Determination of Cyanuric Acid in Swimming Pool Water and Milk by Differential Pulse Polarography

Cyanuric acid is a suspected gastrointestinal or liver toxicant in humans. Therefore, determination of trace cyanuric acid is very important, in this work a novel, sensitive, and reliable method was developed using differential pulse polarography. Optimum conditions for analytical determination were found to be at a pH of 9.5, Britton–Robinson at a reduction potential of ?105 mV. Experimental results indicate an excellent linear correlation between the peak current and the concentration in the range of cyanuric acid from 0.5 to 27.0 µM (0.06–3.5 µg mL^?1) with a correlation coefficient of 0.997. The limit of detection and limit of quantification were obtained as 0.15 and 0.5 µM (0.02–0.06 µg mL^?1), respectively. The proposed method was successfully applied to the determination of cyanuric acid in pool water and in spiked milk. Cyanuric acid level in swimming pool water was found as 2.54 ± 0.47 µg mL^?1 (19.7 ± 2.29 µM) in swimming pool water for N = 4 and 95% confidence interval. The recoveries were found to be sufficient. Also, the standard deviation of the data was low which shows high accuracy and precision of proposed differential pulse polarographic method. The influences of some other commonly found inorganic salts on the determination of cyanuric acid were also examined. Some interfering species were eliminated using complexing agents, e.g., EDTA.     

Flame Atomic Absorption Spectrometry Determination of Trace Amounts of Cadmium and Zinc in Water Samples after Preconcentration onto Modified Amberlite XAD‐4 Resin

In the present article, a procedure for the simultaneous separation and preconcentration of trace amounts of cadmium and zinc is proposed. It is based on the adsorption of cadmium and zinc ions onto a column of Amberlite XAD‐4 resin loaded with aluminon reagent. Cadmium and zinc ions are quantitatively retained on the column in the pH range from 6.5–7.5, at a flow rate of 2 mL min^–1. The cadmium and zinc ions are eluted with 5.0 mL of 5 mol L^–1 HNO₃ solution. Cadmium and zinc are measured by flame atomic absorption spectrometry (FAAS). In the present case, 0.1 μg of cadmium and 0.5 μg of zinc can be concentrated in the column from 1000 mL of aqueous sample, where their concentrations are as low as 0.1 and 0.5 ng mL^–1, respectively. The relative standard deviations, for seven replicated determinations of 1.0 μg mL^–1 of cadmium and zinc, are 1.2 and 1.1%, respectively. The detection limits for cadmium and zinc in the original solution are 0.02 and 0.11 ng mL^–1, respectively. The interference of a large number of anions and cations has been studied and the optimized conditions are utilized for the determination of trace amounts of cadmium and zinc in different environmental and standard samples.     

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.     

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.     

Determination of Copper in Water Samples after Solid‐phase Extraction Using Dimethylglyoxime‐modified Silica

This work describes the modification of silica gel with dimethylglyoxime, in order to prepare an effective sorbent for the preconcentration and determination of copper. The sorption capacity of dimethylglyoxime‐modified silica‐gel (DMGMS) was 71.37 mg g^–1 and the optimum pH for the quantitative recovery of copper was found to be 5.0. The optimum flow rate, sorbent amount, and sample volume were 1 mL min^–1, 300 mg, and 50 mL, respectively. 10 mL of 0.1 mol L^–1 HCl was the most suitable eluent. The detection limit of copper was 6.0 ng mL^–1. The recommended method, for the determination of copper, is simple and reliable, without any notable matrix effect and can be successfully applied to environmental water samples. Copper recovery in the range from 99–100% was obtained from seawater and thermal spring water using this method. The method was applied to standard reference materials, NIST‐1515 (apple leaves) and NIST‐1643e (simulated fresh water), for the determination of copper and the results were in good agreement with certified values.     

On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L^?1 HNO₃ solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L^?1, and a relative standard deviation of 1.2% at 0.2 µg mL^?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.     

Occurrence of an Algal Mass Development in an Acidic (pH 2.5):, Iron and Aluminium‐rich Coal Mining Pond

A bloom of Chlamydomonas botryopara was observed in an extremely acid coal mining pond (pH 2.5) with high concentrations of iron and aluminium (1160...3760 mg L^–1 Fe, 133...387 mg L^–1 Al). Cell density of algae was counted as 6.45 · 10⁶ mL^–1 corresponding to 700 mg L^–1 fresh weight and 2660 μg L^–1 chlorophyll‐a. The nutrient concentrations were 3.5 mg L^–1 soluble reactive phosphorus and 0.15 mg L^–1 dissolved inorganic nitrogen. This observation supports the hypothesis that a low nutrient availability rather than extreme conditions (e.g. high acidity and low pH) limit the development of phytoplankton in many acidified lakes.     

