Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Sorption‐desorption kinetics of some organochlorine insecticides in silt‐water suspensions

Kinetic (batch) sorption and desorption experiments for some organochlorine insecticides in silt‐water suspensions are described. The effect of possible experimental artifacts on the results is examined. The influence of the silt/water ratio on the linear sorption coefficient and on the “nonextractable”; solute fraction is determined. The sorption process is described in terms of some kinetic models.     

Determination of pentachlorophenol in human urine using solid phase extraction and GC‐MS analysis with stable isotope dilution

A method for the determination of pentachlorophenol (PCP) in human urine was developed. Urine samples were fortified with ¹³C₆‐IabeIed PCP and hydrolyzed with sulfuric acid prior to extraction. The urine samples were then passed through preconditioned solid phase extraction cartridges containing octadecylsilane adsorbent. The PCP was subsequently eluted from the cartridge with ethyl acetate and converted to pentachloroanisole prior to GC‐MS analysis. GC‐MS quantitation was performed using the technique of stable isotope dilution. Percent recoveries averaging 100, 97, and 111% were obtained for replicate urine samples fortified with approximately 2, 20, and 200 ng/mL of PCP, respectively. The method detection limit was estimated to be 0.2 ng/mL.     

Improvement of sampling and analytical methods for polychlorinated dibenzo‐p‐dioxins and dibenzofurans in environmental samples and its quantitative evaluation

Sampling of PCDDs/Fs in flue gas from a MSW incinerator was conducted using a modified apparatus of the 5 train method, which has been widely used for the sampling of PCDDs/Fs emission. In the atmosphere a high volume air sampler with special packings was used. Collection efficiencies of PCDDs/Fs were more than 98% for both samplers, using ¹³C₁₂—PCDD reference standard isomers. It was suggested that these sampling methods were adaptable for the measurements of PCDDs/Fs at sources and in the environment. To validate the applicability of existing methodologies on the PCDD/F determination, interlaboratory comparisons were undertaken. From high resolution GC/MS analysis, 2,3,7,8‐TCDD concentrations in reference ash samples were 0.052±0.013 ng/g as comparable results between the laboratories. In addition, the daily intakes of PCDDs/Fs for exposed persons in the MSW incineration facilities in Japan were estimated ranging of 0.053 to 0.28 pg/kg/day by the international toxic equivalent calculations.     

Stability studies of cholesterol lowering statin drugs in aqueous samples using HPLC and LC–MS

In this study, stability of statin drugs in different conditions, such as various pH, diverse solvents ratio, presence of UV, and sunlight have been investigated. Results suggest strong dependence of statins upon pH, potential environmental persistence towards sun light, and UV light degradation via singlet excited state obtained by excitation into the π–π* band. In acidic conditions interconversion between lactone and hydroxy acid forms in aqueous solutions at room temperature is retarded, while for the same sun-exposed samples are accelerated. Longer exposures lead to the degradation processes. Statin interconversion in water is much lower than in acetonitrile.     

Gas phase equilibria for dibenzo‐p‐dioxin,dibenzo‐p‐furan and biphenyl in the C‐H‐O system

The gas phase equilibrium calculation for the C‐H‐O system at atmospheric pressure and temperature from 773 to 1773 K at intervals of 250 K was performed to understand the generation and decomposition behavior of dibenzo‐p‐dioxin (DD), dibenzo‐p‐furan (DF) and biphenyl (BP) in relation to the existing oxygen potential. It is possible to categorize these results into three regions from the viewpoint of this potential: region (A), region (B) and region (C) are that of the higher, modest and lower oxygen potential, respectively. In region (A), the equilibrium amounts of DD, DF and BP are nearly zero. In region (B), they increase once and then decrease with rise in temperature. In the most characteristic region (C), they increase uniformly with rise in temperature.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

Characterisation and classification of hoarfrost samples collected in Poland (2003–2005) by discriminant analysis

