Mercury determination by CV-AAS in wastewater and sewage sludge from a stabilization pond system

The mercury concentrations in wastewater and sewage sludge of a stabilization pond system have been evaluated. The system is built by three parallel facultative ponds followed by two systems of three maturation ponds in series. The samples of wastewater and sludge were digested using nitric acid and placed into a Parr-type bomb for 4 h at 110° C. Mercury was measured by Cold Vapour Atomic Absorption Spectrometry (CV-AAS) at 253.7 nm with sodium tetrahydroborate as reductant. The methodologies were checked with an USEPA quality control sample, a standard reference material from NIST and with another method of mineralization (cold mineralization) showing good results. Concentrations of mercury in wastewater between 1.47 ± 0.75 gl^–1 have been found at the entrance of the system and 0.74 ± 0.0 gl^–1 at the exit, while in sludge the results were between 0.29 ± 0.12 gkg^–1 in the facultative pond and 0.04 ± 0.02 gkg^–1 in the second maturation pond (exit).     

Sunlight inactivation of Escherichia coli in waste stabilization microcosms in a sahelian region (Ouagadougou,Burkina Faso)

Experiments on sunlight inactivation of Escherichia coli were conducted from November 2006 to June 2007 in eight outdoors microcosms with different depths filled with maturation pond wastewater in order to determine pond depth influence on sunlight inactivation of E. coli. The long-term aim was to maximize sunlight inactivation of waterborne pathogens in waste stabilization ponds (WSPs) in sahelian regions where number of sunny days enable longer exposure of wastewater to sunlight. The inactivation was followed during daylight from 8.00 h to 17.00 h and during the night. Sunlight inactivation rates (K_S), as a function of cumulative global solar radiation (insolation), were 16 and 24 times higher than the corresponding dark inactivation (K_D) rates, respectively in cold and warm season. In warm season, E. coli was inactivated far more rapidly. Inactivation of E. coli follows the evolution of radiation during the day. In shallow depth microcosms, E. coli was inactivated far more rapidly than in high depth microcosms. The physical chemical parameters [pH, dissolved oxygen (DO)] of microcosms water were higher in shallow depth microcosms than in high depth microcosms suggesting a synergistic effect of sunlight and these parameters to damage E. coli. To increase the efficiency of the elimination of waterborne bacteria, the use of maturation ponds with intermediate depths (0.4 m) would be advisable in view of the high temperatures and thus evaporation recorded in sahelian regions.     

Anaerobic waste stabilization ponds: a low-cost contribution to a sustainable wastewater reuse cycle

Waste stabilization ponds (WSP) have been used extensively all over Europe over the last 50 yr for the treatment of municipal and industrial wastewaters. Models presented in manuals should be used only for guidance, and local experience from pilot and full-scale plants of a particular pond type is extremely valuable. Anaerobic WSP are single-stage, continuous-flow, anaerobic reactors operating at ambient temperatures and low volumetric organic loading as a pretreatment method. This article presents a literature review on the different available operational parameters of anaerobic ponds and exmaples from full-scale plant performance world-wide. On a wastewater management scheme, involving reuse for agriculture, the zero-energy demand of a waste stabilization pond series for the effective removal of organic and microbiological loading under existing legislation and guidelines will remain a valuable tool for sustainable development.     

Determination of bisphenol A in sewage effluent and sludge by solid-phase and supercritical fluid extraction and gas chromatography/mass spectrometry

Methods have been developed for the determination of bisphenol A (BPA) residues in municipal sewage and sludge samples. BPA in wastewater samples was enriched with a C18 solid-phase extraction cartridge, eluted with acetone, and converted to the pentafluoropropionyl derivative. For sludge samples, BPA was acetylated and extracted with supercritical carbon dioxide. In both cases, BPA-d16 was used as a surrogate to monitor extraction efficiency. Final analyses of derivatized sample extracts were performed by gas chromatography/mass spectrometry operating in the electron impact mode. For water samples, mean recoveries and standard deviations were 89 +/- 6, 94 +/- 4, and 85 +/- 7% at fortification levels of 1, 0.1, and 0.025 microg/L, respectively, with a method detection limit of 0.006 microg/L. For solid waste samples, mean recoveries and standard deviations were 93 +/- 5 and 92 +/- 6% at fortification levels of 2.5 and 0.25 microg/g, respectively, and the method detection limit was 0.05 microg/g. For the Canadian samples under investigation, concentrations of BPA ranged from 49.9 to 0.031 microg/L in sewage influent and effluent, and from 36.7 to 0.104 microg/g in sludge.     

