Behavior of fluoroquinolones and trimethoprim during mechanical, chemical, and active sludge treatment of sewage water and digestion of sludge

The behavior and fate of three fluoroquinolones (norfloxacin, ofloxacin, and ciprofloxacin), one sulfonamide (sulfamethoxazole), and trimethoprim were investigated at a sewage treatment plant in Ume?, Sweden, in 2004. This plant uses conventional mechanical, chemical, and activated sludge methods to treat the sewage water and digest the sludge; the dewatered digested sludge is pelleted (dry weight > 90% of total weight). Raw sewage water and particles as well as effluents and sludge from specific treatment areas within the plant were sampled. In addition to quantifying the antibiotics within the plant, we characterized the sample matrixes to facilitate evaluation of the results. Of the five substances examined, only norfloxacin, ciprofloxacin, and trimethoprim were present in concentrations higher than their limits of quantification. Norfloxacin and ciprofloxacin sorbed to sludge in a manner that was independent of changes in pH during sewage treatment, and more than 70% of the total amount of these compounds passing through the plant was ultimately found in the digested sludge. The results suggest that fluoroquinolones undergo thermal degradation during pelleting, but more studies are needed to confirm this. Trimethoprim was found in the final effluent at approximately the same concentration and mass flow as in the raw sewage, and could not be quantified in any solid sample. Predicted environmental concentrations, based on consumption data for Ume? municipality, correlated well with the results obtained, especially when the predicted concentrations were corrected to account for the amount of each active substance excreted in urine. The results obtained were compared to those of previous studies of these three substances' behavior and fate and were found to be similar, although some of the other plants studied employed the various treatment steps in different orders.     

Electrochemical study of arsenate and water reduction on iron media used for arsenic removal from potable water

Zerovalent iron filings have been proposed as a filter medium for removing As(III) and As(V) compounds from potable water. The removal mechanism involves complex formation of arsenite and arsenate with the iron surface and with iron oxides produced from iron corrosion. There is conflicting evidence in the literature on whether As(V) can be reduced to As(III) by iron filter media. This research uses electrochemical methods to investigate the redox reactions that occur on the surface of zerovalent iron in arsenic solutions. The effect of arsenic on the corrosion rate of zerovalent iron was investigated by analysis of Tafel diagrams for iron wire electrodes in anaerobic solutions with As(V) concentrations between 100 and 20,000 microg/L. As(V) reduction in the absence of surface oxides was investigated by analysis of chronoamperometry profiles for iron wire electrodes in solutions with As(V) concentrations ranging from 10000 to 106 microg/L. The effect of pH on As(V) reduction was investigated by analyses of chronopotentiometry profiles for iron wire electrodes at pH values of 2, 6.5, and 11. For freely corroding iron, the presence of As(III) and As(V) decreased the iron corrosion rate by a factor of 5 as compared to that in a 3 mM CaSO4 blank electrolyte solution. The decrease in corrosion rate was independent of the arsenic concentration and was due to the blocking of cathodic sites for water reduction by arsenic compounds chemisorbed to the iron surface. The chronoamperometry and chronopotentiometry experiments showed that elevated pH and increased As(III) to As(V) ratios near the iron surface decreased the thermodynamic favorability for As(V) reduction. Therefore, reduction of As(V) occurred only at potentials that were significantly below the apparent equilibrium potentials based on bulk solution pH values and As(III) to As(V) ratios. The potentials required to reduce more than 1% of the As(V) to As(III) were below those that are obtainable in freely corroding iron media. This indicates that there will be minimal or no reduction of As(V) in iron media filters under conditions relevant to potable water treatment.     

Formation of dialyzable iron during in-vitro digestion and extraction of mycoprotein

Mycoprotein is the biomass of the fungus Fusarium venenatum. The ability of mycoprotein to enhance production of dialyzable iron following in-vitro digestion or extraction was studied, with the aim of identifying the components responsible. Digested mycoprotein, extracted mycoprotein and digested chicken breast muscle all produced about ten times as much dialyzable iron as the control. All of the dialyzable iron from mycoprotein was ferric. Essentially all the dialyzable iron passed through a 1 kDa molecular weight cut-off membrane. Iron binding components were extracted from mycoprotein using weak acid but not water. Extraction of mycoprotein produced both dialyzable and non-dialyzable components, which bound ferric iron. Analysis of the digests and the dialyzable fraction of acid extraction showed that they contained siderophores, which contributed to the formation of dialyzable iron.     

