Gaschromatographische Bestimmung von polychlorierten Biphenylen in Wasser nach Headspace-Festphasenmikroextraktion

Gas-chromatographic Determination of Polychlorinated Biphenyls in Water after Headspace Solid-phase Microextraction Headspace-analytical techniques are usually applied to the determination of easily volatile substances in water, whereas semivolatiles are generally isolated by liquid-liquid or solid-phase extraction. In the present paper, a method is presented for isolating high boiling polychlorinated biphenyls (PCB) using headspace solid-phase microextraction at elevated temperature. In spite of their low vapor pressure, the analytes are adsorbed very efficiently on a poly-dimethylsiloxane-coated fiber. Thus, in combination with GC/ECD, a very simple and sensitive solventless determination of PCB is accomplished. Using the simplest possible standard conditions, limits of determination in the lowest nanogram-per-liter range are achieved. Further increased sensitivity down to the ppq (parts per quadrillion) range is possible by stirring and increasing the sample volume and adsorption time. Moderate matrix effects have been observed in some surface and groundwaters.     

Untersuchung der Sorptionseigenschaften des Kationenaustauschers KB-2M mit Makronetzstruktur zur Abtrennung von Zinkionen aus Ab- und Spülwässern

Study of Sorptional Properties of the Cation Exchanger KB-2M with Macroreticular Structure for Recovery of Zinc Ions from Sewage and Rinsing Water Although a number of ion-exchange methods have been employed for the recovery of some transition metals from industrial effluents, knowledge about ion-exchange resins with macroreticular structure is poor. The present paper describes the mechanism of sorption on such exchangers and their application for recovery of zinc from sewage rinsing water. Ion exchanger of macroreticular structure are polymers with long-chained cross-linking agents. We have synthesized carboxylic ion-exchange resins by hydrolysis of copolymerisates of methyl acrylate with different cross-linking agents: divinylbenzene, divinyl sulfide, divinyl ester of ethylene glycol and divinyl ester of di- or triethylene glycol. The sorption process on modifications of the carboxylic resins KB-2 of various structure was studied with different methods: potentiometric titration, infrared spectroscopy, electron microscopy, X-ray structural analysis. The initial zinc concentration in rinsing water was 0.05 mol/L at pH from 3 to 6. For the sorption, 0.2…1.0 g of resin were equilibrated with 100 mL of zinc solution. After equilibrium (12 h), the resin was separated from solution. The zinc ions were determined by atomic absorption spectrometry after stripping with 100 mL of 10% sulfuric acid. The distribution ratio D was calculated (D: mmole of Zn sorbed per gram of resin divided by mmole of Zn per millilitre of solution). By means of infrared spectroscopy, the mechanism of sorption of zinc ions from rinsing water was determined. There may be a possibility of the formation of complexes in the cation-exchange resin phase. It was found out in this paper that the cation-exchanger KB-2M of macroreticular structure is the most effective for the sorption of the Zn²⁺-ions from sewage and rinsing water.     

Ein kompetitiver Immunoassay zur Bestimmung des Herbizids Fluazifop in Trink- und Grundwasser

A Competitive Immunoassay for the Determination of the Herbicide Fluazifop in Drinking Water and Groundwater A competitive solid-phase enzyme immunoassay using rabbit polyclonal antibodies was developed for the detection of the herbicide fluazifop [(RS)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid] in drinking water and groundwater. Present regulatory limits for drinking water in Germany were taken as the critical level. The carrier protein was bovine serum albumin; horseradish peroxidase was used as marker enzyme with 3,3′,5,5′-tetramethylbenzidine as substrate. A high concentration of high-affinity antibodies in the serum, optimization of test conditions (antibody and enzyme tracer concentration, incubation time etc.), and very low cross reactivities to substances of similar structures led to a highly sensitive and specific ELISA with a detection limit below 0.1 μg/L for fluazifop as free acid. On testing the suitability of the assay's use as a screening test with one hundred drinking-water samples, the three samples which had been spiked in the laboratory were recognized as positive with respect to their fluazifop content. Confirmation by gas chromatography-mass spectrometry showed the test results of two other samples to be false positive. False negative results did not appear. The concentration was in the detection limit region of 0.1 μg/L.     