On-line hyphenation of capillary electrophoresis with flame-heated furnace atomic absorption spectrometry for trace mercury speciation

Capillary electrophoresis (CE) was directly interfaced to flame-heated furnace atomic absorption spectrometry (FHF-AAS) via a laboratory-made thermospray interface for nanoliter trace element speciation. The CE-FHF-AAS interface integrated the superiorities of stable CE separation, complete sample introduction, and continuous vaporization for AAS detection without the need of extra external heat sources and any post-column derivation steps. To demonstrate the usefulness of the developed hybrid technique for speciation analysis, three environmentally significant and toxic forms of methylmercury (MeHg), phenylmercury (PhHg), and inorganic mercury (Hg(II)) were taken as model analytes. Baseline separation of the three mercury species was achieved by CE in a 60 cm long x 75 microm inner diameter fused-silica capillary at 20 kV and using a mixture of 100 mM boric acid and 10% v/v methanol (pH 8.30) as running electrolyte. The precision (relative standard deviation, RSD, n = 7) of migration time, peak area and peak height for the mercury species at 500 microg x L(-1) (as Hg) level were in the range of 0.9-1.2%, 1.5-1.9%, and 1.4-2.0%, respectively. The detection limit (S/N = 3) of three mercury species was 3.0 +/- 0.15 pg (as Hg), corresponding to 50.8 +/- 2.4 microg x L(-1) (as Hg) for 60 nL sample injection, which was almost independent on specific mercury species. The developed hybrid technique was successfully applied to the speciation analysis of mercury in a certified reference material (DORM-2, dogfish muscle).     

荧光素酶法测定活性污泥中的ATP

选择了４种不同的提取剂，对曝气池活性污泥的腺苷三磷酸进行提取，并用荧光素酶法进行了测定。结果表明，不同提取剂所提取的ＡＴＰ量有很大不同；同一提取剂对不同水样ＡＴＰ的提取效果也不同。     

Determination of ink photoinitiators in packaged beverages by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry

A new analytical method, using gas chromatography-mass spectrometry (GC/MS) and liquid chromatography-mass spectrometry (LC/MS) techniques, was developed for the determination in packaged food beverages of five ink photoinitiator residues: 2-isopropylthioxanthone (ITX), benzophenone, 2-ethylhexyl-4-dimethylaminobenzoate (EHDAB), 1-hydroxycyclohexyl-1-phenyl ketone (IRGACURE 184) and ethyl-4-dimethylaminobenzoate (EDAB). Samples were extracted from selected beverages (milk, fruit juices and wine) and relative packagings, using n-hexane and dichloromethane, respectively, purified on solid-phase extraction (SPE) silica gel cartridges, and then analyzed in GC/MS and LC/MS. The recovery percentages, obtained spiking the beverage samples at concentrations of 4 and 10 microgl(-1) with a standard mixture of photoinitiators, were in the range 42-108% (milk), 50-84% (wine), and 48-109% (fruit juices). The repeatability of the method was assessed in all cases by the % of correlation value, that was lower than 19%. The lowest limits of detection (LODs) and limits of quantification (LOQs), obtained using GC/MS, were in the range 0.2-1 and 1-5 microgl(-1), respectively. The method was applied to the analysis of forty packaged food beverages (milk, fruit juices and wine samples). The most significant contamination was that of benzophenone, found in all samples in a concentration range of 5-217mugl(-1). Its presence was confirmed by an LC/Atmospheric-Pressure PhotoIonization (APPI)/MS/MS analysis. The photoinitiator (EHDAB) was found in eleven out of forty beverages in a concentration range of 0.13-0.8 microgl(-1). Less important was the ITX contamination, found in three out of forty samples in a range 0.2-0.24 microgl(-1). The work proposes a new method to analyze ink photoinitiator residues in polycoupled carton packaging and in contained food beverages.     

