Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 μg·L⁻¹, and the method detection limits were less than 0.1 μg·L⁻¹. For the reagent water samples fortified at 1.0 μg·L⁻¹ and 2.0 μg·L⁻¹, the obtained mean absolute recoveries were 70%–130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 μg·L⁻¹, the obtained mean absolute recoveries were 50%–130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

Copper and zinc interaction on water clearance and tissue metal distribution in the freshwater mussel, Cristaria plicata, under laboratory conditions

Copper and zinc interaction on clearance from water and distribution in different tissues was investigated for the freshwater mussel, Cristaria plicata, under laboratory conditions. Clearance rate of Cu or Zn from water was highly dependent on exposure concentration. Interaction effect was most evident at 300 μg·L⁻¹ Cu exposure and depressed the Zn clearance rate significantly (p<0.05). However, the presence of 100 μg·L⁻¹ and 300 μg·L⁻¹ Zn hardly affected the Cu clearance rate. The 300 μg·L⁻¹ Cu presence enhanced Cu accumulation in each tissue most significantly (p<0.01), but caused Zn content to decrease in the gills by 62% (p<0.05), viscera by 49% (p<0.05) and foot by 31% (p<0.05), and increase in the mantle by 97% (p<0.05) and the muscles by 243% (p<0.05) for different Zn exposure treatments. The response of metal accumulation in various tissues of the test mussels indicated that Zn transferred from the gills, viscera and foot to the mantle and muscles might be one of the important characteristics of the Zn regulatory mechanism by leading to a narrow range of Zn concentration in the different tissues.     

Ultrasound-assisted emulsification solidified floating organic drop microextraction for the determination of trace amounts of copper in water samples

A simple and efficient liquid-phase microextraction (LPME) technique was developed using ultrasound-assisted emulsification solidified floating organic drop microextraction (USAE-SFODME) combined with flame atomic absorption spectrometry, for the extraction and determination of trace copper in water samples. 1-(2-Pyridylazo)-2-naphthol (PAN) was used as chelating agent. Microextraction efficiency factors (including extraction solvent type, extraction volume, time, temperature, and pH), the amount of the chelating agent, and salt effect were investigated and optimized. Under the optimum extraction conditions, figures of merit of the proposed method were evaluated. The calibration graph was linear in the range of 20–600 μg·L⁻¹ with a detection limit of 0.76 μg·L⁻¹. The relative standard deviation (R.S.D) for ten replicate measurements of 20 and 400 μg·L⁻¹ of copper was 3.83% and 2.65%, respectively. Finally, the proposed method was applied to tap water, river water, and sea water, and accuracy was assessed through the analysis of certified reference water or recovery experiments.     

Dilution sampling and analysis of particulate matter in biomass-derived syngas

Thermochemical biomass gasification, followed by conversion of the produced syngas to fuels and electrical power, is a promising energy alternative. Real-world characterization of particulate matter (PM) and other contaminants in the syngas is important to minimize damage and ensure efficient operation of the engines it powers and the fuels created from it. A dilution sampling system is demonstrated to quantify PM in syngas generated from two gasification plants utilizing different biomass feedstocks: a BioMax?15 Biopower System that uses raw and torrefied woodchips as feedstocks, and an integrated biorefinery (IBR) that uses rice hulls and woodchips as feedstocks. PM_2.5 mass concentrations in syngas from the IBR downstream of the purification system were 12.8–13.7 μg·m⁻³, which were significantly lower than the maximum level for catalyst protection (500 μg·m⁻³) and were 2–3 orders of magnitude lower than those in BioMax?15 syngas (2247–4835 μg·m⁻³). Ultrafine particle number concentration and PM_2.5 chemical constituents were also much lower in the IBR syngas than in the BioMax?15. The dilution sampling system enabled reliable measurements over a wide range of concentrations: the use of high sensitivity instruments allowed measurement at very low concentrations (∼1 μg·m⁻³), while the flexibility of dilution minimized sampling problems that are commonly encountered due to high levels of tars in raw syngas (∼1 g·m⁻³).     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L⁻¹ and gave detection limits of 0.5–1.5 ng·L⁻¹ for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

