Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

废水中总氰化物测定的新方法

研究了用气提法测定废水中总氰化物的条件的方法.实验结果表明,与蒸馏法相比,气提法简便安全,分析结果的准确度和精密度能满足监测要求.     

用Excel制作环境监测声像报告

阐述了运用办公自动化应用软件电子表格Ｅｘｃｅｌ制作及播放新型声像片的方法，并以环境监测工作中的实例介绍了具体的制作过程。     

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid–solid extraction with ultrasound or mechanical grinding, followed by liquid–liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography–electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg^?1, in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤8.9 %. The limits of quantification (LOQ) were 0.002 mg kg^?1 for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.     

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.     

测定双酚A的流动注射化学发光法研究

在鲁米诺-高碘酸钾化学发光体系中加入双酚A,可以抑制该体系的化学发光,据此建立了双酚A的流动注射化学发光监测分析新方法。该法的线性范围为6 0×10-6～1 0×10-3g L,检测限为1 3×10-7g L。方法可用于水体中双酚A的测定。     

Derivative spectrophotometric method for copper determination

A simple, sensitive and selective method by solvent extraction-first derivative spectrophotometry is described for the determination of microamounts of copper in water by means of its reaction and extraction at pH 8.0 with 3-(4-phenyl-2-pyridinyl-5-phenyl-1,2,4-triazine) (PPT) and picrate (2,4,6-trinitro-phenol) into 1,2-dichloroethane. Copper was thus determined in the range 7.5–350 ng/ml with a detection limits (3) of 2.3 ng/ml. The relative standard deviations were in all instances less than 2.0%. The proposed method was successfully applied for the determination of copper in several kinds of water.     

测定废水重金属样品的高压蒸汽消解方法

本文采用正交实验方法,用自己研制的“自控式高压蒸汽消解器”,详细研究了测定废水重金属,样品的最佳消解条件,并用于实际废水样的消解和重金属的测定,准确度和精密度均优于传统的敞口消解法,并具有试剂用量少、时间短、不受污染、操作简单,批处理样品量大等优点,可作为测定废水中重金属,样品的常规消解方法。     

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.     

Risk assessment and monitoring of dinotefuran and its metabolites for Chinese consumption of apples

Residues of dinotefuran and its metabolites, 1-methyl-3-(tetrahydro-3-furylmethyl)urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl)guanidine (DN), in apple were investigated using a “QuEChERS” (quick, easy, cheap, effective, rugged, safe) pretreatment and liquid chromatography–tandem mass spectrometry. Limits of detection (LODs) and quantification (LOQs) of dinotefuran, UF, and DN in apples were 0.011–0.960 and 0.037–3.200 μg/kg, respectively. The average recoveries of dinotefuran, UF, and DN in apple ranged from 70.0 to 83.6% with relative standard deviations less than 13%. A formulation of 20% water-dispersible dinotefuran granules was sprayed at 1–1.5-fold the recommended dose 3–4 times on apple trees. Total terminal residues of dinotefuran in apple were less than 2 mg/kg, which is the maximum residue limit (MRL) set by Japan. When following the recommended application guidelines, dinotefuran is unlikely to present significant health concerns to the Chinese population because the risk quotient (RQ) is less than 100%. This work could provide guidance for the safe use of dinotefuran and serve as a reference for the establishment of a maximum residue limit of dinotefuran in apple in China.     

A new method for the determination of trichloroacetic acid in spruce foliage and other environmental media

Trichloroacetic acid (TCAA) is a phytotoxic chemical, present throughout the environment. The majority of methods for analysis of TCAA require chemical derivatisation and multiple extraction steps prior to analysis by gas-chromatography. Here, a new analytical method for TCAA determination in environmental matrices is reported. The method is based on a modified Nielsen-Kryger steam distillation that combines into one 1 h reflux the thermal decarboxylation of TCAA to CHCl3 and the partitioning and concentration of the CHCl3 into 5 ml of hexane, which is analysed by GC. Sample preparation is minimal and no matrix standard additions are required. The background CHCl3 in the sample is removed prior to extraction by degassing the solution for 1 h with nitrogen. Optimisation of the method gave recoveries from three separate solutions of 0.31 ppb aqueous TCAA standards of 93 +/- 15% (n = 9), 110 +/- 9% (n = 9) and 105 +/- 11% (n = 6). The extraction method has been compared with a decarboxylation and headspace GC method for determination of TCAA in Sitka spruce needles. No significant difference in TCAA concentration or replicate precision between the two methods was observed.     