Enantiomeric determination of azole antifungals in wastewater and sludge by liquid chromatography–tandem mass spectrometry

A sensitive and reliable liquid chromatographic-tandem mass spectrometric method for enantiomeric determination of five chiral azole antifungals (econazole, ketoconazole, miconazole, tebuconazole, and propiconazole) in wastewater and sludge has been established and validated. An isotope-labeled internal standard was used for quantification. Recovery of the individual enantiomers was usually in the range of 77-102 % for wastewater and 71-95 % for sludge, with relative standard deviations within 20 %. No significant difference (p>0.05) was observed between recovery of pairs of enantiomers of the chiral azole antifungals except for those of tebuconazole. Method quantification limits for individual enantiomers were 0.3-10 ng L(-1) and 3-29 ng g(-1) dry weight for wastewater and sludge, respectively. The method was used to investigate the enantiomeric composition of the azole pharmaceuticals in wastewater and sludge samples from a sewage treatment plant in China. Enantiomers of miconazole, ketoconazole, and econazole were widely detected. The results showed that the azole antifungals in wastewater and sludge were generally racemic or marginally non-racemic. The method is a useful tool for investigation of the enantiomeric occurrence, behavior, and fate of the chiral azole antifungals in the environment.     

Mercury determination with ICP-MS: signal suppression by acids

When mercury is quantified by ICP-MS under routine conditions (external calibration) in reference materials, which require mineralization with nitric acid, the experimental concentrations are almost always unacceptably low in comparison to certified values. Sorption of mercury on the Teflon surfaces of the digestion vessels, changes in the viscosity of the aspirated solutions, in the efficiency of the nebulization, in the aerosol transport, and memory effects cannot be responsible for the low results. The intensity of a mercury signal is strongly dependent on the concentration of nitric acid (and other mineral acids) in the measured solutions. Correct results for mercury in the SRM GBW-90101 (Chinese human hair; 2.16+/-0.21 mg Hg/kg certified) can only be obtained, when the solutions, with which the external calibration curves were established, have exactly the same nitric acid concentration as the aspirated digests (2.03+/-0.01 mg Hg/kg; n = 5), when mercury is determined by the standard addition method (2.10+/-0.01 mg Hg/kg; n = 5), or when the experimental mercury concentration obtained at a nitric acid concentration in the digest, different from the concentration in the external calibration solutions, is corrected mathematically based on a pre-established function [Hg2+] = f [HNO3]. The concentrations found by this mathematically based correction 2.04+/-0.01 mg Hg/kg (n = 5) is in good agreement with the values obtained by acid matched calibration or by the standard addition method. For practical work with large numbers of samples the mathematical correction appears to be the method of choice. For occasional mercury determinations, the standard addition method seems to be the most practicable.     

Comprehensive study of the parameters influencing the detection of organotin compounds by a pulsed flame photometric detector in sewage sludge

An investigation of the operating conditions of a pulsed flame photometric detection (PFPD) system for the determination of organotin compounds (OTCs) in sewage sludge is reported. During the analyses, some spectral interferences were observed. For their elimination detector parameters such as gate delay and gate width were investigated. In addition, the applicability of three different internal standards was evaluated. Under optimised analytical conditions (gate delay 3 ms, gate width 2 ms, tripropyltin as internal standard) limits of detection (LOD) were determined. The LOD for butyltins ranged between 8 and 16 ng Sn g(-1), for phenyltins around 8 ng Sn g(-1) and for octyltins between 5 and 10 ng Sn g(-1). Since there is no certified reference material (CRM) available for sewage sludge, the accuracy of the analytical procedure was checked by the analysis of CRM PACS-2 (marine sediment) and a spiked sludge sample. Good agreement between determined and certified values was obtained. Sewage sludge from a local wastewater treatment plant was analysed and the results compared with data from the literature.     