Discharges of nutrients, urea, dissolved organic matter and heavy metals by a sewage underwater pipeline are analysed in comparison to environmental conditions in a shallow coastal zone. Variable thermo-haline stratifications of the water column and currents in upper (2.62–34.97 cm s^?1) and deeper (0.83–10.91 cm s^?1) layers drive vertical diffusion and lateral transport of wastewaters. Loads of reactive phosphorus (0.13 tons d^?1) and ammonium (1.62 tons d^?1) by the pipeline are not negligible compared to the major river loads in the gulf. High concentrations of urea (≤11.51 μmol N dm^?3) were found in the area of wastewater release. Ammonium uptake (6.14–534 nmol N dm^?3 h^?1) strongly exceeded nitrate uptake (0.19–138 nmol N dm^?3 h^?1), indicating that discharges of ammonium by the pipeline are actively assimilated by plankton community even at low levels of light. Distribution of Zn (≤27.7 ppb), Cu (≤25.6 ppb), Cd (≤0.80 ppb) and Pb (≤13.5 ppb) in the water column and the measurement of their complex-forming capacity in seawater did not indicate a persistent perturbation of the pelagic environment due to heavy metals.     

Concentrations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans in outdoor air of North‐Rhine‐Westphalia,Germany

Measurements of polychlorinated dibenzo‐p‐dioxins (PCDD) and dibenzofurans (PCDF) in outdoor air of North‐Rhine‐Westphalia were carried out. Fifty‐six samples were taken at different sites in areas of different land use and emission structures. A special filter system allowed analysis of the gas and particle phases separately. It was found that higher chlorinated PCDD/PCDF (7 or 8 chlorine atoms) are collected on glass fiber filter and lower chlorinated PCDD/PCDF (tetra‐ and penta‐CDD/CDF) are absorbed on polyurethane foam. The following isomers were determined: OCDD, OCDF and 11 isomers with chlorine substitution in 2,3,7,8‐position as well as the sum of TCDD, PeCDD, HxCDD, HpCDD, TCDF, PeCDF, HxCDF, HpCDF and the sum of PCDD (4–8) and PCDF (4–8). No 2,3,7,8‐TCDD could be detected but 2,3,7,8‐TCDF was found at 15 sites. Mean concentration in the Rhine‐Ruhr‐District for the sum of PCDD (4–8) and PCDF (4–8) was 3.2pg/m³ and 5.5pg/m³ respectively. Detection limit for TCDD and PCDD/PCDF (5–8) was 0.1–0.2 pg/m³ and 0.005–0.015 pg/m³ respectively. There is no significant indication that 2,3,7,8‐chlorinated isomers of PCDD/PCDF are predominantly decomposed by photochemical reactions in outdoor air.     

The occurrence of disinfection by‐products in Taiwan drinking water

In this study, samples were taken from six conventional water treatment plants for disinfection by‐products analysis. Results from the analysis revealed that trihalomethanes (THMs) concentrations in all samples were below regulatory levels (100 μg/L). Although the national standard for haloacetic acids (HAA5) has not yet been promulgated in Taiwan, samples from two water plants contained HAA5 concentrations exceeding the USEPA limit (MCL of HAA5 of Stage 1, 60 μg/L). THMs and HAA5 were found to be the major disinfection by‐products in all water treatment plants. It was noted that the concentration of HAA5 in most samples was higher than that of the trihalomathanes. However, the formation potential of THM (THMFP) was found to be higher than that of HAA (HAAFP). Good correlation also was found between THMFP (or THMFP) and HAA5 (or THMs). In evaluating the performance of the treatment processes, it was found that conventional water treatment processes followed by activated carbon were effective in removing disinfection by‐products (DBPs) from source water with pre‐ozonation. The treatment processes were at their optimum performance in removing contaminants when O₃/TOC₀ was held at 0.75.     

