Bestimmung polarer Phosphorsäureester in Trink‐ und Oberflächenwasser mittels HPLC‐MS‐MS

Determination of Organophosphorus Pesticides in Water by HPLC‐MS‐MS In the EC Water Framework Directive 2000/60/EG and in CEC 76/464/EEC there are 16 organophosphorus pesticides (insecticides and acaricides) listed which belong to so‐called priority substances. The committed quality aims of these substances frequently require maximum concentrations below 0.1 μg/L. In this paper a HPLC‐MS‐method is described. The reported limits of determination of organophosphorus pesticides are lower than the demanded limits. High analytical sensitivity is reached by solid‐phase extraction (SPE) and by injecting large volumes. For some of these substances no sample enrichment is needed and low detection limits are obtained by direct injection of the original water sample.     

GC/MS-Nontargetanalytik zur Aufklärung einer organischen Grundwasserkontamination. Teil I: Probennahme – Analytik – Identifikation der organischen Verbindungen

GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part I: Sampling – Analysis – Identification GC/MS nontarget analysis is a combination of an extraction sequence and a GC/MS analysis without standards. The extraction sequence should enrich a wide range of organic substances with different chemical and physical properties. The GC/MS analysis without standards evaluates the total chromatogram whereas the possibilities of compound identification are limited. This kind of view is suited very well if the task of examinations are unknown organic contaminations and the conventional target analysis has to be expanded to a large number of compounds with the uncertainty of detecting the main contaminants. The extraction sequence is similar to the EPA 625 analysis of base/neutral and acid extractable organic compounds. Basis are liquid extraction and solid-phase extraction at different pH values. This extraction procedure covers approximately 30 % of total organic carbon of these groundwater samples from a contaminated area near a low temperature carbonization plant. Relevant groups of organic compounds analyzed in the contaminated groundwater or in the reference sample are substituted aromatics, phenols, benzoamines (anilines), and derivates of benzothiophene. Differences in the trace substance mixtures between the contaminated samples and the reference sample are demonstrated by applying modern graphical methods.     

Examining the Extraction Efficiency of Petroleum-Derived Dissolved Organic Matter in Contaminated Groundwater Plumes

The extraction efficiency of petroleum-derived dissolved organic matter (DOM) was examined for groundwater samples from an aquifer contaminated with crude oil. Five different types of extraction techniques were investigated to determine which method is best suited for the analysis of potentially toxic petroleum-derived DOM. The five types were a liquid-liquid extraction (LLE) with dichloromethane (DCM) and total petroleum hydrocarbons-diesel range (TPH_d) with DCM (EPA method 3510C), and three solid-phase extraction (SPE) stationary phases that are routinely used for extraction of polar analytes from water. For the LLE and TPH_d, that is selective for nonpolar compounds, the extraction efficiency of petroleum-derived DOM decreased downgradient as the petroleum-derived DOM becomes increasingly polar due to biodegradation. In contrast, the average extraction efficiency by the SPE methods was greater than 65% across the gradient. The results showed that SPE is more efficient for extracting petroleum-derived DOM at hydrocarbon-contaminated sites. The use of a method with greater extraction efficiency for partially oxidized hydrocarbons may prove useful in determining relationships between their composition and structure and potential for risks to human health or the environment.     

Automated Ion-pair extraction and Ion-pair chromatography — a versatile method in water analysis for the determination of highly polar micropollutants

