Herbicides runoff in vegetative filter strips: evaluation and validation of a recent rainfall return period model

Vegetative filter strips reduce herbicide runoff from cultivated fields owing to the ability of vegetation to delay surface runoff, promote infiltration, and adsorb herbicides. Previous research has shown that the annual runoff of each herbicide is typically less than 1 g ha^?1. A model for the detection of the return period of rainfall events was recently proposed for a site in the north-eastern Po Valley, Italy. The return period model suggested that most of the herbicide loss by runoff (about 98%) is caused by a few, or even just one, extreme rainfall event with a return period of about 25–27 years, whereas ordinary events (4–5 each year) account for the rest. The present study aims to validate that model by comparing model predictions with the experimental results obtained in the 2010–2011 sampling season (independent test data), and to evaluate the effectiveness of the VFS. In addition, a 7-yr dataset of metolachlor and terbuthylazine concentration in real runoff events is summarised in order to highlight the medium-term magnitude of the pollution. Results show that on the Po Valley plain, 3–4 runoff events of low intensity are expected in spring–summer and that the consequent annual runoff of the herbicides metolachlor and terbuthylazine is about 0.5–0.7 g ha^?1 yr^?1. A summary shows that, owing to their chemical-physical properties, concentrations of the two herbicides are similar, both varying from about 0.01–300 μg l^?1, with a potential pulse-like exposure risk for aquatic communities in waterways. This study showed that vegetative filter strips can reduce herbicide transfer to surface water by 90–98%, and should be suggested for environmental schemes at field and catchment scale.     

Polychlorobiphenyls in Antarctica

The presence and the distribution of polychlorobiphenyls (PCBs) in Antarctic environmental components and the effect of the seasonal formation/melting process of pack ice on the pollution level of seawater were investigated. Seawater, marine, and lake sediment and soil samples were collected in a large area of the Ross Sea and Victoria Land during the 1988–1989, 1989–1990, 1990–1991, and 1991–1992 Italian expeditions. The results obtained highlighted a low and quite homogeneous PCB contamination of the studied area. Surface seawater samples from Gerlache Inlet and Wood Bay showed a typical PCB concentration of 130 pg/liter, and an increase after pack ice melting of about 30–40%. Marine sediment, lake sediment, and soil samples showed normalized mean PCB contents of 150, 240, and 130 (pg/g)/(m²/cm³), respectively.     

Development and Validation of a Simple and Efficient Method for the Determination of Pendimethalin and Its Metabolite M455H001 in Soil by Liquid Chromatography–Tandem Mass Spectrometry (LC-MS/MS)

A new analytical method has been developed and described for the rapid determination of pendimethalin and its major metabolite M455H001 in soil by liquid chromatography coupled with ion-spray tandem mass spectrometry (LC-MS/MS) after a single acidic solvent extraction. The chromatographic separation of the analytes was achieved using a Zorbax C18 reversed phase column and water/0.1% formic acid and methanol as the mobile phase at a flow rate of 0.2?mL?min^?1. The recoveries of the method ranged from 78.8% to 119.8% for pendimethalin and from 73.7% to 108.8% for M455H001, and the relative standard deviation was lower than 16% for both analytes. The validated limit of quantification was 0.01?µg?g^?1 soil dry weight for both compounds. The matrix effects were evaluated and were less than 20% for both substances in the examined soil samples. It is concluded that the method is easy, with reasonable consumption of reagents, characterized by reliability and sensitivity, and therefore, it is suitable for monitoring the levels of pendimethalin and its major metabolite M455H001 in soils.     

Pendimethalin in surface waters of rivers in the proximity of irrigated paddy fields by solid phase microextraction and gas chromatography

The aim of this study was to develop an analytical methodology for the determination of the herbicide pendimethalin in river waters in the towns of Turvo and Meleiro in the southern region of Santa Catarina State, Brazil. The method, based on solid phase microextraction (SPME) followed by separation and detection by gas chromatography (GC) and electron capture detection (ECD), respectively, was optimised and validated. The limits of detection (LOD) and quantification (LOQ) of 0.02 and 0.06?µg?L^?1, respectively, and recovery values in the range of 86.2 (±11.5)% to 103.4 (±9.5)% were obtained. It was verified that 53 river water samples showed contamination by pendimethalin at levels that ranged from 0.06 to 0.38?µg?L^?1.     