Application of the Response Surface Method for Optimization of Headspace Liquid Phase Microextraction of Trihalomethanes in Drinking Water

An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R²) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.     

Kinetic Determination of Trace Amounts of Nitrite Using an Optical Chemical Sensor

An optical chemical sensor (optode) is proposed for the kinetic determination of nitrite ion. The optode was fabricated by the immobilization of methyl violet on a triacetylcellulose polymeric membrane. Methyl violet is covalently bonded to a transparent triacetylcellulose film. By immersion of the sensor into an acidic nitrite solution, the absorbance of the sensor at 596 nm decreases with time that is due to the reaction of nitrite with the immobilized methyl violet. A fixed time method of 15 min was used to monitor the reaction. The linear range for the determination of nitrite was 0.20–8.00 µg mL^?1 and the limit of detection was 0.08 µg mL^?1. The optodes were one‐shot, they had durability more than 2 months and were easily prepared. The optode was successfully applied to the determination of nitrite ion in spring water and sewage samples.     

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.     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

Improvement of a Monoclonal Antibody-based Immunoassay for the Determination of Terbutryn Verbesserung eines Immunassays mit monoklonalen Antikörpern zur Bestimmung von Terbutryn

The performance of an existing enzyme immunoassay (EIA) with monoclonal antibodies (mAb) for the determination of terbutryn was improved by the application of a new enzyme tracer. For this purpose the triazine derivative 6-chloro-2-(tert-butylamino)-1,3,5-triazine-4-(6-aminohexane carboxylic acid) was coupled to horseradish peroxidase (HRP). The competitive EIA on microwell plates made it possible to determine terbutryn in the range from 0.05 to 1 μg/L with a 50% B/B₀ value of the test at 0.2 μg/L. The application of the EIA to determine terbutryn in spiked surface waters provided good recoveries of terbutryn without matrix effects.     

Detection of Pharmaceuticals and Personal Care Products in Agricultural Soils Receiving Biosolids Application

Increasing research has suggested that biosolids generated from municipal wastewater treatment can be a major sink for many pharmaceuticals and personal care products (PPCPs) and their land application potentially introduces these contaminants into the terrestrial and aquatic environments. In this study, methods were developed for the analysis of 14 PPCPs in biosolids and soils using pressurized liquid extraction, solid phase extraction and liquid chromatography‐tandem mass spectrometry. Recoveries were over 50% for all analytes except diphenhydramine (?30%) in soils. Soil properties or type of biosolids showed minor effects on method recoveries. Estimated method limits of quantification (LOQ) range from 0.1–15 ng g^–1 for soil and 0.3–27 ng g^–1 for biosolids. A field study utilizing the methods revealed that other than carbamazepine‐10,11‐epoxide, all targeted compounds were detected in biosolids. Diphenhydramine, fluoxetine, triclosan and triclocarban were detected up to the μg g^–1 range with the highest concentration of 23 μg g^–1 for triclocarban. Seven of the PCCPs found in biosolids were also detected in agricultural soils amended with these biosolids and several (carbamazepine, diphenhydramine, and triclocarban) appeared to be persistent in soils. Triclocarban was also found most abundant in soils with the highest average concentration of 0.2 μg g^–1 while the rest of compounds were in the lower ng g^–1 range. Generally, the concentrations found on the fields were 2–3 degrees of magnitude lower than in the biosolids, which is likely to be due to dilution, degradation and leaching processes.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Novel Polymeric Resin for Solid Phase Extraction and Determination of Lead in Waters

Interest in preconcentration techniques for the determination of metals at ultratrace levels still continues increasingly because of some disadvantages of flameless atomic absorption spectrometry and the high costs of other sensitive methods in compared to flame atomic absorption spectrometry (FAAS). Among preconcentration techniques, solid‐phase extraction is the most popular because of a number of advantages. In this work, thiol‐containing sulfonamide resin was synthesized, characterized, and applied as a new sorption material for solid phase extraction and determination of lead in natural water samples. The optimization of experimental conditions was performed using the parameters including pH, contact time, and volumes of initial and elution solutions. After preconcentration procedure, FAAS was used for determinations. The synthesized resin exhibits the superiority in compared to the other adsorption reagents because of the fact that there is no necessity of any complexing reagent as well as high sorption capacity. Consequently, 280‐fold improvement in the sensitivity of analytical scheme was achieved by combining the slotted tube atom trap‐atomic absorption spectrometry (STAT‐FAAS) and the developed preconcentration method. The limit of detection was found to be 0.15 ng mL^?1. The Pb²⁺ concentrations in the studied water samples were found to be in the range of 0.9–6.7 ng mL^?1.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Channel response to a dam-removal sediment pulse captured at high-temporal resolution using routine gage data