An automated HPLC method is presented which combines on-line ion-pair extraction on small exchangeable RP-C18 precolumns (RP-IPE) with ion-pair chromatography (RP-IPC). Weakly acidic herbicides — carboxylic acids, phenols, and the N-H acidic bentazone — and strong acids, e.g. aromatic sulfonic acids, can be determined simultaneously. Performance data are given. The tetrabutylammonium ion pairs of all investigated compounds are readily transferred from the RP-C18 precolumn to the analytical column by a phosphate buffer/methanol gradient. This is also true for the chlorinated phenoxy acids which, in earlier off-line extraction experiments, could not be desorbed from the RP-C18 material by the lower polar acetone. The RP-IPC is carried out at neutral pH where weakly acidic compounds appear in their stronger UV absorbing dissociated form. Compared to conventional reversed phase chromatography using an acidified eluent, the sensitivity of UV detection is markedly enhanced, especially for the phenol herbicides and bentazone. In addition, phenols can be detected more selectively because they show a second intense absorption band in the wavelength range between 280 nm and 290 nm, where there are only little interferences with the matrix. Due to miniaturization and automation, the online combination IPE/IPC allows a large sample throughput at a lower consumption of solid phase material and organic solvents. Time consuming manual steps are totally missing. The IPE/IPC technique is well suited as a screening method for fate studies of polar micropollutants, e. g. for monitoring the efficiency of different water treatment technologies. An example for balancing an activated carbon filter is presented.     

Analysis of Pulp Mill EOP Bleaching Process Effluent by Thin-layer Chromatography with Automated Multiple Development (AMD-HPTLC)

High-performance thin-layer chromatography with automated multiple development (AMD-HPTLC) was applied for the examination of pulp mill bleachery effluents from an alkali-oxygen-peroxide (EOP) bleaching stage of a sulfite pulp. A gradient based on methanol and dichloro-methane was developed for the separation of the effluent compounds over a wide range of migration distances. A series of reference substances such as lignin phenols and other aromatic acids, aldehydes, and alcohols as well as two resin acids were investigated in parallel using the AMD-HPTLC method. Characterization of the effluent compounds was possible using the migration distances and the recorded spectra. The composition of different samples of effluent were found to be very similar. The application of the AMD-HPTLC to effluent fractions from acidic liquid-liquid extraction using diethyl ether and from RP C18 solid-phase extraction allowed us to follow the behaviour of the effluent compounds in the extraction procedure.     

Determination of Pesticides by HPLC Bestimmung von Pestiziden durch HPLC

Using solid phase extraction followed by HPLC, various pesticides of different chemical structure, thermolabile or polar components included, can be separated and quantitated chromatographically in a single run. Due to longer elution times compared to gas chromatography, only a limited number of components can be determined at the same time. According to our experience, all components relevant for a water catchment area can be covered. With the use of diode-array-detectors the identification of components can be done with sufficient security by comparison of spectra of reference sample and analytical peak. The determination limit is 0.025 μg/L with few exceptions.     

Bestimmung von Atrazin,Terbutylazin und ihrer Desethyl- sowie Hydroxymetaboliten in Boden mittels SFE und HPLC/UV-DAD

Determination of Atrazine, Terbutylazine and their Deethyl- and Hydroxymetabolites in Soil by SFE and HPLC/UV-DAD The supercritical fluid extraction (SFE) (CO₂ and CH₃OH as modifier) of the herbicides atrazine and terbutylazine as well as their deethyl- and hydroxymetabolites from soil was investigated. The analytes were determined after extraction by HPLC/UV-DAD using a C18 column. The limits of detection of the chromatographic step were between 0.01 μg/mL and 0.07 μg/mL, the relative standard deviations between 0.8% and 1.4%. With the aid of a control chart, the stability of the chromatographic system was evaluated. For extraction, soil was spiked with 5 μg/g for each component. For SFE, CO₂ and methanol as modifier were used, and a pressure program was applied. Beside SFE, Soxhlet extraction with methanol and a solid-liquid extraction with acetone/water by shaking were carried out. For chlorine-containing triazines, the recovery rates were comparable for all extraction methods. The following recovery rates for SFE were obtained: deethylterbutylazine 77.4%, terbutylazine 80.2%, deethylatrazine 87.4%, atrazine 92.6%. However, the recovery rates for the hydroxymetabolites (4.1% for hydroxyatrazine, 21% for hydroxyterbutylazine) were not satisfying compared with the “classical” methods of extraction (above 50%). The limits of detection for the total process (SFE and HPLC/UV-DAD) estimated by the signal to noise ratio amounted 0.08 μg/g soil for chlorine-containing derivates, for hydroxyatrazine 2…3 μg/g, and for hydroxyterbutylazine 0.8 μ/g.     

