Analysis of accumulation,extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.     

Organocopper complexes during roxarsone degradation in wastewater lagoons

Background, aim, and scope  

Organoarsenical-containing animal feeds that promote growth and resistance to parasites are mostly excreted unchanged, ending up in nearby wastewater storage lagoons. Earlier work documented the partial transformation of organoarsenicals, such as, 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to the more toxic inorganic arsenate [As(V)] and 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA). Unidentified roxarsone metabolites using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC/ICP-MS) were also inferred from the corresponding As mass balance. Earlier batch experiments in our laboratory suggested the presence of organometallic (Cu) complexes during relevant roxarsone degradation experiments. We hypothesized that organocopper compounds were complexed to roxarsone, mediating its degradation in field-collected swine wastewater samples from storage lagoons. The objective of this study was to investigate the role of organometallic (Cu) complexes during roxarsone degradation under aerobic conditions in swine wastewater suspensions, using electrospray ionization mass spectrometry (ES-MS).     

On-line speciation of arsenical compounds in fish and mussel extracts by HPLC-ICP-MS

The separation and determination of sub-μmol/l levels of six environmentally significant As compounds was accomplished by means of high performance liquid chromatography (HPLC) combined online with inductively coupled plasma mass spectrometry (ICP-MS). The species of interest (arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine) were quantified in fish and mussel extracts after separation on a Dionex AS7 column equipped with an on-guard AG7 column using a bicarbonate buffer as the mobile phase in a gradient mode. The species thus eluted were directly forwarded to the ICP-MS detector. The detection power of the overall system allows each As form to be determined at concentrations as low a 0.0013–0.0027 μmol 1⁻¹.     

Adsorption and photocatalytic decomposition of roxarsone by TiO2 and its mechanism

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid) has been widely used as organic arsenic additive in animal industry. In this study, the adsorption of roxarsone on TiO₂ under dark conditions, the photocatalytic decomposition of roxarsone under UV/TiO₂, and the possible photocatalytic pathway were investigated. At the initial concentration of 5–35 mg/L, the adsorption of roxarsone fitted well with the pseudo-second-order kinetics. The isotherms analysis showed that the Langmuir model was better than the Freundlich and Dubinin–Radushkevich models for describing the adsorption process. After 7 h of photocatalytic decomposition, a complete disappearance of roxarsone was achieved. The pH value has a significant effect on both adsorption and photocatalytic decomposition of roxarsone. The results of high-performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) and gas chromatography-mass spectrometry (GC/MS) analyses proved the cleavage of the As-C bond during the photocatalytic decomposition process by TiO₂ and the intermediates of the decomposition. Based on the results, a possible photocatalytic decomposition pathway was proposed.     

The fate and transport of arsenic species in the aquatic ecosystem: a case study on Bestari Jaya,Peninsular Malaysia

The field of arsenic pollution research has grown rapidly in recent years. Arsenic constitutes a broad range of elements from the Earth’s crust and is released into the environment from both anthropogenic and natural sources due to its relative mobility under different redox conditions. The toxicity of arsenic is described in its inorganic form, as inorganic arsenic compounds can leach into different environments. Sampling was carried out in the Bestari Jaya catchment while using a land use map to locate the site, and experiments were conducted via sequential extraction and inductively coupled plasma optical emission spectroscopy to quantify proportions of arsenic in the sediment samples. The results show that metals in sediments of nonresidual fractions, which are more likely to be likely released into aquatic environments, are more plentiful than the residual sediment fractions. These findings support the mobility of heavy metals and especially arsenic through sediment layers, which can facilitate remediation in environments heavily polluted with heavy metals.     

A Study of Cooling Pond Fog Generation

Airborne particulate and soil materials sampled in the vicinity of a lead/zinc smelter and subsequently digested In nitric-perchloric acids have been analyzed using an inductively coupled plasma-atomic emission spectrometer (ICP/AES). The samples were collected in two communities; a study community situated immediately adjacent to the smelter complex and a control community some 50 kilometers distant. Enrichment of airborne as well as soil materials is discussed and there is evidence of lead, zinc, copper, cadmium, arsenic, and antimony enrichment from the smelting processes. In addition, an aqueous extraction of the airborne materials isolated sulfate, nitrate, fluoride, and ammonia and gave evidence of enrichment due to fugitive SO _x , NO _x , HF, and NH₃ gaseous emissions.     

