Effect of roxarsone metabolites in chicken manure on soil biological property.

Roxarsone (ROX), an organoarsenic feed additive, occurs as itself and its metabolites including As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in animal manure. Animal manure improves soil biological property, whereas As compounds impact microorganisms. The integral influence of animal manure bearing ROX metabolites on soil biological quality is not clear yet. Herein, the effect of four chicken manures excreted by chickens fed with four diets containing 0, 40, 80 and 120 mg ROX kg-1, on soil biological attributes. ROX addition in chicken diets increased total As and ROX metabolites in manures, but decreased manure total N, ammonium and nitrate. The elevated ROX metabolites in manures increased soil total As, As species and total N, and increased first and then decreased soil nitrate and nitrite, but did not affect soil ammonium in manure-applied soils. The promoting role of both soil As(III) and ammonium on soil microbial biomass carbon and nitrogen, respiration and saccharase activity, were exceeded or balanced by the inhibiting effect of soil nitrate. The suppression of soil catalase activity by soil As(V) was surpassed by the enhancement caused by soil nitrate and nitrite. Soil urease, acid phosphatase and polyphenol oxidase activities were not suitable bioindicators in the four manure-amended soils. Soil DMA did not affect soil biological properties, and MMA was not detectable in all manure-amended soils. The above highlights the complexity of joint influence of soil As and N on biological attributes. Totally, when ROX is used at allowable dose in chicken diet, soil biological quality would be suppressed in manure-amended soil.

Influence of Different Arsenic Species on the Bioavailability and Bioaccumulation of Arsenic by Sargassum horneri C. Agardh: Effects under Different Phosphate Conditions.

The growth response and incorporation of As into the Sargassum horneri was evaluated for up to 7 days using either arsenate (As(V)), arsenite (As(III)) or methylarsonate (MMAA(V) and DMAA(V)) at 0, 0.25, 0.5, 1, 2, and 4 µM with various phosphate (P) levels (0, 2.5, 5 and 10 µM). Except As(III), algal chlorophyll fluorescence was almost similar and insignificant, regardless of whether different concentrations of P or As(V) or MMAA(V) or DMAA(V) were provided (p > 0.05). As(III) at higher concentrations negatively affected algal growth rate, though concentrations of all As species had significant effects on growth rate (p < 0.01). Growth studies indicated that toxicity and sensitivity of As species to the algae followed the trend: As(III) > As(V) > MMAA(V) ~ DMAA(V). As bioaccumulation was varied significantly depending on the increasing concentrations of all As species and increasing P levels considerably affected As(V) uptake but no other As species uptake (p < 0.01). The algae accumulated As(V) and As(III) more efficiently than MMAA(V) and DMAA(V). At equal concentrations of As (4 µM) and P (0 µM), the alga was able to accumulate 638.2 ± 71.3, 404.1 ± 70.6, 176.7 ± 19.6, and 205.6 ± 33.2 nM g-1 dry weight of As from As(V), As(III), MMAA(V), and DMAA(V), respectively. The influence of low P levels with increased As(V) concentrations more steeply increased As uptake, but P on other As species did not display similar trends. The algae also showed passive modes for As adsorption of all As species. The maximum adsorption of As (63.7 ± 6.1 nM g-1 dry weight) was found due to 4 µM As(V) exposure, which was 2.5, 7.3, and 6.9 times higher than the adsorption amounts for the same concentration of As(III), MMAA(V), and DMAA(V) exposure, respectively. The bioavailability and accumulation behaviors of As were significantly influenced by P and As species, and this information is essential for As research on marine ecosystems.

Arbuscular Mycorrhizal Fungi Alter Arsenic Translocation Characteristics of Iris tectorum Maxim.