Chloride effect on TNT degradation by zerovalent iron or zinc during water treatment

Addition of corrosion promoters, such as sodium and potassium chloride, accelerated TNT degradation during water treatment using zerovalent zinc and iron. It was theorized that corrosion promoters could be used to accelerate electron generation from metallic species, create new reactive sites on the surface of metals during contaminated water treatment, and minimize passivating effects. The surface area normalized pseudo-first-order rate constant for the reaction of zerovalent zinc with TNT in the absence of KCl was 1.364 L x m(-2) x h(-1). In the presence of 0.3 mM and 3 mM KCI, the rate constant increased to 10.5 L x m(-2) x h(-1) and 51.0 L x m(-2) x h(-1), respectively. For the reaction with zerovalent iron and TNT, the rate constant increased from 6.5 (L/m2 x h) in the absence of KCl to 37 L x m(-2) x h(-1) using 3 mM KCl. The results demonstrate that chloride based corrosion promoters enhance the rate of TNT degradation. The in-situ breakage of the oxide layer using corrosion promoters was applied as a treatment to maintain the long-term activity of the metallic species. Zinc maintained a high reactivity toward TNT, and the reactivity of iron increased after 5 treatment cycles using 3 mM KCI. Zinc and iron scanning electron micrographs indicate that TNT degradation rate enhancement is caused by the pitting corrosion mechanism.     

Comparison of a chemical and enzymatic extraction of arsenic from rice and an assessment of the arsenic absorption from contaminated water by cooked rice

Rice is a target food for arsenic speciation based analyses because of its relatively high arsenic concentration and per capita consumption rates. Improved speciation data for rice can be helpful in estimating inorganic arsenic exposures in the U.S. and in endemic populations. The inorganic arsenic exposure for cooked rice should include both the arsenic in raw rice plus the arsenic absorbed from the water used to prepare it. The amount of arsenic absorbed from water by rice during preparation was assessed using five different types of rice cooked in both contaminated drinking water and arsenic-free reagent water. The rice samples were extracted using trifluoroacetic acid (TFA) and speciated using IC-ICP-MS. The TFA procedure was able to extract 84-104% of the arsenic (As) from the five different cooked rice samples. Chromatographic recoveries ranged from 99% to 116%. The dimethylarsinic acid (DMA) and inorganic arsenic concentration ranged from 22 to 270 ng of As/g of rice and from 31 to 108 ng of As/g of rice, respectively, for samples cooked in reagent water. The overall recoveries, which relate the sum of the chromatographic species back to the total digested concentration, ranged from 89% to 117%. The absorption of arsenic by rice from the total volume of water [1:1 to 4:1 (water:rice)] used in cooking was between 89% and 105% for two different contaminated drinking water samples. A comparison of the TFA extraction to an enzymatic extraction was made using the five rice samples and NIST 1568a rice flour. The two extraction procedures produced good agreement for inorganic arsenic, DMA, and the overall recovery. Through the use of IC-ESI-MS/ MS with a parent ion of m/z 153 and fragment ions of m/z 138, 123, and 105, the structure dimethylthioarsinic acid was tentatively identified in two of the rice samples using the enzymatic extraction.     

亚临界水萃取技术检测茶叶中铅、铬、镉、砷4种重金属元素残留量

目的建立以亚临界水萃取(subcritical water extraction,SCWE)及电感耦合等离子体质谱(inductively coupled plasma mass spectrometry,ICP-MS)检测茶叶中铅(Pb)、铬(Cr)、镉(Cd)、砷(As)4种重金属元素残留量的方法。方法待测茶叶样品在5 MPa、150℃的亚临界条件下经提取15 min后,用ICP-MS测定。结果各目标物在1~50 mg/kg范围内线性关系良好,相关系数均大于0.999。对茶叶基质进行1.0、5.0和10.0 mg/kg三个水平的加标回收实验,4种重金属元素的回收率为70.19%~113.25%,相对标准偏差RSD8.2%。结论本方法的灵敏度、准确度和精密度均符合重金属元素残留测定的技术要求,适用于茶叶中重金属元素残留的检测。     

