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1.
Large quantities of arsenic are introduced into the environment through land application of poultry litter containing the organoarsenical feed additive roxarsone (3-nitro-4-hydroxyphenylarsonic acid). The objective of this study was to evaluate the bioconversion of roxarsone and related N-substituted phenylarsonic acid derivatives under anaerobic conditions. The results demonstrate that roxarsone is rapidly transformed in the absence of oxygen to the corresponding aromatic amine, 4-hydroxy-3-aminophenylarsonic acid (HAPA). The formation of HAPA is attributable to the facile reduction of the nitro group. Electron-donating substrates, such as hydrogen gas, glucose, and lactate, stimulated the rate of nitro group reduction, indicating a microbial role. During long-term incubations, HAPA and the closely related 4-aminophenylarsonic acid (4-APA) were slowly biologically eliminated by up to 99% under methanogenic and sulfate-reducing conditions, whereas little or no removal occurred in heat-killed inoculum controls. Arsenite and, to a lesser extent, arsenate were observed as products of the degradation. Freely soluble forms of the inorganic arsenical species accounted for 19-28% of the amino-substituted phenylarsonic acids removed. This constitutes the first report of a biologically catalyzed rupture of the phenylarsonic group under anaerobic conditions.  相似文献   

2.
Roxarsone is an organoarsenic feed additive that can be metabolised to other higher toxic arsenic (As) species in animal manure such as arsenate, arsenite, monomethylarsonic acid, dimethylarsinic acid, 3-amino-4-hydroxyphenylarsonic acid and other unknown As species. The accumulation, transport and distribution of As species in turnip (Brassica rapa L.) and lettuce (Lactuca sativa L.) amended with roxarsone and its metabolites in chicken manure were investigated. Results showed arsenite was the predominant As form, followed by arsenate in turnip and lettuce plants, and a low content of dimethylarsinic acid was detected only in lettuce roots. Compared with the control plants treated with chicken manure without roxarsone and its metabolites, the treatments containing roxarsone and its metabolites increased arsenite content by 2.0–3.2% in turnip shoots, by 6.6–6.7% in lettuce shoots, by 11–44% in turnip tubers and by 18–20% in lettuce roots at two growth stages. The enhanced proportion of arsenate content in turnip shoots, turnip tubers and lettuce roots was 4.3–14%, 20–35% and 70%, respectively, while dimethylarsinic acid content in lettuce roots increased 2.4 times. Results showed that the occurrence of dimethylarsinic acid in lettuce roots might be converted from the inorganic As species and the uptake of both inorganic and organic As compounds in turnip and lettuce plants would be enhanced by roxarsone and its metabolites in chicken manure. The pathway of roxarsone metabolites introduced into the human body via roxarsone → animal → manure → soil → crop was indicated.  相似文献   

3.
Roxarsone, 3-nitro-4-hydroxyphenylarsonic acid, is an organoarsenic compound that is used extensively in the feed of broiler poultry to control coccidial intestinal parasites, improve feed efficiency, and promote rapid growth. Nearly all the roxarsone in the feed is excreted unchanged in the manure. Poultry litter composed of the manure and bedding material has a high nutrient content and is used routinely as a fertilizer on cropland and pasture. Investigations were conducted to determine the fate of poultry-litter roxarsone in the environment Experiments indicated that roxarsone was stable in fresh dried litter; the primary arsenic species extracted with water from dried litter was roxarsone. However, when water was added to litter at about 50 wt % and the mixture was allowed to compost at 40 degrees C, the speciation of arsenic shifted from roxarsone to primarily arsenate in about 30 days. Increasing the amount of water increased the rate of degradation. Experiments also suggested that the degradation process most likely was biotic in nature. The rate of degradation was directly proportional to the incubation temperature; heat sterilization eliminated the degradation. Biotic degradation also was supported by results from enterobacteriaceae growth media that were inoculated with litter slurry to enhance the biotic processes and to reduce the concomitant abiotic effects from the complex litter solution. Samples collected from a variety of litter windrows in Arkansas, Oklahoma, and Maryland also showed that roxarsone originally present had been converted to arsenate.  相似文献   