Arsenic (As) pollution in wetlands, mainly as As(III) and As(V), has threatened wetland plant growth. It has been well documented that arbuscular mycorrhizal (AM) fungi can alleviate As stress in terrestrial plants. However, whether AM fungi can protect natural wetland plants from As stress remains largely unknown. Therefore, three hydroponic experiments were conducted in which Iris tectorum Maxim. (I. tectorum) plants were exposed to As(III) or As(V) stresses, to investigate the effects of mycorrhizal inoculation on As uptake, efflux, and accumulation. The results suggested that short-term kinetics of As influx in I. tectorum followed the Michaelis-Menten function. Mycorrhizal inoculation decreased the maximum uptake rate (Vmax) and Michaelis constant (Km) of plants for As(III) influx, while yielding no significant difference in As(V) influx. Generally, mycorrhizal plants released more As into environments after 72 h efflux, especially under As(V) exposure. Moreover, mycorrhizal plants exhibited potential higher As accumulation capacity, probably due to more active As reduction, which was one of the mechanisms through which AM fungi mitigate As phytotoxicity. Our study has revealed the role of aerobic microorganism AM fungi in regulating As translocation in wetland plants and supports the involvement of AM fungi in alleviating plant As stress in anaerobic wetlands.

Microbes drive changes in arsenic species distribution during the landfill process.

Landfills are considered an anthropogenic source of arsenic (As). The As species mediated by microbes in landfills vary significantly in toxicity. Based on random matrix theory, 16S rRNA genes were used to construct four microbial networks associated with different stages over 12 years of landfill ages. The results indicated that network size and microbial structure varied with landfill age. According to the network scores, about 208 taxa were identified as putative keystones for the whole landfill; the majority of them were Firmicutes, which accounted for 66.8% of all specialists. Random Forest analysis was performed to predict the keystone taxa most responsible for As species distribution under different landfill conditions; 17, 10 and 14 keystone taxa were identified as drivers affecting As species distribution at early, middle, and later landfill stages, respectively.

Distribution and speciation of arsenic in seasonally stratified reservoirs: Implications for biotransformation mechanisms governing interannual variability.

HPLC-ICPMS was used to analyze the spatiotemporal variation of As species in different sections and tributaries of the Aha Reservoir over four seasons, and the migration and transformation mechanisms were clarified by combined analysis of hydrochemical parameters and microbial composition. The results showed that the internal release of As from the reservoir sediments is mainly due to the reduction of iron oxide and the release of adsorbed As(V). The average proportion of As(III) increased from 27.2% in autumn to 46.5% in summer, 68.9% in winter, and up to 70.8% in spring. In spring and summer, the high concentration of As(III) and organic arsenic in the epilimnion under phosphorus restriction was caused by the reductive metabolism of phytoplankton after intake of As(V). The arsenic species in the metalimnion were mainly affected by the oxidation-reduction potential (ORP). In summer and autumn, As-oxidizing bacteria used As(III) as an electron donor, and nitrate played an important role as an electron acceptor, maintaining the dominance of As(V) in the hypolimnion. However, in winter and spring, temperature-controlled ORP was the main process, which was dominated by As(III). In conclusion, As species show annual cycles in different layers of seasonally thermal stratified reservoirs. It provides a systematic mechanism of As species transformation in reservoirs, especially the effect of biological transformation mechanism.

Determination of As species distribution and variation with time in extracted groundwater samples by on-site species separation method.

It is challenging to dependably keep the native distribution of arsenic (As) species before sample analysis in the laboratory. The on-site separation method can avoid sample contamination and species change in the process of sample collection and transportation from field to laboratory. In this study, As species distribution and variation of the extracted groundwater was first analyzed by an on-site species separation method in Jianghan Plain, China. Our study illustrated that: 1) high-As groundwater generally existed under mildly reducing conditions (Eh < 200 mV), weak alkaline conditions (pH < 7.2), elevated concentrations of dissolved Fe(II) and S(-II), and high proportions of As (III); 2) As species in the groundwater changed dramatically at room temperature in 36 hours post extraction (HPE). Fe-sulfide and Fe oxides minerals, which adsorbed As (V), were the main reasons influencing the As species concentration; 3) Acidification and strong complexing agents cannot preserve As species effectively. The average proportion of As (III) in the wells, where groundwater samples from the depth of 25 m exceed 10 µg L-1 As, can be reduced by 61% and 63% after HCl and EDTA were added, respectively. Accurate assessment of concentrations and distribution variation of As species in groundwater can guide the removal of As and the safe use of water resources, especially in drought areas relying on drinking well water.

