Transformation of arsenic(V) by the fungus Fusarium oxysporum melonis isolated from the alga Fucus gardneri

A fungus isolated from the macroalga Fucus gardneri was identified by using 28S rDNA sequence analysis, 99% similarity match, as Fusarium oxysporum meloni. The fungus was exposed to arsenic(V) (500 ppb) in artificial seawater to investigate the possibility that the fungus is the source of the metabolic activity that results in the presence of arsenosugars in the macroalga. High‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry was used to identify the arsenic species in the fungus, and in the growth medium. The fungus was able to accumulate arsenic(V) and an increase in arsenite and dimethylarsinate was also observed. Some reduction of arsenate led to a small increase of arsenite in the growth medium. The fungus does not seem to be involved with the accumulation of arsenosugars by the Fucus. Copyright © 2002 John Wiley & Sons, Ltd.     

Seasonal changes in arsenic speciation in Fucus species

Arsenic speciation in a brown alga, Fucus gardneri, collected in Vancouver, B.C., Canada, was carried out by using high-performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC–ICP–MS). Hydride generation–atomic absorption spectrometry (HG–AAS) was used for total arsenic determination. The relative amounts of some arsenosugars 1 in growing tips are found to be different in comparison with the remainder of the plant. Fucus samples collected in summer contain 9 ppm of total arsenic. Most of the arsenic species are extractable. Fucus samples collected in winter contain relatively higher amounts of arsenic, 16–22 ppm, but only low amounts of this are extractable. © 1998 John Wiley & Sons, Ltd.     

Ion chromatography–inductively coupled plasma mass spectrometry determination of arsenic species in marine samples

Arsenic speciation analysis in marine samples was performed using ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP‐MS) detection. The separation of eight arsenic species, viz. arsenite, monomethyl arsonic acid, dimethylarsinic acid, arsenate, arsenobetaine, tetramethylarsine oxide, arsenocholine and tetramethylarsonium ion was achieved on a Dionex AS4A (weaker anion exchange column) by using a nitric acid pH gradient eluent (pH 3.3 to 1.3). The entire separation was accomplished in 12 min. The detection limits for the eight arsenic species by IC–ICP‐MS were in the range 0.03–1.6 µ g l^?1, based on 3σ of the blank response (n = 6). The repeatability and day‐to‐day reproducibility were calculated to be less than 10% (residual standard deviation) for all eight species. The method was validated by analyzing a certified reference material (DORM‐2, dogfish muscle) and then successfully applied to several marine samples, e.g. oyster, fish muscle, shrimp and marine algae. The low power microwave digestion was employed for the extraction of arsenic from seafood products. Copyright © 2004 John Wiley & Sons, Ltd.     

Arsenic Compounds in Zoo- and Phyto-plankton of Marine Origin

Major water-soluble arsenic compounds accumulated in some zoo- and phyto-plankton were identified. Zooplankton were collected at sampling stations in the Sea of Japan by a Norpac net towed from 600 m depth to the surface. Phytoplankton were cultivated under axenic conditions. Water-soluble arsenic compounds were extracted repeatedly from plankton tissues by aqueous methanol. The arsenic compounds in the extracts were analyzed by HPLC–ICP/MS. Among zooplankton analyzed in the present study, two carnivorous species, i.e. Amphipoda ( Themisto sp.) and Sagittoidea ( Sagitta sp.), contained arsenobetaine as the dominant arsenic species. Arsenobetaine was the major species in Euphausiacea ( Euphausia sp.), also. The most abundant arsenic compound in the herbivorous Copepoda species ( Calanus sp.), on the other hand, was an arsenic-containing ribofuranoside with a sulfate ester group, and arsenobetaine was only a minor component. Phytoplankton contained arsenic-containing ribofuranosides apparently in a species-speific manner. The arsenic compounds in zooplankton seem to reflect their feeding habit; i.e. carnivorous species eating zooplankton or other small animals accumulate arsenobetaine, while herbivorous ones eating phytoplankton accumulate arsenic-containing ribofuranosides as major arsenic compounds.     