4.
The main objective was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. F15 above the Spanish maximum recommended concentration for food crops, 1 mg kg-1 on a fresh weight basis. Only organic arsenicals, methylarsonic and dimethylarsinic acids were used because they were: (1) the only arsenic species allowed for agricultural applications and (2) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic-upward translocation is higher in sensitive than in tolerant plants. A 2 ×3 factorial experiment was conducted with two organic arsenic species (methylarsonic acid, dimethylarsinic acid) and three arsenic concentrations (0.2, 0.5, 1.0 mg l-1). Experimental results showed that the low bean plant tolerance to arsenic was possibly due to the high arsenic-upward transport to shoots, which could result in profound negative metabolic consequences. Even under extreme adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It is concluded that the major drawback of organic arsenical herbicides is that of decreased productivity rather than high arsenic intake by consumers of edible products from sensitive plant species.  相似文献   

5.
Concerning the residual organoarsenical feed additives, an effective method has been developed for the separation and determination of organoarsenic species including p-arsanilic acid (ASA), nitarsone (NIT) and roxarsone (ROX) in the food of animal tissue origin by high-performance liquid chromatography coupled to ultraviolet oxidation hydride generation atomic fluorescence spectrometry using a C18 column with 50 mM KH2PO4, 0.1 %?v/v trifluoroacetic acid at pH 2.43 as the mobile phase. Accelerated solvent extraction (ASE) as an effective sample preparation method was used to deal with animal meat to extract organoarsenic species. The ASE conditions, including extraction solvent, temperature, static extraction time, flush volume and cycle time, were investigated in terms of extraction yield and species stability. In this paper, aimed to separate these species efficiently, the conditions of the mobile phase and HG system were also investigated. The methodology developed allows us limits of detection and quantification of 0.24, 0.74, 0.41 and 0.72, 2.24, 1.24 ng?mL?1 for ASA, NIT and ROX, respectively. This method was used to separate and determine three organoarsenic species in porcine and chicken liver samples that were purchased at a supermarket in China. At the optimized conditions, the ranges of concentrations of the three arsenic species were found to be varied from 3 to 9 ng?mL?1. The results of recovery rates and RSDs, which were higher than 94 % and lower than 5 %, respectively, approved it to be a convenient, fast and efficient method for the determination of organoarsenic species in animal tissue.  相似文献   

6.
Nine low-rank coal samples from three different coal basins (Velenje and Trbovlje basins, Slovenia, and Sokolov basin, Czech Republic) were analyzed for their elemental composition and the presence of arsenic compounds. Total arsenic concentrations in the samples were 1.59-5.77 microg g(-1) with one exception, 142 microg g(-1) for a sample from the Sokolov basin. A methanol/water mixture (1:1) extracted 15.1 - 38.7% of the total arsenic from Velenje basin samples but only 2.2-7.1% from Sokolov and Trbovlje basin samples. Extracts from the Velenje basin samples contained mainly the tetramethylarsonium ion (0.14 - 0.92 microg g(-1)) with considerable amounts of arsenate (0.15 - 0.85 microg g(-1)) and monomethyl arsonic acid 0.04 - 0.27 microg g(-1)). In methanol/water extracts from samples from the Sokolov and Trbovlje basins inorganic arsenic (arsenate) prevailed (0.26 - 37.1 microg g(-1)), but at least trace amounts of organic arsenic compounds were found as well. It is likely that biogeochemical degradation of organic material is related to the unexpected organoarsenic compounds found in low-rank coals. However, it should also not be ruled out that abiogenic synthesis could have taken place in the carbon-rich environment under the harsh conditions present (elevated temperature and pressure).  相似文献   