Leaching Mechanism and Health Risk Assessment of As and Sb in Tailings of Typical Antimony Mines: A Case Study in Yunnan and Guizhou Province, Southwest China.

The weathering and leaching of mining tailings have released large amounts of antimony (Sb) and arsenic (As), causing serious pollution in the surrounding soil, water, and sediments. To understand the leaching characteristics of Sb and As in mining tailings, Zuoxiguo and Qinglong mining tailings were collected for analysis. The average content of Sb in Zuoxiguo and Qinglong tailings was 5902.77 mg/kg and 1426.43 mg/kg, respectively, while that of As was 412.53 mg/kg and 405.26 mg/kg, respectively, which exceeded the local background value. Furthermore, the concentrations of Sb in the leachate of Zuoxiguo and Qinglong increased with time; the average Sb concentration in the leachate of Zuoxiguo and Qinglong was 1470.48 µg/L and 70.20 µg/L, respectively, while that of the As concentration was 31.20 µg/L and 6.45 µg/L, respectively. This suggests that the concentrations of Sb and As in the leachate of Zuoxiguo are both higher than those in the leachate of Qinglong and that the pH of the leachate of Zuoxiguo and Qinglong significantly changed within the first day under different initial pH conditions, and tended to be between 6 and 8, after one day. The results of the average health risk index showed that As in the leachate from Zuoxiguo and Qinglong for children was 5.67 × 10-4 and 9.13 × 10-5, respectively, and 4.43 × 10-4 and 7.16 × 10-5, respectively, for adults. As in the leachate from Zuoxiguo poses serious carcinogenic risks for residents, and in the study area, As poses a serious threat to human health. Therefore, the local government must manage As in these areas.

Effects of Fe-Mn-Ce oxide-modified biochar on As accumulation, morphology, and quality of rice (Oryza sativa L.).

The fluidity of arsenic (As) in soil used for rice cultivation under flooding conditions is the main reason for its high accumulation in rice, which poses a serious threat to human's health. Biochar can immobilize heavy metal (for example lead) of soil because of the strong binding of heavy metals to the inner biochar particles. We conducted a pot experiment to evaluate the effects of biochar (BC) and Fe-Mn-Ce oxide-modified biochar composites (FMCBCs) on the morphology, As accumulation, and grain quality of rice grown in As-contaminated soils. The biochar and FMCBC treatments significantly increased the dry weight of roots, stems, leaves, and rice grains grown in As-contaminated soil (P < 0.05). The As concentration in different parts of rice was significantly lower with treatment FMCBC3-2 (BC, Fe, Mn, and Ce weight ratio of 24:2:3:10) than with the BC and control (no BC) treatments. The application of FMCBC3-2 maximized the yield and quality of rice grains: rice grain yields were 61.45-68.41% higher over control and the proportion of essential amino acids in the rice grains was 31.01-44.62%. The application of FMCBCs also increased the concentration of Fe-Mn plaques, which prevent the uptake of As by rice, thereby mitigating the toxic effects of As-contaminated soil on rice. In summary, Fe-Mn-Ce oxide-modified BC composites fixed As, reducing its fluidity and the As concentration in rice. Our results show that FMCBC3 could play an important role in reducing As accumulation and increasing the grain yield and quality of rice, thus ensuring food safety in regions contaminated with As.

Soil calcium significantly promotes uptake of inorganic arsenic by garland chrysanthemum (ChrysanthemumL coronarium) fertilized with chicken manure bearing roxarsone and its metabolites.

Roxarsone (ROX), a widely used feed organoarsenic additive, occurs as itself and its metabolites in animal manure that is commonly land used as fertilizer. Soil property impacts arsenic (As) speciation and bioavailability. Fourteen soils across China were used to conduct culture experiments to investigate As uptake by garland chrysanthemum (ChrysanthemumL coronarium), with the soils fertilized with chicken manure bearing ROX and its metabolites. The results show As(III) was the sole As form in garland chrysanthemum shoots, and As(III) and As(V) occurred in roots. Only inorganic As was detected in all soils when the plants were harvested. Stepwise regression analysis shows soil-exchangeable Ca predominated shoot As(III) concentration (shoot As(III) = 1.60030 soil Ca, R 2 = 0.8832***). Therefore, ROX is transferred into the human food chain finally as inorganic As in plants. Application of animal manure bearing ROX and its metabolites is not recommended in Ca-rich soils to avoid excess inorganic As dietary exposure.

