Arsenic(III) oxidation by iron(VI) (ferrate) and subsequent removal of arsenic(V) by iron(III) coagulation

We investigated the stoichiometry, kinetics, and mechanism of arsenite [As(III)] oxidation by ferrate [Fe(VI)] and performed arsenic removal tests using Fe(VI) as both an oxidant and a coagulant. As(III) was oxidized to As(V) (arsenate) by Fe(VI), with a stoichiometry of 3:2 [As(III):Fe(VI)]. Kinetic studies showed that the reaction of As(III) with Fe(VI) was first-order with respect to both reactants, and its observed second-order rate constant at 25 degrees C decreased nonlinearly from (3.54 +/- 0.24) x 10(5) to (1.23 +/- 0.01) x 10(3) M(-1) s(-1) with an increase of pH from 8.4 to 12.9. A reaction mechanism by oxygen transfer has been proposed for the oxidation of As(III) by Fe(VI). Arsenic removal tests with river water showed that, with minimum 2.0 mg L(-1) Fe(VI), the arsenic concentration can be lowered from an initial 517 to below 50 microg L(-1), which is the regulation level for As in Bangladesh. From this result, Fe(VI) was demonstrated to be very effective in the removal of arsenic species from water at a relatively low dose level (2.0 mg L(-1)). In addition, the combined use of a small amount of Fe(VI) (below 0.5 mg L(-1)) and Fe(III) as a major coagulant was found to be a practical and effective method for arsenic removal.     

Iron(VI) and iron(V) oxidation of copper(I) cyanide

Copper(Il) cyanide (Cu(CN)4(3-)) in the gold mine industry presentsthe biggest concern in cyanide management because it is much more stable than free cyanide. Cu(CN)4(3-) is highlytoxic to aquatic life; therefore, environmentally friendly techniques are required for the removal of Cu(CN)4(3-) from gold mine effluent. The oxidation of Cu(CN)4(3-) by iron-(VI) (FeVIO4(2-), Fe(VI)) and iron(V) (FeVO4(3-), Fe(V)) was studied using stopped-flow and premix pulse radiolysis techniques. The stoichiometry with Fe(VI) was determined to be 5HFeO(4-) + Cu(CN)4(3-) + 8H2O - > 5Fe(OH)3 + Cu2+ + 4CNO- +3/202 + 6OH-. The rate law for the oxidation of Cu(CN)4(3-) by Fe(VI) was found to be first-order with each reactant. The rates decreased with increasing pH and were mostly related to a decrease in concentration of reactive protonated Fe(VI) species, HFeO4-. A mechanism is proposed that agrees with the observed reaction stoichiometry and rate law. The rate constant for the oxidation of Cu(CN)4(3-) by Fe(V) was determined at pH 12.0 as 1.35 +/- 0.02 x 10(7) M(-1) s(-1), which is approximately 3 orders of magnitude larger than Fe(VI). Results indicate that Fe(VI) is highly efficient for removal of cyanides in gold mill effluent.     

Reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides

Under oxic conditions, Tc exists as the soluble, weakly sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2 x nH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) adsorbed on Al (hydr)oxides [diaspore (alpha-AlOOH) and corundum (alpha-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (M?ssbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11 (diaspore suspension) and 4 days (corundum suspension). M?ssbauer measurements revealed thatthe Fe(II) signal became less intense with Tc(VII) reduction and was accompanied by an increase in the intensity of the Fe(III) doublet and magnetically ordered Fe(III) sextet signals. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2 x nH2O.     

表没食子儿茶素没食子酸酯的甲基化分子修饰

研究表没食子儿茶素没食子酸酯(EGCG)的甲基化分子修饰。以碘甲烷作为甲基供体,采用化学合成方法研究EGCG 的甲基化分子修饰,并通过HPLC-MS 和NMR 等对反应产物进行结构鉴定。结果表明：采用化学合成方法能有效完成EGCG 的甲基化分子修饰,并分离鉴定出5 个EGCG 甲基化衍生物,分别为4″-Me-EGCG、4′,4″-di-Me-EGCG、5,3′,4′,5′,3″,4″,5″-hepta-Me-EGCG、5,7,3′,4′,3″,4″,5″-hepta-Me-EGCG、5,7,3′,4′,5′,3″,4″,5″-octa-Me-EGCG。     

Mind the (yield) gap(s)

This paper explores the origin of the notion of ??yield gap?? and its use as a framing device for agricultural policy in sub-Saharan Africa. The argument is that while the yield gap of policy discourse provides a simple and powerful framing device, it is most often used without the discipline or caveats associated with the best examples of its use in crop production ecology and microeconomics. This argument is developed by examining how yield gap is used in a selection of recent and influential agricultural policy documents. The message for policy makers and others is clear: ??mind the (yield) gap(s)??, for they are seldom what they appear.     