7.
Arsenic speciation and reactivity in poultry litter   总被引:1,自引:0,他引:1  
Recent U.S. government action to lower the maximum concentration levels (MCL) of total arsenic (As) (10 ppb) in drinking water has raised serious concerns about the agricultural use of As-containing biosolids such as poultry litter (PL). In this study, solid-state chemical speciation, desorbability, and total levels of As in PL and long-term amended soils were investigated using novel synchrotron-based probing techniques (microfocused (micro) synchrotron X-ray fluorescence (SXRF) and micro-X-ray absorption near-edge structure (XANES) spectroscopies) coupled with chemical digestion and batch experiments. The total As levels in the PL were as high as approximately 50 mg kg(-1), and As(II/III and V) was always concentrated in abundant needle-shaped microscopic particles (approximately 20 microm x 850 microm) associated with Ca, Cu, and Fe and to a lesser extent with S, Cl, and Zn. Post-edge XANES features of litter particles are dissimilar to those of the organo-As(V) compound in poultry feed (i.e., roxarsone), suggesting possible degradation/transformation of roxarsone in the litter and/or in poultry digestive tracts. The extent of As desorption from the litter increased with increasing time and pH from 4.5 to 7, but at most 15% of the total As was released after 5 d at pH 7, indicating the presence of insoluble phases and/or strongly retained soluble compounds. No significant As accumulation (< 15 mg kg(-1)) was found in long-term PL-amended agricultural surface soils. This suggests that As in the PL may have undergone surface and subsurface transport processes. Our research results raise concerns about long-term PL amendment effects on As contamination in surrounding soil-water environments.  相似文献   

8.
食用菌中的总砷和砷形态分布研究   总被引:1,自引:0,他引:1  
研究总砷超标食用菌样品中砷的形态分布,对食用菌中总砷含量与食用安全性的关系及其限量规定进行探讨。方法从2010年深圳口岸进出口食用菌批量监测结果的各种食用菌样品中选择总砷超标的几类样品,采用液相色谱-氢化物发生原子荧光光谱联用技术(LC-HGAFS)分析了不同种类食用菌中的砷形态,准确测定了总无机砷与总砷含量。结果发现形态分析方法能够准确定性定量食用菌中的总无机砷含量,而食用菌中总砷含量和总无机砷含量并不存在对应关系,干香菇中总砷和总无机砷含量均较高,有一定食用风险,而蘑菇中总砷含量高,总无机砷含量却很低,主要以一甲基砷等其他无毒的砷形态存在,可以放心食用。结论食用菌中砷形态分布测定更能科学体现砷超标和食用安全性的关系,我国现行食用菌卫生标准仅规定总砷限量指标,建议进行修订。  相似文献   

9.
Presence and distribution of arsenical species in beers   总被引:1,自引:0,他引:1  
The total content of arsenic and of its inorganic (As(III) and As(V)) and organic (monomethylarsonic acid, MMAA, and dimethylarsinic acid, DMAA) species were determined in a set of 21 alcoholic and alcohol-free beer samples using the technique of Hydride Generation Atomic Absorption Spectrometry. For total arsenic analysis, beer samples were dried and then microwave digested with nitric acid in polytetrafluoroethylene containers. For the speciation analysis, beers were previously subjected to ion exchange chromatography to elute the mentioned inorganic and organic arsenical species. Both microwave digestion and chromatographic separation methods were validated from certified reference materials and prepared standard solutions, respectively. The results obtained are presented in terms of the distribution and occurrence of arsenical species in the samples. The As levels of the beer samples were in the range of 1.5-12.4mug/l. The influence of the production process for the alcoholfree beers in the speciation of arsenic is discussed. In alcoholic beers MMAA was the most abundant species, and for non-alcoholic beers inorganic As(III) was similar to the organic species. An estimated intake of total As of 0.47mug/person/day and 11.4mug/person/day was obtained for average consumers and for heavy drinkers, respectively.  相似文献   

10.
Rice is a target food for arsenic speciation based analyses because of its relatively high arsenic concentration and per capita consumption rates. Improved speciation data for rice can be helpful in estimating inorganic arsenic exposures in the U.S. and in endemic populations. The inorganic arsenic exposure for cooked rice should include both the arsenic in raw rice plus the arsenic absorbed from the water used to prepare it. The amount of arsenic absorbed from water by rice during preparation was assessed using five different types of rice cooked in both contaminated drinking water and arsenic-free reagent water. The rice samples were extracted using trifluoroacetic acid (TFA) and speciated using IC-ICP-MS. The TFA procedure was able to extract 84-104% of the arsenic (As) from the five different cooked rice samples. Chromatographic recoveries ranged from 99% to 116%. The dimethylarsinic acid (DMA) and inorganic arsenic concentration ranged from 22 to 270 ng of As/g of rice and from 31 to 108 ng of As/g of rice, respectively, for samples cooked in reagent water. The overall recoveries, which relate the sum of the chromatographic species back to the total digested concentration, ranged from 89% to 117%. The absorption of arsenic by rice from the total volume of water [1:1 to 4:1 (water:rice)] used in cooking was between 89% and 105% for two different contaminated drinking water samples. A comparison of the TFA extraction to an enzymatic extraction was made using the five rice samples and NIST 1568a rice flour. The two extraction procedures produced good agreement for inorganic arsenic, DMA, and the overall recovery. Through the use of IC-ESI-MS/ MS with a parent ion of m/z 153 and fragment ions of m/z 138, 123, and 105, the structure dimethylthioarsinic acid was tentatively identified in two of the rice samples using the enzymatic extraction.  相似文献   