Olive mill wastewater treatment by a pilot-scale subsurface horizontal flow (SSF-h) constructed wetland

Performances of a pilot-scale reed bed for the olive mill wastewater (OMW) treatment were investigated, by monitoring influent and effluent pH, total suspended solids (TSS), chemical oxygen demand (COD), total Kjeldahl nitrogen (TKN), total phosphorus and polyphenols. In order to reduce the suspended matter concentration and to avoid clogging, OMW was pre-treated by adding lime putty, calcium hydroxide and hydraulic lime. The best results were obtained with 2 g/L of hydraulic lime. Pre-treated OMW was dosed in the reed bed at dilution ratios of 1/3 and 1/10 (v/v), pointing up that the latter only did not give rise to reed suffering and allowed to obtain good and durable removal efficiencies, above all for COD (74.1+/-17.6%) and polyphenols (83.4+/-17.8%). Recycling of the effluent was quite effective for the improvement of the wastewater quality, allowing a further removal of 26-70%, depending on the parameter taken into account. A post-dosage study, carried out by feeding the reed bed with the effluent of an activated sludge plant, pointed up a rapid decreasing of the outlet concentrations of the investigated parameters to values compatible with Italian regulations concerning wastewater discharge in surface water. Polyphenols were the exception, being their outlet concentration at the end of post-dosage study around 2 mg/L.     

Use of volatile amines as ion-pairing agents for the high-performance liquid chromatographic-tandem mass spectrometric determination of aromatic sulfonates in industrial wastewater.

The use of trialkylamines (triethylamine, N,N-dimethyl-n-butylamine, and tri-n-butylamine) as volatile ion-pairing agents for the high-performance liquid chromatographic separation of aromatic sulfonates was investigated. Negative ion electrospray tandem mass spectrometry was used to detect both singly and multiply charged analyte ions. Sensitivity of detection was strongly reduced by amine concentrations above 2.5 mmol l(-1) in the eluent. With tributylamine as ion-pairing agent 19 aromatic sulfonic acids could be determined using time-scheduled selected reaction monitoring. Lowest orders of detection range from 3 to 74 microgl(-1). Several naphthalenesulfonic acids were determined in dyeing baths and textile wastewater in concentrations ranging from 0.1 mgl(-1) to 2.1 mgl(-1). A degradation product of sulfonated azodyes was identified in the effluent of a laboratory treatment plant.     

Investigation of methyl tert-butyl ether levels in river-, ground-, and sewage-waters analyzed using a purge-and-trap interfaced to a gas chromatograph-mass spectrometer

River water collected from 27 sites in 21 rivers, groundwater from 66 sites in 34 cities, and 2 sewage plants in the Niigata Prefecture, Japan (total 301 samples) were analyzed for methyl tert-butyl ether (MTBE) using an improved purge-and-trap-GC-MS method. The amount of MTBE found in water samples from the 27 river sites ranged from 0.003 to 5.3 microg l(-1). MTBE was found in all 27 sites during winter but it was found at only 9 sites and 14 sites, respectively, during the summer. MTBE was found most frequently (in 21 sites) at levels ranging from 0.003 to 0.009 microg l(-1) during February. The highest levels of MTBE were always found in the samples collected from the same site. The amount of MTBE found in sewage water samples ranged from <0.003 to 0.025 microgl(-1). No significant differences were observed between the amounts of MTBE recovered from inflow and outflow waters. Relatively high levels (0.02-0.034 microg l(-1) ) of MTBE were found in January at two sites, which were located on the upper course of the Shinano River. MTBE levels ranged from 0.004 to 0.035 microgl(-l) and from 0.005 to 0.041 microgl(-1) at the mouths of the Shinano River and Agano River, respectively. The levels of MTBE in groundwater collected from 66 sites in 34 cities in Niigata Prefecture ranged from <0.003 to 5.9 microg l(-1).     

Fermentative Hydrogen Production from Soybean Protein Processing Wastewater in an Anaerobic Baffled Reactor (ABR) Using Anaerobic Mixed Consortia

Fermentative H(2) production from soybean protein processing wastewater (SPPW) was investigated in a four-compartment anaerobic baffled reactor (ABR) using anaerobic mixed cultures under continuous flow condition in the present study. After being inoculated with aerobic activated sludge and operated at the inoculants of 5.98?gVSS?L(-1), COD of 5000?mg?L(-1), HRT of 16?h and temperature of (35?±?1) °C for 22?days, the ABR achieved stable ethanol-type fermentation. The specific hydrogen production rate of anaerobic activated sludge was 165?LH(2)?kg MLVSS(-1)?day(-1), the substrate conversion rate was 600.83?LH(2)?kg COD(-1)and the COD removal efficiency was 44.73% at the stable operation status. The ABR system exhibited a better stability and higher hydrogen yields than continuous stirring tank reactor under the same operational condition. The experimental data documented the feasibility of substrate degradation along with molecular H(2) generation utilizing SPPW as primary carbon source in the ABR system.     