Comparison of extraction techniques for quantitative analysis of pendimethalin from soil and rice grain

The paper exploits the development, optimization, and comparison of fast, efficient, quantitative analytical extraction techniques such as ultrasonic-assisted extraction (UAE) and matrix solid-phase dispersion (MSPD) for proficient extraction of pendimethalin from soil and rice samples. Residues of pendimethalin were quantified using high-performance liquid chromatography. Impact of several experimental parameters of UAE and MSPD techniques on extraction of pendimethalin from soil and rice samples was also evaluated. Under the optimized conditions, the mean percent recoveries obtained from both methods were in the range of 80.3–101.3 and 81.7–103.1, respectively, with relative standard deviation <10. Linearity was in the range of 0.003–5.0?µg?mL^?1 with limit of detection and limit of quantification as 0.001 and 0.003?µg?g^?1, respectively. MSPD method was found superior in terms of low solvent consumption, small sample size, and reduced matrix coextracts due to simultaneous extraction and cleanup steps. Both extraction methodologies were successfully applied in monitoring routine soil and rice samples, in which pendimethalin residues (0.003–0.007?µg?g^?1) were detected in few rice samples while residues in soil samples were below the quantification limit.     

Influence of Air Velocity,Application Dose,and Test Area Size on the Volatilisation of Lindane

Abstract

The volatilisation of lindane from soil and French beans was tested in a wind tunnel under defined conditions. Volatilised lindane was determined directly by passing a partial air stream through an adsorbent. Applications of a lindane formulation onto soil and plant surfaces were performed using a moving nozzle.

Soil volatilisation experiments were conducted using different air velocities (0.4, 1.1, 1.7 m/s). At higher air velocities the volatilisation rate increased from 12% to 31% within 24 h (initial dose 100%). For plant experiments with different velocities (0.4,1.0,2.0 m/s) the volatilisation rate increased from 52% to 62% at the highest velocity. Additionally, as higher air velocities were applied, air concentrations of lindane during the first hour decreased from 1.61 μg/m3 at 0.4 m/s to 0.61 μg/m3 at 2.0 m/s.

In soil experiments with different application doses of lindane (33 mg/m², 117 mg/m²) the volatilisation rate was decreased (23%) at the higher application dose in comparison to the lower dose (39%). The volatilisation rate was also influenced by the size of the treated area in the wind tunnel. From a larger soil surface (0.84 m2) a lower amount of lindane (23%) volatilised than from a smaller surface (31% at 0.28 m).     

Development of a headspace-gas chromatography (HS-GC-PID-FID) method for the determination of VOCs in environmental aqueous matrices: Optimization, verification and elimination of matrix effect and VOC distribution on the Fortaleza Coast, Brazil

An analytical protocol combining a headspace technique with gas chromatography and detection by photoionization detector and flame ionization detector (HS-GC-PID-FID) was developed. This procedure was used to measure volatile organic compounds (VOCs) in environmental aqueous matrices and was applied in determination of VOCs on the coast of Fortaleza, Brazil. At optimum operating conditions, analytical figures of merit such as linearity (R ranged from 0.9983 to 0.9993), repeatability (5.62 to 9.63% and 0.02 to 0.19% for the quantitative and qualitative analyses, respectively), detection limits (0.22 to 7.48 μg L⁻¹) and sensibility were estimated. This protocol favors a fast sampling/sample preparation (in situ), minimizes the use of laboratory material, eliminates the matrix effect from environmental samples, and can be applied to river, estuarine and oceanic waters. The advantage of detectors in series is that a low sensitivity in detection in one is compensated by the other. Toluene was the most abundant VOC in the studied area, with an average concentration of 1.63 μg L⁻¹. It was followed by o-xylene (1.15 μg L⁻¹), trichloroethene (1.08 μg L⁻¹), benzene (0.86 μg L⁻¹), ethylbenzene (0.74 μg L⁻¹), carbon tetrachloride (0.55 μg L⁻¹), m/p-xylene (0.48 μg L⁻¹) and tetrachloroethene (0.46 μg L⁻¹), compounds which are very commonly detected in urban runoff from most cities. The results of the VOC distribution showed that port activity was not the main source of VOCs along the Fortaleza Coast, but that the contribution from urban runoff seemed more significant.     