煤基腐殖酸对外源砷胁迫下玉米生长及生理性状的影响简

为了筛选用于砷污染土壤治理的煤基腐殖酸,采用盆栽实验研究了施用不同种类和浓度的煤基腐殖酸及EDTA对外源砷胁迫下玉米株高、株鲜重、株干重、根干重、砷积累量、叶片抗氧化酶（POD,SOD和CAT）活性和脯氨酸含量的影响。结果表明,11种供试煤基腐殖酸均促进了玉米生长,提高了叶片POD、SOD和CAT活性。其中6和10号腐殖酸可降低土壤砷活性和显著抑制玉米吸收和积累砷,而8和9号腐殖酸增加了土壤活性砷和显著促进了玉米对砷的吸收和累积,且不同程度地强于EDTA。除8和9号外,其余腐殖酸均可明显降低玉米叶片脯氨酸的含量。EDTA可显著促进玉米吸收和积累砷,且加剧了砷对玉米的危害。因此,8和9号供试煤基腐殖酸可以替代EDTA活化土壤砷,与植物配合以提高砷污染土壤的植物修复速度和效果,而6和10号供试煤基腐殖酸则可用于土壤砷钝化剂,以保证作物产品的安全。     

LC–ICP–MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf (Northern Aegean Sea,Greece)

The content of total arsenic and arsenic compounds in the dominant seaweed species in the Thermaikos Gulf, Northern Aegean Sea was determined in samples collected in different seasons. Total arsenic was determined by acid digestion followed by ICP–MS. Arsenic speciation was analyzed by water extraction followed by LC–ICP–MS. Total arsenic concentrations in the seaweeds ranged from 1.39 to 55.0 mg kg⁻¹. Cystoseira species and Codium fragile showed the highest total As contents, while Ulva species (U. intestinalis, U. rigida,U. fasciata) had the lowest Arsenosugars, the most common arsenic species in seaweeds, were found in all samples, and glycerol-arsenosugar was the most common form; however, phosphate-arsenosugar and sulfate-arsenosugar were also present. Inorganic arsenic was measured in seven algae species and detected in another. Arsenate was the most abundant species in Cystoseira barbata (27.0 mg kg⁻¹). Arsenobetaine was measured in only one sample. Methylated arsenic species were measured at very low concentrations. The information should contribute to further understanding the presence of arsenic compounds in dominant seaweeds from the Thermaikos Gulf.     

Measurement of arsenic compounds in littoral zone algae from the Western Mediterranean Sea. Occurrence of arsenobetaine

The determination of arsenic compounds in algae collected on the Catalan coast (Western Mediterranean) is reported. Ten algae species and the seagrass Posidonia oceanica were analyzed. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). Arsenic speciation in water extracts of samples was analyzed by liquid chromatography with both anionic and cationic exchange with ICPMS detection (LC-ICPMS). The total arsenic content of the algae samples ranged from 2.96 to 39.0mg As kg(-1). The following compounds were detected: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO3-sug), sulfate sugar (SO4-sug), phosphate sugar (PO4-sug), arsenobetaine (AB), arsenocholine (AC), trimethylarsine oxide (TMAO) and glycerol sugar (Gly-sug). The main arsenic species found were arsenosugars. Significant percentages of arsenobetaine (0.54 mg As kg(-1), 28% of the extractable arsenic and 0.39 mg As kg(-1), 18% of the extractable arsenic) were found in Ulva rigida and Enteromorpha compressa. These results are discussed in relation to the presence of epiphytes.     

Acid washing and stabilization of an artificial arsenic-contaminated soil.

