Behaviour and Quantification Studies of Terbacil and Lenacil in Environmental Samples Using Cyclic and Adsorptive Stripping Voltammetry at Hanging Mercury Drop Electrode

The cyclic voltammograms of terbacil and lenacil at the hanging mercury drop electrode showed a single well defined four electron irreversible peak in universal buffer of pH 4.0 for both compounds. The peak potentials were shifted to more negative values on the increase of pH of the medium, implying the involvement of protons in the electrode reaction and that the proton transfer reaction precedes the proper electrode process. The four electron single peak may be attributed to the simultaneous reduction of carbonyl groups present in 2 and 4 in pyrimidine ring of terbacil and lenacil to the corresponding hydroxy derivative. Based on the interfacial adsorptive character of the terbacil and lenacil onto the mercury electrode surface, a simple sensitive and low cost differential pulse adsorptive stripping voltammetric procedure was optimized for the analysis of terbacil and lenacil. The optimal operational conditions of the proposed procedure were accumulation potential E _acc = −0.4 V, accumulation time t _acc = 80 s, scan rate = 40 mV s⁻¹, pulse amplitude = 25 mV using a universal buffer pH 4.0 as a supporting electrolyte. The linear concentration range was found to be 1.5 × 10⁻⁵ to 1.2 × 10⁻⁹ mol/l and 1.5 × 10⁻⁵ to 2.5 × 10⁻⁸ mol/l with the lower detection limit of 1.22 × 10⁻⁹ and 2.0 × 10⁻⁸ mol/l. The correlation coefficient and relative standard deviation values are found to be 0.942, 0.996, 1.64% and 1.23%, respectively, for 10 replicants. The procedure was successfully applied for determination of terbacil and lenacil in formulations, mixed formulations, environmental samples such as fruit samples and spiked water samples.     

Differential pulse adsorptive stripping voltammetric determination of simeton in its formulations and vegetables

A sensitive adsorptive stripping voltammetric method for the determination of simeton with universal buffer solution has been described. The method was based on the adsorption accumulation of simeton at a hanging mercury drop electrode. The overall reduction process is under controlled diffusion. The adsorptive peak was observed at ?0.8 V vs SCE in acidic solution 2 < pH < 6. The peak response was characterized with respect to pH, accumulation potential, time, and scan rate. The calibration plot was found to be linear from 1.13 × 10^???5 to 3.5 × 10^???8 M with a limit of detection of 2.0 × 10^???8 M. Finally, the method has been applied for the determination of simeton in its formulations and vegetable samples.     

Determination of ametryn in sugarcane and ametryn–atrazine herbicide formulations using spectrophotometric method

A sensitive spectrophotometric method has been developed for determination of ametryn in agricultural samples. The proposed method was based on reaction with pyridine and further coupling with sulfanilic acid to form a colored product. The absorbance was measured at 400 nm with a molar absorptivity of 2.1 × 10⁵ L mol⁻¹ cm⁻¹. The method shows a linear range from 0.2–20 μg mL⁻¹ with limit of detection and limit of quantification 0.16 and 0.54 μg mL⁻¹, respectively. The method has been successfully applied to the determination of ametryn in sugarcane juice and commercial formulations after separation of ametryn from triazine herbicides based on solvent extraction. Recovery values were found to be in the range of 96.0 ± 0.2% to 98.4 ± 0.1%.     

Facile and Sensitive Spectrophotometric Determination of Carbosulfan in Formulations and Environmental Samples