Detection and Identification of the Herbicide Isoproturon and its Metabolites in Field Samples After a Heavy Rainfall Event

Abstract

The occurence of isoproturon [N-(4-isopropylphenyl)-N′, N′-dimethyl urea] and its metabolites was investigated in soil solution, runoff and creek water from a farm in Scheyern (Bavaria, FRG) after a heavy rainfall event following the application in spring 1994. The analytical procedure included enrichment by C 18 solid-phase extraction and reversed-phase HPLC with diode array detection. The major degradation product in most of the samples was identified as 2-hydroxy-isoproturon [N-(4-(2-hydroxyisopropyl)-phenyl)-N′. N′ dimethyl urea] using the authentic compound. The latter has been isolated from wheat cell culture medium and its structure elucidated by NMR and MS. Furthermore, the polar metabolites monodesmethyl-isoproturon [N-′ (4-Isopropylphenyl)-N′-methyl urea] and 2-hydroxy-monodesmethyl-isoproturon [N-(4-Isopropylphenyl)-N′-methyl urea] and 2-hydroxy-monodesmethyl-isoproturon [N-(4-(2-hydroxyisopropyl)-phenyl)-N′-methyl urea] were identified by comparison of their retention times and DAD-UV spectra with reference compounds.

The detection of isoproturon in soil solution down to 170 cm depth and in creek water in concentrations exceeding 4 μg/1 and also of the polar metabolites in concentrations up to 0,9 μg/1 indicated the mobility of this phenylurea herbicide and its degradation products. Therefore the metabolites should be considered in studies on the migration of isoproturon and in the ecotoxicological evaluation.     

Fast Gas Chromatographic Assessment of Polychlorobiphenyl Levels in Wall Plaster Coats

Abstract

Sampling (“scrape test”) and analytical procedures were defined to determine PCBs in sorbing solid surfaces such as wall plaster. After sampling, samples were extracted by means of a mechanical device. Following steps included clean-up on a multilayer chromatographic column and assessment with macrobore capillary gas chromatography equipped with an electron capture detector. Mean recovery yields were ≧75% for PCB levels from 2.00 to 7000μg/m² (0.550–1940 μg/kg). Intralaboratory tests performed by two independent operators yielded: (a) maximum deviation from expected value, 25%; (b) maximum deviation between operators, 17%; and (c) maximum variation coefficient, 20%. Background PCB levels in wall surface layer samples were ≧2.9μg/m² (≧0.81 μg/kg). The analytical procedure tested with agricultural topsoil samples provided mean recovery yields >65% for PCB levels ≧500 μg/ kg (≧ 50 mg/m²).     

Simultaneous determination of saflufenacil and its two metabolites in soil samples by ultra‐performance liquid chromatography with tandem mass spectrometry

Saflufenacil is a new protoporphyrinogen‐IX‐oxidase inhibitor herbicide. When used, it can enter the soil and has a high risk to reach and contaminate groundwater and aquatic systems. A rapid and sensitive method of ultra‐performance LC with MS/MS was developed for the simultaneous determination of saflufenacil and its two metabolites in soil samples. A modified quick, easy, cheap, effective, rugged, and safe method was applied as the pretreatment procedure. The method was validated by five types of soil samples collected from several regions of China, which all showed good linearity (R² ≥ 0.9914) and precision (RSD ≤ 26.2%). The average recoveries of the three analytes ranged between 74.1 and 118.9% at spiking levels of 3–300 μg/kg. The method limits of detection (S/N 3:1) and method limits of quantification (S/N 10:1) achieved are in the ranges of 0.25–2.75 and 0.83–9.16 μg/kg, respectively. This indicated that the developed ultra‐performance LC with MS/MS method is a promising analytical tool for monitoring the environmental risks posed by saflufenacil.     

