Degradation of benomyl, picloram, and dicamba in a conical apparatus by zero-valent iron powder.

Reduction of some pesticides (benomyl, picloram, and dicamba) was studied in an aerobic batch conical pilot system to investigate the disappearance of these pesticides on contact with iron powder (20 g/l, 325-mesh). Aqueous buffered solutions of the compounds were added to the system followed by zero-valent iron powder (ZVIP), and the decline in the pesticide concentrations was monitored over time. HPLC analyses show a complete disappearance of picloram (1.20 mg/l) after 20 min of reaction. Benomyl (1.00 mg/l) and dicamba (1.25 mg/l) disappear after 25 and 40 min, respectively. The t50 values ranged from 3 to 5.5 min, and were about slightly less than the t1/2 values reported when the log of the relative HPLC peak area was plotted versus time, where the relative peak area was calculated by dividing the measured peak area by the initial peak area. Pathways for the degradation of the studied pesticides by ZVIP are proposed.

Reductive degradation of carbaryl in water by zero-valent iron.

Reduction of carbaryl solution by zero-valent iron powder (ZVIP) was studied in a rotator batch system (70 rpm) in order to evaluate the utility of this reaction in remediation of carbamate contaminated water. Degradation with different amount of ZVIP: 0.01, 0.02, 0.03, 0.04 g/ml at pH 6.6 and at ambient temperature was investigated. The results show that the process exhibits a degradation rate appearing to be directly proportional to the surface contact area of ZVIP (325-mesh) with the carbaryl molecules. Three analytical techniques were used to monitor carbaryl degradation: (1) A UV-Vis diode array spectrophotometer was used to record all spectra. (2) A high performance liquid chromatography was used to separate by-products and examine the evolution of breakdown products. (3) A home-built spectrophosphorimeter that uses the solid surface room temperature phosphorescence (SSRTP) was employed to observe selectively the decline of the carbaryl concentration at different amount of ZVIP on Whatman no. 1 filter paper. Results show that the reducing degradation of carbaryl with ZVIP as the source of electrons is effective with a half-life close to several minutes.

Remediation of s-triazines contaminated water in a laboratory scale apparatus using zero-valent iron powder.

Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide's concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.

Use of diffuse reflectance spectrometry in spot test reactions for quantitative determination of cations in water.

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka-Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A(R) vs log of the mol l(-1) concentration. Limits of detection at the 10(-4) M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.

Determination of carbaryl and biphenyl through optical fiber ccd-assisted flash lamp induced room temperature phosphorescence.

A fiber-optic sensor for solid surface room temperature phosphorescence of carbaryl and biphenyl pesticides was designed. A xenon flash lamp was used as excitation source, and a cooled two-dimensional charge coupled device was employed as the detector. Room temperature phosphorescence spectra of carbaryl and biphenyl were recorded by an imaging spectrograph. Limits of detection at the picogram/spot level were obtained for the investigated compounds. The linear dynamic range extended over three orders of magnitude. The standard addition method and the internal standard method were employed to analyze the studied compounds in mixtures. The feasibility of the SS-RTP apparatus developed was evaluated by the identification of carbaryl in a real sample.

Room temperature phosphorescence analyses of polycyclic aromatic hydrocarbons using an imaging sensing system combined with a bifurcated optical fiber and a cooled charge coupled device detector.

This paper presents a development of a solid support RT phosphorescence procedure for the determination of polycyclic aromatic hydrocarbons, based on the use of a Xenon flash lamp as the excitation source, a fiber optic sensor as a guide of light, an imaging spectrograph and a cooled two dimensional charge coupled device as the detector. Non fluorescent Whatman N degrees 1 filter paper was used as the solid substrate and, thallium nitrate and sodium iodide were used to enhance room temperature phosphorescence of pyrene, benzo (a) anthracene, naphtalene, phenanthrene, dibenzothiophene, fluorene, coronene and fluoranthene. Analytical curves of eight phosphors give linear dynamic ranges from one and a half to two decades and limits of detection of femtomolar to picomolar/spot were reported. Quantitative analyses in mixtures were also carried out using the internal standard method. Results led to a 10% better accuracy for determinations of pyrene and benzo (a) anthracene.

Rapid treatment of water contamined with atrazine and parathion with zero-valent iron.

The utility of fine-grained iron metal in the remediation of water contamined with Atrazine and Parathion was investigated. Batch procedures under water treatment conditions (ambient temperature and pH of approximately 7) indicated that these pesticides degrade rapidly in the presence of iron powder (40-60 mesh, 40 g/l). The decline in the concentration of pesticide was monitored by HPLC. Experiments with unbuffered solutions showed a steady increase in pH values during the reactions. Therefore, experiments were run in buffered solutions. Different buffered solutions resulted in different degradation rates indicating that the buffer plays an important role in enhancing the degradation process. Tests were also performed on an industrial effluent solution containing a variety of pesticides. Although the products of degradation were not characterized, our HPLC results indicated the disappearance of all the parent pollutants.

Quantitative measurements of ammonium, hydrogenophosphate and Cu(II) by diffuse reflectance spectrometry.

Diffuse reflectance spectrometry is shown to be useful for the quantitative determination of small amounts of pollutants. The relation between sample concentration and reflectance is described by the Kubelka-Munk equation. The experiments were performed with a laboratory constructed diode array spectrophotometer. We can obtain the quantitative reflectance values of different precipitates like ammonium with Nessler's reagent, hydrogenophosphate with silver nitrate and a complex such as Cu(II) with dithiooxamide 'rubeanic acid' by forming a spot colour on filter paper. We have obtained for each reagent a calibration curve by plotting the relative intensity of reflectance versus the log of the mol (dm(3))(-1) concentration. The linearity was obtained for Cu(II) from 8x10(-4) to 2.5x10(-2) mol l(-1) with r(2)=0.9838 and from 10(-3) to 10(-1) mol l(-1) for polyphosphate with r(2)=0.9975 and from 5x10(-4) to 5x10(-2) mol l(-1) for ammonium with r(2)=0.9889. We can consider that for a direct measurement of the intensity of reflectance, it is possible to perform quantitative spot-test analysis.