Plant-substrate biochar properties critical for mediating reductive debromination of 1,2-dibromoethane.

Dibromoethane is a widespread, persistent organic pollutant. Biochars are known mediators of reductive dehalogenation by layered Fe-Fe hydroxides (green rust), which can reduce 1,2-dibromoethane to innocuous bromide and ethylene. However, the critical characteristics that determine mediator functionality are lesser known.

Biochar catalyzed dechlorination - Which biochar properties matter?

Bone char catalyzed dechlorination of trichloroethylene (TCE) by green rust (iron(II)-iron(III) hydroxide, GR) has introduced a promising new reaction platform for degradation of chlorinated solvents. This study aimed to reveal whether a broader class of biochars are catalytically active for the dechlorination reaction and to identify which biochar properties are the most important for the catalytic activity. Biochars produced by pyrolysis of animal, plant, and sewage waste substrates at 950 °C were prepared for catalytic dechlorination of TCE by GR tested in batch experiments with 0.

Single sheet iron oxide: An efficient heterogeneous electro-Fenton catalyst at neutral pH.

In order to overcome the inefficiency of heterogeneous electro-Fenton process for water treatment at neutral pH, single sheet iron oxide (SSI) derived from layered Fe(II)-Fe(III) double hydroxides (green rusts) was fabricated on an indium tin oxide electrode via layer by layer assembly and used in an undivided electrolysis cell. Use of radical scavengers demonstrated the formation of oxygen radicals by electrochemical reduction of oxygen at the SSI electrode, and the key role of hydroxyl radicals (OH) and superoxide anion (O) radicals in degradation of the azo dye orange II. Analysis of degradation products by UV-vis, LC-MS and GC-MS further demonstrated that direct reduction toke place in addition to indirect oxidation.

A Silicate/Glycine Switch To Control the Reactivity of Layered Iron(II)-Iron(III) Hydroxides for Dechlorination of Carbon Tetrachloride.

Layered Fe-Fe hydroxide chloride (chloride green rust, GR) has high reactivity toward reducible pollutants such as chlorinated solvents. However, this reactive solid is prone to dissolution, and hence loss of reactivity, during storage and handling. In this study, adsorption of silicate (Si) to GR was tested for its ability to minimize GR dissolution and to inhibit reduction of carbon tetrachloride (CT).

Copper-mediated reductive dechlorination by green rust intercalated with dodecanoate.

A layered Fe-Fe hydroxide (green rust, GR) was intercalated with dodecanoate (known as GR) and then amended with Cu (GR(Cu)) before reaction with chloroform (CF), carbon tetrachloride (CT), trichloroethylene (TCE) or tetrachloroethylene (PCE). Reduction of CT by GR(Cu) was 37 times faster than with GR alone before the active Cu species was consumed. The Cu mediated reaction followed the dichloroelimination pathway as observed for GR alone, with carbon monoxide (82.

Amino Acid-Assisted Dehalogenation of Carbon Tetrachloride by Green Rust: Inhibition of Chloroform Production.

Layered Fe-Fe hydroxides (green rusts, GRs) are promising reactants for reductive dechlorination of chlorinated solvents due to high reaction rates and the opportunity to inject reactive slurries of the compounds into contaminant plumes. However, it is necessary to develop strategies that reduce the formation of toxic byproducts such as chloroform (CF). In this study, carbon tetrachloride (CT) dehalogenation by the chloride form of GR (GR) was tested in the presence of glycine (GLY) and other selected amino acids.

Screening of inorganic and organic contaminants in floodwater in paddy fields of Hue and Thanh Hoa in Vietnam.

In the rainy season, rice growing areas in Vietnam often become flooded by up to 1.5 m water. The floodwater brings contaminants from cultivated areas, farms and villages to the rice fields resulting in widespread contamination.

Glycine buffered synthesis of layered iron(II)-iron(III) hydroxides (green rusts).

Layered Fe-Fe hydroxides (green rusts, GRs) are efficient reducing agents against oxidizing contaminants such as chromate, nitrate, selenite, and nitroaromatic compounds and chlorinated solvents. In this study, we adopted a buffered precipitation approach where glycine (GLY) was used in the synthesis of sulfate-interlayered GR (GR) by aerial oxidation of Fe or co-precipitation by adding Fe salt to an aqueous solution of Fe at constant pH. In both the oxidation and the co-precipitation methods pure crystalline GR was precipitated in the presence of 70mM GLY (pH 8.

Graphene oxide-mediated rapid dechlorination of carbon tetrachloride by green rust.

Graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of chlorinated aliphatic hydrocarbons. In this study as low amounts as ∼0.007 % of graphene oxide (GO) was found to catalyze the reduction of carbon tetrachloride by layered Fe(II)-Fe(III) hydroxide (Green Rust, GR) in aqueous solutions with chloroform being the reduction product.

Nitrogen regulation of the xyl genes of Pseudomonas putida mt-2 propagates into a significant effect of nitrate on m-xylene mineralization in soil.

The nitrogen species available in the growth medium are key factors determining expression of xyl genes for biodegradation of aromatic compounds by Pseudomonas putida. Nitrogen compounds are frequently amended to promote degradation at polluted sites, but it remains unknown how regulation observed in the test tube is propagated into actual catabolism of, e.g.

Ptaquiloside in Irish Bracken Ferns and Receiving Waters, with Implications for Land Managers.

Ptaquiloside, along with other natural phytotoxins, is receiving increased attention from scientists and land use managers. There is an urgent need to increase empirical evidence to understand the scale of phytotoxin mobilisation and potential to enter into the environment. In this study the risk of ptaquiloside to drinking water was assessed by quantifying ptaquiloside in the receiving waters at three drinking water abstraction sites across Ireland and in bracken fronds surrounding the abstraction sites.

Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes.

Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes.

The naturally occurring carcinogen ptaquiloside is present in groundwater below bracken vegetation.

The present study demonstrates unequivocally the presence of the natural carcinogen ptaquiloside and its transformation product pterosin B in groundwater and surface water. Groundwater concentrations up to 0.23 nmol/L (92 ng/L) ptaquiloside and up to 2.

Vivianite precipitation and phosphate sorption following iron reduction in anoxic soils.

Phosphorus retention in lowland soils depends on redox conditions. The aim of this study was to evaluate how the Fe(III) reduction degree affects phosphate adsorption and precipitation. Two similarly P-saturated, ferric Fe-rich lowland soils, a sandy and a peat soil, were incubated under anaerobic conditions.

Efficient dechlorination of carbon tetrachloride by hydrophobic green rust intercalated with dodecanoate anions.

The reductive dechlorination of carbon tetrachloride (CT) by Fe(II)-Fe(III) hydroxide (green rust) intercalated with dodecanoate, Fe(II)(4)Fe(III)(2)(OH)(12)(C(12)H(23)O(2))(2) · yH(2)O (designated GR(C12)), at pH ~ 8 and at room temperature was investigated. CT at concentration levels similar to those found in heavily contaminated groundwater close to polluted industrial sites (14-988 μM) was reduced mainly to the fully dechlorinated products carbon monoxide (CO, yields >54%) and formic acid (HCOOH, yields >6%). Minor formation of chloroform (CF), the only chlorinated degradation product, was also detected (yields <6.

A liquid chromatography-electrospray ionization-mass spectrometry method for quantification of cyclotides in plants avoiding sorption during sample preparation.

Cyclotides are plant-produced, bioactive, cyclic mini-proteins with interesting pharmaceutical and agricultural applications. A reverse phase liquid chromatography electrospray ionization mass spectrometry (RP-LC-ESI-MS) method for analysis of cyclotides in plant materials with a minimum of sample pre-treatment is presented. Three exemplary cyclotides (kalata B1, kalata B2 and cycloviolacin O2) were used as reference substances for the method development.

Degradation of the potato glycoalkaloid alpha-solanine in three agricultural soils.

The toxic glycoalkaloids produced by the potato plant (Solanum tuberosum L.) have previously been found in upper soil from a potato field during several months. Further insight into the fate of the glycoalkaloids is needed, as only little information about their degradation in soil is available.

Degradation of the potato glycoalkaloids--alpha-solanine and alpha-chaconine in groundwater.

The potato glycoalkaloids alpha-chaconine and alpha-solanine are produced in high amounts in potato plants from where release to soil takes place. Degradation of the compounds in groundwater was investigated, as their fate in the terrestrial environment is unknown. Abiotic and microbial degradation were followed in groundwater sampled from below a potato field and spiked with the glycoalkaloids (115 nmol/l).

Fate of toxic potato glycoalkaloids in a potato field.

The toxic glycoalkaloids, alpha-solanine and alpha-chaconine, are present in all parts of the potato plant and are possibly transferred to the terrestrial environment. The amounts of glycoalkaloids in plant, soil, and groundwater were followed in a potato field to investigate their distribution and fate during the season. The amount of glycoalkaloids in the plants was up to 25 kg/ha during maturity and decreased to below 0.

Quantification of ptaquiloside and pterosin B in soil and groundwater using liquid chromatography-tandem mass spectrometry (LC-MS/MS).

The carcinogenic compound ptaquiloside is produced by bracken fern (Pteridium aquilinum L.). Ptaquiloside can enter the soil matrix and potentially leach to the aquatic environment, and methods for characterizing ptaquiloside content and fate in soil and groundwater are needed.

Potato glycoalkaloids in soil-optimising liquid chromatography-time-of-flight mass spectrometry for quantitative studies.

Potato glycoalkaloids are produced in high amounts in potato fields during the growth season and losses to soil potentially impact shallow groundwater and via tiles to fresh water ecosystems. A quantitative liquid chromatography-electrospray ionization time-of-flight mass spectrometry (LC-ESI-TOF-MS) method for determination and quantification of potato glycoalkaloids and their metabolites in aqueous soil extracts was developed. The LC-ESI-TOF-MS method had linearities up to 2000microg/L for alpha-solanine and alpha-chaconine and up to 760microg/L for solanidine.

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure.

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days).

Kinetics of ptaquiloside hydrolysis in aqueous solution.

Ptaquiloside (PTA) is a well-known toxin produced by the bracken fern (Pteridium aquilinum (L.) Kuhn). It is proposed that PTA from bracken stands can leach through soil and sediments into drinking-water reservoirs, thus representing a concern for human health.

Transformation of the herbicide 2,6-dichlorobenzonitrile to the persistent metabolite 2,6-dichlorobenzamide (BAM) by soil bacteria known to harbour nitrile hydratase or nitrilase.

In soil the herbicide 2,6-dichlorobenzonitrile (dichlobenil) is degraded to the persistent metabolite 2,6-dichlorobenzamide (BAM) which has been detected in 19% of samples taken from Danish groundwater. We tested if common soil bacteria harbouring nitrile-degrading enzymes, nitrile hydratases or nitrilases, were able to degrade dichlobenil in vitro. We showed that several strains degraded dichlobenil stoichiometrically to BAM in 1.

Transport of phosphate through artificial macropores during film and pulse flow.

Flow through artificial macropores may occur as a water film along the macropore walls (film flow) or as moving water segments separated by air bubbles (pulse flow). To investigate the effect of macropore flow pattern (i.e.