单级和两级串联臭氧-生物活性炭深度处理垃圾渗滤液的比较研究

使用单级和两级串联臭氧-生物活性炭(O3-BAC)处理垃圾焚烧渗滤液的二级生物处理尾水,比较研究了污染物去除效果.结果表明,臭氧投加量为200 mg·L-1时,两级串联O3-BAC对COD、UV254和色度的去除率分别为75.9%±2.1%、78.8%±2.9%和96.8%±0.9%,处理出水COD基本保持在100 mg·L-1以下,色度低于40倍,满足GB 16889-2008排放要求;而单级O3-BAC对COD、UV254和色度的去除率分别为68.2%±1.3%、69.7%±0.5%和92.5%±1.1%,处理出水COD和色度分别为150 mg·L-1和60倍,不能达到排放要求.单级O3-BAC在290 mg·L-1臭氧投加量下,才能达到两级串联O3-BAC在200mg·L-1臭氧投加量下的污染物去除效果.此外,两级串联O3-BAC在臭氧投加量200 mg·L-1时的总磷去除率为63.5%±4.4%,出水总磷浓度稳定在1 mg·L-1以下,直接满足GB 16889-2008排放要求.     

Evaluate HAA removal in biologically active carbon filters using the ICR database

The effects of biologically active carbon (BAC) filtration on haloacetic acid (HAA) levels in plant effluents and distribution systems were investigated using the United States Environmental Protection Agency’s Information Collection Rule (ICR) database. The results showed that average HAA5 concentrations in all locations were 20.4 μg·L⁻¹ and 29.6 μg·L⁻¹ in ICR plants with granular activated carbon (GAC) and ICR plants without GAC process, respectively. For plants without GAC, the highest HAA levels were observed in the quarters of April to June and July to September. However, for plants with GAC, the highest HAA levels were observed in the quarters of April to June and January to March. This HAA level profile inversely correlated well with water temperature, or biologic activity. For GAC plants, simulated distribution samples matched well with distribution system equivalent samples for Cl₃AA and THMs. For plants with and without GAC, simulated distribution samples overestimated readily biodegradable HAAs in distribution systems. The study indicated that through HAA biodegradation, GAC process plays an important role in lowering HAA levels in finished drinking water.     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F⁻ concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F⁻ concentrations (C ₀ = 5–1000 mg·L⁻¹), the amount of F⁻ adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F⁻ concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L⁻¹. The QF increases significantly by continuously modifying the pH level. At C ₀<5–100 mg·L⁻¹, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F⁻ binding. As the C ₀ increases, F⁻, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L⁻¹, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^−11.94 mol·L⁻¹, cryolite forms, while at [Al³⁺]<10^−11.94 mol·L⁻¹, AlF₃ is formed. At low C ₀ (0.3–1.5 mg·L⁻¹), proton transfer occurs, and the F⁻ adsorption capabilities of the clay minerals increase with time.     

Development of pretreatment protocol for DNA extraction from biofilm attached to biologic activated carbon (BAC) granules

The biologic activated carbon (BAC) process is widely used in drinking water treatments. A comprehensive molecular analysis of the microbial community structure provides very helpful data to improve the reactor performance. However, the bottleneck of deoxyribonucleic acid (DNA) extraction from BAC attached biofilm has to be solved since the conventional procedure was unsuccessful due to firm biomass attachment and adsorption capacity of the BAC granules. In this study, five pretreatments were compared, and adding skim milk followed by ultrasonic vibration was proven to be the optimal choice. This protocol was further tested using the vertical BAC samples from the full-scale biofilter of Pinghu Water Plant. The results showed the DNAyielded a range of 40 μg·g⁻¹ BAC (dry weight) to over 100 μg·g⁻¹ BAC (dry weight), which were consistent with the biomass distribution. All results suggested that the final protocol could produce qualified genomic DNA as a template from the BAC filter for downstream molecular biology researches.     