Organoarsenic compounds in plants and soil on top of an ore vein

Plants and soil collected above an ore vein in Gasen (Austria) were investigated for total arsenic concentrations by inductively coupled plasma mass spectrometry (ICP‐MS). Total arsenic concentrations in all samples were higher than those usually found at non‐contaminated sites. The arsenic concentration in the soil ranged from ∼700 to ∼4000 mg kg⁻¹ dry mass. Arsenic concentrations in plant samples ranged from ∼0.5 to 6 mg kg⁻¹ dry mass and varied with plant species and plant part. Examination of plant and soil extracts by high‐performance liquid chromatography–ICP‐MS revealed that only small amounts of arsenic (<1%) could be extracted from the soil and the main part of the extractable arsenic from soil was inorganic arsenic, dominated by arsenate. Trimethylarsine oxide and arsenobetaine were also detected as minor compounds in soil. The extracts of the plants (Trifolium pratense, Dactylis glomerata, and Plantago lanceolata) contained arsenate, arsenite, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, the tetramethylarsonium ion, arsenobetaine, and arsenocholine (2.5–12% extraction efficiency). The arsenic compounds and their concentrations differed with plant species. The extracts of D. glomerata and P. lanceolata contained mainly inorganic arsenic compounds typical of most other plants. T. pratense, on the other hand, contained mainly organic arsenicals and the major compound was methylarsonic acid. Copyright © 2002 John Wiley & Sons, Ltd.     

Determination of arsenic species by inductively coupled plasma mass spectrometry with ion chromatography

Five arsenic species, trimethylarsine oxide, dimethylarsenic acid, monomethylarsonic acid, arsenobetaine and sodium arsenite, in urine were analysed by inductively coupled plasma mass spectrometry with ion chromatography (IC ICP MS). Since the toxicities of different arsenic compounds are different, speciation of arsenic compounds is very important in the investigation of metabolisms. In this paper, we applied ion chromatography (IC) as a separation device and inductively coupled plasma mass spectrometry (ICP MS) as a detection device. For separation of the five arsenic compounds, an anion-exchange column and, as mobile phase, tartaric acid were used. The eluent from the IC column was introduced directly into the nebulizer of the ICP MS and analysed at 75 amu. Detection limits were from 4 to 9 pg as arsenic.     

Speciation of Arsenic Compounds in the Urine of Rats Orally Exposed to Dimethylarsinic Acid Ion Chromatography with ICP–MS as an Element-Selective Detector

A combined ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP—MS) system as an element-selective detector has been used for the determination of arsenic compounds. Seven arsenic compounds were separated by cation-exchange chromatography. Subsequently, the separated arsenic compounds were directly introduced into the ICP—MS and were detected at m/z =75. Detection limits for the seven arsenic compounds ranged from 0.8 to 3.8 μg As/l. The IC–ICP–MS system was applied to the determination of arsenic compounds in the urine of dimethylarsinic acid (DMAA)-exposed rats. DMAA was the most abundant arsenic compound detected. Arsenous acid, monomethylarsonic acid and trimethylarsine oxide were also detected.     

The analysis of volatile trace compounds in landfill gases,compost heaps and forest air

Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd.     

Analysis of diphenylarsinic acid in human and environmental samples by HPLC–ICP‐MS

A simple, rapid and robust analytical method for determining diphenylarsinic acid in human and environmental samples was developed based on a combination of hydrophilic polymer‐based gel‐permeation high‐performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP‐MS). Hair and nail samples were digested with alkali, and liberated diphenylarsinic acid (derivative) was extracted with diethyl ether, redissolved in water and injected for HPLC–ICP‐MS analysis. Human urine, groundwater and water extracts from soils were injected for HPLC–ICP‐MS directly after filtration. Using the method, diphenylarsinic acid in a solution was quantified in 7 min duration for an analysis with a detection limit of sub‐nanograms per milliliter. The method has been applied to groundwater arsenic pollution recently uncovered in Japan. Copyright © 2005 John Wiley & Sons, Ltd.     