苦草(Vallisneria spiralis)释放的酚酸类物质对铜绿微囊藻(Microcystis aeruginosa)的化感作用

采用广谱性固相萃取小柱富集以10 g( FW)/L的密度培养三天后的苦草(Vallisneria spiralis)种植水,不同溶剂洗脱得到的各组分对铜绿微囊藻(Microcystis aeruginosa)的生长表现出不同程度的抑制,其中甲醇洗脱组分抑藻活性最强.去除该组分中的酚酸后,其抑藻活性下降了22.8％,表明...     

Estrogen receptor (ER) agonists and androgen receptor (AR) antagonists in effluents from Norwegian North Sea oil production platforms

The in vitro estrogen receptor (ER) agonist and androgen receptor (AR) antagonist potencies of offshore produced water effluents collected from the Norwegian Sector were determined using recombinant yeast estrogen and androgen screens. Solid phase extraction (SPE) concentrates of the effluents showed E2 agonist activities similar to those previously reported for the United Kingdom (UK) Continental Shelf (<0.1-4 ng E2 L(-1)). No activity was detected in the filtered oil droplets suggesting that produced water ER activity is primarily associated with the dissolved phase. Targeted analysis for methyl- to nonyl-substituted alkylphenol isomers show the occurrence of known ER agonists in the analysed samples. For the first time, AR antagonists were detected in both the dissolved and oil associated phase at concentrations of between 20 and 8000 microg of flutamide equivalents L(-1). The identity of the AR antagonists is unknown, however this represents a significant input into the marine environment of unknown compounds that exert a known biological effect. It is recommended that further analysis using techniques such as bioassay-directed analysis is performed to identify the compounds/groups of compounds that are responsible in order to improve the assessment of the risk posed by produced water discharges to the marine environment.     

Toxicity-directed Fractionation of Tannery Wastewater Using Solid-phase Extraction and Luminescence Inhibition in Microtiter Plates

A four-step solid-phase extraction (SPE) method is presented for toxicity-directed fractionation of industrial wastewater. This fractionation procedure serves as a key step for identifying unknown organic toxicants in complex samples. Toxicity was determined as luminescence inhibition of Vibrio fischeri using microtiter plates. This method was compared to standard tests in glass cuvettes using both 37 standard chemicals and 24 wastewater fractions with EC₅₀ values covering five orders of magnitude. Results of both methods correlated well. 22 tannery wastewater samples were sequentially extracted using C₁₈e and polystyrene-divinylbenzene phases in combination with pH-changes. Final solid-phase filtrates showed low inhibition, so toxicity of inorganics could be neglected. Using 1/EC₅₀ values, the SPE eluates showed clearly different toxicity patterns. Even in eluates of the fourth extraction step, high toxic effects could be observed. In several cases, luminescence inhibition was increasing at the anaerobic treatment step compared to the corresponding untreated samples. After aerobic treatment, toxicity of most wastewater fractions was greatly diminished. HPLC/DAD analyses of the wastewater fractions showed a fair separation concerning compound polarity. However, the samples were still too complex to identify single compounds responsible for the detected toxicity. Therefore, a further clean-up step accompanied with toxicity testing is needed.     

Off-line and On-line Extraction of Explosives and Related Compounds from Aqueous Samples Using Solid Sorbents

Explosives belonging to the group of nitrotoluenes may be readily extracted with C18 adsorbent in the off-line mode and also in on-line coupling of the extraction unit to HPLC, while polar explosives like hexyl, HMX, and RDX show a substantial breakthrough and low recoveries. However, these compounds are quantitatively extracted using a new polymeric phase, LiChrolut EN, in the off-line mode. Preliminary results show that this new adsorbent may in principle also be used in the on-line mode for explosives. In this case, the cartridges have to be eluted in the backflush mode. Method detection limits of ? 0.1 μg/L are achieved for on-line extraction of explosives and related compounds with water samples as small as 10…30 mL.     