Reactivity of Pb(II) at the Mn(III,IV) (oxyhydr)oxide--water interface

In this study, the reactivity of lead (Pb(II)) on naturally occurring Mn(III,IV) (oxyhydr)oxide minerals was evaluated using kinetic, thermodynamic, and spectroscopic investigations. Aqueous Pb(II) was more strongly adsorbed to birnessite (delta-MnO1.7) than to manganite (gamma-MnOOH) under all experimental conditions. The isoteric heat of Pb adsorption (delta HT) or birnessite was 94 kJ mol-1 at a surface loading of 1.1 mmol g-1, and decreased with increasing adsorption density. This indicated that adsorption was an endothermic process and that birnessite possessed heterogeneous sites of reactivity for Pb. X-ray absorption fine structure (XAFS) spectra revealed that Pb was adsorbed as inner-sphere complexes on both birnessite and manganite with no evidence to suggest oxidation as an operative sorption mechanism. Lead appeared to coordinate to vacancy sites in the birnessite layer structure with concurrent release of Mn to solution, which resulted in a greater number of second shell Mn scatterers in Pb-birnessite when compared to Pb-manganite samples. The difference in Pb coordination apparently explained the contrasting desorption behavior between the two Mn minerals. These results have significant implications for Pb partitioning in soil environments containing solid-phase Mn(III,IV) (oxyhydr)oxides.     

Supercritical fluid extraction (SFE) of 4(5)-methylimidazole (4-MeI) and 2-acetyl-4(5)-(1,2,3,4)-tetrahydroxybutyl-imidazole (THI) from ground-coffee with high-performance liquid chromatographic-electrospray mass spectrometric quantification (HPLC/ESI-MS).

Two polar analytes, 4(5)-methylimidazole (4-MeI) and 2-acetyl-4(5)-(1,2,3,4)-tetrahydroxybutyl-imidazole (THI), were extracted with supercritical carbon dioxide (CO2) modified with aqueous methanol. The method was applied to a roasted coffee powder with good recovery rates. Method efficiency was compared with that of solid-phase extraction using SCX Disc cartridges and validated for spiked solid matrix. The analytes were determined using isocratic liquid chromatography-mass spectrometry (LC/MS) on an Atlantis HILIC Silica column (150 x 2.1 mm, 3 microm) with 80% methanol and 20% 0.01 mol l-1 ammonium formate as the mobile phase. The limit of quantification was around 1.5 pg for 4-MeI and 2.0 pg for THI. The linearity of the calibration curves was satisfactory as indicated by correlation coefficients of >0.999. The coefficient of variation for the intra-day and inter-day precisions was <4% (n = 6). Accuracy was in the range 98-101%; recovery rates were > or = 98 and > or = 99% for THI and 4-MeI, respectively. Several samples of Arabica coffee from various locations and commercially available 'off-the-shelf' coffee products (Arabica/Robusta mixtures) were analysed to test the method.     

Iron(VI) and iron(V) oxidation of thiocyanate

Thiocyanate (SCN-) is used in many industrial processes and is commonly found in industrial and mining waste-waters. The removal of SCN- is required because of its toxic effects. The oxidation of thiocyanate (SCN-) by environmentally friendly oxidants, Fe(VI) and Fe(V), has been studied anaerobically using stopped-flow and premix pulse radiolysis techniques. The stoichiometry with Fe(VI) was determined to be 4HFeO(4-) + SCN(-) + 5H2O-->4Fe(OH)3 + SO4(2-) + CNO(-) + O2 + 2OH-. The rate law for the oxidation of SCN- by Fe(VI) was found to be -d[Fe(VI)]/dt = k11([H+]/([H+] + Ka,HFeO4)) [Fe(VI)][SCN-] where k11 = 2.04 +/- 0.04 x 10(3) M-1 s-1 and pKa,HFeO4 = 7.33. A mechanism is proposed that agrees with the observed reaction stoichiometry and rate law. The rate of oxidation of SCN- by Fe(V) was approximately 3 orders of magnitude faster than Fe(VI). The higher reactivity of Fe(V) with SCN- indicates that oxidations by Fe(VI) may be enhanced in the presence of appropriate one-electron-reducing agents. The results suggest that the effective removal of SCN- can be achieved by Fe(VI) and Fe(V).     