Determination of organoarsenic species in blood plasma by HPLC–ICP MS

A study of arsenic speciation in blood plasma of patients undergoing renal dialysis has been performed using HPLC coupled with ICP MS. It was found that the only detectable arsenic species present in the plasma was arsenobetaine. The limit of detection using an injection volume of 175 µl was found to be 0.25 ng of arsenic as arsenobetaine. Spiking experiments demonstrated recoveries of approximately 100%. In the absence of certified reference materials or an alternative technique, we believe this was the best way to demonstrate that the method was reliable and accurate. Arsenobetaine concentrations in pre‐dialysis plasma were similar to those for the healthy volunteers, although after dialysis the concentrations were significantly reduced. It is thus concluded that, except for a few patients, dialysis removed the arsenobetaine efficiently (hence preventing an accumulation of arsenic) and that no biotransformations were occurring. The exceptions to this conclusion were in a few patients whose arsenobetaine levels increased marginally after dialysis, but this was attributed to the levels both pre‐ and post‐dialysis being very close to the detection limit. Copyright © 1999 John Wiley & Sons, Ltd.     

Chemical characterisation of bioactive compounds in Medicago sativa growing in the desert of Oman

Medicago sativa Linn growing in Omani desert were chemically characterised using flame photometry, inductively coupled plasma, gas chromatography–mass spectrometry and high performance liquid chromatographic (HPLC) analysis. HPLC analyses were performed to determine the phenolics and flavonoids present in M. sativa. The major compounds detected in M. sativa leaves were protchaechenic acid (3.22%), hydroxyl benzoic acid (1.05%), β-Phenyl caffate (0.97%) and kaempherol (0.89%). Pterostilbene, a cholesterol-lowering compound, was detected in M. sativa.     

HPLC–QTOF–MS/MS-based rapid screening of phenolics and triterpenic acids in leaf extracts of Ocimum species and their interspecies variation

Species of genus Ocimum are traditionally used for their medicinal and flavoring properties. These are rich sources of essential oils and found as an ingredient in many Ayurvedic preparations and food products. Phenolics and triterpenic acids are the medicinally active compounds mainly concentrated in the leaves of Ocimum species. This study aimed to develop an efficient and reliable analytical method for the rapid screening and characterization of phenolics and triterpenic acids in the leaf extracts of 6 Ocimum species using high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (HPLC–ESI–QTOF–MS/MS). A total of 50 compounds were identified and characterized on the basis of their accurate MS and MS/MS information, out of which 23 compounds were confirmed by authentic standards. Identified compounds include 28 flavonoids, 4 propenyl phenol derivatives, 2 triterpenic acids, 11 phenolic acids, and 5 phenolic acid esters. The developed method was applied to study the interspecies variation of identified compounds. Significant variation in the distribution of identified phenolics and triterpenic acids was observed among studied Ocimum species. Hence, the established method provides an effective and reliable tool for screening and characterization of phytoconstituents in Ocimum species.     

Quality assessment of Cortex Phellodendri by high‐performance liquid chromatography coupled with electrospray ionization mass spectrometry

A simple method based on liquid chromatography coupled with diode array detection and electrospray ionization mass spectrometry (LC‐DAD‐ESI‐MS) was developed for the quality assessment of Cortex Phellodendri (CP), which was mainly derived from two species of Phellodendron chinense Schneid and Phellodendron amurense Rupr. Total 41 compounds, including 14 phenols, 24 alkaloids and three liminoidal triterpenes were identified or tentatively characterized from the 75% methanol extract of CP samples by online ESI‐MSⁿ fragmentation and UV spectra analysis. Among them, two phenols and six alkaloids were simultaneously quantified using HPLC‐DAD method. The validated HPLC‐DAD method showed a good linearity, precision, repeatability and accuracy for the quantification of eight marker compounds. Furthermore, the plausible fragmentation pathway of the representative compounds were proposed in the present study. The differences of the chemical constituents content and the comprehensive HPLC profiles between the two CP species using LC‐DAD‐ESI‐MS method are reported for the first time, indicating that the CP drugs from different resources should be used separately in the clinic. Copyright © 2009 John Wiley & Sons, Ltd.     

