Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

组合工艺在养猪废水处理中的工程应用研究

针对某猪场养殖废水排放所造成的严重污染问题,采用“固液分离+ UBF厌氧反应器+接触氧化+曝气生物滤池”的组合工艺,对废水中的COD、BOD、氨氮、SS去除效果明显,去除率分别为93.7％、94.4％、95％、77.1％,处理后的水质达到《国家畜禽养殖业污染物排放标准》.该工程运行费用仅为1.509元/m3,处理成本低.同时UBF池中产生的沼气可以收集并利用,猪粪和污泥可制作有机肥,实现了废物资源化利用.     

Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

Threatened and Endangered Species: At What Cost? The Corps of Engineers Looks at Expenditures and Priorities

Current political conditions, primarily budgetary uncertainty, and the related reluctance to make funding commitments for future generations, have raised questions about the costs of conservation and environmental protection that have not previously been asked. As Federal investments are scrutinized and budgets become ever more constrained, the costs associated with environmental requirements could begin to be of greater importance and to influence decisions on Federal projects. In response to concerns about the U.S. Army Corps of Engineers (Corps) spending under the Endangered Species Act (P.L. 93-205) (ESA), a limited investigation was performed to determine the accuracy of reported Corps expenditures. The investigation showed that, for particular groups of species, actual conservation costs for threatened and endangered species may be twice the amounts previously reported in the annual ESA expenditure reporting to the U.S. Fish and Wildlife Service. In light of this finding, the Corps has sought a means to provide more accurate and consistent reporting of expenditures for addressing threatened and endangered species. A Species Costs Template (template) has been developed to identify the types and magnitude of costs related to the ESA and to counteract the impediments (legal, institutional, and practical) to underreporting costs. The template will be used by the Corps for reporting ESA costs beginning with Fiscal Year 2005 (FY05) (reported in January 2006). Five broad categories of expenditures (effects determination costs, ESA protection and conservation costs, equipment costs, opportunity costs, and other species costs) are identified by the template.     

低温下废铁屑对厌氧氨氧化系统的影响

考察了在低温条件下(<20℃)废铁屑及其投加方式对厌氧氨氧化反应器脱氮性能和微生物群落的影响.结果表明,当废铁屑投加量为10g/L时,直接(R2)和间接(R3)投加方式均会对厌氧氨氧化反应造成短期抑制,总氮去除率分别降低4.7%和3.4%;30d连续运行后,2组反应器总氮去除率均提升至70%左右;反应器稳定运行阶段,R2的R_s(NO₂^--N与NH₄⁺-N去除量之比)和R_p(NO₃^--N生成量与NH₄⁺-N去除量之比)为1.57和0.22, R3的R_s和R_p为1.49和0.23,比R2更接近厌氧氨氧化反应理论值.废铁屑在水中发生腐蚀,降低DO并提高pH值,且R2,R3污泥中铁含量分别为对照组的1.64倍和1.93倍,废铁屑不仅改善了厌氧氨氧菌的生境,还满足了其对铁元素的需求.高通量测序结果显示,在20~50d的运行过程中, R1,R2,R3中优势厌氧氨氧化菌属Candidatus_Kuenenia的相对丰度分别增加-1.05%,0.14%和0.96%,废铁屑的投加促进了厌氧氨氧化菌在低温下的生长,且间接投加促进效果更为显著.     

Dosing low-level ferrous iron in coagulation enhances the removal of micropollutants, chlorite and chlorate during advanced water treatment

Drinking water utilities are interested in upgrading their treatment facilities to enhance micropollutant removal and byproduct control. Pre-oxidation by chlorine dioxide (ClO₂) followed by coagulation-flocculation-sedimentation and advanced oxidation processes (AOPs) is one of the promising solutions. However, the chlorite (ClO₂^–) formed from the ClO₂ pre-oxidation stage cannot be removed by the conventional coagulation process using aluminum sulfate. ClO₂^– negatively affects the post-UV/chlorine process due to its strong radical scavenging effect, and it also enhances the formation of chlorate (ClO₃^–). In this study, dosing micromolar-level ferrous iron (Fe(II)) into aluminum-based coagulants was proposed to eliminate the ClO₂^– generated from ClO₂ pre-oxidation and benefit the post-UV/chlorine process in radical production and ClO₃^– reduction. Results showed that the addition of 52.1-µmol/L FeSO₄ effectively eliminated the ClO₂^– generated from the pre-oxidation using 1.0 mg/L (14.8 µmol/L) of ClO₂. Reduction of ClO₂^– increased the degradation rate constant of a model micropollutant (carbamazepine) by 55.0% in the post-UV/chlorine process. The enhanced degradation was verified to be attributed to the increased steady-state concentrations of HO^· and ClO^· by Fe(II) addition. Moreover, Fe(II) addition also decreased the ClO₃^– formation by 53.8% in the UV/chlorine process and its impact on the formation of chloro-organic byproducts was rather minor. The findings demonstrated a promising strategy to improve the drinking water quality and safety by adding low-level Fe(II) in coagulation in an advanced drinking water treatment train.     