An acid-washing process was studied on a laboratory scale to extract the bulk of arsenic(V) from a highly contaminated Kuroboku soil (Andosol) so as to minimize the risk of arsenic to human health and the environment. The sorption and desorption behavior of arsenic in the soil suggested the possibility of arsenic leaching under acidic conditions. Artificially contaminated Kuroboku soil (2830 mg As/kg soil) was washed with different concentrations of hydrogen fluoride, phosphoric acid, sulfuric acid, hydrogen chloride, nitric acid, perchloric acid, hydrogen bromide, acetic acid, hydrogen peroxide, 3:1 hydrogen chloride-nitric acid, or 2:1 nitric acid-perchloric acid. Phosphoric acid proved to be most promising as an extractant, attaining 99.9% arsenic extraction at 9.4% acid concentration in 6 h. Sulfuric acid also attained high percentage extraction. The arsenic extraction by these acids reached equilibrium within 2 h. Elovich-type equation best described most of the kinetic data for dissolution of soil components as well as for extraction of arsenic. Dissolution of the soil components could be minimized by ceasing acid washing in 2 h. The acid-washed soil was further stabilized by the addition of lanthanum, cerium, and iron(III) salts or their oxides or hydroxides which form insoluble complex with arsenic. Both salts and oxides of lanthanum and cerium were effective in immobilizing arsenic in the soil attaining less than 0.01 mg/l As in the leaching test.     

Ascorbic acid, β-carotene,sugars, phenols,and heavy metals in sweet potatoes grown in soil fertilized with municipal sewage sludge

Municipal sewage sludge (MSS) used for land farming typically contains heavy metals that might impact crop quality and human health. A completely randomized experimental design with three treatments (six replicates each) was used to monitor the impact of mixing native soil with MSS or yard waste (YW) mixed with MSS (YW +MSS) on: i) sweet potato yield and quality; ii) concentration of seven heavy metals (Cd, Cr, Mo, Cu, Zn, Pb, and Ni) in sweet potato plant parts (edible roots, leaves, stem, and feeder roots); and iii) concentrations of ascorbic acid, total phenols, free sugars, and β-carotene in sweet potato edible roots at harvest. Soil samples were collected and analyzed for total and extractable metals using two extraction procedures, concentrated nitric acid (to extract total metals from soil) as well as CaCl₂ solution (to extract soluble metals in soil that are available to plants), respectively. Elemental analyses were performed using inductively coupled plasma mass spectrometry (ICP-MS). Overall, plant available metals were greater in soils amended with MSS compared to control plots. Concentration of Pb was greater in YW than MSS amendments. Total concentrations of Pb, Ni, and Cr were greater in plants grown in MSS+YW treatments compared to control plants. MSS+YW treatments increased sweet potato yield, ascorbic acid, soluble sugars, and phenols in edible roots by 53, 28, 27, and 48%, respectively compared to plants grown in native soil. B-carotene concentration (157.5 μg g^?1 fresh weight) was greater in the roots of plants grown in MSS compared to roots of plants grown in MSS+YW treatments (99.9 μg g^?1 fresh weight). Concentration of heavy metals in MSS-amended soil and in sweet potato roots were below their respective permissible limits.     

Effect of EDTA and NTA on cadmium distribution and translocation in Pennisetum purpureum Schum cv. Mott

The primary objective of this research was to investigate the cadmium (Cd) distribution in Pennisetum purpurem (Napier grass) in the presence of 30 mg/L of Cd and different types and concentrations of chelating agents (ethylenediaminetetraacetic acid disodium dihydrate (EDTA), nitrilotriacetic acid (NTA), and EDTA-NTA mixtures). Plant samples were collected every 15 d during a 105-d experimental period. Accumulation of Cd in each part of the plant was determined using atomic absorption spectrometer (AAS), and the distribution of Cd was determined by laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) and synchrotron radiation micro X-ray fluorescence (SR-micro-XRF). The highest concentrations of Cd accumulation of 889?±?53 mg kg^?1 in the underground part (roots) and 265?±?26 mg kg^?1 in the aboveground part (stems and leaves) in the presence of 1:1 M ratio of Cd:EDTA after 30 d of exposure were observed. Plants grown in the presence of either NTA or EDTA-NTA mixtures showed significant lower Cd accumulation levels. The LA-ICP-MS analysis showed that Cd was primarily accumulated in the aboveground part (stems and leaves), especially in the xylem and intercalary meristem. In addition, translocation factor was very low. Thus, P. purpurem could be considered as a candidate plant for cadmium phytostabilization.

