Determination of Polycyclic Aromatic Hydrocarbons in Soil by Miniaturized Ultrasonic Extraction and Gas Chromatography‐Mass Selective Detection

A miniaturized ultrasonic extraction procedure was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil by gas chromatography‐mass spectrometry. After determination of the most suitable extraction solvent with 5 min sonication time, several other parameters (sample amount, solvent volume and number of extraction times) were optimized using a 2³ factorial experimental design. Recoveries of PAHs from spiked soil samples were over 90% for three different fortification levels between 50 and 300 μg/kg, and relative standard deviations of the recoveries were in the range of < 1–15%. The limits of detection ranged from 0.002 to 1.87 μg/kg. The performance of the developed procedure was also compared with other traditional Soxhlet, shake flask and large scale ultrasonic extraction procedures on real soil samples, and extraction methods showed comparable efficiencies. The proposed procedure required small volumes of solvent and sample. It was practicable, rapid and easy to use for analysis of PAHs in soils.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Application of Dispersive Liquid–Liquid Microextraction Based on Solidification of Floating Organic Droplet Multi‐residue Method for the Simultaneous Determination of Polychlorinated Biphenyls,Organochlorine, and Pyrethroid Pesticides in Aqueous Sample

Dispersive liquid–liquid microextraction based on solidification of floating organic droplet (DLLME‐SFO) technique was successfully applied for simultaneous assay of eight polychlorinated biphenyls, two organochlorine, and four pyrethroid pesticides multi‐residue in aqueous samples by using GC‐electron capture detection. The effects of various parameters such as kind of extractant and dispersant and volume of them, extraction time, effect of salt addition, and pH were optimized. As a result, 5.0 µL 1‐dodecanol was chosen as extraction solvent, 600 µL methanol were used as dispersive solvent without salt addition, pH was adjusted to 7. Under the optimized conditions, the limits of detection (LOD) were ranged from 1.4 to 8.3 ng L^?1. Satisfactory linear range was observed from 5.0 to 2000 ng L^?1 with correlation coefficient better than 0.9909. Good precisions were also acquired with RSD better than 13.6% for all target analytes. The enrichment factors of the method were ranged from 786 to 1427. The method can be successfully applied to simultaneous separation and determination of three class residues in real water samples and good recoveries were obtained ranging from 76 to 130, 73 to 129, and 78 to 130% for tap water, lake water, and industrial waste water, respectively.     

Interaction of Humic Substances and Polycyclic Aromatic Hydrocarbons (PAHs) during the Biodegradation of PAHs

The influence of humic substances (HS) on the biodegradation of naphthalene, phenanthrene, and pyrene was studied. As a source of HS, water samples of a bog lake (Hohlohsee) were used. PAH degradation experiments, both in the presence and absence of HS were carried out. All investigated PAHs were degradable by the used bacterial mixed culture. A correlation between the number of aromatic rings of the PAHs and the influence of HS on biodegradation has been shown. Adding of HS led to a decrease in degradation rate in the case of naphthalene. By way of contrast, the presence of HS gave rise to an increase of degradation rate in the case of phenanthrene. The degradation processes of pyrene revealed a marked alteration in the presence of HS which could be deduced from the biochemical oxygen demand (t(1/2BOD_max) values). With regard to the total turnover of the PAHs, there was no noticeable difference between degradation experiments with and without HS. Analyses of the HS after degradation experiments using liquid chromatography coupled with DOC detection (LC/OCD) verify that there was no formation of stable associations between HS and PAHs or their metabolites. The determination of the toxicity of the degradation media as luminescence inhibition against Vibrio fischeri (Photobacterium phosphoreum) showed no detoxification as a result of the presence of HS.     

Simultaneous and Sensitive HPLC Determination of Mono‐ and Disaccharides,Uronic Acids,and Amino Sugars after Derivatization by Reductive Amination

The reductive amination of low‐molecular‐weight saccharides, uronic acids, and amino sugars, followed by a separation of the derivates by means of ion‐pair chromatography or RP‐HPLC, offers an interesting alternative to HPAEC‐PAD for the environmental analysis of these compounds. Under this aspect various potential amination reagents, i.e., p‐amino‐benzoic acid (p‐AMBA), p‐AMBA propyl ester, 1‐aminopyrene, 2‐(2‐aminophenyl)indole, and 4‐aminoazobenzene, were tested with regard to the formation of derivates and to the chromatographic properties of the formed derivates. p‐AMBA, p‐AMBA propyl ester and 4‐aminoazobenzene proved to be especially suited, because they facilitate the amination of all carbohydrate reference components together with a complete separation and sensible detection (detection limits < 0.5 mg/L) of the derivates. Mainly the following elution sequence was ascertained: amino sugars (hexosamines) / disaccharide(s) / monosaccharides (hexoses) / hexuronic acid(s) / N‐acetyl‐D‐glucosamine. Detection limits down to 0.1 μmol/L were realized using p‐AMBA as reagent, facilitating the determination of the target compounds in landfill leachates and lysimeter percolates. Applying the p‐AMBA propyl ester for derivatization, chromatographic interferences with weakly retained derivates and the coelution of the reagent with its galactosamine derivate can be avoided, since the ester elutes after its derivates unlike p‐AMBA itself.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