Facile, selective and sensitive spectrophotometric method has been developed for the determination of carbosulfan in insecticidal formulations, fortified water, food grains, agriculture wastewater and soil samples with newly synthesized reagents. The method was based on acid and alkaline hydrolysis of the carbosulfan pesticide, and the resultant hydrolysis product of carbosulfan was coupled with 2,6-dibromo-4-methylaniline to give a yellow color product with λ _max of 464 nm or interaction with 2,6-dibromo-4-nitroaniline to produce yellow colored product with λ _max of 408 nm or coupling with 2,4,6-tribromoaniline to form red colored product has a λ _max of 471 nm. Under optimal conditions, Beer’s law range for 2,6-dibromo-4-methylaniline (DBMA) was found to be 0.2–12.0 μg ml⁻¹, 0.6–16.0 μg ml⁻¹ for 2,6-dibromo-4-nitroaniline (DBNA) and 0.4–15.0 μg ml⁻¹ for 2,4,6-tribromoaniline (TBA). The molar absorptivity of the color systems were found to be 3.112 × 10⁴ l mol⁻¹ cm⁻¹ for DBMA, 3.214 × 10⁴ l mol⁻¹ cm⁻¹ for DBNA and 3.881 × 10⁴ l mol⁻¹ cm⁻¹ for TBA. Sandell’s of the color reactions are 0.013 μg cm⁻² (DBMA), 0.012 μg cm⁻² (DBNA) and 0.011 μg cm⁻² (TBA) respectively. The effect of the non-target species on the determination of carbosulfan was studied to enhance the selectivity of the proposed methods. The formation of colored derivatives with the coupling agents is instantaneous and stable for 28, 30, and 26 h. Performance of the proposed methods were compared statistically in terms Student’s F and t-tests with the reported methods. An erratum to this article can be found at     

Selective and sensitive extractive spectrophotometric determination of micro amounts of palladium(II) in spiked samples: using a new reagent N-ethyl-3-carbazolecarbaxaledehydethiosemicarbazone

N-Ethyl-3-cabazolecarboxaldehydethiosemicarbazone (ECCT) is proposed as a new, sensitive and selective complexing reagent for the separation and extractive spectrophotometric determination of palladium(II) at pH: 4.0 to form a yellowish orange colored 1:1 chelate complex, which is very well extracted in to n-butanol. The absorbance was measured at a maximum wavelength, 410 nm. This method obeys Beer’s law in the concentration range 0.0–6.6 μg mL⁻¹ and the correlation coefficient of Pd(II)-ECCT complex is 0.998, which indicates an excellent linearity between the two variables with good molar absorptivity and Sandell’s sensitivity, 1.647 × 10⁴ l mol⁻¹cm⁻¹, 6.49 × 10⁻³ μg cm⁻², respectively. The instability constant of complex calculated from Edmond’s method, 2.724 × 10⁻⁵ was in good agreement with the value calculated from Asmus’ method 2.624 × 10⁻⁵, at room temperature. The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.839. Edmond’s method was observed to be a more selective method in the presence of EDTA, oxalate and phosphate ions. The method was successfully applied for the determination of Pd(II) in water samples, synthetic mixtures and hydrogenation catalysts, employing an atomic absorption spectrometer for comparing these results.     

Concentrations of cadmium and lead heavy metals in Dardanelles seawater

Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10⁻⁵ M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l⁻¹ (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l⁻¹ (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.     

Solid phase extraction of gold(III) on Amberlite XAD-2000 prior to its flame atomic absorption spectrometric determination

A solid phase extraction method for the determination of gold(III) at trace levels by flame atomic absorption spectrometer (FAAS) was developed. The method was based on retention of gold as chloro complexes through the Amberlite XAD-2000. The effect of some analytical parameters including hydrochloric acid concentration, sample volume, sample and eluent flow rates, eluent volume, eluent concentration and interfering ions on the recovery of gold(III) was investigated. The retention of gold(III) from 1.5 mol l⁻¹ HCl solution and the recovery of gold with 0.07 mol l⁻¹ NH₃ solution were quantitative (≥95%). The relative standard deviation (RSD) was calculated as 3.2% (n = 10). The detection limit for gold was 2 μg l⁻¹. The accuracy was checked with the determination of gold spiked an artificial seawater and a pure copper samples.     

