Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

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.     

Aqueous high‐temperature chemistry of arsenic‐containing compounds in water at 300°C

Arsenic compounds, and especially organo‐arsenic derivatives, are highly toxic and many have been manufactured as chemical warfare agents. This study was designed to provide background information relevant to the potential application of aquathermolysis techniques for the detoxification of such potent military warfare agents. Six arsenic‐containing compounds with structural features which mimic known agents were studied in neutral superheated water: 4‐aminophenylarsine oxide, 4‐arsanilic acid, 4‐nitrophenylarsonic acid, 5, 10‐dihydro‐10‐ethylphenarsazine, tetraphenylarsonium chloride hydrate, and (3‐cyanopropyl)dimethyl(2‐phenethyl)arsonium bromide. Most of these compounds were moderately susceptible to hydrolysis for 1h at 300°C. o‐ and p‐Aminosubsituted arsenic compounds were more reactive than compounds with an electron‐withdrawing group substituent. Aromatic C—As bonds were more resistant to cleavage than aliphatic C—As bonds.     

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.     

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.     

Analytical solution of two-dimensional advection–dispersion equation with spatio-temporal coefficients for point sources in an infinite medium using Green’s function method

In the present study analytical solutions of a two-dimensional advection–dispersion equation (ADE) with spatially and temporally dependent longitudinal and lateral components of the dispersion coefficient and velocity are obtained using Green’s Function Method (GFM). These solutions describe solute transport in infinite horizontal groundwater flow, assimilating the spatio-temporal dependence of transport properties, dependence of dispersion coefficient on velocity, and the particulate heterogeneity of the aquifer. The solution is obtained in the general form of temporal dependence and the source term, from which solutions for instantaneous and continuous point sources are derived. The spatial dependence of groundwater velocity is considered non-homogeneous linear, whereas the dispersion coefficient is considered proportional to the square of spatial dependence of velocity. An asymptotically increasing temporal function is considered to illustrate the proposed solutions. The solutions are validated with the existing solutions derived from the proposed solutions in three special cases. The effect of spatially/temporally dependent heterogeneity on the solute transport is also demonstrated. To use the GFM, the ADE with spatio-temporally dependent coefficients is reduced to a dispersion equation with constant coefficients in terms of new position variables introduced through properly developed coordinate transformation equations. Also, a new time variable is introduced through a known transformation.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

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.     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

Variations in heavy metal contamination of stream water and groundwater affected by an abandoned lead–zinc mine in Korea

This study evaluated variations in heavy metal contamination of stream waters and groundwaters affected by an abandoned lead–zinc mine, where a rockfill dam for water storage will be built 11 km downstream. For these purposes, a total of 10 rounds of stream and groundwater samplings and subsequent chemical analyses were performed during 2002–2003. Results of an exploratory investigation of stream waters in 2000 indicated substantial contamination with heavy metals including zinc (Zn), iron (Fe) and arsenic (As) for at least 6 km downstream from the mine. Stream waters near the mine showed metal contamination as high as arsenic (As) 8,923 μg L⁻¹, copper (Cu) 616 μg L⁻¹, cadmium (Cd) 223 μg L⁻¹ and lead (Pb) 10,590 μg L⁻¹, which greatly exceeded the Korean stream water guidelines. Remediation focused on the mine tailing piles largely improved the stream water qualities. However, there have still been quality problems for the waters containing relatively high concentrations of As (6–174 μg L⁻¹), Cd (1–46 μg L⁻¹) and Pb (2–26 μg L⁻¹). Rainfall infiltration into the mine tailing piles resulted in an increase of heavy metals in the stream waters due to direct discharge of waste effluent, while dilution of the contaminated stream waters improved the water quality due to mixing with metal free rain waters. Levels of As, Cu and chromium (Cr) largely decreased after heavy rain but that of Pb was rather elevated. The stream waters were characterized by high concentrations of calcium (Ca) and sulfate (SO₄), which were derived from dissolution and leaching of carbonate and sulfide minerals. It was observed that the proportions of Ca and SO₄ increased while those of bicarbonate (HCO₃) and sodium and potassium (Na+K) decreased after a light rainfall event. Most interestingly, the reverse was generally detected for the groundwaters. The zinc, being the metal mined, was the most dominant heavy metal in the groundwaters (1758–10,550 μg L⁻¹) near the mine, which far exceeded the Korean standard of 1000 μg L⁻¹ for drinking water. The decreases in the heavy metals contents in the groundwaters associated with reduced rainfall were quite different from the increases observed for the stream waters, which is not clearly understood at this time and warrants further investigation.     

The international toxicity equivalency factor (I‐TEF) method for estimating risks associated with exposures to complex mixtures of dioxins and related compounds∗

The International Toxicity Equivalency Factor (I‐TEF) method of risk assessment is a revised interim procedure for assessing the risks associated with exposures to complex mixtures of chlorinated dibenzo‐p‐dioxins and dibenzofurans (CDDs and CDFs). This updated scheme was developed by a working group of the North Atlantic Treaty Organization's Committee on the Challenges of Modern Society and has been officially adopted by the U.S. Environmental Protection Agency (EPA), Canada, Ontario Ministry of the Environment, the Nordic countries, the Netherlands, and the United Kingdom. Prior to the development of the I‐TEF method, at least ten slightly different schemes had been used throughout the world which complicated communication among scientists and regulatory agencies concerning the toxicological significance of complex mixtures of CDDs and CDFs. The I‐TEF approach facilitates risk communication internationally by reducing large volumes of analytical data into a single number‐International Toxicity Equivalents (I‐TEQ). As a result, the I‐TEF method represents an improvement in an already useful risk assessment/regulatory tool.     

Trace analysis of off-flavor/odor compounds in water using liquid-liquid microextraction coupled with gas chromatography—positive chemical ionization-tandem mass spectrometry

A rapid, inexpensive and laboratory friendly method was developed for analysis of off-flavor/odor compounds in fresh and salt water using gas chromatography with chemical ionization-tandem mass spectrometry. Off-flavor/odor compounds included geosmin, 2- methylisoborneol (MIB), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP). Using this method, a single sample can be extracted within minutes using only 1 mL of organic solvent. The ion transitions for IPMP, IBMP, MIB, and geosmin were 153>121, 167>125, 152>95, and 165>109, respectively. The linearity of this method for analyzing MIB ranged from 4 to 200 ng·L^–1, and from 0.8 to 200 ng·L^–1 for the other analytes. Method recoveries ranged from 97% to 111% and percent relative standard deviations ranged from 3% to 9%, indicating that the method is accurate, precise, and reliable.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.