Attractancy of diethyl ether extracts of Arachis hypogaea (Linnaeus) (Papilionaceae), Citrullus lanatus (Thunberg) (Cucurbitaceae) and Irvingia gabonensis var. excelsa (Baillon) (Irvingiaceae) to Oryzaephilus mercator (Fauvel) (Coleoptera: Silvanidae)

Volatiles of the diethyl ether extracts of I. gabonensis, C. lanatus and A. hypogaea attracted 1–7 and 28–42-day-old adult O. mercator when tested in a two-choice pitfall Petri dish bioassay. For both age groups, a significant difference was observed in response between fed and starved adults to the different extracts. Differences in starvation time did not affect responses of individuals in the 1–7-day-old group; a significant effect was observed in the 28–42-day-old group.

Adults, 28–42-day-old were significantly more responsive to virtually all extracts than 1–7-day-old adults. Responses of adults in each age group to the different extracts were not significantly different. The time of trial within the period 0900–1900 h did not significantly affect the response of adults in both age groups, starved for 2 days, to any extract.     

羟丙基壳聚糖亚铁配合物的合成

采用壳聚糖先与Fe2+配合,再用环氧丙烷改性,研究了羟丙基壳聚糖-Fe2+的合成工艺,并用紫外和红外光谱对衍生物结构进行了表征。结果表明,在壳聚糖用量为0.1g、Fe2+起始浓度为16mg/mL、溶液pH为2的条件下,制得壳聚糖亚铁配合物。接着在壳聚糖-Fe2+∶环氧丙烷∶25%四甲基氢氧化铵为1mg∶10mL∶0.8mL条件下,制得羟丙基壳聚糖-Fe2+(HPCS-Fe2+)。位于1160～1030cm-1处有特征吸收峰,说明衍生化后得到的HPCS和HPCS-Fe2+上两个羟基上都发生了反应。     

Oxidation of sulfonamide antimicrobials by ferrate(VI) [Fe(VI)O4(2-)

Sulfonamide antimicrobials are used in both human therapy and animal husbandry. Sulfonamides are not readily biodegradable and have been detected in surface water and in secondary wastewater effluents. The chemical oxidation of sulfonamides by an environmentally friendly oxidant, ferrate(VI) (Fe(VI)O4(2-), Fe(VI)), was conducted. The sulfonamides used in the oxidation studies were sulfisoxazole, sulfamethazine, sulfamethizole, sulfadimethoxine, and sulfamethoxazole. Kinetics of the reactions were determined as a function of pH (7.0-9.7) and temperature (15-45 degrees C) by a stopped-flow technique. The rate law for the oxidation of sulfonamides by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constants decreased nonlinearly with an increase in pH and are possibly related to the protonation of Fe(VI) (HFeO4- <==> H+ + FeO4(2-); pK(a,HFeO4) = 7.23) and sulfonamides (SH <==> H+ + S-; pK(a,SH) = 5.0-7.4). The activation parameters of the reactions vary with pH due to temperature dependence on the protonation of Fe(VI) and sulfonamides. These results were used to obtain enthalpy of dissociation of sulfonamides. Stoichiometry and products of sulfamethoxazole (SMX) reactions with Fe(VI) were studied in detail using various analytical techniques to evaluate the effect of the oxidation process on the fate of sulfonamides in water. At a stoichiometric ratio of 4:1 (Fe(VI): SMX), complete removal of SMX was achieved. Analyses of oxidation products of the reaction as well as kinetic measurements of substructural models of SMX suggest that the attack of Fe(VI) occurs at the isoxazole moiety as well as at the aniline moiety with minimal preference. The results of the studies reported suggest that Fe(VI) has the potential to serve as a chemical oxidant for removing sulfonamides and converting them to relatively less toxic byproducts in water.     