Environmental assessment of 2-mercaptobenzimidazole based on the surface plasmon resonance band of gold nanoparticles

A colorimetric assay method is described for the environmental detection of 2-mercaptobenzimidazole (MBI) using surface plasmon resonance of gold nanoparticles (AuNPs). Stable and dispersed AuNPs with intensified plasmon resonance were prepared in situ using a simple, rapid, and eco-friendly procedure by applying ascorbic acid as a reducer and cetyltrimethylammonium bromide as a stabilizer. The presence of MBI has a strong effect on the plasmon absorbance of AuNPs, which was employed for the detection of MBI. The calibration curve was linear in the range of 1.0?×?10^?6–5.5?×?10^?5 mol/L of MBI; the detection limit was 8.4?×?10^?7 mol/L. The relative standard deviations for eight replicate measurements of 3.0?×?10^?6 and 5?×?10^?5 mol/L MBI were 3.9 and 1.4 %, respectively. The method was successfully applied to the determination of MBI in tap, river, sea, and heat exchanger cooling water samples.     

A spectrophotometric assay method for vanadium in biological and environmental samples using 2,4-dinitrophenylhydrazine with imipramine hydrochloride

A simple, rapid, and sensitive method involving the interaction of 2,4-dinitrophenylhydrazine with imipramine hydrochloride in presence of vanadium (V) in sulfuric acid medium has been proposed for the determination of vanadium. The purple-colored product developed showed an absorption maximum at 560 nm and was stable for 24 h. The working curve was linear over the concentration range of 0.1–2.8 μg ml^− 1, with sensitivity of detection of 0.0124 μg ml^− 1. Molar absorptivity and Sandell’s sensitivity were found to be 2.6 × 10⁴ l/mol cm and 0.0039 μg cm^− 1, respectively. The accuracy of the proposed method was assessed by Student’s t test and variance ratio F test, and the results were on par with the reported method. The method was successfully used in the determination of V in water, human urine, soil, and plant samples, and it was free from interference by various concomitant ions.     

Radiocaesium Activity Concentrations in Wheat Grains in the Republic of Croatia for 1965–2003 and Dose Assessment

Results of systematic, long-term measurements of ¹³⁷Cs activities in wheat for the period 1965–2003 are summarized. Radiocaesum fallout activities affect wheat activity concentrations, the coefficient of correlation being 0.91. In the observed period, the highest activity of ¹³⁷Cs deposited by fallout, 6321 Bq m⁻², was recorded in 1986, i.e., in the year of Chernobyl accident, causing peak ¹³⁷Cs activity concentration in wheat of 38.0 ± 13.0 Bq kg⁻¹. After the Chernobyl nuclear accident the ¹³⁴Cs:¹³⁷Cs activity ratio in wheat was ≈0.5, and did not differ from the value found in other environmental samples. The transfer coefficient from ¹³⁷Cs fallout deposition to wheat was calculated to be 8.6 × 10⁻³ Bq y kg⁻¹ per Bq m⁻², indicating the low transfer of radiocaesium from fallout to wheat. The upper limit for the collective effective dose for the Croatian population due to ¹³⁷Cs and ¹³⁴Cs ingestion by wheat and wheat products consumption for period 1965–2003 was estimated to be 665 person-Sv, the upper limit for the annual collective effective dose in 2003 being only about 0.061 person-Sv.     

A nanosilver-based spectrophotometric method for determination of malachite green in surface water samples

A new spectrophotometric method is reported for the determination of nanomolar level of malachite green in surface water samples. The method is based on the catalytic effect of silver nanoparticles on the oxidation of malachite green by hexacyanoferrate (III) in acetate–acetic acid medium. The absorbance is measured at 610 nm with the fixed-time method. Under the optimum conditions, the linear range was 8.0?×?10^?9–2.0?×?10^?7?mol?L^?1 malachite green with a correlation coefficient of 0.996. The limit of detection (S/N?=?3) was 2.0?×?10^?9?mol?L^?1. Relative standard deviation for ten replicate determinations of 1.0?×?10^?8?mol?L^?1 malachite green was 1.86 %. The method is featured with good accuracy and reproducibility for malachite green determination in surface water samples without any pre-concentration and separation step.     