11.
Forty-five wine samples from the south of Spain of different alcoholic strength were analysed for total arsenic and its inorganic [As(III), As(V)] and organic (monomethylarsonic acid [MMAA], dimethylarsinic acid [DMAA]) species. The As levels of the wine samples ranged from 2.1 to 14.6 µg l-1. The possible effect of the alcoholic fermentation process on the levels of the total arsenic and arsenical species was studied. The average total arsenic levels for the different samples were very similar, without significant differences between all types of wines. In table wines and sherry, the percentages of total inorganic arsenic were 18.6 and 15.6%, with DMAA or MMAA being the predominant species, respectively. In most samples, DMAA was the most abundant species, but the total inorganic aresenic fraction was considerable, representing 25.4% of the total concentration of the element. The estimated daily intakes of total arsenic and total inorganic arsenic for average Spanish consumers were 0.78 and 0.15 µg/person day-1, respectively. The results suggest that the consumption of these types of wines makes no significant contribution to the total and inorganic arsenic intake for normal drinkers. However, wine consumption contributes a higher arsenic intake than through consumption of beers and sherry brandies.  相似文献   

12.
建立QuEChERS试剂盒联用高效液相色谱检测鸡蛋中阿散酸和洛克沙砷的方法。样品经混匀后用乙腈与10%三氟乙酸的甲醇溶液(1:1,V/V)萃取,离心,取上清液于QuEChERS净化管(内含净化填料400 mg PSA、400 mg C18 EC、45 mg GCB、1199 mg MgSO4)中净化萃取液,之后于高效液相色谱进行检测。结果表明,阿散酸和洛克沙砷在1.00~100.00 mg/L之间呈现良好线性关系,相关系数均大于0.999;方法检出限分别为0.044、0.063 mg/kg;定量限分别为0.149、0.211 mg/kg,阿散酸回收率在92.32%~95.95%,相对标准偏差1.54%~4.92%;洛克沙砷回收率是89.84%~94.91%,相对标准偏差2.19%~5.87%。本方法准确度高、精密度好、简便、快速,适用于鸡蛋中有机砷类兽药残留的检测,该研究为动物源性食品中禁用有机砷制剂的痕量分析奠定了方法基础。  相似文献   

13.
The objective of this research was to develop a robust preservation method for stabilizing inorganic As(IlI/V) species in synthetic and actual groundwaters. Ethylenediaminetetraacetic acid (EDTA), H2SO4, H3PO4, and EDTA-acetic acid (HAc) were evaluated in synthetic groundwater containing 3 mg/L Fe(ll) in the pH range 6.5-8.4 and Eh range -100 to +200 mV at room temperature. In the absence of strong UV light, only EDTA-HAc was found to be an effective preservative under all the experimental conditions tested. A total of 89 samples (including 16 samples in triplicate) from 55 drinking waterwells in Minnesota, California, and North Dakota were preserved with a combination of EDTA-HAc and speciated to evaluate its effectiveness for preserving inorganic arsenic species in actual groundwater samples. The preserved and field-speciated samples were repeatedly speciated and analyzed in the laboratory for up to 85 days after collection. Field-speciated As(lll) concentrations were compared with the As(lll) concentrations in the preserved samples. The results were highly correlated (slope 0.9773, R2 = 0.9986), which indicates that during sample transportation and storage the distribution of arsenic species did not change for samples preserved with EDTA-HAc.  相似文献   