Quantification of transformation products of rocket fuel unsymmetrical dimethylhydrazine in air using solid-phase microextraction

Quantification of unsymmetrical dimethylhydrazine transformation products in ambient air is important for assessing the environmental impact of heavy rocket launches. There are very little data of such analyses, which is mainly caused by the low number of analytes covered by the available analytical methods and their complexity. A simple and cost-efficient method for accurate simultaneous determination of seven unsymmetrical dimethylhydrazine transformation products in air using solid-phase microextraction followed by gas chromatography-mass spectrometry was developed. The method was optimized for air sampling and solid-phase microextraction from 20-mL vials, which allows full automation of analysis. The extraction for 5 min by Carboxen/polydimethylsiloxane fiber from amber vials and desorption for 3 min provided the greatest analytes' responses, lowest relative standard deviations, linear calibration (R² ≥ 0.99), and limits of detection from 0.12 to 0.5 μg/m³. Samples with concentrations 500 μg/m³ can be stored at 21 ± 1°C without substantial losses (1–11%) for up to 24 h, while air samples with concentrations 10 and 50 μg/m³ stored for up to 24 h can be used for accurate quantification of only two and four out of seven analytes, respectively. The developed method was successfully tested for the analysis of air above real soil samples contaminated with unsymmetrical dimethylhydrazine rocket fuel.     

Pendimethalin determination in natural water, baby food and river sediment samples using electroanalytical methods

This work describes the electroanalytical determination of pendimethalin herbicide levels in natural waters, river sediment and baby food samples, based on the electro-reduction of herbicide on the hanging mercury drop electrode using square wave voltammetry (SWV). A number of experimental and voltammetric conditions were evaluated and the best responses were achieved in Britton-Robinson buffer solutions at pH 8.0, using a frequency of 500 s^− 1, a scan increment of 10 mV and a square wave amplitude of 50 mV. Under these conditions, the pendimethalin is reduced in an irreversible process, with two reduction peaks at − 0.60 V and − 0.71 V, using a Ag/AgCl reference system. Analytical curves were constructed and the detection limit values were calculated to be 7.79 μg L^− 1 and 4.88 μg L^− 1, for peak 1 and peak 2, respectively. The precision and accuracy were determinate as a function of experimental repeatability and reproducibility, which showed standard relative deviation values that were lower than 2% for both voltammetric peaks. The applicability of the proposed methodology was evaluated in natural water, river sediments and baby food samples. The calculated recovery efficiencies demonstrate that the proposed methodology is suitable for determining any contamination by pendimethalin in these samples. Additionally, adsorption isotherms were used to evaluate information about the behavior of pendimethalin in river sediment samples.     

The determination of hydrogen chloride in ambient air with diffusion/denuder tubes

A manual method for the determination of hydrogen chloride in air, based on diffusion/denuder tube separation from particulate chloride aerosol is described. When air is drawn through a tube coated with a selective absorbent (sodium fluoride), separation is achieved because gaseous hydrogen chloride diffuses much more rapidly to the tube walls than particulate chloride aerosol, which passes through virtually unabsorbed. After the sampling period (the length of which depends on the concentration of gaseous hydrogen chloride expected), the sorbed hydrogen chloride is washed from the tube and measured with a highly sensitive chloride ion-selective electrode with a mercury (I) chloride membrane. The method is examined theoretically and experimentally. The experimentally derived absorption efficiencies of the diffusion/denuder tubes were > 90% and the standard deviation of the method was 0.023 μg m^?3 for hydrogen chloride concentrations of 0.16–0.55 μg m^?3. Interference from particulate chloride salts was negligible; this was confirmed by tests with artificially generated aerosol particles from an aerosol generator. The diffusion/denuder tubes have high capacity; level as high as 330 μg m^?3 hydrogen chloride can be sampled for 60 min without affecting performance. A detection limit of (50/t) μg m^?3 can be achieved, where t is the sampling rime (min); e.g., 1μg m^?3 hydrogen chloride can be detected with a sampling period of 50 min.     

137Cs profiles in erosion plots with different soil cultivation

Summary Cesium-137 methodology has been successfully used to assess soil erosion. Seven erosion plots were sampled to determine the ¹³⁷Cs profile and to assess the erosion rates. Cesium-137 profile for native pasture plot showed an exponential decline below 5 cm depth, with little ¹³⁷Cs activity in the superficial layer (0-5 cm). Cesium-137 profile for wheat-soybean rotation plot in conventional tillage showed a uniform distribution with depth. For this plot, the soil loss occurs more in middle than upper and lower level. Cesium-137 profile for wheat-soybean rotation and wheat-maize rotation plots in no-tillage showed a similar result to the native pasture, with a minimum soil loss in the superficial layer. Cesium-137 profile for bare soil and cultivated pasture plots are similar, with a soil erosion rate of 229 t ha^-1 year ^-1 . In the plots with a conventional tillage a greater soil loss occur in middle than upper and lower level. In no-tillage cultivation plots occurs soil loss in lower level, but no sign of soil loss neither gain in the upper level is observed. Cesium-137 methodology is a good tool to assess soil erosion and the ¹³⁷Cs profile gives possibility to understand the soil erosion behavior in erosion plots.     