Water quality assessment: surface water sources used for drinking and irrigation in Zaria,Nigeria are a public health hazard

We assessed the quality and pollution status of source surface waters in Zaria, Nigeria by monitoring the nature, cause and extent of pollution in Samaru stream, Kubanni River and Kubanni dam over a period of 10 months, between March and December 2002. A total of 228 water samples was collected from 12 sites and analysed for a total of ten physicochemical and one bacteriological quality indicators, using standard methods. Aesthetic water quality impairment parameters were also observed. The mean values of most water quality parameters were significantly higher (P < 0.05) in both the stream and river than in the dam. There was no significant correlation between faecal coliform counts (FCC) and water temperature (in the range 15–33°C); pH (5.77–7.32); and turbidity (1.4–567 NTU). The high FCC ranged from 2.0 × 10¹ to 1.6 × 10⁶ MPN/100 ml and exceeded the WHO standards for drinking water and water used for fresh-produce irrigation, and correlated positively (P < 0.05) with conductivity (in the range 68–1,029 μS/cm); TDS (10.0–70.0 mg/l); TSS (10.0–70.0 mg/l); Cl (7.5–181 mg/l); PO₄⁻P (0.01–0.41 mg/l); NO₃⁻N (0.6–3.8 mg/l) and BOD₅ (0.1–14.9 mg/l). The main pollution sources were municipal wastewater, stormwater runoffs, the ABU sewage treatment plant, abattoir effluents and irrigation farms treated with chemical fertilisers. We conclude that these water bodies are potentially hazardous to public health and that proper sewage treatment and river quality monitoring are needed to warn against hazards to public health.     

Analysis and evaluation of nitrate levels in groundwater at Al-Hashimiya area, Jordan

Water with high nitrate concentration (NO₃ ⁻) is unfit for human consumption, especially when its concentration exceeded the threshold limit (50 mg/l) recommended by the health authorities such as the World Health Organization (WHO). In Jordan, there is a great concern for determination and monitoring organic and inorganic pollutants that may reach groundwater. Nitrate is highly mobile and present in domestic, agricultural and industrial waste in Jordan, and thus this study focused initially on nitrate as both a contaminant of concern and as an indicator of potential groundwater contamination. The present study determined the extent of nitrate contamination in groundwater in the study area and examined the likely sources of NO₃ ⁻. A total of 248 groundwater samples were collected from 16 wells in different sites of Al-Hashimiya area, Zerqa Governorate, Jordan, and investigated for NO₃ ⁻ concentrations. Moreover, measurements of temperature, electrical conductivity and pH were carried out in the field. Analysis was carried out according to the methods described by the American Public Health Association (APHA). Results showed that there was a dramatic increasing in NO₃ ⁻ concentrations from the year 2001 to 2006 for some selected wells in the present study. NO₃ ⁻ concentration in 2006 was ranged from 10 to 330 mg/l with an average of 77 mg/l. Overall, groundwater had elevated nitrate concentration with 92% of the samples containing more than 20 mg/l NO₃ ⁻, indicating the influence of human activities. This study has shown that there is a strong correlation between the nitrate concentration and the wastewater effluents as a source of pollution.     

Development of simple and sensitive spectrophotometric method for the determination of bendiocarb in its formulations and environmental samples

Facile, selective and sensitive spectrophotometric method has been developed for the determination of bendiocarb in its insecticidal formulations, fortified water, food grains, agriculture wastewater and agriculture soil samples with prepared reagents. The method was based on alkaline hydrolysis of the bendiocarb pesticide, and the resultant hydrolysis product of bendiocarb was coupled with 2,6-dibromo-4-methylaniline to give a yellow color product with λmaxof457 nmorcouplingwith2, 6−dibromo−4−nitroanilinetoproducearedcoloredproductwithλ_max of474~nmorcouplingwith2, 4, 6−tribromoanilinetoformorangeredcoloredproducthasaλ_max of465 nm.Underoptimalconditions, Beer'slawrangefor2, 6−dibromo−4−methylaniline(DBMA)wasfoundtobe0.6−−14.0~μgmL ^-1, 0.8−−10.0 μgmL ^-1 for2, 6−dibromo−4−nitroaniline(DBNA)and0.4−−10.0 μgmL ^-1 for2, 4, 6−tribromoaniline(TBA).Themolarabsorptivityofthecolorsystemswerefoundtobe4.126~×~10⁴ lmol ^-1 cm ^-1 forDBMA, 3.254×10⁴ l~mol ^-1 cm ^-1 forDBNAand2.812×10⁴ lmol ^-1 cm ^-1 forTBA.Sandell'softhecolorreactionsare0.018 μgcm ^-2(DBMA), 0.052 μgcm ^-2(DBNA)and0.065 μgcm ^-2$ (TBA) respectively. The effect of the non-target species on the determination of bendiocarb was studied. The formation of colored derivatives with the coupling agents is instantaneous and stable for 18 h, 30 h, and 12 h. Performance of the proposed methods were compared statistically in terms Student's F and t-tests with the reported methods.     