环境空气中苯系物测定方法的优化

探讨了《环境空气苯系物的测定活性炭吸附/二硫化碳解吸-气相色谱法》(HJ 584-2010)中存在的问题,并对此方法进行了改进。重新确定了方法检出限,使方法检出限更为合理;通过实验室计算出方法检测的浓度范围;改变了样品保存条件,使样品的保存周期更长,便于分析。     

Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Persistence behaviour of imidacloprid and its metabolites in soil under sugarcane

The persistence and metabolism of imidacloprid in soil under sugarcane were studied following application of imidacloprid at 20 and 80 g active ingredient (a.i.) ha^?1. Soil samples were collected at different time intervals (7, 15, 30, 45, 60 and 90 days after application), and the residues of imidacloprid and its metabolites (6-chloronicotinic acid, nitrosimine, imidacloprid-NTG, olefin, urea and 5-hydroxy) were quantified by high-performance liquid chromatography. In soil, the total imidacloprid residues were mainly constituted by the parent compound followed by 6-chloronicotinic acid, nitrosimine and imidacloprid-NTG metabolites. Maximum residues of imidacloprid and its metabolites were 4.29 and 7.81 mg kg^?1 in soil samples collected 7 days after the application of imidacloprid at 20 and 80 g a.i. ha^?1, respectively. At both doses, these residues declined to below the detectable limit in soil after 90 days of application. Olefin, urea and 5-hydroxy metabolites were not detected in soil. Dissipation of total imidacloprid residues did not follow the first-order kinetics with a coefficient of determination value of 0.883 and 0.838 for the recommended dose and four times the recommended dose, respectively. The half-life (T _1/2) value of total imidacloprid was observed to be 10.64 and 10.10 days for the recommended dose and four times the recommended dose, respectively.     

Kinetic parameters for the removal of lead and chromium from wastewater using activated carbon developed from fertilizer waste material

The waste slurry generated in fertilizer plants in India has been converted into a cheap carbonaceous adsorbent material. The prepared adsorbent has been characterised and used for the removal of lead and chromium metals. The kinetics of adsorption and the extent of adsorption at equilibrium are dependent on the physical and chemical characteristics of the adsorbate, adsorbent and experimental system. Results of laboratory scale studies conducted to delineate the effect of such parameters on the kinetics of adsorption of metal ions are reported. Parameters evaluated include: hydronium ion concentration, temperature, initial adsorbate concentration, size of adsorbent, and amount of adsorbent. On the basis of these studies the various physical parameters such as effective diffusion coefficient, activation energies and entropy of activation are evaluated, as these provide some information regarding the mechanistic aspects. Mass transfer coefficient values suggest a rapid transport of the adsorbate from bulk to solid phase.     

A simple method for the extraction of mutagens from airborne particles

Organic materials were extracted with acetone from filters of airborne particles by soaking, shaking, soxhletion, and sonication. These extracts were tested with and without S9 for mutagenicity using Ames assay and arabinose-resistant assay of Salmonella typhimurium. Among the extraction methods, soaking extract had the highest mutagenic activity followed by sonication, shaking, and soxhletion in both the assays. With the samples studied, it was concluded that soaking with acetone for 1/2 hr is the simplest and an efficient procedure for the extraction of mutagens from airborne particles.Results of cooperative investigation of NIOSH and West Virginia Agricultural and Forstry Experimental Station. Published with the approval of the Director of the West Virginia Agricultural and Forestry Experiment Station as Scientific Paper No. 1822.     