PSORALEN PLUS ULTRAVIOLET RADIATION-INDUCED INHIBITION OF DNA SYNTHESIS AND VIABILITY IN HUMAN LYMPHOID CELLS IN VITRO*

Abstract— 8-Methoxypsoralen (8-MOP) plus high intensity long wavelength ultraviolet radiation (UV-A) is presently being used to induce remissions of psoriasis and mycosis fungoides. Previous studies demonstrated inhibition of DNA synthesis in circulating leukocytes from some patients during this therapy. The present study is designed to determine whether conditions of 8-MOP concentration and UV-A exposure attained during therapy might be sufficient to result directly in decreased lymphoid cell DNA synthesis and viability in vitro. Tritiated thymidine (³HTdR) incorporation and cell growth in suspension culture following UV-A exposure alone or with therapeutic concentrations of 8-MOP was examined in peripheral blood lymphocytes and in Ebstein-Barr virus transformed human lymphoblas-toid cell lines. UV-A exposure alone induced a dose-dependent inhibition of HTdR incorporation in both types of lymphoid cells (3000 J/m² resulted in 77% of control ³HTdR incorporation). Pre-incubation with 0.1 μg/m/ 8-MOP before UV-A exposure induced a significantly greater inhibition of ³HTdR incorporation (3000 J/m² resulted in 61% of control ³HTdR incorporation). Greater inhibition of ³HTdR incorporation was observed by preincubation of the lymphoblastoid cells with 1.0μg/mC 8-MOP (3000 J/m² resulted in 41% of control) but not in the lymphocytes (3000 J/m² resulted in 63% of control). The concentration of viable lymphoblastoid cells did not decrease below the original concentration after the highest dose of UV-A alone (29,000 J/m²) but preincubation with 0.1 μg/mC 8-MOP resulted in 40% survival after 3000 J/m² (D₃₇ approximately 3000 J/m²) and preincubation with 1.0 μg/ 8-MOP resulted in 0.6% survival after 3000 J/,² (D₃₇ approximately 800 J/m²). This study suggests that the low doses of 8-MOP and UV-A received by patients' lymphocytes may be sufficient to explain the decreased DNA synthesis found in their circulating leucocytes. The long term consequences of such damage remain to be determined.     

Comparison of passive and active sampling methods for the determination of nitrogen dioxide in urban air

Three different methods for sampling and determination of nitrogen dioxide in urban air are compared: an NO/NO_x-monitor and an active (pumped) and a passive sampling method. For the latter two methods, sodium iodide is used as absorbent. For weekly averages the results from the passive sampler are within 10–20% of the results for the two other methods in the concentration range 15–30 μg NO₂/m³. The detection limit for the passive sampler is 1 μg NO₂/m³ (7 days), the precision is 5% and the accuracy is estimated to 20%. The active iodide method agrees very well with the NO/NO_x-monitor. Compared on 24 h basis for a period of 3 months, covering a concentration range of 5–45 μg NO₂/m³, the deviation between the two methods is within 5%, and the absorption capacity of the iodide reagent is excellent as the breakthrough is below 1%.     

Determination of triallate and its metabolite 2,3,3-trichloro-prop-2-en-sulfonic acid in soil and water samples

A method based on solid phase extraction was developed for the determination of the herbicide triallate and its metabolite 2,3,3-trichloro-prop-2-en-sulfonic acid (TCPSA). Soil samples were extracted with methanol and diluted with water to yield a methanol/water ratio of 1?:?4. Triallate was adsorbed on C₁₈ cartridges while TCPSA was enriched on quaternary amine anion exchange resins. Cartridges were eluted with methanol/ethyl acetate and methanol/sulfuric acid mixture, respectively. TCPSA methyl ester was formed using trimethyl orthoformate and subsequently analyzed by GC/ECD. Determination limits of both target compounds were 5 μg/kg soil with recoveries of 100 ± 12% for triallate and 57 ± 5% for TCPSA. In water analysis, determination limits were 0.05 μg/L with recoveries of 84 ± 14% for triallate and 100 ± 22% for TCPSA. In laboratory batch experiments, concentration of triallate decreased from 2690 to 1550 μg/kg soil within 59 days. 14 days after triallate application, TCPSA was determined to be 14 μg/kg which increased to 98 μg/kg soil at the end of the incubation period. Soil/water distribution coefficients in loamy sand soil were 102 for triallate and 0.02 for TCPSA which indicated a higher leaching tendency of the polar metabolite.     