Cloud Point Extraction for the Preconcentration of Silver and Palladium in Real Samples and Determination by Atomic Absorption Spectrometry

A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag⁺ and Pd²⁺ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10^–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag⁺ and Pd²⁺, respectively. The enrichment factors were 35.0 and 28.0 for Ag⁺ and Pd²⁺, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.     

Ultrasound‐Assisted Emulsification–Microextraction Combined with Graphite Furnace Atomic Absorption Spectrometry for the Determination of Trace Lead in Water

The ultrasound‐assisted emulsification–microextraction (USAEME) method was combined with graphite furnace atomic absorption spectrometry (GFAAS) for the determination of trace Pb using dithizone (H²DZ) as chelating reagent. Some effective parameters influenced the detection and microextraction, such as ashing temperature and atomization temperature, pH, extraction solvent, sample volume, extraction time, and extraction temperature were selected and optimized. After extraction, the calibration curves for Pb was in the concentration range of 0.1–10 ng mL^?1, and the linear equation was y = 0.097 x + 0.023 (R = 0.99). Under the optimized conditions, the detection limit of the method was 20 pg mL^?1 with an enrichment factor of 70 and the relative standards deviation (RSD) for seven determinations of 1 ng mL^?1 Pb was 11%. The proposed method was successfully applied to determine trace Pb in Yueya Lake water, pond water, and spiked samples. Furthermore, a certified reference material of Environment Water (GBW08607) was analyzed and the determined value was in good agreement with the certified value, which showed the accuracy, recovery, and applicability of the reported method.     

Contamination of some reservoirs and lakes in Republic of Bulgaria by microcystins

This paper presents the results from analyses of water samples from 15 Bulgarian reservoirs and lakes for detection of microcystins presence by high‐performance liquid chromatography (HPLC) coupled to a ultraviolet (UV) and photo diode array (PDA) detector. In 3 of the studied drinking water reservoirs cyanobacterial blooms were not detected. Cyanobacterial blooms were observed in 6 of 12 investigated water bodies used for fishing and water sports. Microcystis was the dominant cyanobacterial genus. The concentration of total microcystins in the biomasses ranged from 8 to 1070 μg g^–1 (d.w.). Microcystin‐LR and microcystin‐RR were the predominant microcystins, followed by microcystin‐YR. Presence of dissolved microcystins was obtained in one water sample with concentration of total microcystins 1.64 μg L^–1. Presence of microcystin‐LF and ‐LW or unknown peaks possessing characteristic microcystin‐like UV‐spectra were not detected. Those first results for occurrence of microcystins in some Bulgarian reservoirs and lakes are a contribution to the knowledge on their distribution.     

Carcinogenic Risk Assessment of Trihalomethanes in Major Drinking Water Sources of Baghdad City

Three standard methodological approaches used for carcinogenic risk assessment of the four trihalomethanes (THMs) species: Dibromochloromethane (CHClBr₂), Bromodichloromethane (CHCl₂Br), Bromoform (CHBr₃) and Chloroform (CHCl₃), in water collected from public water supplies which included main water source (raw water of the Tigris River), water treatment plants (treated water) and distribution system (tap water) in Baghdad City. The total concentration of THMs ranged between 13.78 and 63.1 μg/L in winter and summer respectively. The occurrence of THMs followed the given order: CHClBr₂ (36%) > CHCl₂Br (27%) > CHCl₃ (25%) > CHBr₃ (12%). The annual levels of THMs concentrations in the distribution networks of Baghdad City ranged between 12 and 97.3 μg/L in winter and summer, respectively, and followed the given order: CHClBr₂ (37%) > CHCl₂Br (33%) > CHCl₃ (21%) > CHBr³ (9%). The World Health Organization (WHO) index for additive toxicity approach was in compliant with the WHO guideline value, and does not pose any adverse toxic health impacts. The hazard index does not suggest any potential noncancer risk to the exposed population, whereas the total multi-pathway cancer risk analysis suggests that total cancer risk exceeds the USEPA acceptable level of 10–6.     