     

Dynamic studies on the mobility of trace elements in soil and sediment samples influenced by dumping of residues of the flood in the Mulde River region in 2002

In the analysis of soil samples, batch sequential extraction procedures are traditionally used for the fractionation of trace elements to access their mobility and potential risk for the contamination of groundwater. In the present work a continuous-flow technique has been used that enables not only the fast and efficient leaching of trace elements but as well as time-resolved studies on the mobilization of arsenic and selected heavy metals in different forms to be made. Rotating coiled columns (RCC) earlier used mainly in countercurrent chromatography have been successfully applied to the dynamic leaching of heavy metals from soils contaminated by flooding sludge's. The sample was retained in a PTFE rotating column as the stationary phase whereas aqueous solutions were continuously pumped through. The contents of elements were determined by on-line coupling of RCC and inductively coupled plasma atomic emission spectrometry (ICP-AES). This enables real-time data on the leaching process to be obtained. Dynamic and traditional batch procedures were compared. It has been shown that the aqueous elution under centrifugal forced conditions is much more effective for the mobilization of heavy metals. Hence, the dynamic leaching is characterized by a substantially more intensive interaction between solid and water and is besides substantially more time-saving than the conventional batch procedure. The RCC procedure was also employed for preliminary leaching studies with a simulated "acid rain". In comparison with the water leaching, the mobilization of heavy metals and arsenic from soil samples with employment of simulated acid rain as eluent was less effective.     

Oxidation of triphenylarsine to triphenylarsineoxide by Trichoderma harzianum and other fungi

Arsenic resistant strains of bacteria and fungi were isolated from soil contaminated by chemical warfare agents. Until now, no metabolic products of microbial attack against the phenyl residues of the model substrate triphenylarsine (TP) were found if it was incubated together with these strains in liquid culture assays. However, one of the isolated fungi, Trichoderma harzianum As 11, was found to oxidize TP to triphenylarsineoxide (TPO). The yeast Trichosporon mucoides SBUG 801 and the white-rot fungus Phanerochaete chrysosporium were also able to oxidize the As(III) in TP. In addition, P. chrysosporium transformed phenylarsineoxide (PAO) to phenylarsonic acid (PAA) under O2-atmosphere. By means of a respirometer system, the oxidation of TP by T. harzianum As 11 was confirmed by a significantly higher consumption of oxygen in the presence of these compounds. HPLC analysis of the oxidation products TPO and PAA in the medium of the assays provided evidence for the transfer reaction of As(III) to As(V) in organic bonds. The oxidation products TPO and PAA are more hydrophilic than TP and PAO. Therefore, it was concluded that particular fungi contribute to the mobilization of arsenic in soil contaminated by chemical warfare agents.     

煤基腐殖酸对外源砷胁迫下玉米生长及生理性状的影响

为了筛选用于砷污染土壤治理的煤基腐殖酸,采用盆栽实验研究了施用不同种类和浓度的煤基腐殖酸及EDTA对外源砷胁迫下玉米株高、株鲜重、株干重、根干重、砷积累量、叶片抗氧化酶（POD,SOD和CAT）活性和脯氨酸含量的影响。结果表明,11种供试煤基腐殖酸均促进了玉米生长,提高了叶片POD、SOD和CAT活性。其中6和10号腐殖酸可降低土壤砷活性和显著抑制玉米吸收和积累砷,而8和9号腐殖酸增加了土壤活性砷和显著促进了玉米对砷的吸收和累积,且不同程度地强于EDTA。除8和9号外,其余腐殖酸均可明显降低玉米叶片脯氨酸的含量。EDTA可显著促进玉米吸收和积累砷,且加剧了砷对玉米的危害。因此,8和9号供试煤基腐殖酸可以替代EDTA活化土壤砷,与植物配合以提高砷污染土壤的植物修复速度和效果,而6和10号供试煤基腐殖酸则可用于土壤砷钝化剂,以保证作物产品的安全。     

Dynamics of water soluble phosphorus from surface applied broiler litter

Deionized water is routinely used as an extractant to determine soluble phosphorus (P) in broiler litter, but under N.E. Georgia conditions this technique may underestimate the hazard of P loss in runoff because the alkalinity of the broiler litter-water suspension limits the solubility of P compounds that may be solubilized after being spread on acidic field conditions. In this study under controlled conditions we measured soluble P in thatch and top soil after applying untreated broiler litter, residue of broiler litter after water extraction (WER), or residue of broiler litter after extraction with a 2-(N-morpholino) ethanesulfonic acid (MES) buffer at pH 6 (BER). During the 60 d incubation, the WER released 18 % more Total Dissolved P (TDP) than was determined through a conventional water extraction procedure, whereas the BER released 28 % less TDP than the WER, which reflects the greater amount of TDP removed from the broiler litter by the buffer at pH 6.0. However, the total amount of TDP extracted by the MES buffer, which includes that removed at the initial extraction plus that released during the incubation, was 30 % greater than the total amount of TDP extracted with water from the untreated litter plus the TDP extracted with water from the WER during the incubation. This result suggests the need to fine-tune the solid: liquid ratio and shaking time when the MES buffer is used.     