Bildung bromhaltiger Desinfektionsnebenprodukte nach Chlorung von Bodenseewasser in Abhängigkeit von Aufbereitungsschritten und der Bromidkonzentration

Formation of Brominated Disinfection By-products after Chlorination of Water from Lake Constance Depending on Treatment Steps and Bromide Concentration The formation of halogenated disinfection by-products (DNP) (trihalomethanes (THM), haloacetic acids (HES), haloacetonitriles (HAN), haloketones (HKE) and chloropicrin (TCNM)) was studied after chlorination (0.5 mg/L) of raw water and drinking water from Lake Constance. The objectives of this study were to investigate the effect of bromide ion on the distribution of DNP-species resulting from chlorination and to draw up a bromide mass-balance. The treatment of water from Lake Constance with ozone decreased the formation of DNP about 35% and of total organic halogens (AOX) about 45%. This decline in DNP-formation is mainly due to the formation of chloroform, dichloro- and trichloroacetic acid. Though there is only a small amount of bromide (6.2 μg/L) in water from Lake Constance, about 32% of THM, 16% of HES, and 30% of HAN contained bromine after chlorination of treated water. The addition of bromide ion (up to 1 mg/L) shifted the DNP-composition to more brominated species. The distribution of the DNP-species depends on the initial molar bromide-to-chlorine ratio. A mathematic model showed the same pattern of DNP-species depending on the initial molar bromide-to-chlorine ratio that was observed experimentally in microstrained raw water and drinking water from Lake Constance. After chlorination of microstrained raw water, 27% of the bromide were incorporated in known DNP, 34% in unknown substances, and about 39% of bromide were not converted to organic bromine. After chlorination of treated water, only 16% of the bromide were incorporated in unknown substances, whereas 34% were found in known DNP. About 50% were found as bromide again. After addition of bromide (up to 25 μg/L) to ozonated and treated water from Lake Constance, between 60 and 72% of the bromide that had reacted after chlorination were found in analyzed low-molecular DNP.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

单管高压旋喷注浆技术在砂层加固、止水工程中的应用

就其他工艺在砂层的加固、止水工程中难以解决的问题，提出了单管高压旋喷注浆技术，并通过一些工程实例证实此工艺的可行性。     

The influence of floodplain geohydrology on the distribution of Sarcocornia pillansii in the Olifants Estuary on the West Coast, South Africa

The distribution of Sarcocornia pillansii (Moss) A.J. Scott was determined by water-table depth and electrical conductivity (EC) of the groundwater. Where the groundwater was accessible (<1.5 m) and had a low EC (<80 mS cm⁻¹), S. pillansii extended its roots down to the water-table where a suitable water potential gradient was shown to exist between the soil and roots. In areas where the groundwater was too deep and/or hypersaline, the plants grew on hummocks. The unconfined aquifer below the floodplain is linked to the estuary and although diurnal tidal waves were dampened, water-table level fluctuations were recorded between tidal events. The complex geomorphology of the floodplain influences groundwater flow, in turn affecting the distribution of the salt marsh vegetation.     

Distribution of trace metals in the Odra River system: Water–suspended matter–sediments