Biological methane production coupled with sulfur oxidation in a microbial electrosynthesis system without organic substrates

Methane is produced in a microbial electrosynthesis system (MES) without organic substrates. However, a relatively high applied voltage is required for the bioelectrical reactions. In this study, we demonstrated that electrotrophic methane production at the biocathode was achieved even at a very low voltage of 0.1 V in an MES, in which abiotic HS⁻ oxidized to SO₄²⁻ at the anodic carbon-cloth surface coated with platinum powder. In addition, microbial community analysis revealed the most probable pathway for methane production from electrons. First, electrotrophic H₂ was produced by syntrophic bacteria, such as Syntrophorhabdus, Syntrophobacter, Syntrophus, Leptolinea, and Aminicenantales, with the direct acceptance of electrons at the biocathode. Subsequently, most of the produced H₂ was converted to acetate by homoacetogens, such as Clostridium and Spirochaeta 2. In conclusion, the majority of the methane was indirectly produced by a large population of acetoclastic methanogens, namely Methanosaeta, via acetate. Further, hydrogenotrophic methanogens, including Methanobacterium and Methanolinea, produced methane via H₂.     

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe₃O₄/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO₂ extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.     

Growth and Foliar Nitrogen Status of Four Plant Species Exposed to Atmospheric Ammonia

A chamber study was conducted to evaluate the growth response and leaf nitrogen (N) status of four plant species exposed to continuous ammonia (NH₃) for 12 weeks (wk). This was intended to evaluate appropriate plant species that could be used to trap discharged NH₃ from the exhaust fans in poultry feeding operations before moving off-site. Two hundred and forty bare-root plants of four species (Juniperus virginiana (red cedar), Gleditsia triacanthos var. inermis (thornless honey locust), Populus sp. (hybrid poplar), and Phalaris arundinacea (reed canary grass) were transplanted into 4- or 8-L polyethylene pots and grown in four environmentally controlled chambers. Plants placed in two of the four chambers received continuous exposure to anhydrous NH₃ at 4 to 5 ppm while plants in another two chambers received no NH₃. In each of the four chambers, 2 to 4 plants per species received no fertilizer while the rest of the plants were fertilized with a 100 ppm solution containing 21% N, 7% phosphorus, and 7% potassium. The results showed that honey locust was the fastest-growing species. The superior growth of honey locust among all species was also supported by its total biomass, root, and root dry matter (DM) weights. For all species there was a trend for plants exposed to NH₃ to have greater leaf DM than their non-exposed counterparts at 6 (43.0 vs. 30.8%; P = 0.09) and 12 wk (47.9 vs. 36.6%; P = 0.07), and significantly greater (P ≤ 0.05) leaf N content at 6 (6.44 vs. 3.67%) and 12 wk (7.05 vs. 3.51%) when exposed to NH₃. Numerically greater leaf DM due to NH₃ exposure was also consistently measured in poplar at both sampling periods. Hybrid poplar, as well as honey locust and reed canary grass, deposited 1.5 to 2-fold greater N in their leaves than red cedar tissues as a result of NH₃ exposure compared to non-exposed plants. Regardless of the effect of NH₃ on foliar color and damage score of the plants, the increase of foliar N content (g 100 g^?1 of fresh foliage weight) after NH₃ exposure at 6 and 12 wk was 0.45 and 0.87 for grass,1.25 and 1.34 for locust, and 2.67 and 6.09 for poplar. However, only honey locust likely benefited from ambient NH₃ as indicated by its consistent leaf color quality and lower damage score, compared with other species that were adversely affected by atmospheric NH₃.     

H2O2 treatment boosts activity of NiFe layered double hydroxide for electro-catalytic oxidation of urea

Urea oxidation reaction (UOR) provides a method for hydrogen production besides wastewater treatment, but the current limited catalytic activity has prevented the application. Herein, we develop a novel H₂O₂ treatment strategy for tailoring the surface oxygen ligand of NiFe-layered double hydroxides (NiFe-LDH). The sample after H₂O₂ treatment (NiFeO-LDH) shows significant enhancement on UOR efficiency, with the potential of 1.37 V (RHE) to reach a current density of 10 mA/cm². The boost is attributed to the richness adsorption O ligand on NiFeO-LDH as revealed by XPS and Raman analysis. DFT calculation indicates formation of two possible types of oxygen ligands: adsorbed oxygen on the surface and exposed from hydroxyl group, lowered the desorption energy of CO₂ product, which lead to the lowered onset potential. This strategy is further extended to NiFe-LDH nano sheet on Ni foam to reach a higher current density of 440 mA/cm² of UOR at 1.8 V (RHE). The facile surface O ligand manipulation is also expected to give chance to many other electro-catalytic oxidations.