Pr0.5Ba0.1Sr0.4MnO3的电磁性能及其庞磁电阻效应

用固态反应法制备了半掺杂锰氧化合物Pr0.5Ba0.1Sr0.4MnO3块材,结果显示,当温度从5K增加到300K时,样品依次由反铁磁绝缘体转变为铁磁半导体、铁磁金属、顺磁半导体。在发生反铁磁-铁磁和铁磁-顺磁两种转变时,样品在较低的磁场（1T）作用下,都表现出了较强的庞磁电阻效应。     

Control potential of Anisopteromalus calandrae (Howard) (Hymenoptera: Pteromalidae) against Lasioderma serricorne (F.) (Coleoptera: Anobiidae)

The control potential of Anisopteromalus calandrae (Howard) (Hymenoptera: Pteromalidae) against Lasioderma serricorne (F.) (Coleoptera: Anobiidae) was evaluated in laboratory. The longevity and progeny production of A. calandrae were investigated at 25, 30, and 35 °C. Parasitism preference of A. calandrae to different life stages of L. serricorne was studied at the parasitoid-to-host ratio of 1:15. Effectiveness of A. calandrae against L. serricorne larvae was investigated at different parasitoid-to-host ratios of 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, and 1:40 for 24, 48, and 72 h at a photoperiod of 12:12 (L:D) h, 28 ± 2 °C, and 75 ± 5% RH. Effectiveness of A. calandrae against L. serricorne larvae was also evaluated at different volumes (10, 55, 100, 150, 200, 250, 1500, and 2800 ml) of glass vials when the parasitoid-to-host ratio was 1:15. The favorable temperature for survival and progeny production of female A. calandrae was 25 °C. Female A. calandrae could parasitize mature larvae of L. serricorne and produce their offspring during the whole adult stage of the wasp. Female A. calandrae could control 3-, 4-, 5-, and 6-week-old mature larvae and pupae of L. serricorne. Anisopteromalus calandrae offspring only emerged from 6-week-old mature larvae and pupae of L. serricorne. The parasitoid-to-host ratio and space size dramatically affected the parasitism rate of A. calandrae against L. serricorne and the number of A. calandrae offspring. These results suggest that A. calandrae has great potential for controlling L. serricorne infestation.     

Formation of layered Fe(II)-Al(III)-hydroxides during reaction of Fe(II) with aluminum oxide

The reactivity of aqueous Fe(II) with aluminum oxide in anoxic solutions was investigated with batch kinetic experiments combined with Fe K edge X-ray absorption spectroscopy measurements to characterize Fe(II) sorption products. Formation of Fe(II)-Al(III)-layered double hydroxides with an octahedral sheet structure similar to nikischerite (NaFe(II)(6) Al(3)(SO(4))(2)(OH)(18) (H(2)O)(12)) was observed within a few hours during sorption at pH 7.5 and aqueous Fe(II) concentrations of 1-3 mM. These Fe(II) phases are composed of brucite-like Fe(II)(OH)(2) sheets with partial substitution of Al(III) for Fe(II), charge balanced by anions coordinated along the basal planes. Their fast rate of formation suggests that these previously unrecognized Fe(II) phases, which are structurally and compositionally similar to green rust, may be an important sink of Fe(II) in suboxic and anoxic geochemical environments, and impact the fate of structurally compatible trace metals, such as Co(II), Ni(II), and Zn(II), as well as redox-reactive species including Cr(VI) and U(VI). Further studies are required to assess the thermodynamics, formation kinetics, and stability of these Fe(II) minerals under field conditions.     

Bacteriological quality assurance (BQA) of mechanically deboned meat (MDM)

Adequacy of bacteriological quality assurance during the commercial production of mechanically deboned meat (MDM) was assessed. Lax standards of hygiene during production were observed, resulting in high numbers of Staphylococcus aureus, viz. 10⁴ to 10⁵ cfu g⁻¹, and severe contamination with Enterobacteriaceae: 10⁵ to 10⁶ cfu g⁻¹. These data indicate that measures of hygiene observed during boning of carcasses and during collection, storage and transport of bones or poultry parts should be markedly tightened, while conditions of refrigerated storage of raw materials and MDM should be improved. Use of bones of poor sensory quality (discoloration, abnormal smell) generally resulted in MDM of inferior bacteriological quality.

Phage typing, biotyping and assessment of enterotoxin production was carried out with 136 St. aureus cultures, isolates from mechanically deboned pork produced at one plant. Fifty-five per cent of the isolates was not typable, 28% was typable with human phages, 8% with bovine phages. The majority of the strains could not be explicitly assigned to any Meyer and/or Hájek and Mar álek types. Applying the simplified system of Devriese to eighteen strains isolated in our investigation, ten were found to belong to the poultry ecovar, one to the bovine ecovar, while seven strains were non-host specific. None of the isolates produced enterotoxins A–E.