CANON工艺处理石油催化剂废水的性能研究

以石油裂化催化剂废水为研究对象,采用电絮凝作为废水的预处理单元,研究CANON工艺的启动及脱氮性能.结果表明:电絮凝对原水浊度的去除率达到98.7%±1.2%,对COD去除率达到32.3%±4.5%.利用人工模拟高氨氮废水成功启动CANON工艺,TN去除率最高达到62.0%,TN去除负荷最高达到0.19 kg·m~(-3)·d~(-1)(以N计).使用石油裂化催化剂废水对微生物进行了驯化,经过108 d的运行,微生物成功驯化。利用CANON工艺处理石油裂化催化剂废水,COD去除率为40.9%±13.2%,TN去除率为67.3%±12.7%,TN去除速率为(0.07±0.02)kg·m~(-3)·d~(-1)(以N计).反应器出水COD100 mg·L-1,NH_4~+-N10 mg·L~(-1),满足石油化工企业污水的排放标准(GB8978—1996).     

Migration of manganese and iron during the adsorption-regeneration cycles for arsenic removal

Fe-Mn binary oxide incorporated into porous diatomite (FMBO-diatomite) was prepared in situ and regenerated in a fixed-bed column for arsenite [As(III)] and arsenate [As(V)] removal. Four consecutive adsorption cycles were operated under the following conditions: Initial arsenic concentration of 0.1 mg·L⁻¹, empty bed contact time of 5 min, and pH 7.0. About 3000, 3300, 3800, and 4500 bed volumes of eligible effluent (arsenic concentration ⩽ 0.01 mg·L⁻¹) were obtained in four As (III) adsorption cycles; while about 2000, 2300, 2500, and 3100 bed volumes of eligible effluent were obtained in four As(V) adsorption cycles. The dissection results of FMBO-diatomite fixed-bed exhibited that small amounts of manganese and iron were transferred from the top of the fixed-bed to the bottom of the fixed-bed during As(III) removal process. Compared to the extremely low concentration of iron (<0.01 mg·L⁻¹), the fluctuation concentration of Mn²⁺ in effluent of the As(III) removal column was in a range of 0.01–0.08 mg·L⁻¹. The release of manganese suggested that manganese oxides played an important role in As(III) oxidation. Determined with the US EPA toxicity characteristic leaching procedure (TCLP), the leaching risk of As(III) on exhausted FMBO-diatomite was lower than that of As(V).     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium, kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔGo° ( − 0.8–4.58 kJ·mol⁻¹), ΔH° (15.6–44.4 kJ·mol⁻¹), and ΔS° (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr (III) concentration. The analysis of the values of biosorption activation energy (E _a = −7 kJ·mol⁻¹) and the intraparticle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

A hybrid membrane process for simultaneous thickening and digestion of waste activated sludge

A hybrid membrane process for simultaneous sludge thickening and digestion (MSTD) was studied. During one cycle (15 d) of operation under a hydraulic retention time of 1 d, the concentration of mixed liquor suspended solids (MLSS) continuously increased from about 4 g·L⁻¹ to 34 g·L⁻¹, and the mixed liquor volatile suspended solids (MLVSS) increased from about 3 g·L⁻¹ to over 22 g·L⁻¹. About 42% of the MLVSS and 39% of the MLSS reduction were achieved. The thickening and digestion effects in the MSTD were further analyzed based on a mass balance analysis. Test results showed that biopolymers and cations of biomass were gradually released to the bulk solution during the process. It was also found that the capillary suction time, colloidal chemical oxygen demand, soluble microbial products, viscosity, and MLSS had significant positive correlations with the membrane fouling rate, whereas extracellular polymeric substances, polysaccharides, and proteins extracted from biomass had negative impacts on membrane fouling.     

Continuous biohydrogen production from diluted molasses in an anaerobic contact reactor