生活饮用水中砷含量的测定

以镍作为基体改进剂，选择合适的仪器分析条件，用石墨炉原子吸收分光光度法测定砷的含量，该法具有样品处理简单、快速、准确、选择性高且试样用量少等优点，具有较强的适用性，方法的精密度和准确度都令人满意。     

Kinetics of daidzin and genistin transformations and water absorption during soybean soaking at different temperatures

The kinetics of the isoflavone transformations (diadzin, diadzein, genistin and genistein) and moisture content in soaked soybeans were studied in the temperature range 30–85 °C. The evolution of the moisture was described by Peleg’s model, and a modified first order kinetic equation was used to predict the transformation profiles of different isoflavones in the soaked soybeans. The dependency, on temperature, of the kinetic parameter was modelled by the Arrhenius equation and empirical equations. The measured β-glucosidase activity at different temperatures justifies the experimental profiles of isoflavone conversion.     

Green rust and iron oxide formation influences metolachlor dechlorination during zerovalent iron treatment

Electron transfer from zerovalent iron (Fe0) to targeted contaminants is affected by initial Fe0 composition, the oxides formed during corrosion, and surrounding electrolytes. We previously observed enhanced metolachlor destruction by Fe0 when iron or aluminum salts were present in the aqueous matrix and Eh/pH conditions favored formation of green rusts. To understand these enhanced destruction rates, we characterized changes in Fe0 composition during treatment of metolachlor with and without iron and aluminum salts. Raman microspectroscopy and X-ray diffraction (XRD) indicated that the iron source was initially coated with a thin layer of magnetite (Fe3O4), maghemite (gamma-Fe2O3), and wüstite (FeO). Time-resolved analysis indicated that akaganeite (beta-FeOOH) was the dominant oxide formed during Fe0 treatment of metolachlor. Goethite (alpha-FeOOH) and some lepidocrocite (gamma-FeOOH) formed when Al2(SO4)3 was present, while goethite and magnetite (Fe3O4) were identified in Fe0 treatments containing FeSO4. Although conditions favoring formation of sulfate green rust (GR(II); Fe6(OH)12SO4) facilitated Fe0-mediated dechlorination of metolachlor, only adsorption was observed when GR(II) was synthesized (without Fe0) in the presence of metolachlor and Eh/pH changed to favor Fe(III)oxyhydroxide or magnetite formation. In contrast, dechlorination occurred when magnetite or natural goethite was amended with Fe(II) (as FeSO4) at pH 8 and continued as long as additional Fe(II) was provided. While metolachlor was not dechlorinated by GR(II) itself during a 48-h incubation, the GR(II) provided a source of Fe(II) and produced magnetite (and other oxide surfaces) that coordinated Fe(II), which then facilitated dechlorination.     

Removal of methylated arsenic in groundwater with iron filings

Field and laboratory experiments were conducted to study the potential use of Fe filings to remove monomethyl arsenate (MMA) and dimethyl arsenate (DMA) from contaminated waters. Batch experiments show that the affinity of MMAfor Fe filings is comparable to that of inorganic arsenate, but lower than that for arsenite. In contrast, very little DMA was retained by Fe filings or their corrosion products. The wide range of affinities of different As species for Fe filings was confirmed by a series of retention and selective-leaching experiments using small columns and As-spiked groundwater. The effectiveness of Fe filings was also demonstrated with a field deployment at a U.S. Superfund site where groundwater is highly contaminated with both organic and inorganic As species. Over the course of 4 months, a 3 L cartridge of Fe filings removed > 85% of As contained in 16000 L of groundwater containing 1-1.5 mg/L total dissolved As, approximately 30% of which was organic As. The results indicate that Fe filings could be used to treat groundwater contaminated with MMA, which is the main organic form of As at most contaminated sites. Indications of partial demethylation in the column of Fe filings suggest conditions might be optimized further to enhance the removal of DMA.     