Occurrence of the Antimicrobials Sulfamethoxazole and Trimethoprim in Hospital Effluent and Study of Their Degradation Products after Electrocoagulation

In this study, an investigation was carried out into the occurrence of sulfamethoxazole (SMX) and trimethoprim (TMP) in the effluent of the university hospital (HUSM) of the UFSM. The degradation of these antimicrobials by the electrocoagulation (EC) process was also examined, in both the aqueous solution and hospital effluent, and a study was conducted in order to identify the subproducts formed. The experiments were optimized through factorial planning and, also, checked by response surface methodology. The best conditions for EC (achieving 58.0% of chemical oxygen demand (COD) reduction) were obtained by using 13 mA cm^?2, 500 mg L^?1 of NaCl, and 30 mm of interelectrode distance. The quantification of SMX (27.8 µg L^?1) and TMP (6.65 µg L^?1) in the hospital effluent, and the identification of the degradation products were carried out through liquid chromatography‐mass spectrometry quadrupole linear and ion trapping with electrospray ionization (LC‐ESI‐MS/MS_QTrap). Removals of 88.0% (degradation only) and 33.0% (adsorption only) were achieved for aqueous solutions of SMX and TMP, respectively, under optimized conditions. In hospital effluent samples, fortified with additions of SMX and TMP, corresponding removals of 16.0% (degradation) and 28.0% (adsorption) were achieved. This suggests that the EC process is efficient in degrading SMX in aqueous solution, although the same was not the case with TMP. The degradation products of SMX were identified (m/z 256.0 and 288.5); however, only the latter is mentioned in the literature. Toxicological aspects were not considered in this study.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

Communicating human health risks associated with disinfection by-products in drinking water supplies: a fuzzy-based approach

Chlorine used for the disinfection of water supplies can react with naturally occurring organic compounds and form potentially harmful disinfection by-products (DBPs). A risk index for two regulated groups of chlorinated DBPs—trihalomethanes (THMs) and haloacetic acids (HAAs), using fuzzy C-means (FCM) clustering algorithm and fuzzy rule-based modeling is proposed for risk communication. The proposed index evaluates the cancer and non-cancer risks individually for THMs and HAAs using the FCM algorithm. Subsequently, two different fuzzy rule-bases were used to evaluate the overall risk-index based on cancer and non-cancer risks. The overall risk-index will provide drinking water utilities with an effective communication tool for communicating aggregated water quality compliance. Simulated DBP occurrence data obtained from the City of Quebec, Canada, is used to demonstrate the application of this methodology.     

Surveillance of Invasive Bacterial Pathogens and Human Enteric Viruses in Wastewater Final Effluents and Receiving Water Bodies – a Case Study from Durban,South Africa

The physico‐chemical characteristics and microbial composition of the final effluents of two municipal wastewater treatment plants in South Africa were assessed between July and September 2009. The impact of the treated final effluents on the receiving water bodies was also evaluated. The temperature across all sampling points ranged between 14 and 22°C, while pH varied from 6.9 to 7.6. High levels of turbidity, chemical oxygen demand (COD), ammonia, nitrate, nitrite and orthophosphate (PO₄) were observed in many cases. Turbidity of the samples was in the range of 2.2–288.6 NTU. The concentrations (mg/L) of other physico‐chemical parameters are as follows: COD (9.33–289); ammonia (0.000340–45.4); nitrate (0.062–539); nitrite (0.021–22.6); PO₄ (5.3–33.2). The microbial quality of the effluents discharged from the plants did not comply with the limits set by the South African guidelines with respect to pathogens such as Salmonella, Shigella, Escherichia coli, total coliform, faecal coliform, enterococci, faecal streptococci, and viral particles for effluents intended for discharge into receiving watersheds. This study revealed an undesirable impact on the physico‐chemical and microbial qualities of the receiving water bodies as a result of the discharge of inadequately treated effluents from the wastewater treatment facilities. This poses a health risk to several rural communities which rely on the receiving water bodies primarily as their sources of domestic water and recreational purposes. There is therefore a need for the intervention of appropriate regulatory agencies in South Africa to ensure compliance of treatment facilities with wastewater effluent quality standards.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Extraction of highly polar organophosphorus pesticides from water

Some of the pesticides listed in the European 76/464/EC Directive and in the Directive 2000/60/EC are very polar and require special analytical methodology with respect to their extraction from water. The extraction of the organophosphorus pesticides methamidophos, omethoate, oxydemeton‐methyl, mevinphos and trichlorfon with lg P_OW below 1 was investigated using 21 different solid‐phase materials. Each material was tested on spiked natural water at 4 different pH values, adjusted prior to extraction. The following range of materials were tested: octadecyl silica, polymers, modified silica, ion exchange and carbon. Extraction of the above compounds from water is possible. A relationship between the octanol‐water partition coefficient and recovery rates was obtained not only for octadecyl solid phases but also for some polymeric materials. General conclusions about the use of solid‐phase materials and specific conclusions about the extraction of particular compounds were made. An optimized extraction procedure was deduced and confirmed.     