An anaerobic contact reactor (ACR) system comprising a continuous flow stirred tank reactor (CSTR) with settler to decouple the hydraulic retention time (HRT) from solids retention time (SRT) was developed for fermentative hydrogen production from diluted molasses by mixed microbial cultures. The ACR was operated at various volumetric loading rates (VLRs) of 20–44 kgCOD·m⁻³·d⁻¹ with constant HRT of 6 h under mesophilic conditions of 35°C. The SRT was maintained at about 46–50 h in the system. At the initial VLR of 20 kgCOD·m⁻³·d⁻¹, the hydrogen production rate dropped from 22.6 to 1.58 L·d⁻¹ as the hydrogen was consumed by the hydrogentrophic methanogen. After increasing the VLR to 28 kgCOD·m⁻³·d⁻¹ and discharging the sludge for 6 consecutive times, the hydrogentrophic methanogens were eliminated, and the hydrogen content reached 36.4%. As the VLR was increased to 44 kgCOD·m⁻³·d⁻¹, the hydrogen production rate and hydrogen yield increased to 42.1 L·d⁻¹ and 1.40 mol H₂·molglucose-consumed-1, respectively. The results showed that a stable ethanoltype fermentation that favored hydrogen production in the reactor was thus established with the sludge loading rate (SLR) of 2.0–2.5 kgCOD·kgMLVSS⁻¹·d⁻¹. It was found that the ethanol increased more than other liquid fermentation products, and the ethanol/acetic acid (mol/mol) ratio increased from 1.27 to 2.45 when the VLR increased from 28 to 44 kgCOD·m⁻³·d⁻¹, whereas the hydrogen composition decreased from 40.4% to 36.4%. The results suggested that the anaerobic contact reactor was a promising bioprocess for fermentative hydrogen production.     

Seasonal variation of nitrogen and phosphorus in Xiaojiang River—A tributary of the Three Gorges Reservoir

A yearlong monitoring program in the backwater area of Xiaojiang River (XBA) was launched in order to investigate the eutrophication of backwater areas in tributaries of the Yangtze River in the Three Gorges Reservoir (TGR) in China, starting after the impoundment water level of the TGR reached 156 m. From March 2007 to March 2008, the average concentration of total nitrogen (TN) and total phosphorus (TP) were (1553±484) μg·L⁻¹ and (62±31) μg·L⁻¹, respectively. The mean value of chlorophyll was (9.07±0.91) μg·L⁻¹. The trophic level of XBA was meso-eutrophic, while the general nutrient limitation was phosphorus. The results indicated that XBA has a strong ability to purify itself and has non-point source pollution from terrestrial runoff. The variation of TN/TP ratio was caused by a variation in TN rather than in TP when TN/TP < 22. N-fixation from cyanobacteria occurred and became an important process in overcoming the nitrogen deficit under a low TN/TP ratio. When TN/TP ⩾ 22, the variation of TP affected the TN/TP ratio more significantly than TN. The increase of TP in XBA was caused mainly by particulate phosphorus, which could originate from a non-point source as adsorptive inorganic forms after heavy rainfall and surface runoff. An increase in the river’s flow could also contribute to an unstable environment for the growth of phytoplankton.     

Influence of influent on anaerobic ammonium oxidation in an Expanded Granular Sludge Bed-Biological Aerated Filter integrated system

Shortcut nitrification-denitrification, anaerobic ammonium oxidation (ANAMMOX), and methanogenesis have been successfully coupled in an Expanded Granular Sludge Bed-Biological Aerated Filter (EGSB-BAF) integrated system. As fed different synthetic wastewater with chemical oxygen demand (COD) of 300–1200 mg·L⁻¹ and NH₄⁺-N of 30–120 mg·L⁻¹ at the outer recycle ratio of 200%, the influence of influent on ANAMMOX in the integrated system was investigated in this paper. The experimental results showed that higher COD concentration caused an increase in denitrification and methanogenesis but a decrease in ANAMMOX; however, when an influent with the low concentration of COD was used, the opposite changes could be observed. Higher influent NH₄⁺-N concentration favored ANAMMOX when the COD concentration of influent was fixed. Therefore, low COD =NH₄⁺-N ratio would decrease competition for nitrite between ANAMMOX and denitrification, which was favorable for reducing the negative effect of organic COD on ANAMMOX. The good performance of the integrated system indicated that the bacterial community of denitrification, ANAMMOX, and methanogenesis could be dynamically maintained in the sludge of EGSB reactor for a certain range of influent.     

Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane: effects of arsenic concentration, pH, and co-existing ions

A laboratory-scale investigation was performed to study arsenic (As (V)) removal by negatively charged GE-HL nanofiltration (NF) membrane in simulated drinking water. Effects of As (V) concentration (0–200 μg·L⁻¹), pH, and co-ions and counter-ions were investigated. The NF membrane presented good stability, and the rejection rates exceeded 90%. The rejection rates of As (V) decreased with the increase of As (V) concentration, while it increased with the increase of pH (reached 96% at pH 6.75). Moreover, a negative relationship was observed between the co-existing ions of Cl⁻, Na⁺, SO₄²⁻, and Ca²⁺ and the removal of As (V), in which bivalent ions presented more significant effects than monovalent ions.     