Activated carbon as adsorbent for alkyllead in air

A method is described for the determination of alkyllead in air with activated carbon as adsorbent. The main factor affecting the adsorption capacity of the activated carbon for alkyllead was the concentration of hydrocarbons in the sampled air, as these were also adsorbed. Particulate inorganic lead was collected on a membrane filter in front of the adsorbent. The alkyllead was extracted from the adsorbent into hot nitric acid, and the concentration determined by electrothermal atomic absorption spectrometry. The detection limit was 0.002 μg Pb m^?3 (sample volume 1 m³), and precision was 9.5% r.s.d. at 2.1 μg Pb m^?3 alkyllead. The method was used to monitor exposure of gasoline tank truck drivers to alkyllead. During the filling of tank trucks with leaded gasoline, alkyllead concentrations from 1 to 750 μg Pb m^?3 were found in the drivers' breathing zone, but most were well below the Norwegian TLV of 75 μg Pb m^?3.     

Determination of Methylamines and Methylamine-N-oxides in Particulate Matter Using Solid Phase Extraction Coupled with Ion Chromatography

Currently, the concentrations of methylamines in fine particulate matter (PM) are most often measured by aerosol time-of-flight mass spectrometry. A novel method for identification and determination of methylamines and methylamine-N-oxides in fine particles based on solid phase extraction (SPE) coupled with ion chromatography (IC) was developed. The experimental conditions including SPE conditions and chromatographic conditions were optimized. The quartz filter loaded with particulate matter (PM) samples was ultrasonically extracted with 20 mL of methanol and water (1:3, V/V) and the extraction process was repeated twice. After extraction, a total of 60 mL of extraction solvent was dropped into the extraction equipment for SPE. The Agilent AccuBond C₁₈ was chosen for enriching the methylamine, dimethylamine, trimethylamine and trimethylamine-N-oxide in fine particles. Under the optimum conditions, the target species on Agilent AccuBond C₁₈ were washed by 0.5 mL of acetonitrile solution and then concentrated (2 mL) before injecting into IC for analysis. A PRP X-200 (250 mm × 4 mm i.d.) was used for separation of analytes at 25 °C. The mobile phase was a mixture of 3% (V/V) acetonitrile solution and 5 mM nitric acid with the flow rate of 1 mL min^–1. The four aliphatic amine species were fully resolved and completely separated within 30 min. The linearity of the four compounds ranged from 0.45 μg kg^–1 to 1000 μg kg^–1 with precisions of 2%–4% and detection limits of 0.002–0.003 μg m^–3. The recoveries of the four aliphatic amine species in real PM samples were higher than 90%. This method was successfully applied in the analysis of real fine PM samples collected in Beijing. The concentrations of trimethylamine and methylamine-N-oxides were in the range of (0.01 ± 0.001) μg m^–3–(0.08 ± 0.002) μg m^–3 and (0.05 ± 0.001) μg m^–3–(0.14 ± 0.002) μg m^–3 for Beijing dust and haze PM samples, respectively.     

Trace determination of gaseous chlorine: a comparison between an electrometric method and the methyl orange photometric method

Two methods for the determination of molecular chlorine in air are critically compared. An electrometric method based on measurement of the reduction current of chlorine to chloride is superior to the photometric determination based on bleaching of an acidic solution of methyl orange. The limit of detection for the electrometric method is 50 μg m^-3; the standard error of the mean is better than 2%, and the sensitivity is 5.9 μg m^-3 μ A^-1 at +50 mV applied potential versus SCE with a mercury cathode. The limit of detection for the photometric method is 300 μg m^-3; the precision is of the order of 5%, and the sensitivity is 80 μg m^-3 for an error of 1% in the absorption measurements. The accuracy of the electrometric method is good whereas the photometric method yields consistently low results. The electrometric method is less subject to interferences than the photometric method.