Extensive investigations of trace metals concentrations in water, suspended particulate matter (SPM) and bottom sediments of the whole Odra River system were carried out over the years 1997–2000. The vertical distribution of selected metals and their mobility were also studied in the sediment cores from upper and middle river sections. Significant levels of metal contamination were found. Median concentrations (Cd, Pb, Cu, Zn and As) in the SPM and sediments were (mg kg⁻¹) 7.1 and 8.9 Cd, 128 and 146 Pb, 81 and 119 Cu, 1198 and 1204 Zn, 48 and 54 As, respectively. The highest metal pollution of the Odra River solids was found with cadmium, zinc, lead and arsenic, showing high similarity in their frequency distributions in both SPM and sediments. Cd, Zn and As appear to be of particular concern because of the high levels, that appear to be bioavailable, and their high mobility. The exchangeable and carbonate chemical forms of Cd and Zn reached up to 50% of their total amount. Besides the determination of total metal concentration, the metal chemical forms in river solids were investigated. The results of very wide studies of the Odra River system through 4 years suggest that metal pollution decreased, especially for Zn, Pb and Cu. Among all metals studied in the Odra River sediments, substantial reductions of Cd contamination were observed neither in the period after ’97 flood, nor if compared with the earlier results obtained before ’97. No essential differences of the metal contents were observed among the samples for the same river compartment, from the same locality, taken within the five sampling campaigns. The pattern of spatial and vertical metal distributions in the river solids indicates that a variety of sources might be responsible for the contamination; very intensive, historical and current mining and smelting activities probably are the most important ones.     

Experimental and theoretical study of stability of dense hydrous magnesium silicates in the deep upper mantle

Fluid-undersaturated experiments were conducted to determine the phase relations in the simplified peridotite system MgO-SiO₂-H₂O (MSH) at 11.0-14.5 GPa and 800-1400 °C. Stability relations of dense hydrous magnesium silicates (DHMSs) under fluid-undersaturated conditions were experimentally examined. From the fluid-absent experimental results, we retrieved thermodynamic data for clinohumite, phase A, phase E, and hydrous wadsleyite, consistent with the published data set for dry mantle minerals. With this new data set, we have calculated phase equilibria in the MSH system including dehydration reactions. The dehydration reactions calculated with lower water activities of 0.68-0.60 match the fluid-present experiments of this study above 11.0 GPa and 1000 °C, indicating that considerable amounts of silicate component were dissolved into the fluid phase. The calculated phase equilibria illustrate the stability of the post-antigorite phase A-bearing assemblages. In the cold subducting slab peridotite, phase A + enstatite assemblage survives into the transition zone, whereas phase A + forsterite + enstatite assemblage forms hydrous wadsleyite at a much shallower depth of about 360-km. The slab is subducted with no dehydration reactions occurring when entering the transition zone. The phase equilibria also show the high temperature stability of phase E. Phase E is stable up to 1200 °C at 13.5 GPa, a plausible condition in the mantle of relatively low temperature, i.e., beneath subduction zones. Phase E is a possible water reservoir in the mantle as well as wadsleyite and ringwoodite.     

Aquatic fungi growing on dead fragments of submerged plants

The authors investigated the dead fragments of 22 species of submerged plants in the water from three limnological and trophical different water bodies (spring, river and pond). A total of 184 species of aquatic fungi, including 119 zoosporic and 65 conidial species were found on the fragments investigated plants. The most common fungus species were Aphanomyces laevis, Saprolegnia litoralis, Pythium rostratum (zoosporic fungi) and Acrodictys elaeidicola, Anguillospora longissima, Angulospora aquatica, Lemonniera aquatica, Mirandina corticola, Tetracladium marchalianum, Tetracladium maxiliformis, Trinacrium subtile (conidial fungi).

Most fungus species were observed on the specimens of Elodea canadensis (33 fungus species), Hippuris vulgaris f. submersa (33), Myriophyllum spicatum (34) and Potamogeton crispus (33), fewest on Ceratophyllum demersum (24), Fontinalis dalicarlica and Potamogeton nitens (each 25).

The most fungi were growing in the water from River Supraśl (107), the fewest in the water from Pond Dojlidy (99). Some aquatic fungus species were observed in the water of only one of the three water bodies – in Pond Dojlidy (30), in Spring Jaroszówka (32) and in the River Supraśl (39) species. Seventy-five species growing only on fragments of single submerged plants. A number of zoosporic and conidial species (22 and four, respectively) appeared new to Polish waters. Out of these 119 zoosporic species, some are known as parasites or necrotrophs of fish.