The source of DDT and its metabolites contamination in Turkish agricultural soils

The concentration and impact of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)-ethane (DDT) and its metabolites (DDE: 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene) on the environment was expected to decrease after its ban in the mid-1980s. Unfortunately, DDT contamination via its presence as an impurity in dicofol (2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol) has led to a new source of contamination. This is particularly true especially in cotton production in Söke Plain, Turkey, where difocol-based pesticides are being used. The aim of this research was to investigate the extent and source of DDT contamination in cotton soils. Söke Plain soil samples were collected from 0–30, 30–60, and 60–90-cm depth and analyzed by GC/MS/MS. o,p′-DDT and p, p′-DDE were detected at 16.2 % and 17.6 % of the sites in the 0–30-cm depth of soils. In the 30–60 cm, p, p′-DDT (14.9 %), o, p′-DDE (8.1 %) and p, p′-DDE (2.7 %) were found in soil samples, and p, p′-DDT was the most prevalent with 9.5 % of the sampling sites. The dominant source of DDT particularly in the 60–90-cm depth was due to historic use of DDT. The presence of p, p′-DDE, o, p′-DDE and p,p′-DDT in the topsoil was attributed to recent dicofol applications.     

Modified APHA closed-tube reflux colorimetric method for TOC determination in water and wastewater

The analysis of total organic carbon (TOC) by the American Public Health Association (APHA) closed-tube reflux colorimetric method requires potassium dichromate (K₂Cr₂O₇), silver sulfate (AgSO₄), and mercury (HgSO₄) sulfate in addition to large volumes of both reagents and samples. The method relies on the release of oxygen from dichromate on heating which is consumed by carbon associated with organic compounds. The method risks environmental pollution by discharging large amounts of chromium (VI) and silver and mercury sulfates. The present method used potassium monochromate (K₂CrO₄) to generate the K₂Cr₂O₇ on demand in the first phase. In addition, miniaturizing the procedure to semi microanalysis decreased the consumption of reagents and samples. In the second phase, mercury sulfate was eliminated as part of the digestion mixture through the introduction of sodium bismuthate (NaBiO₃) for the removal of chlorides from the sample. The modified method, the potassium monochromate closed-tube colorimetry with sodium bismuthate chloride removal (KMCC-Bi), generates the potassium dichromate on demand and eliminates mercury sulfate. The semi microanalysis procedure leads to a 60% reduction in sample volume and ≈?33.33 and 60% reduction in monochromate and silver sulfate consumption respectively. The LOD and LOQ were 10.17 and 33.90 mg L^?1 for APHA, and 4.95 and 16.95 mg L^?1 for KMCC-Bi. Recovery was between 83 to 98% APHA and 92 to 104% KMCC-Bi, while the RSD (%) ranged between 0.8 to 5.0% APHA and 0.00 to 0.62% KMCC-Bi. The method was applied for the UV-Vis spectrometry determination of COD in water and wastewater. Statistics was done by MINITAB 17 or MS Excel 2016.

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A new assessment method for urbanization environmental impact: urban environment entropy model and its application

The thermodynamic law is one of the most widely used scientific principles. The comparability between the environmental impact of urbanization and the thermodynamic entropy was systematically analyzed. Consequently, the concept "Urban Environment Entropy" was brought forward and the "Urban Environment Entropy" model was established for urbanization environmental impact assessment in this study. The model was then utilized in a case study for the assessment of river water quality in the Pearl River Delta Economic Zone. The results indicated that the assessing results of the model are consistent to that of the equalized synthetic pollution index method. Therefore, it can be concluded that the Urban Environment Entropy model has high reliability and can be applied widely in urbanization environmental assessment research using many different environmental parameters.     

萘的极谱测定法及其应用

研究了萘的极谱吸附波及其性质。萘在５０％ Ｎ,Ｎ－二甲基甲酰胺和０．１ｍ ｏｌ／Ｌ氨－氯化铵介质中于－ １．０５ｖ（ｖｓ．ＳＣＥ）处产生一波形好的二阶导数极谱波。在此实验条件下,萘浓度在５．００×１０－ ６ ｍ ｏｌ／Ｌ～５．００×１０－ ４ ｍ ｏｌ／Ｌ范围内与导数波峰电流（Ｉｐ）呈良好的线性关系。检测下限为５．００×１０－ ６ｍ ｏｌ／Ｌ。本方法可测煤、卫生球和沥青中的萘含量。