14.
Speciation of arsenic in Dutch total diets: methodology and results   总被引:1,自引:0,他引:1  
In the last decade 311 duplicate portions of the 24-h diet of Dutch citizens were collected and lyophilized. All samples were assayed for total arsenic and, in addition, the 20 samples which ranked highest in total arsenic were selected for arsenic speciation i.e., the separate determination of organic-bound arsenic and inorganic arsenic. For the determination of total arsenic, the test portion is wet-digested and the digest reduced with KI/SnCl2/Zn to give AsH3 which is measured by molecular absorption spectrometry. Inorganic arsenic is also measured as AsH3 after acid extraction of the test portion and subsequent NaBH4 reduction of the extract. The residue of the acid extraction and the NaBH4-reduced extract are combined, wet-digested and the digest reduced with NaBH4 to give AsH3 originating from organic-bound arsenic. Samples spiked at different levels with inorganic and organic-bound arsenic were analysed and gave recoveries for inorganic arsenic of 94% to 122% (n = 6) and for organic-bound arsenic of 87% to 104% (n = 6). On average, the inorganic fraction is 30% of the total arsenic intake; range 3% to 50% (n = 14). The inorganic arsenic fraction decreases with increasing level of total arsenic intake. The highest oral inorganic arsenic intake was 60 micrograms; the tolerable daily intake (TDI) for a 60-kg individual is 120 micrograms inorganic arsenic. Organic and inorganic arsenic measured were summed and compared with the results of the total arsenic determination; differences were less than 15%. (Since inorganic arsenic is a contaminant and not an additive, the abbreviation TDI is preferred here over ADI (acceptable daily intake) which is retained for additives.)  相似文献   

15.
It has been evidenced that arsenic in garlic is present in the most toxic inorganic species As(III) and As(V). A non-chromatographic speciation method has been developed for the screening of inorganic toxic species of As in garlic samples by hydride generation atomic fluorescence spectrometry. The determination of As(III) and As(V) was based on the different efficiencies of hydride generation with NaBH4 with and without a previous reduction with ascorbic acid and KI using a system of two proportional equations corresponding to these two different measurement conditions. The extraction efficiency of total arsenic and the stability of As(III) and As(V) in different extraction media (sulphuric acid, perchloric acid, and methanol/water) were evaluated. Based on the extraction yield and the stability of extracted species, 1.0 mol L−1 H2SO4 was selected as the best extracting solution for speciation analysis. The methodology developed allows us a limit of detection of 0.8 and 0.6 ng g−1 for As(III) and As(V), respectively. The relative standard deviation values were 4% for As(III) and 7% for As(V). This method was applied to determine As(III), As(V), and total As in different Spanish garlic samples. The arsenic (III) content varied from 17.1 to 22.1 ng g−1 and As(V) from 54.7 to 67.6 ng g−1. The accuracy of the method was confirmed by the analysis of a certified reference material of tomato leaves treated in the same way as the garlic samples.  相似文献   

16.
正交试验优化海带中砷的脱除方法   总被引:1,自引:0,他引:1  
以总砷和无机砷脱除率为考察指标,通过最佳食用脱除剂选择、单因素试验、正交试验和感官评定选出最佳脱砷工艺。结果表明,以3%柠檬酸脱除剂、料液比1:15(g/mL)、温度40℃、时间40min的脱砷工艺效果较为理想,总砷脱除率达到65.71%,无机砷脱除率达到74.39%。对脱砷后的海带样品进行基本营养成分分析发现,粗蛋白、粗脂肪、氨基酸和总糖含量均显著增加,灰分和矿物质元素含量有所减少,未对营养成分造成影响。  相似文献   