Relationships between octan‐1‐ol/water partition coefficients,aqueous activity coefficients and reversed phase HPLC capacity factors of alkylbenzenes,chlorobenzenes, chloronaphthalenes and chlorobiphenyls

Linear relationships between logarithms of octan‐1‐ol/water partition coefficients (K_d,oct), aqueous activity coefficients (y_aq) and extrapolated RP HPLC capacity factors (k‘_w) are found for four types of aromatic hydrocarbons (alkylbenzenes and poly‐chlorinated benzenes, ‐naphthalenes and ‐biphenyls).

Both log K,_d,oct and logk‘_w increase with the increasing number of chlorine or methyl‐ene substituents. These increases of log K,_d,oct and log k‘_w are proportional and almost independent of the parent compound. In addition, these increases are linear to increases of logy_aq. The slopes of logk‘_w‐logy_aq and log K,_d,oct‐logv_aq relationships deviate significantly from 1.0. This suggests that the activity coefficients of the test compounds in both octan‐1‐ol and in the stationary phase of the RP column increase after substitution of aromatic compounds with methylene or chlorine.     

Determination of carazolol in pharmaceutical formulations by gas‐liquid‐chromatography (GLC)

A gas‐liquid‐chromatographic procedure for the quantitative determination of authentic carazolol and carazolol in tablets (Conducton^(R)?) has been described. Carazolol in tablets was extracted with absolute alcohol before injecting onto the gas Chromatograph. The concentration range adopted varied between 0.2 mg to 1.0 mg/ml of carazolol in alcohol solution. The results obtained were 97.6%±3.2 and 98.4%±2.6 for the stated and added amounts respectively.     

Concentration profiles of various toxic and non‐toxic elements in sized coal fly ashes from coals of the León basin

The concentration levels of major (Al, Ca, Fe, K, Mg, Mn, Na, Si, Ti) and some trace (Be, Se, Tl) elements were determined by atomic absorption spectrometry for the coal fly ashes emitted in the combustion of anthracite and soft coals. Total contents and concentration profiles were established for all elements studied as a function of the mean particle size. The content of those elements volatilized during coal combustion (Se, Tl) decreases with increasing particle size, while the unvolatilized elements show small changes in their concentration profiles. The content of aluminium shows a minimum level at a mean particle size of about 25 μm.     

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/Fs) in dated environmental samples,and their connection to known sources

This article investigates available environmental data from measurements of the everywhere present contaminants polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) in dated trends in sediment, soil and herbage from locales in Europe and North America. The PCDD/F data are examined in relation to potential major PCDD/F sources based on volume: wood and coal, example of natural combustion; pentachlorophenol (PnCP), example of chlorinated aro‐matics; and polyvinyl chloride (PVC) pyrolysis, example of chlorinated aliphatic. Collected PCDD/F data of congener sums and 2, 3, 7, 8‐substituted congener (PCDD/F profiles) have been investigated with multivariate methods: principal component analysis (PCA) and partial least squares projection to latent structures model (PLS). The results show that PCDD/F data from 12 locales can be separated in one to three independent profiles. Normally one profile is related to the PCDD/F found in PnCP and another to combustion. A subtype of the ‘PnCP’ and ‘combustion’ profiles indicates PCDD/F contributions from PVC‐related combustions. The environmental profiles exhibit some differences from the suggested sources. The relatively unprotected PCDD/F related to PnCP is suggested to have passed photolytic and/or thermal dechlorinations. Lower‐chlorinated congeners in environmental profiles related to combustion appear to have been influenced by environmental distribution processes. PCDD/F data before industrial production of chlorinated organics have only limited similarity to PCDD/F in technical PnCP profiles; an average 4.6% of the PCDD/F is related to PnCP. This suggests that PnCP similarity in recent deposition profiles cannot be a result of environmental transformation. The average proportion of PnCP‐related PCDD/F profile in recent depositions is 35% with North America high (average 57%) and Europe low (average 24%).     