Analysis of Nitroaromatics and Nitramines in Ammunition Waste Water and in Aqueous Samples from Former Ammunition Plants and Other Military Sites Analyse von Nitroaromaten und Nitraminen in Munitionsabwasser und wäßrigen Proben ehemaliger Munitionsfabriken und anderen Rüstungsaltlasten

Waste water from ammunition production sites and aqueous samples (ground and surface water) on or near former military sites on which explosives were produced or filled, e.g. into shells, may be contaminated by the original explosives—mainly nitrotoluenes (such as dinitrotoluenes, trinitrotoluene (TNT)) and nitramines (such as hexogen (RDX), octogen (HMX), and tetryl) or hexyl, but also by byproducts and compounds formed by biodegradation of the explosives such as aminonitrotoluenes, chlorinated nitrobenzenes and nitrophenols. These compounds can be extracted from aqueous samples by liquid/liquid extraction (using dichloromethane or toluene) or by solid phase extraction using C-18 adsorbents with high recoveries (usually ≥85%) provided they contain only one amino group. Nitrotoluenes, chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chromatography (GC) using selective detectors such as an electron capture detector (ECD), a nitrogen-phosphorus detector (NPD) or a chemiluminescence detector (thermal energy analyzer, TEA). The use of combined gas chromatography/mass spectrometry (GC/MS) under electron impact conditions is even more specific. Detection limits comparable to an ECD or NPD, however, are only achieved if the mass spectrometer is operated under selected ion monitoring (SIM). Nitrophenols are derivatized after extraction by heptafluorobutyric anhydride or by acetic anhydride where the latter method can be directly applied to the aqueous sample. The nitramine explosives, such as RDX, HMX, and tetryl, hexyl, the nitrate esters, such as nitropenta (PETN) and nitroguanidine as well as picric acid cannot, or only with difficulty, be analyzed by gas chromatography. They may be determined by high performance liquid chromatography (HPLC) with UV-detection. The HPLC analysis can be extended to include also nitrotoluenes and nitroaminotoluenes.     

Nachweis von Industriechemikalien (HPS,BPS und SPS) im Oberflächenwasser

Occurrence of Industrial Chemicals (HPS, BPS, and SPS) in Surface Water The paper gives the results of water examinations for different phenylsulfonamides. Random samples taken every month between May 1999 and August 2000 from surface water out of the river Rhine (kilometer 838), the river Ruhr (Mülheim Styrum) and the river Emscher (Oberhausen center) were tested for the corrosion inhibiting agent 6‐[methyl(phenylsulfonyl)amino]‐hexanoic acid (HPS) as well as its metabolites 4‐[methyl‐(phenylsulfonyl)amino]‐butanoic acid (BPS) and sarkosin‐N‐(phenylsulfonyl) (SPS). Furthermore, the sewage plant effluents of two municipal wastewater treatment plants from the rural area were also included in the monitoring program. The analytical method includes solid‐phase extraction (SPE), a derivatization step as well as gas chromatography mass spectrometry (GC‐MS). SPS is regularly found in all investigated surface waters, but only occasionally in the effluents of the two rural sewage plants. The median values for SPS amount to 0.09 μg/L in the river Rhine, 0.60 μg/L in the river Ruhr, and 0.70 μg/L in the river Emscher. BPS can only be found in the river Ruhr (median value: 0.08 μg/L) and in the river Emscher (median value: 0.41 μg/L). HPS was regularly found in a surface water for the first time. This substance can be detected in the Emscher through the whole measurement period. The median value for HPS amounts to 1.78 μg/L. Aditionally, the validation characteristics of an alternative analytical method including solid‐phase microextraction (SPME) is worked out. The fully automated process includes an on‐fiber methylation step and the GC‐MS. The repeatability standard deviation of the process amounts to RSD < 12%. Detection limits between 0.07 and 0.70 μg/L are achieved.     