Microbiological inspection of end products is recommended as part of an integrated quality assurance system. The following reference values for the final product (maximal colony counts to be expected under GMP conditions expressed as 95th percentile) were calculated: Pig MDM: log₁₀ mesophilic colony count 6·8 and log₁₀ cfu mesophilic Enterobacteriaceae g⁻¹ 4·8; Poultry MDM: log₁₀ mesophilic colony count 6·6 and log₁₀ cfu mesophilic Enterobacteriaceae g⁻¹ 4·7.     

关于函数(S)k(n)的均值

研究了函数S^-k（n）的均值性质,并用初等方法得到了关于它的一个渐近公式.     

白酒生产检验（二十二）：白酒食品安全检测（续）

本期介绍白酒食品安全指标中糖精钠及甜蜜素的检测方法。     

Structure of the hydrated (1014) surface of rhodochrosite (MnCO3)

The three-dimensional structure of the hydrated (1014) surface of MnCO3 at 90% relative humidity and 295 K is determined from measurements of X-ray scattering along ten crystal-truncation rods (CTRs). The scattering data provide both vertical and lateral information about the interfacial structure. The model that best fits the scattering data is a surface having a first layer of manganese carbonate and an overlayer of oxygen (as water). Within the measurement uncertainty, the overlayer of oxygen (O(w)) and the first-layer of manganese (Mn1) have equal occupancies of 0.84. The Mn1-O(w) distance between these layers is 2.59 +/- 0.04 angstroms. The overlayer O atoms are displaced laterally by 0.157 angstroms in the x- and 0.626 angstroms in the y-direction relative to the first-layer Mn atoms. The first-layer carbonate groups tilt by -4.2 +/- 2.1 degrees in phi (toward the surface plane) and -2.6 +/- 1.2 degrees in chi (an axis perpendicular to phi). The second-layer carbonate groups do not tilt, at least within measurement uncertainty. The spacing between Mn atom layers remains unchanged within measurement error whereas the spacing between layers of C atoms in carbonate contracts for the top three layers. Knowledge of the detailed atomic structure of the hydrated (1014) surface of MnCO3 provides a structural baseline for the interpretation of chemical reactivity.     

The persistence of infectious adenovirus (type 35) in mussels (Mytilus edulis) and oysters (Ostrea edulis)

Microbiological analyses of fruits and vegetables produced by farms in Minnesota and Wisconsin were conducted to determine the prevalence of Escherichia coli in pre-harvest fruits and vegetables. During the 2003 and 2004 harvest seasons, 14 organic (certified by accredited organic agencies), 30 semi-organic (used organic practices but not certified) and 19 conventional farms were sampled to analyze 2029 pre-harvest produce samples (473 organic, 911 semi-organic, 645 conventional). Before each harvest season, a farmer survey was conducted to collect relevant information on farm management practices that might affect the risk of E. coli contamination in fresh produce. The use of animal wastes for fertilization of produce plants increased the risk of E. coli contamination in organic (OR = 13.2, 95% CI = 2.2–61.2, P-value < 0.0001) and semi-organic (OR = 12.9, 95% CI = 2.9–56.3, P-value < 0.0001) produce significantly. Improper ageing of untreated animal manure significantly increased this risk in organic produce (OR = 4.2 95% CI = 1.7–12.3, P-value = 0.005) grown using such manure as a fertilizer. Organic growers who used cattle manure for fertilization of their crops showed significantly greater risk of contamination with the E. coli (OR = 7.4, 95% CI = 1.6–36.8, P-value = 0.003), compared to those who used other types of manure-based fertilizer. In Minnesota, organic and semi-organic produce collected from the southeastern (SE) part of the state were at a significantly greater risk of E. coli contamination (OR = 3.45, 95% CI = 1.8–35.2, P = 0.008), compared to those collected from farms located in the southern (S) regions of the state. In Wisconsin, organic and semi-organic produce collected from the southern (S) cluster of farms were at approximately 3-times greater risk of E. coli contamination (OR = 2.67, 95% CI = 1.3–9.4, P = 0.004), compared to those grown in the northern (N) cluster of farms.