One- and two-stage upflow anaerobic sludge-bed reactor pretreatment of winery wastewater at 4–10°C

The operating performance of a single and two (in series) laboratory upflow anaerobic sludge-bed (UASB) reactors (2.7-L working volume, recycle ratio varied from 1:1 to 1:18) treating diluted wine vinasse was investigated under psychrophilic conditions (4-10 degreesC). For a single UASB reactor seeded with granular sludge, the average organic loading rates (OLRs) applied were 4.7, 3.7, and 1.7 g of chemical oxygen demand (COD)/(L.d) (hydraulic retention times [HRTs] were about 1 d) at 9-11, 6 to 7, and 4 to 5 degreesC, respectively. The average total COD removal for preacidified vinasse wastewater was about 60% for all the temperature regimes tested. For two UASB reactors in series, the average total COD removal for treatment of non-preacidified wastewater exceeded 70% (the average OLRs for a whole system were 2.2, 1.8, and 1.3 g of COD/[L.d] under HRTs of 2 d at 10, 7, and 4 degreesC, respectively). In situ determinations of kinetic sludge characteristics (apparent Vm and Km) revealed the existence of substantial mass transfer limitations for the soluble substrates inside the reactor sludge bed. Therefore, application of higher recycle ratios is essential for enhancement of UASB pretreatment under psychrophilic conditions. The produced anaerobic effluents were shown to be efficiently posttreated aerobically: final effluent COD concentrations were about 0.1 g/L. Successful operation of the UASB reactors at quite low temperatures (4-10 degreesC) opens some perspectives for application of high-rate anaerobic pretreatment at ambient temperatures.     

Development and validation of a solid phase micro-extraction-gas chromatography-mass spectrometry method for the determination of furan in baby-food

An efficient and simple method for the determination of furan in baby-food (vegetables and fruits) by solid phase micro-extraction-gas chromatography-mass spectrometry (SPME-GC-MS) was developed and validated. Experimental design was used to investigate the effects of temperature and time of extraction. The calculated regression model was used to find the experimental conditions providing the optimal SPME extraction yield. Validation was carried out in terms of limit of detection (LOD), limit of quantitation (LOQ), linearity, precision and trueness. LOD and LOQ values in the low ngkg(-1) were achieved, whereas linearity was established over two order of magnitude. Good precision was obtained both in terms of intra-day repeatability and between-day precision on two concentration levels (RSD% lower than 3.6%). Recovery values of 91.5+/-6.2% and of 96.1+/-1.3% (n=3) were calculated at 75 ngkg(-1) and 75 microgkg(-1) level. Finally, the applicability of the method to the determination of furan in a number of commercial and home-made baby-food samples was demonstrated.     

Mercury speciation by HPLC-cold-vapour radiofrequency glow-discharge optical-emission spectrometry with on-line microwave oxidation

Hollow-cathode (HC) radiofrequency glow-discharge (rf-GD) optical-emission spectrometry (OES) has been used as detector for the determination of inorganic mercury by cold-vapour (CV) generation in a flow-injection (FI) system. Both NaBH4 and SnCl2 were evaluated as reducing reagents for production of mercury CV. The conditions governing the discharge (pressure, He flow rate, and delivered power) and Hg CV generation (NaBH4 or SnCl2 concentration and reagent flow rate) were optimized using both reducing agents. The analytical performance characteristics of FI-CV-rf-GD-OES for mercury detection were evaluated at the 253.6 nm emission mercury line. Detection limits (DL) of 0.2 ng mL(-1) using SnCl2 and 1.8 ng mL(-1) using NaBH4 were obtained (100 microliter sample injections were used). When the optimized experimental conditions using SnCl2 had been determined, the analytical potential of this CV-rf-GD-OES method was investigated as on-line detector for high-performance liquid chromatographic (HPLC) speciation of mercury (Hg(II) and methylmercury). The HPLC-CV-rf-GD-OES detection limits for 100 microliter sample injections were found to be 1.2 and 1.8 ng mL(-1) (as mercury) of inorganic mercury and methylmercury, respectively. The reproducibility observed was below +/- 8% for both species. Finally, the HPLC-CV-rf-GD-OES system developed was successfully applied to the determination of methylmercury (speciation) in two certified reference materials, Dorm-2 and Dolt-2.     