新型后置反硝化工艺处理低C/N(C/P)比污水脱氮除磷性能研究

从内碳源有效利用角度出发,开发了新型连续流后置反硝化AOA工艺,将厌氧段混合液按一定比例分流至缺氧段,从而强化缺氧段反硝化除磷作用.进水NH₄⁺-N和PO₄^3--P浓度保持在(38.31±2.03) mg·L^-1和(5.74±0.13) mg·L^-1,在不同运行阶段进水COD分别控制在300 mg·L^-1和250 mg·L^-1,考察了AOA工艺处理低C/N(C/P)比污水过程影响因素.当进水C/N比和C/P比分别为7.41±0.26和52.36±1.25时,通过将SRT由10 d延长到16 d,系统TN和PO₄^3--P去除率分别稳定在65.86%±2.06%和90.00%±3.97%;当进水C/N比、C/P比降至6.14±0.32和43.40±1.37时,在SRT为16 d条件下,将A/O/A体积比由1/3/1调整为1/2/2,TN和PO₄^3--P去除率分别升至69.76%±3.36%和98.73%±1.82%.结果表明,采用控制SRT、调整好氧/缺氧HRT等策略,可保证处理低C/N(C/P)比污水AOA工艺高效稳定运行.     

Carbon dioxide fixation by Chlorella sp. USTB-01 with a fermentor-helical combined photobioreactor

A promising microalgal strain isolated from fresh water, which can grow both autotrophically on inorganic carbon under lighting and heterotrophically on organic carbon without lighting, was identified as Chlorella sp. USTB-01 with the phylogenetic analysis based on 18S ribosomal ribonucleic acid (rRNA) gene sequences. In the heterotrophic batch culture, more than 20.0 g·L⁻¹ of cell dry weight concentration (DWC) of Chlorella sp. USTB-01 was obtained at day 5, and which was used directly to seed the autotrophic culture. A novel fermentor-helical combined photobioreactor was established and used to cultivate Chlorella sp. USTB-01 for the fixation of carbon dioxide (CO₂). It showed that the autotrophic growth of Chlorella sp. USTB-01 in the combined photobioreactor was more effective than that in the fermentor alone and the maximum DWC of 2.5 g·L⁻¹ was obtained at day 6. The highest CO₂ fixation of 95% appeared on day 1 in the exponential growth phases of Chlorella sp. USTB-01 and 49.8% protein was found in the harvested microalgal cells.     

Influence of aeration intensity on the performance of A/O-type sequencing batch MBR system treating azo dye wastewater

Among the numerous parameters affecting the membrane bioreactor (MBR) performance, the aeration intensity is one of the most important factors. In the present investigation, an anoxic/aerobic-type (A/O-type) sequencing batch MBR system, added anoxic process as a pretreatment to improve the biodegradability of azo dye wastewater, was investigated under different aeration intensities and the impact of the aeration intensity on effluent quantity, sludge properties, extracellular polymeric substances (EPS) amount generated as well as the change of permeation flux were examined. Neither lower nor higher aeration intensities could improve A/O-type sequencing batch MBR performances. The results showed 0.15 m³·h⁻¹ aeration intensity was promising for treatment of azo dye wastewater under the conditions examined. Under this aeration intensity, chemical oxygen demand (COD), ammonium nitrogen and color removal as well as membrane flux amounted to 97.8%, 96.5%, 98.7% and 6.21 L·m⁻²·h⁻¹, respectively. The effluent quality, with 25.0 mg·L⁻¹COD, 0.84 mg·L⁻¹ ammonium nitrogen and 8 chroma, could directly meet the reuse standard in China. In the meantime, the sludge relative hydrophobicity, the bound EPS, soluble EPS and EPS amounts contained in the membrane fouling layer were 70.3%, 52.0 mg·g⁻¹VSS, 38.8 mg·g⁻¹VSS and 90.8 mg·g⁻¹VSS, respectively, which showed close relationships to both pollutant removals and membrane flux.