slotted-tube atom trap tubes, respectively. Their levels were, in general, below the maximum limits establish by the Spaniard legislation; however, the As concentration in the licorice sticks was above this maximum limit (0.11 +/- 0.01 microg g(-)(1)). Statistics proved that quality of raw materials and the production lines both significantly affected As and Cu concentrations in the final products. The licorice extract and molasses were found as the common source for As and Cu pollution. The As concentration in the licorice extract was 0.503 +/- 0.01 microg g(-)(1), and could represent a serious hazard to human health if it is used in high proportions.     

Speciation analysis of mercury in cereals by liquid chromatography chemical vapor generation inductively coupled plasma-mass spectrometry

A simple and rapid procedure for the separation and determination of inorganic, methyl, and ethyl mercury compounds was described using liquid chromatography (LC) followed by vapor generation inductively coupled plasma-mass spectrometry (VG-ICP-MS). Well resolved chromatograms were obtained within 5 min by reversed-phase liquid chromatography with a C8 column as the stationary phase and a pH 4.7 solution containing 0.5% v/v 2-mercaptoethanol and 5% v/v methanol as the mobile phase. The separated mercury compounds were converted to mercury vapors by an in situ nebulizer/vapor generation system for their introduction into ICP. The concentrations of NaBH4 and HNO3 required for vapor generation were also optimized. The method was applied for the speciation of mercury in reference materials NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and also rice flour and wheat flour samples purchased locally. The accuracy of the procedure was verified by analyzing the certified reference material NRCC DOLT-3 Dogfish Liver for methyl mercury. Precision between sample replicates was better than 13% for all the determinations. The detection limits of the mercury compounds studied were in the range 0.003-0.006 ng Hg mL(-1) in the injected solutions, which correspond to 0.02-0.06 ng g(-1) in original flour samples. A microwave-assisted extraction procedure was adopted for the extraction of mercury compounds from rice flour, wheat flour, and fish samples using a mobile phase solution.