Identification of dicarboxylic acids and aldehydes of PM10 and PM2.5 aerosols in Nanjing,China

In this study aerosol samples of PM10 and PM2.5 collected from 18 February 2001 to 1 May 2001 in Nanjing, China were analyzed for their water-soluble organic compounds. A series of homologous dicarboxylic acids (C_2–10) and two kinds of aldehydes (methylglyoxal and 2-oxo-malonaldehyde) were detected by GC and GC/MS. Among the identified compounds, the concentration of oxalic acid was the highest at all the five sites, which ranged from 178 to 1423 ng/m³. The second highest concentration of dicarboxylic acids were malonic and succinic acids, which ranged from 26.9 to 243 ng/m³. Higher level of azelaic acid was also observed, of which the maximum was 301 ng/m³. As the highest fraction of dicarboxylic acids, oxalic acid comprised from 28% to 86% of total dicarboxylic acids in PM10 and from 41% to 65% of total dicarboxylic acids in PM2.5. The dicarboxylic acids (C₂, C₃, C₄) together accounted for 38–95% of total dicarboxylic acids in PM10 and 59–87% of dicarboxylic acids in PM2.5. In this study, the total dicarboxylic acids accounted for 2.8–7.9% of total organic carbon (TOC) of water-soluble matters for PM10 and 3.4–11.8% of TOC for PM2.5. All dicarboxylic acids detected in this study together accounted for about 1% of particle mass. The concentration of azelaic acid was higher at one site than others, which may be resulted from higher level of volatile fat used for cooking. The amounts of dicarboxyic acids (C_2,3,4,9) and 2-oxo-malonaldehyde of PM2.5 were higher in winter and lower in spring. Compared with other major metropolitans in the world, the level of oxalic acid concentration of Nanjing is much higher, which may be contributed to higher level of particle loadings, especially for fine particles.     

电感耦合等离子体发射光谱在分析废液晶显示器面板主要元素中的应用

采用电感耦合等离子体发射光谱(ICP-AES)法对废液晶显示器(TFT-LCD)面板主要元素含量进行了测定。结果表明:(1)在酸体系下回收废TFT-LCD面板中In时,尽管不同酸体系下各元素浓度变化较大,但是主要伴随元素以Al、Fe为主。(2)绝大多数元素测定结果的相对标准偏差低于3%。(3)不同元素加标回收率基本在86%～110%。ICP-AES法具有灵敏度高、检出限较低、多元素同时测定等优点,能满足元素测定误差要求,可有效应用于废TFT-LCD面板中主要元素的测定。     

Total and inorganic arsenic in Antarctic macroalgae

The Antarctic region offers unparalleled possibilities of investigating the natural distribution of metals and metalloids, such as arsenic. Total and inorganic As were analysed in nine species of Antarctic macroalgae collected during the 2002 summer season in the Potter Cove area at Jubany-Dallmann Station (South Shetland Islands, Argentinian Base). Total As was determined by inductively coupled plasma-optical emission spectrometry after microwave-assisted acid digestion. Inorganic As was determined by acid digestion, solvent extraction, flow injection-hydride generation-atomic absorption spectrometry. Total As ranged from 5.8 microg g(-1) dry weight (dw) (Myriogramme sp.) to 152 microg g(-1)dw (Himantothallus grandifolius). Total As concentrations were higher in Phaeophytes (mean+/-SD: 71+/-44 microg g(-1)dw) than in Rhodophytes (mean+/-SD: 15+/-11 microg g(-1)dw). Inorganic As ranged from 0.12 microg g(-1) (Myriogramme sp.) to 0.84 microg g(-1)dw (Phaeurus antarcticus). The percentage of inorganic As with respect to total As was 0.7 for Phaeophytes, but almost 4 times higher for Rhodophytes (2.6). The work discusses possible causes for the presence of As in marine organisms in that pristine environment.