Metabolites of sulfur‐containing derivatives of the fungicides pentachloronitrobenzene and hexachlorobenzene in mammals,separated by capillary gas chromatography and identified by negative and positive Cl mass spectrometry

Biotransformation products of sulfur‐containing derivatives of pentachloronitro‐benzene and hexachlorobenzene in mammals, such as thiophenols, thioanisoles, phenols, anisoles and chlorinated benzenes have been identified by mass spectrometry of negative and positive ions produced by chemical ionisation. The capillary gas chromatograms of extracts from excreta of rats after application of N‐acetyl‐S‐(pentachlorophenyI)‐D,L‐cysteine, as well as of rabbits after application of S,S'‐(tetrachloro‐p‐phenylene)‐L,L'‐dicysteine, are shown.     

Investigation of the hemolytic effects of various organophosphoric acid triesters (OPEs) and their structure‐activity relationship

The hemolytic effects of various organophosphonc acid triesters (OPEs) were investigated and they showed strong hemolyic toxicity except triethyl phosphate and tris(chloroethyl)phosphate. 2‐Ethylhexyl diphenyl phosphate (EHDP) showed the strongest toxicity. By quantitative structure‐activity relationship (QSAR) study, one‐parameter regression equation to estimate hemolysis was not obtained. But, two‐parameter regression equations were obtained which were enought to estimate EC₅₀ and EC₂₀. The correlation coefficients with the two‐parameter regression equations were 0.939 for log(l/EC₅₀) and 0.946 for log(l/EC₂₀).     

Metallothionein induction in mice by CCL4: Hepatic Zn‐status and distribution of administered Cd∗

Induction of metallothionein (MT), Zn status and the subcellular distribution of administered Cd were studied in liver after single administration of CC1₄ to mice. Hepatic MT was increased up to 153±16 μMT/g liver 18 h after injection of 2ml CCl₄/kg body weight. The observed decrease in Zn bound to cytosolic high molecular weight proteins from 25.5 ± 0.6 to 19.8±1.1 resp. 19.0 ± 1.7 μgZn/g and the increase in MT bound Zn from 4.0±0.5 to 9.5 ± 1.1 resp. 10.9±1.1 μgZn/g compensate each other.

Zn content of whole liver and hepatic cytosol remained unchanged. Hepatic subcellular distribution of 4 mg Cd/kg body weight, administered 2 h prior termination was also influenced by CC1₄. Cd bound to high molecular weight proteins decreased from 10.0±1.0 to 7.2±1.6 resp. 3.7 ± 2.6 μg Cd/g and Cd bound to MT increased from 12.5 ± 1.4 to 18.0 ± 3.8 resp. 23.1± 6.4 μgCd/g. Cd content of both, whole liver and cytosol was not significantly different from control. The induction of MT has been suggested to be beneficial due to its role in the sequestration of toxic metals. The depletion of Zn from cytosolic high molecular weight proteins however might adversively influence essential physiological processes.     

Levels and distributions of organochlorine pesticides in the soil–groundwater system of vegetable planting area in Tianjin City,Northern China

To study the influence of long-term pesticide application on the distribution of organochlorine pesticides (OCPs) in the soil–groundwater system, 19 soil samples and 19 groundwater samples were collected from agricultural area with long-term pesticide application history in Northern China. Results showed that the composition of OCPs changed significantly from soil to groundwater. For example, ∑DDT, ∑HCH, and ∑heptachlor had high levels in the soil and low levels in the groundwater; in contrast, endrin had low level in the soil and high level in the groundwater. Further study showed that OCP distribution in the soil was significantly influenced by its residue time, soil organic carbon level, and small soil particle contents (i.d. <0.0002 mm). Correlation analysis also indicates that the distribution of OCPs in the groundwater was closely related to the levels of OCPs in the soil layer, which may act as a pollution source.     

Presence of Cd‐binding proteins in pre‐exposed and not pre‐exposed cadmium brine shrimp Artemia

The presence of metal binding proteins has been variously suggested as indicating involvement in uptake, storage, transport and elimination of toxic metals and in the routine metabolism of metals in mammals and a variety of marine invertebrates. This report describes results on the characterization of Cd‐BPs obtained from cadmium pre‐exposed and not pre‐exposed Anemia. The effect of pre‐exposure in the Cd‐binding protein induction in Artemia is discussed.