Biofilms coating Schoenoplectus californicus as indicators of water quality in the Río de la Plata Estuary (Argentina)

N-ethyl-3-carbazolecarboxaldehyde-3-thio- semicarbazone (ECCT) as an new analytical reagent used for the development of a highly sensitive extractive spectrophotometric method for the determination of copper(II). The ECCT forms a greenish-yellow colored 1:1 (M:L) complex with copper(II) at pH 3.0, which is well extracted into n-butanol and shows maximum absorbance at 380nm. The color of the complex is stable for more than forty eight hours. The system obey Beer's law in the range 0.4–3.6 with 2.243 × 10⁴lmol⁻¹cm⁻¹, 2.83 × 10^-3μgcm⁻² molar absorptivity and Sandell's sensitivity respectively. The regression coefficient is 0.412 with 0.99 correlation coefficient. The precision and accuracy of the method was checked by finding the relative standard deviation (0.422%). This developed method has been successfully employed for the determination of copper(II) in environmental and pharmaceutical samples. The method is evaluated by analyzing samples from the bureau of analyzed samples (BCS 233, 266, 216/1, 207 and 179) and by inter comparison of experimental values using AAS.     

Determination of hydrazine hydrate based on electrochemiluminescence of Ru(bpy) 3 2+

Considering of the basic properties and also the two nitrogen atoms in the structure, hydrazine hydrate was employed to be an amine additive candidate, to build a Ru(bpy) ₃ ²⁺ /hydrazine electrochemiluminescence (ECL) system, and ECL of Ru(bpy) ₃ ²⁺ has been employed for the determination of hydrazine hydrate in the paper. The result demonstrated that the logarithmic ECL increasing (ΔECL?=?ECL_{after addition of hydrazine}???ECL_{before addition of hydrazine}) versus the logarithmic concentration of hydrazine hydrate is linear over a concentration range of 1.0?×?10^?9 to 1.0?×?10^?5?mol/L, on both glassy carbon and Pt electrodes in a pH 9 phosphate buffer. The hydrazine hydrate detection limit was down to 1.0?×?10^?9?mol/L, comparatively lower than other detection methods. To check its applicability, the proposed method was applied to the determination of hydrazine hydrate added into a tap water sample with good reproducibility and stability. All these provide a possibility to develop a novel ECL detection method for hydrazine in water.     

Spatio-Temporal Fluxes in Particulate Organic Carbon in a Tropical Coastal Lagoon

Temporal and spatial variations in particulate organic carbon (POC) in relation to primary production, chlorophyll a, phaeophytin, plankton abundance, secondary production and suspended particulate matter (SPM) were studied monthly for 1 year from April 1996 to March 1997 in a shallow tropical coastal lagoon on the southwest coast of India. Though temporal variations in all components were significant, spatial variabilities were not statistically significant. POC values range from 200 to 5690 mg C m³ h⁻¹, while primary production, chlorophyll a, and phaeophytin varied between 0.02 and 14.53 mg C m⁻³ h⁻¹, 0.87 and 23.11 mg m⁻³ and 3.02 and 30.581 mg m⁻³, respectively. Phytoplankton and zooplankton abundance varied from 0.01 to 655.5×10⁵ no m⁻³ and negligible to 7.08×10⁵ no m⁻³ respectively; secondary production from 10 to 490 mg C m⁻³ and SPM between 0.38 and 74.43×10⁴ mg m⁻³ during this study. Temporally, postmonsoon months were observed to have the highest concentrations of POC in the lagoon waters. The bulk of the POC pool in the lagoon was composed of secondary producers (72%), followed by chlorophyll a (21%), phaeophytin (7%) and suspended particulate matter of inorganic origin (< 0.1%).     