In this study, we captured how a river channel responds to a sediment pulse originating from a dam removal using multiple lines of evidence derived from streamflow gages along the Patapsco River, Maryland, USA. Gages captured characteristics of the sediment pulse, including travel times of its leading edge (~7.8 km yr⁻¹) and peak (~2.6 km yr⁻¹) and suggest both translation and increasing dispersion. The pulse also changed local hydraulics and energy conditions, increasing flow velocities and Froude number, due to bed fining, homogenization and/or slope adjustment. Immediately downstream of the dam, recovery to pre-pulse conditions occurred within the year, but farther downstream recovery was slower, with the tail of the sediment pulse working through the lower river by the end of the study 7 years later. The patterns and timing of channel change associated with the sediment pulse were not driven by large flow or suspended sediment-transporting events, with change mostly occurring during lower flows. This suggests pulse mobility was controlled by process-factors largely independent of high flow. In contrast, persistent changes occurred to out-of-channel flooding dynamics. Stage associated with flooding increased during the arrival of the sediment pulse, 1 to 2 years after dam removal, suggesting persistent sediment deposition at the channel margins and nearby floodplain. This resulted in National Weather Service-indicated flood stages being attained by 3–43% smaller discharges compared to earlier in the study period. This study captured a two-signal response from the sediment pulse: (1) short- to medium-term (weeks to months) translation and dispersion within the channel, resulting in aggradation and recovery of bed elevations and changing local hydraulics; and (2) dispersion and persistent longer-term (years) effects of sediment deposition on overbank surfaces. This study further demonstrated the utility of US Geological Survey gage data to quantify geomorphic change, increase temporal resolution, and provide insights into trajectories of change over varying spatial and temporal scales.     

Response Surface Approach for the Bisorption of Ag(I) by Macrofungus Pleurotus platypus

Response surface methodology (RSM) employing the three‐level Box–Behnken factorial design was used to optimize the biosorption of Ag(I) by the macrofungus Pleurotus platypus. The initial Ag(I) concentration (100–300 mg/L), pH (3.0–9.0), and biomass dosage (1.0–5.0 g/L) were chosen as the process variables for the optimization. A coefficient of determination (R²) value (0.99), model F value (234.18), and its low p‐value (F < 0.0001) along with the lower value of coefficient of variation (2.44%) indicated the fitness of response surface quadratic model during the present study. At the optimum pH (6.0), initial metal concentration (220 mg/L), and biomass dosage (3.0 g/L), the model predicted 46.7 mg/g Ag(I) uptake and an experimental 46.77 mg/g Ag(I) uptake by P. platypus was obtained. This is the first report on Ag(I) sorption by P. platypus using statistical experimental design employing RSM which may be helpful towards the treatment of industrial effluent containing silver.     

Trace metal levels in coastal sea water investigation of Danish waters

The concentration levels of Cd (25 ng l^?1), Cu (0.45 μg l^?1), Ni (0.48 μg l^?1), Fe (0.2–7.0 μg l^?1), Pb (40 ng l^?1) and Zn (0.80 μg l^?1) have been determined in the Danish Sounds and in the Kattegat. Different sampling techniques have been used and analyses have been carried out separately by two different investigators, both using freon-extraction followed by determination by atomic absorption spectrometry (a.a.s.). Except for iron, found mainly in the particulate phase, the metals are found predominantly in a dissolved and labile (extractable) form. The results are compared with trace metal levels found in the two main water masses entering the Kattegat—the North Sea and the Baltic Sea.     

The occurrence of arsenic in selected marine macroalgae from two coastal areas of South Australia

Total arsenic concentrations have been measured in macroalgae specimens from two coastal areas of South Australia. Phaeophyta in both areas were found to contain elevated arsenic concentrations (42.2–179 μg g^?1 and 26.3–65.3 μg g^?1) relative to Rhodophyta (17.6–31.3 μg g^?1 and 12.5–16.2 μg g^?1) and Chlorophyta (6.3–16.3 μg g^?1 and 9.9–10.8 μg g^?1).