Speciation of essential and toxic elements in edible mushrooms: size‐exclusion chromatography separation with on‐line UV–inductively coupled plasma mass spectrometry detection

Size‐exclusion liquid chromatography was coupled to UV and inductively coupled plasma mass spectrometry (ICP‐MS) for detection to perform elemental speciation studies on different edible mushrooms. Molecular weight (MW) distribution patterns of several elements among different fractions present in various edible mushrooms are presented. The association of the elements with the high and low MW fractions was observed using sequential detection by UV and ICP‐MS. Separation was performed using a Superdex 75 column. Variability of the fractionation patterns with three different extraction media (0.05 mol l^?1 NaOH; 0.05 mol l^?1 HCl; hot water at 60°C) was evaluated for mushroom species. A comparative elemental speciation study was performed in order to determine the differences in the fractionation patterns of silver, arsenic, cadmium, mercury, lead, and tin in Boletus edulis, Agaricus bisporus, and Lentinus edodes. Differences in the fractionation patterns of the elements were found to depend on the mushroom species and the extraction medium. Most of the elements were associated with high mw fractions. It was not possible to assess the trace metal contributions from the mushroom growth media. Copyright © 2004 John Wiley & Sons, Ltd.     

高效液相色谱-电感耦合等离子体质谱联用同时测定鸡肉与鸡肝中的7种砷形态

建立了一种同时测定阿散酸、亚砷酸根、砷酸根、砷胆碱、砷甜菜碱、一甲基砷和二甲基砷等7种砷形态的高效液相色谱-电感耦合等离子体质谱分析方法。样品采用人工胃液作为提取液进行超声处理,再以碳酸铵溶液和水作为流动相,采用阴离子分析柱将样品提取液进行分离,最后进入电感耦合等离子体质谱测定。各砷形态在1～50 μg/kg范围内线性关系良好,相关系数r2均在0.999以上;在1、2、10 μg/kg 3个添加水平进行了方法学验证,平均回收率为84.3%～106.6%,相对标准偏差为1.4%～4.2%; 7种砷形态的定量限均为1 μg/kg。方法重现性好、灵敏度高、前处理简单,适用于鸡肉和鸡肝中主要有机砷和无机砷残留的分析检测。     

Distribution and fate of biologically formed organoarsenicals in coastal marine sediment

Marine organisms, including phyto‐ and zoo‐plankton, macroalgae, and animals, concentrate arsenic in various organic forms. However, the distribution and fate of these organoarsenicals in marine environments remains unclear. In this study, the distribution of organoarsenicals in coastal marine sediment in Otsuchi Bay, Japan, has been determined. Methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, arsenobetaine, arsenocholine and other unidentified arsenic species were detected in marine sediment by high‐performance liquid chromatography–inductively coupled plasma mass spectrometry analysis of methanol–water extracts. Arsenobetaine was the dominant organoarsenical at four of the seven stations where tests were carried out, and unidentified species or dimethylarsinic acid dominated at the other stations. Total organoarsenicals (as arsenic) in the surface sediment amounted to 10.6–47.5 µg kg^?1 dry sediment. Core analysis revealed that concentrations of organoarsenicals decreased with depth, and they are considered to be degraded within 60 years of deposition. These results show that organoarsenicals formed by marine organisms are delivered to the sediment and can be degraded within several decades. Copyright © 2005 John Wiley & Sons, Ltd.     

Investigation of mercury metallothionein complexes in tissues of rat after oral intake of HgCl2