Difference in tenderness and pH decline between water buffalo meat and beef during postmortem aging

The objective of this research was to determine the difference in tenderness and some characteristics of water buffalo meat and beef during postmortem aging. Five female crossbred water-buffalo (Philippine Carabao×Bulgarian Murrah) and five female crossbred cattle (Brahman×Philippine Native), were finished on the same diet for 6 months and slaughtered at 30 months of age. The muscle pH was measured at 40min, 3h, 7h, 24h, and 48h postmortem. Longissimus thoracis (LT) and semimembranosus (SM) muscles were excised at 2d postmortem, and shear force was measured at 2, 4, 7, and 14d postmortem. Glycogen and lactate concentrations were determined from 0, 2, and 4d LT samples, and myosin heavy chain type of buffalo and cattle LT was determined by ELISA methods. Myofibrillar protein degradation was also observed by SDS-PAGE and Western blotting of fast-type troponin T. Results showed that the buffalo meat had significantly lower shear force values compared to beef for LT and SM muscles, which was supported by a difference in troponin T degradation. Postmortem pH decline of buffalo meat was significantly slower than that of beef, which was confirmed by lactic acid concentrations, but was not explained by glycogen content. In addition, there was no significant difference in the ratio of slow to fast type muscle fibers in buffalo and cattle, indicating that myosin heavy chain type was not responsible for the difference in pH decline and tenderness between the buffalo meat and beef. This study demonstrated that the tenderness of water buffalo meat was superior to that of Brahman beef, which may have been due to the difference in pH decline and the subsequent effect on muscle protease activity.     

Thermal decomposition and oxidation of β-caryophyllene in black pepper during subcritical water extraction

Food Science and Biotechnology - Subcritical water extraction is an efficient technique for extracting components from various plants by changing the polarity of water. β-caryophyllene is a...     

Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility

Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5-6, whereas, above pH 7-8, As(II) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate that, under most of the chemical conditions investigated in this study, reduction of As(V) in the presence of HFO or goethite would have only minor effects on or even decrease its mobility in the environment at near-neutral pH conditions. As(V) and As(III) sorption isotherms indicate similar surface site densities on the three oxides. Intrinsic surface complexation constants for As(V) are higher for goethite than HFO, whereas As(III) binding is similar for both of these oxides and also for magnetite. However, decrease in specific surface area and hence sorption site density that accompanies transformation of amorphous iron oxides to more crystalline phases could increase arsenic mobility.     

Accumulation of arsenic in drinking water distribution systems

The tendency for iron solid surfaces to adsorb arsenic is well-known and has become the basis for several drinking water treatment approaches that remove arsenic. It is reasonable to assume that iron-based solids, such as corrosion deposits present in drinking water distribution systems, have similar adsorptive properties and could therefore concentrate arsenic and potentially re-release it into the distribution system. The arsenic composition of solids collected from drinking water distribution systems (pipe sections and hydrant flush solids), where the waters had measurable amounts of arsenic in their treated water, were determined. The elemental composition and mineralogy of 67 solid samples collected from 15 drinking water utilities located in Ohio (7), Michigan (7), and Indiana (1) were also determined. The arsenic content of these solids ranged from 10 to 13 650 microg of As/g of solid (as high as 1.37 wt %), and the major element of most solids was iron. Significant amounts of arsenic were even found in solids from systems that were exposed to relatively low concentrations of arsenic (<10 microg/L) in the water.     

Removal of pharmaceuticals during drinking water treatment

The elimination of selected pharmaceuticals (bezafibrate, clofibric acid, carbamazepine, diclofenac) during drinking water treatment processes was investigated at lab and pilot scale and in real waterworks. No significant removal of pharmaceuticals was observed in batch experiments with sand under natural aerobic and anoxic conditions, thus indicating low sorption properties and high persistence with nonadapted microorganisms. These results were underscored by the presence of carbamazepine in bank-filtrated water with anaerobic conditions in a waterworks area. Flocculation using iron(III) chloride in lab-scale experiments (Jar test) and investigations in waterworks exhibited no significant elimination of the selected target pharmaceuticals. However, ozonation was in some cases very effective in eliminating these polar compounds. In lab-scale experiments, 0.5 mg/L ozone was shown to reduce the concentrations of diclofenac and carbamazepine by more than 90%, while bezafibrate was eliminated by 50% with a 1.5 mg/L ozone dose. Clofibric acid was stable even at 3 mg/L ozone. Under waterworks conditions, similar removal efficiencies were observed. In addition to ozonation, filtration with granular activated carbon (GAC) was very effective in removing pharmaceuticals. Except for clofibric acid, GAC in pilot-scale experiments and waterworks provided a major elimination of the pharmaceuticals under investigation.     