Delivery of roxarsone via chicken diet→chicken→chicken manure→soil→rice plant.

Roxarsone (ROX), a widely used feed additive, occurs as itself and its metabolites in animal manure. Rice is prone to accumulate As than other staple food. Four diets with 0, 40, 80 and 120mgROXkg(-1) were fed in chickens, and four chicken manures (CMs) were collected to fertilize rice plants in a soil culture experiment. Linear regression analysis shows that the slopes of As species including 4-hydroxy-phenylarsonic acid, As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in CM versus dietary ROX were 0.033, 0.314, 0.033, 0.054 and 0.138, respectively. Both As(III) and DMA were determined in all rice grains, and As(III), As(V), MMA and DMA in rice hull, but detectable As forms in rice straws and soils increased with increasing ROX dose. Grain As(III) was unrelated to ROX dose but exceeded the Chinese rice As limit (0.15mgAs(III)kg(-1)). Dietary ROX enhanced straw As(III) mostly, with the slope of 0.020, followed by hull DMA (0.006) and grain DMA (0.002). The slopes of soil As(V) and As(III) were 0.003 and 0.001. This is the first report illustrating the quantitative delivery of ROX via food chain, which helps to evaluate health and environmental risks caused by ROX use in animal production.

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls.

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO2(CO3)2(2-) and UO2(CO3)3(4-) species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO3(-) were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As.

Spectrophotometric determination of low levels arsenic species in beverages after ion-pairing vortex-assisted cloud-point extraction with acridine red.

A new, low-cost, micellar-sensitive and selective spectrophotometric method was developed for the determination of inorganic arsenic (As) species in beverage samples. Vortex-assisted cloud-point extraction (VA-CPE) was used for the efficient pre-concentration of As(V) in the selected samples. The method is based on selective and sensitive ion-pairing of As(V) with acridine red (ARH(+)) in the presence of pyrogallol and sequential extraction into the micellar phase of Triton X-45 at pH 6.0. Under the optimised conditions, the calibration curve was highly linear in the range of 0.8-280 µg l(-1) for As(V). The limits of detection and quantification of the method were 0.25 and 0.83 µg l(-1), respectively. The method was successfully applied to the determination of trace As in the pre-treated and digested samples under microwave and ultrasonic power. As(V) and total As levels in the samples were spectrophotometrically determined after pre-concentration with VA-CPE at 494 nm before and after oxidation with acidic KMnO4. The As(III) levels were calculated from the difference between As(V) and total As levels. The accuracy of the method was demonstrated by analysis of two certified reference materials (CRMs) where the measured values for As were statistically within the 95% confidence limit for the certified values.

Roxarsone and its metabolites in chicken manure significantly enhance the uptake of As species by vegetables.

Roxarsone is an organoarsenic feed additive which can be finally degraded to other higher toxic metabolites after excreted by animal. In this work, the uptake of As species by vegetables treated with chicken manure bearing roxarsone and its metabolites was investigated. It was showed that more than 96% of roxarsone added in chicken feed was degraded and converted to arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenate, 4-hydroxyphenylarsonic acid and other unknown As species. Arsenite and arsenate could be found in roots of vegetables but only arsenite transported up to shoots. Chicken manure bearing roxarsone and its metabolites increased 33-175% of arsenite and 28% ∼ seven times of arsenate in vegetable roots, 68-175% of arsenite in edible vegetable shoots. Arsenite, the most toxic As form, was the major extractable As species in vegetables accounted for 79-98%. The results reflected that toxic element As could be absorbed by vegetables via the way: roxarsone in feed → animal → animal manure → soil → crop and the uptake of As species would be enhanced by using chicken manure bearing roxarsone and its metabolites as organic fertilizer.