Mercury, a highly toxic metal found widely throughout the environment, is a potent inducer of metallothionein (MT) expression. The role of MTs in the detoxification of mercury after its oral intake in mammals is studied. After feeding rats with mercuric chloride by gastric gavage, the distribution of heavy metals in rat tissues was investigated by inductively coupled plasma mass spectrometry (ICP‐MS). Extensive accumulation of mercury, copper and zinc in kidney and liver is observed. A homemade preparative size‐exclusion chromatography (SEC) column (30 cm × 1.9 cm) packed with Sephadex G‐75 (40–120 µm particle size) gel (Pharmacia) was used for the purification of MT fractions in rat tissues. Preliminary results from SEC indicate that the mercury‐binding MT levels in liver were much lower than in kidney. The MT fractions were collected, desalted, and then separated by reversed‐phase high‐performance liquid chromatography (HPLC) with UV–Vis spectrometry, ICP‐MS and electrospray ionization MS detection. One major and several minor peaks were observed in the HPLC chromatograms of the MT fraction for the kidney sample. UV absorption spectra indicate that MTs were found to bind with mercury. There were no significant mercury‐binding MTs detected in the liver sample using UV detection. ICP‐MS detection showed that mercury‐binding MTs in kidney contained large amounts of mercury and copper but little zinc. Further characterization with ESI‐MS showed that the major peak found in kidney contained Hg₆Cu, Hg₅Cu₂‐MT‐2c and Hg₆‐MT‐2β, Hg₆Cu‐MT‐1γ, Hg₇‐MT‐2α. However, distinction between copper and zinc could not be made based on current mass spectrometric analysis because of instrumental resolution limitations. Copyright © 2005 John Wiley & Sons, Ltd.     

Arsenic speciation in some environmental samples: a comparative study of HG–GC–QFAAS and HPLC–ICP–MS methods

Some water and soil extracts polluted with arsenic, and a sewage sludge certified for total arsenic have been analysed by high‐performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC–ICP–MS) and hydride generation–gas chromatography– quartz furnace atomic absorption spectrometry (HG–GC–QFAAS techniques.) Detection limits in the range of 200–400 and 2–10 ng l⁻¹ respectively allowed the determination of inorganic [As(III), As(V)] and methylated (DMA, MMA, TMAO) arsenic species present in these samples. Results obtained by both methods are well correlated overall, whatever the arsenic chemical form and concentration range (8–10 000 μg l⁻¹). Comparison of these results enabled us to point out features and disadvantages of each analytical method and to reach a conclusion that they are suitable for arsenic speciation in these environmental matrices. Copyright © 2000 John Wiley & Sons, Ltd.     

Comparing a selenium accumulator plant (Brassica juncea) to a nonaccumulator plant (Helianthus annuus) to investigate selenium-containing proteins

Selenoproteins have been identified in a diverse range of organisms, including bacteria and animals. Their occurrence and role in the plant kingdom are, however, less well-understood. This work investigated the water-soluble selenium-containing proteins extracted from a selenium-accumulating plant species (Brassica juncea) and a nonaccumulator species (Helianthus annuus) exposed to varying forms and concentrations of selenium. Firstly, protein extracts were analyzed by size exclusion chromatography coupled to inductively coupled plasma mass spectrometry; specific detection was achieved by monitoring characteristic isotopes. Then, proteolytic digests of the plant extracts were analyzed by reversed phase chromatography coupled to ICP–MS in order to investigate selenoamino acid and selenopeptide content. Selenomethionine was observed to be the primary constituent of the proteins of the nonaccumulator plant, while selenocystine and selenomethionine were found in the same proportion in the accumulator extract. One main selenium-containing species was present at higher levels in the root digests than in the leaf digests; levels were greater in the nonaccumulator than in the accumulator plant.     

Methylation and Demethylation of Dimethylarsinic Acid in Rats Following Chronic Oral Exposure

Metabolites of dimethylarsinic acid (DMA) were studied in rats chronically exposed to DMA in drinking water. The urine was collected by forced urination at the end of 8, 20 and 30 weeks and the feces at the end of 30 weeks. The samples were analyzed for arsenic species by a combined system of ion chromatography and inductively coupled plasma mass spectrometry (IC–ICP–MS). Increases in arsenite, DMA, trimethylarsine oxide and a still-to-be-identified arsenic compound (which was eluted immediately after monomethylarsonic acid on the chromatogram) were detected in both urine and feces. At the 100 mg l⁻¹ dose, DMA was the main component in the urine; arsenite was a main component in the feces. The results indicate that, besides undergoing methylation, DMA can be demethylated to inorganic arsenic, and demethylation of DMA may be associated with intestinal bacteria