Soil salinity evolution and its relationship with dynamics of groundwater in the oasis of inland river basins: case study from the Fubei region of Xinjiang Province, China

Soil salinization is an important worldwide environmental problem, especially in arid and semi-arid regions. Knowledge of its temporal and spatial variability is crucial for the management of oasis agriculture. The study area has experienced dramatic change in the shallow groundwater table and soil salinization during the 20th century, especially in the past two decades. Classical statistics, geostatistics and geographic information system (GIS) were applied to estimate the spatial variability of the soil salt content in relation to the shallow groundwater table and land use from 1983 to 2005. Consumption of reservoir water for agricultural irrigation was the main cause of a rise in the shallow groundwater table under intense evapotranspiration conditions, and this led indirectly to soil salinization. The area of soil salt accumulation was greater in irrigated than in non-irrigated landscape types with an increasing of 40.04% from 1983 to 2005 in cropland at ∼0.43 t ha⁻¹ year⁻¹, and an increase at ∼0.68 t ha⁻¹ year⁻¹ in saline alkaline land. Maps of the shallow groundwater table in 1985 and 2000 were used to deduce maps for 1983 and 1999, respectively, and the registration accuracy was 99%.     

Determination of total chromium by flame atomic absorption spectrometry after coprecipitation by cerium (IV) hydroxide

A method for the preconcentration of the total chromium based on coprecipitation with cerium (IV) hydroxide is proposed for determination of chromium by flame atomic absorption spectrometry. Different factors including carrier element amount, pH, sample volume and matrix ion effects for the precipitation were examined. The detection limit of the total chromium (k = 3, N = 15) was 0.18 μg l⁻¹. The presented method was applied for the determination of chromium in the wastewater samples from Kayseri and Nigde Organized Industrial Region-Turkey and in drinking water from our laboratory, Kayseri with satisfactory results (relative standard deviations below 8%, recoveries 95%). The analytical results obtained by the proposed method for certified copper sample was in good agreement with the certified value.     

Inorganic nitrogen transformations in the treatment of landfill leachate with a high ammonium load: A case study

The inorganic nitrogen transformations occurring at a municipal waste leachate treatment facility were investigated. The treatment facility consisted of a collection well and an artificial wetland between two aeration ponds. The first aeration pond showed a decrease in ammonium (from 3480 (± 120) to 630(± 90) mg ⋅ L⁻¹), a reduction in inorganic nitrogen load (3480 to 1680 mg N ⋅ L⁻¹), and an accumulation of nitrite (< 1.3 mg-N ⋅ L⁻¹ in the collection well, to 1030 mg-N ⋅ L⁻¹). Incomplete ammonium oxidation was presumably the result of the low concentration of carbonate alkalinity (∼2 mg ⋅ L⁻¹), which may cause a limitation in the ammonium oxidation rate of nitrifiers. Low carbonate alkalinity levels may have been the result of stripping of CO₂ from the first aeration pond at the high aeration rates and low pH. Various chemodenitrification mechanisms are discussed as the reason for the reduction in the inorganic nitrogen load, including; the reduction of nitrite by iron (II) (producing various forms of gaseous nitrogen); and reactions involving nitrous acid. It is suggested that the accumulation of nitrite may be the result of inhibition of nitrite oxidizers by nitrous acid and low temperatures. Relative to the first aeration pond, the speciation and concentration of inorganic nitrogen was stable in the wetlands and 2nd aeration pond. The limited denitrification in the wetlands most probably occurred due to low concentrations of organic carbon, and short retention times.