The Use of Polyphenolic Compounds from Black Tea for the Solid Phase Extraction and Determination of Trace Iron in Drinking Water

A simple and selective solid phase extraction procedure for the trace analysis of iron(III) in water samples has been developed. Sodium dodecyl sulfate coated alumina, modified with polyphenolic compounds (extracted from black tea) was used for the extraction and preconcentration of iron(III) from water samples before determination by flame atomic absorption spectrometry. Due to the complexation reaction between iron(III) and polyphenol compounds, iron(III) was quantitatively extracted on the proposed sorbent and then eluted by 2.0 mL of HCl (1.0 mol/L). The effects of extraction parameters, such as pH and volume of sample solution, amount of polyphenolic compounds, type of eluting agent and the effect of interfering ions on the extraction of iron(III), were investigated. It was found that the proposed method had a good linear range (15.0–100.0 μg/L) and a low detection limit (10.0 μg/L). The procedure was successfully applied for iron determination in drinking water samples.     

A Cloud Point Extraction Approach Developed for Analyzing Pesticides Prometryne and Isoproturon from Multi‐media

A new analytic methodology based on the cloud point extraction coupled with HPLC (CPE‐HPLC) was developed and successfully applied to determination of the pesticides isoproturon (IPU) and prometryne (PRO) from multi‐media (contaminated water, soil, and food vegetable). Several non‐ionic surfactants including poly ethylene glycol 6000 (PEG‐6000), TritonX‐114, and Triton X‐100 were comparatively analyzed as extraction solvents. Other parameters such as surfactant concentration, ionic strength, and equilibration temperature, and duration were also investigated. The optimal conditions for CPE were presented with 2.4% w/v PEG‐6000, 11% w/v Na₂SO₄ and heating assistance at 50°C for 25 min. The calibration curves for the two analytes were linear ranging from 0.001 to 10.0 mg L^?1, with correlation coefficients being 0.99 determined by a HPLC–UV detector. Under the condition, the average recoveries were 85.4–90.6% for water, 84.4–92.7% for soil, and 84.4–92.1% for vegetable. Thus, the method presented here was proved to be rapid, efficient, and green for extraction and determination of isoproturon and prometryne residues from food and multi‐environmental media.     

Determination of Antibiotic Residues in Manure,Soil, and Surface Waters

In the last years more and more often detections of antimicrobially active compounds (“antibiotics”) in surface waters have been reported. As a possible input pathway in most cases municipal sewage has been discussed. But as an input from the realm of agriculture is conceivable as well, in this study it should be investigated if an input can occur via the pathway application of liquid manure on fields with the subsequent mechanisms surface run‐off/interflow, leaching, and drift. For this purpose a series of surface waters, soils, and liquid manures from North Rhine‐Westphalia (Northwestern Germany) were sampled and analyzed for up to 29 compounds by HPLC‐MS/MS. In each of the surface waters antibiotics could be detected. The highest concentrations were found in samples from spring (300 ng/L of erythromycin). Some of the substances detected (e.g., tylosin), as well as characteristics in the landscape suggest an input from agriculture in some particular cases. In the investigation of different liquid manure samples by a fast immunoassay method sulfadimidine could be detected in the range of 1…2 mg/kg. Soil that had been fertilized with this liquid manure showed a content of sulfadimidine extractable by accelerated solvent extraction (ASE) of 15 μg/kg dry weight even 7 months after the application. This indicates the high stability of some antibiotics in manure and soil.     

Identification and quantification of pesticides, industrial chemicals, and organobromine compounds of medium to high polarity in the North Sea

Solid-phase extraction of 20 L seawater samples enabled the enrichment and determination of a wide array of organic substances, including compounds of medium to high polarity, in the pg/L-range. A number of contaminants was detected and quantified throughout the North Sea, among them the pesticides dichlobenil (2,6-dichlorobenzonitrile), metolachlor and terbuthylazine as well as the industrial chemicals dichloropyridines (DCPy, 4 isomers) and nitrobenzene. Concentrations attained values up to 1.4 ng/L for dichlobenil, 0.83 ng/L for terbuthylazine, 0.61 ng/L for metolachlor, 0.13 ng/L for 2,6-DCPy, 4.37 ng/L for nitrobenzene and 1-8 ng/L for tris(chloropropyl)phosphates (TCPP). A number of North Sea water samples was screened for non-target compounds, revealing the presence of further contaminants, e.g., lindane and TCPP, as well as several biogenic and/or anthropogenic organobromine substances, among which bromoindols, -phenols and -anisoles were identified.     