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.     

废纸回收边程中脱墨污泥的处理及其资源化利用

废纸回收以其自身的优点,越来越受到人们的重视.但是,回用过程中排放的脱墨污泥对环境造成严重污染,这些污泥具有极高的回收利用价值.本文主要介绍了脱墨污泥的一些处理方法和资源化利用技术,从而实现可持续发展战略.     

XAS study of iron and arsenic speciation during Fe(II) oxidation in the presence of As(III)

The speciation of As and Fe was studied during the oxidation of Fe(II)-As(III) solutions by combining XAS analysis at both the Fe and As K-edges. Fe(II) and As(III) were first hydrolyzed to pH 7 under anoxic conditions; the precipitate was then allowed to oxidize in ambient air for 33 h under vigorous stirring. EXAFS analysis at the As K-edge shows clear evidence of formation of inner-sphere complexes between As(III) and Fe(II), i.e., before any oxidation. Inner-sphere complexes were also observed when Fe became sufficiently oxidized, in the form of edge-sharing and double-corner linkages between AsIIIO3 pyramids and FeIIIO6 octahedra. XAS analyses at the Fe K-edge reveal that the presence of As(III) in the solution limits the polymerization of Fe(II) and the formation of green rust and inhibits the formation of goethite and lepidocrocite. Indeed, As(III) accelerates the Fe(II) oxidation kinetics and leads to the formation of nanosized Fe-As subunits of amorphous aggregates. These observations, rather than a presumed weaker affinity of As(III) for iron oxyhydroxides, might explain why As(III) is more difficult to remove than As(V) by aerating reducing groundwater.     

Stabilization of available arsenic in highly contaminated mine tailings using iron

To evaluate the stabilization of available As in contaminated tailings from two abandoned metal mines of South Korea (the Myoungbong and Daduck Mines, 6670 and 56,600 mg/kg total As, respectively), characteristics of the tailings were investigated, and the tailings were treated through precipitation of amorphous iron compounds. Steep decreasing trends of extractable (5% NaOCl) As with increasing initial Fe(III) additions were observed in both treated tailings. In general, the treated tailings had the lowest extractable As concentration at pH 6. Available As, defined as the sum of As concentrations for the first four steps of a sequential extraction, was reduced from 2090 to 428 mg/kg (80% reduction) in the Myoungbong tailings and from 1320 to 395 mg/kg (70% reduction) in the Daduck tailings. As levels in the treated tailings decreased even more after a 1-month dormant period. Adsorption/coprecipitation tests performed with mixed As(III) and Fe(III) solutions demonstrated dramatically increased As sequestration via interaction with amorphous iron compounds with increasing pH. The bulk of the As appeared to be affiliated with stable Fe precipitates.     

Critical role of macrophytes in achieving low iron concentrations in mine water treatment wetlands

Aerobic wetlands are increasingly being included in mine water treatment systems which need to achieve low residual iron concentrations (<0.5 mg L(-1)) in final discharges. Traditionally the macrophyte components of such systems have been thought to be insignificant sinks for major contaminants such as iron. However, we report high rates of plant uptake of iron where the latter is present at relatively low concentrations, suggesting that macrophytes may well be critical to achieving low residual iron concentrations in final effluents from such systems. The wetland macrophyte Phragmites australis was grown in waters with a range of iron concentrations (0-50 mg L(-1)). At an Fe supply of 1 mg L(-1) almost 100% of the Fe was taken up into plant tissues. The majority of iron was stored in and around the roots of the plants, which helps allay fears of possible release of contaminants during seasonal die-back of emergent shoots and leaves. The 1 mg L(-1) threshold also proved to be important in terms of plant growth, with significant inhibition (evident in root length and in dry weights of shoots and roots) in plants grown in waters with Fe above this concentration. No direct causal relationship between iron content in aerial tissues and growth inhibition was found, which strongly suggests that iron toxicity cannot explain these results. These results have implications for the design of mine water treatment wetlands, particularly with regard to initial establishment of vegetation and achieving sufficient Fe removal in "polishing" applications (i.e. where it is intended to remove the last few mg L(-1) of Fe).