Adsorption of BTEX on Surfactant Modified Granulated Natural Zeolite Nanoparticles: Parameters Optimizing by Applying Taguchi Experimental Design Method

In this paper, a novel adsorbent developed by means of granulating of natural zeolite nanoparticles (i.e., clinoptilolite) was evaluated for possible removal of the petroleum monoaromatics (i.e., benzene, toluene, ethylbenzene, and xylene, BTEX). To do this, the natural zeolite was ground to produce nanosized particulate, then modified by two cationic surfactants and granulated. The effect of various parameters including temperature, initial pH of the solution, total dissolved solids (TDS), and concentration of a competitive substance (i.e., methyl tert‐butyl ether, MTBE) were studied and optimized using a Taguchi statistical approach. The results ascertained that initial pH of the solution was the most effective parameter. However, the low pH (acidic) was favorable for BTEX adsorption onto the developed adsorbents. In this study, the experimental parameters were optimized and the best adsorption condition by determination of effective factors was chosen. Based on the S/N ratio, the optimized conditions for BTEX removal were temperature of 40°C, initial pH of 3, TDS of 0 mg/L, and MTBE concentration of 100 µg/L. At the optimized conditions, the uptake of each BTEX compounds reached to more than 1.5 mg/g of adsorbents.     

Field Tracer Test for the Design of LNAPL Source Zone Surfactant Flushing

A field tracer test was carried out in a light nonaqueous phase liquid (LNAPL) source zone using a well pattern consisting of one injection well surrounded by four extraction wells (5‐spot well pattern). Multilevel sampling was carried out in two observation wells located inside the test cell characterized by heterogeneous lithology. Tracer breakthrough curves showed relatively uniform flow within soil layers. A numerical flow and solute transport model was calibrated on hydraulic heads and tracer breakthrough curves. The model was used to estimate an average accessible porosity of 0.115 for the swept zone and an average longitudinal dispersivity of 0.55 m. The model was further used to optimize the relative effects of viscous forces versus capillary forces under realistic imposed hydraulic gradients and to establish optimal surfactant solution properties. Maximum capillary number (N_Ca) values between injection and extraction wells were obtained for an injection flow rate of 16 L/min, a total extraction flow rate of 20 L/min, and a surfactant solution with a viscosity of 0.005 Pa?s. The unconfined nature of the aquifer limited further flow rate or viscosity increases that would have led to unrealistic hydraulic gradients. An N_Ca range of 3.8 × 10^?4 to 7.6 × 10^?3 was obtained depending on the magnitude of the simulated LNAPL‐water interfacial tension reduction. Finally, surfactant and chase water slug sizing was optimized with a radial form of the simplified Ogata‐Banks analytical solution (Ogata and Banks 1961) so that injected concentrations could be maintained in the entire 5‐spot cell.     

Pesticide residues analysis in lake water and sediment samples from the Golcuk National Park

Pesticide residues in surface water and sediments are extremely important because of their potential impacts on aquatic ecosystems and their implications on drinking water sources. Pesticide contamination of fresh water is causing concern with respect to long-term and low-dose effects of pesticides on public health, as well as their impact on no target species. Thus, intensive research on the fate and transport of pesticides in the environment is needed. Gas chromatography (GC) with electron-capture detection (ECD) and nitrogen-phosphorous detection (NPD) were employed for the identification of different pesticides in water and sediment samples. For this purpose, extraction procedure with dichloromethane and ethyl acetate were used. The aim of our work was the quantitative determination of pesticides from several compound classes in water and sediment from Gölcük National Park (Turkey). In GC-NPD/ECD, the detection limits were between 2.75–135 ng/L for the studied pesticides, recoveries ranged from 90 to 102% in samples and the relative standard deviations were in the range 1 to 10%. The correlation coefficients obtained from calibration curves of the pesticides standards were found to be 0.999. No pesticides residue was detected in the samples analyzed. This result is highly significant because of its impacts on public health and animals living in the Gölcük National Park.     

Langmuir–Blodgett Film of Asymmetric Calix[4]arene Derivative Modified Electrode for Voltammetric Determination of Silver

A new electrochemical voltammetric sensor, Langmuir–Blodgett (LB) film of 25,27‐dimethoxy‐26‐(N‐trichloroacetyl)carbamoyloxy‐p‐tert‐butylcalix[4]arene (DCA) modified GCE (LB_DCA–GCE), was designed and successfully used for recognition and determination of trace amounts of Ag⁺ in water. Under the optimum experimental conditions, the lowest detectable concentration of Ag⁺ reached 1 × 10^?9 mol L^?1. Moreover, LB_DCA–GCE exhibited a well‐defined response relating to the Ag⁺ with good sensitivity, selectivity, reproducibility, and long stability. The recognizing mechanism of LB_DCA–GCE for silver ion in aqueous solution was also discussed. The results show that the size of calixarene cavity may be the predominate factor affecting recognition of calixarene for silver ions.