A New Method for Determining Compound Specific Carbon Isotope of Chlorinated Solvents in Porewater

A new method for the extraction of chlorinated solvents (CSs) from porewater with dimethylacetamide (DMA) used as a solvent and the determination of δ¹³C by gas chromatography-isotope ratio mass spectrometry (GC-IRMS) with solid-phase microextraction (SPME) are presented. This method was used for the determination of δ¹³C of chloroethenes and chloromethanes. The extraction of the CSs from porewater with DMA led to a minimal loss of mass of solvent and chlorinated compounds. The accuracy of the method was verified with the analysis of the pure injected compounds using elemental analyzer—isotope ratio mass spectrometry (EA-IRMS). It has been effectively applied in a study area in saturated soil samples of a pollutant source zone of perchloroethylene (PCE) and trichloroethylene (TCE). The limit of quantification of the new method was 0.034 μg/g for PCE and TCE for 10–20 g of soil sample. This new method allows for compound-specific isotope analysis of CSs in porewater, which can be beneficial in sites where the identification of contamination sources and the behavior of the contaminants are not clear.     

Sorption von Schwermetallen durch Eisenphosphat-Kolloide in essigsauren Bodenextrakten

Sorption of Heavy Metals from Acetic Acid Extracts by Ferric Phosphate Colloids A conceivable procedure to remedy heavy metal contaminated soil materials is given with extraction of organic acids, i. e. by the use of a biological degradable extraction agent. The following concentration step of heavy metal extracts should be carried out to a great extent without a change of the low pH values. A conventional precipitation of the heavy metals by rising the pH should be avoided in order to introduce no large amounts of salts into the wastewaters of the process and furthermore, to reduce the amount of sludge to be deposited. The process scheme developed with the objective of heavy metals recycling consists of the following steps: the extraction of the heavy metal contaminated soils with weak organic acids like acetic acid or citric acid, the electrolysis of the extract, and a concentration step in order to treat metal concentrations not fully removed by electrolysis. This third step, e.g. could contain sorption on iron phosphate colloids and precipitation within the acidic environment. It has been examined whether a removal of the heavy metals Pb, Cd, Cu, Sb, Cr, Ni and Zn from acetic aqueous solutions of pH between 2 and 3 can be carried out.     

Comparison of Downhole and Surface Sampling for the Determination of Volatile Organic Compounds (VOCs) in Ground Water

The relative precision and accuracy of sampling and analysis methods for the determination of trace concentrations of volatile organic compounds (VOCs) in ground water were compared. Samples were collected from a well containing nanogram-per-liter (ng/L) to microgram-per-liter (μg/L) levels of VOCs. A Keck helical rotor submersible pump was used to collect samples at the surface for analysis by purge and trap (P&T) and for analysis by adsorption/thermal desorption (ATD). Downhole samples were collected by passing water through an ATD cartridge. Although slight spontaneous bubble outgassing occurred when the water was brought to the surface, the relative precisions and comparabilities of the surface and downhole methods were generally found to be equivalent from a statistical point of view. A main conclusion of this study is that bringing sample water to the surface for placement in VOC vials (and subsequent analysis by P&T) can be done reliably under many circumstances. However, care must still be taken to prevent adsorption losses and cross contamination. Samples subject to strong bubble outgassing will need to be handled in a special fashion (e.g., by downhole ATD) to minimize volatilization losses. Additionally, the higher sensitivity of the ATD method allows lower detection limits than are possible with P&T. For example, several compounds present at the ng/L level could be determined with confidence by ATD, but not by P&T.