Adsorption of three azo reactive dyes by metal hydroxide sludge: effect of temperature, pH, and electrolytes

Adsorption of azo reactive dyes by metal hydroxide sludge were investigated using CI Reactive Red 2 (RR-2), CI Reactive Red 120, (RR-120), and CI Reactive Red 141 (RR-141). The adsorption isotherms, including the Langmuir constants (Q degrees and b) and the Freundlich constant (K(f)), for RR-2 decreased with increasing temperature, but this was reversed for RR-120 and RR-141. This behavior implied an exothermic process for RR-2 but an endothermic process for RR-120 and RR-141. The enthalpy value of adsorption for RR-2, RR-120, and RR-141 was -5.56, 2.77, and 6.41 kJ/mol, respectively, indicating that the adsorption of the less charged dyes (RR-2) was mainly physical, but that of the more charged dyes (RR-120 and RR-141) was chemical. The optimum system pH of 8.6+/-0.3 was maintained even when the solution pH was varied from 3 to 10. Higher concentration or more valence of anions of electrolytes in dye solution caused decreasing dye adsorption efficiency of metal hydroxide sludge. A higher dosage of sludge is required for real textile wastewater (>1% w/v) than for the synthetic dye solution (0.2% w/v). The leachates of heavy metals from metal hydroxide sludge to the environment are very low, which are within the standard limit of industrial effluent and leachable substances.     

Assessment of the fate of some household micropollutants in urban wastewater treatment plant

Everyday domestic activity is a significant source of water pollution. The presence of six household micropollutants in an urban wastewater treatment plant (WWTP) was assessed in wastewater and sludge. A multi-target analytical method was developed for the quantification of ibuprofen, erythromycin, ofloxacin, 4-nonylphenol, 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan), and sucralose. The micropollutants were extracted from the liquid and solid phases and their concentrations were determined by LC-MS/MS. The efficiency of micropollutants’ removal within a conventional activated sludge process was assessed. From 50 % to 90 % of ibuprofen and erythromycin was removed from the wastewater liquid phase. Their removal can be attributed to biological degradation as they were not found adsorbed on the outlet sludge. Ofloxacin and triclosan were removed from the liquid phase with similar efficiencies; however, they were adsorbed on the sludge, so it was not possible to determine their removal mechanism (whether biodegradation or displacement to solid phase/sequestration). Sucralose was not removed from wastewater (3 μg L^?1 in inlet and outlet liquid phase) and not adsorbed on the sludge. 4-Nonylphenol concentrations were sometimes higher in the WWTP outlet water; this may relate to the degradation of alkylphenol ethoxylates in the wastewater treatment process. 4-Nonylphenol was always present in the outlet sludge.     

GC-MS analysis of organic compounds in wastewater and sewage sludge

A multimethod based on liquid-liquid extraction and solid-liquid extraction for the analysis of persistent organic pollutants in water and sludge from sewage treatment plants has been established. Traces of 22 organic compounds used in industry and personal care products (PCPs) were analyzed by GC/MS. The LODs for the analytes were less than 2.3 ng/L for wastewater and 31 microg/kg (dry weight matter) for sewage sludge. Satisfactory recoveries (70-130%) were achieved. The validated method permits the analysis of water and sludge samples at various stages of the treatment from different sewage treatment plants. Thus, the distribution between water and sludge as well as the dissipation of the compounds analyzed were balanced. By this means, the efficiency of different wastewater treatment plants (WWTPs) can be evaluated and measures can be taken to optimize the treatment process at different stages.