17.
目的掌握广西主要食品中砷污染的水平,评估居民膳食无机砷暴露量及其潜在健康风险。方法利用2010-2015年广西主要食品中总砷及无机砷含量数据和食物消费量数据,采用简单分布评估的方法 ,计算广西居民膳食中无机砷暴露水平及其分布情况,并利用暴露限值(MOE)法评估其潜在健康风险。结果 16 567份食品样品中,总砷检出率为42.71%(4 735/11 087),无机砷检出率为48.07%(2 634/5 480)。总砷平均含量以海洋甲壳类最高,其次是海水鱼类和软体动物;检测无机砷食品样品中,平均含量为0.018~0.072 mg/kg,其中以大米无机砷平均含量最高。除大米、新鲜水果、蛋及其制品、畜禽内脏直接采用其检测的无机砷结果外,其他食品均通过总砷转换到无机砷而进行暴露评估。一般人群和高消费量人群膳食中无机砷的平均每天暴露量MOE值均1,但18~34岁男性组高消费量人群每天无机砷暴露量的MOE值≤1。大米的贡献率远高于其他食物,是居民膳食中无机砷的主要来源。结论广西居民膳食中无机砷暴露风险总体上是安全的,而对于18~34岁男性组高暴露量人群可能存在一定的健康风险,大米是广西居民的主要食品,大米的安全问题需加以关注。  相似文献   

18.
砷是一种公认的有毒有害物质,现在相关研究中常涉及的砷形态包括亚砷酸盐(arsenite,AsⅢ)、砷酸盐(arsenate,AsⅤ)、一甲基砷酸(monomethyl arsenic acid,MMAⅤ)、二甲基砷酸(dimethyl arsinic acid,DMAⅤ)、砷甜菜碱(arsenobetaine,AsB)以及砷胆碱(arsenocholine,AsC)。砷的形态与其生物可给性、毒性密切相关,烹调过程能够影响食品中砷的形态,进而可能影响到砷对人体健康的风险性。因此,建立食品中砷形态分析的检测方法具有十分重要的意义。本文对砷的形态分析的检测方法及研究现状进行了综述,重点介绍了溶剂提取及微波、超声辅助提取等前处理方法以及砷的形态分析方法在食品中的应用,同时对砷的形态在烹调过程中的变化进行了阐述,并对未来发展方向进行了展望。  相似文献   

19.
目的建立高效液相色谱-电感耦合等离子体质谱法测定大米中无机砷的分析方法。方法采用两种前处理方法对大米中的无机砷进行提取,经高效液相色谱分离后,利用电感耦合等离子体质谱进行测定。同时对大米样品进行微波消解后测定其中的总砷,通过无机砷及有机砷的总和计算两种前处理方法的回收率,从而对前处理方法进行比较。对磷酸二氢铵、碳酸铵以及磷酸氢二铵等缓冲盐进行选择,并对p H值进行优化,确定最优的流动相条件。结果以12.5 mmol/L磷酸氢二铵作为流动相,调节流动相p H为8.5,流速为1 m L/min,可以将5种无机砷形态完全分离。对两种前处理方法进行比较,发现两种前处理方法的提取效率均大于87.5%,其中酸-热辅助提取法的提取效率相对更高。结论该方法准确、简单,适合大米中无机砷的测定。  相似文献   

20.
目的测定14种海藻样品中总砷和无机砷的含量,同时分析样品中6种砷形态。方法将海藻样品经过微波消解的前处理方法,通过电感耦合等离子体质谱(inductively coupled plasma mass spectrometry,ICP-MS)测定总砷含量;根据国标方法中无机砷检测的前处理方法,通过原子荧光光谱(atomic fluorescence spectrometry,AFS)测定无机砷含量;最后通过酸提的前处理方法,利用高效液相色谱-氢化物发生-原子荧光光谱法(high performance liquid chromatography-ultraviolet photo-oxidation-hydride generation-atomic fluorescence spectrometry,HPLC-(UV)-HG-AFS)测定海藻样品中6种形态砷含量并与国标无机砷方法比较。结果 14种海藻样品中总砷含量为0.038~46.2 mg/kg;无机砷含量为0.006~19.3 mg/kg;对HPLC-(UV)-HG-AFS仪器的优化和方法的摸索后,从海藻样品中主要测得的砷形态为As(III)、As(V)和DMA,MMA含量较少,没有测出As B和As C。结论在砷形态较为复杂的海藻样品检测中,通过HPLC-(UV)-HG-AFS检测方法可以有效避免无机砷前处理中可能出现的有机砷向无机砷转变的现象,降低干扰,增加测试的准确性,更为具体地表现海藻样品中主要的砷形态含量。  相似文献   

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