Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

Attempt to adsorb N-nitrosamines in solution by use of zeolites

The strong adsorption of zeolite for N-nitrosamines in solution was first revealed by use of adsorption, and temperature programmed surface reaction (TPSR) techniques. N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) as well as N-nitrosohexamethyleneimine (NHMI) can be adsorbed on zeolite Y, ZSM-5 and A in the solution of methylene chloride or water, which will be helpful for removal of the N-nitrosamines pollution in environmental protection. The equilibrium data were fitted to Freundlich-type isotherms, but the adsorption capacity of zeolites mainly depended on their pore size, surface area and acid-basic properties. Molecular size of adsorbate and solute-solvent interaction also strongly affected the adsorption of N-nitrosamines on zeolite in solution. The extraordinary adsorption properties of NaA zeolite for N-nitrosamines in aqueous solution is first reported and discussed.     

Liquid chromatography study of pyrene degradation by two micromycetes in a freshwater sediment.

Pyrene biodegradation in a freshwater sediment without fungi supply, or inoculated with two sediment micromycetes, Mucor racemosus var. sphaerosporus and Phialophora alba was studied after 0, 5, 13, 28, 60 and 90 days. The influence of glucose addition was estimated, and a liquid chromatographic method for simultaneous quantitative determination of residual anthracene, fluoranthene and pyrene in the sediment was developed. Samples with PAHs were extracted in Soxhlet with ethyl acetate, and LC analysis was performed on a 5 microm Supelcosil column (150 x 4.6 mm I.D.) with gradient elution (2 ml min(-1)) of acetonitrile-water and UV detection at 254 nm. Recoveries of anthracene, fluoranthene and pyrene were 90.3%+/-1.1%, 93.2%+/-0.9% and 90.42%+/-1.9%, respectively, without interference. The native sediment microorganisms (with or without glucose added) have shown 35% pyrene degradation and sediment with glucose inoculated by the strains revealed 40%.     

Evidence of coprostanol estrogenicity to the freshwater mussel Elliptio complanata

Coprostanol (5 beta (H)-cholestan-3 beta ol) is a reduced metabolite of cholesterol produced by micro-organisms found in the intestinal tract of mammals. This substance abounds in urban effluents and is accumulated by organisms living in the vicinity of municipal effluent outfalls. In an earlier study, freshwater mussels exposed to contaminated river water for 62 days accumulated large quantities of coprostanol (Cop) in their soft tissues (16 micrograms/g dry wt.). Moreover, these mussels were found to have elevated levels of vitellin in their hemolymphs, suggesting estrogenic effects. Although municipal wastewaters are known to contain other estrogenic compounds capable of inducing Vn synthesis in mussels, the estrogenic potential of coprostanol was singled out for examination. To this end, mussels were first injected with concentrations of coprostanol via the abductor muscle route, and allowed to stand in aerated water for 72 h at 15 degrees C. The levels of Vn in mussel hemolymph were assayed using the organic alkali-labile phosphate method. A competitive estradiol-binding assay was then devised to measure the ability of coprostanol to compete in the binding of fluorescein-labeled estradiol-albumin to cytosolic proteins. Coprostanol partially reversed the binding of labeled estradiol-albumin to cytosolic proteins with an EC50 of 1 mM. In addition, injections of coprostanol and estradiol-17 beta led to increased levels of vitellins in the hemolymph of treated mussels. Moreover, incubation of cop in gonad homogenate extracts in the presence of NADPH led to the formation of two compounds, as determined by high-performance thin-layer chromatography. One of these compounds appears to be the C17 oxidation product of coprostanol, whose polarity is similar to that of estradiol. The results present evidence that coprostanol is estrogenic to freshwater mussels.     

On the hydro-dispersive equivalence between multi-layered mineral barriers

In the context of municipal solid waste and hazardous waste disposal, the notion of "equivalence" between different barrier designs appears in regulatory documents from several industrialized countries. While in the past, equivalence has been thought of mainly in terms of contaminant travel times, in recent years it has been defined more in terms of the magnitude of a disposal site's potential impact on groundwater resources. This paper presents some original analytical solutions to the problem of contaminant migration through a multi-layered mineral barrier. The solutions account for the two major mechanisms of subsurface contaminant migration, namely, advection and diffusion-dispersion. An example application using the proposed solutions and a numerical model illustrates how one multi-layered mineral barrier can be considered superior to another from a strictly hydro-dispersive viewpoint. The influence of partial saturation of the mineral barrier is investigated using a numerical solution to the Richards equation for unsaturated flow. It is emphasized that conclusions relative to the superiority of one multi-layered barrier, with respect to another, should not only consider hydro-dispersive aspects, but also other processes such as the mechanical and chemical evolutions of the different barrier components. Although such phenomena are poorly addressed by existing models, failure to take them into account, at least in a qualitative fashion, may lead to unconservative conclusions with respect to barrier equivalence.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

The Henry's law coefficient of 2-nitrophenol over the temperature range 278-303 K

Although 2-nitrophenol has been identified as an important environmental chemical there is scarcity in the literature regarding the temperature dependence of its Henry's law coefficient, H. Here a bubble purge method was used to measure H for 2-nitrophenol over the temperature range 278-303 K. A novel approach in the data treatment allowed correction of the data for non-equilibrium partitioning in the apparatus to obtain the true equilibrium H value. The experimentally derived temperature-dependent expression for H of 2-nitrophenol is lnH (M atm(-1)) = (6290/T (K)) - 16.6. The standard enthalpy and entropy of gas-to-liquid transfer for 2-nitrophenol in aqueous solution are -52.3 +/- 8.1 kJ mol(-1) and -138 +/- 28 J mol(-1) K(-1), respectively. (Errors are 95% confidence intervals.)     

Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

Contaminant residues in seabird eggs from the Canadian Arctic. II. Spatial trends and evidence from stable isotopes for intercolony differences

Eggs of glaucous gulls (Larus hyperboreus), black-legged kittiwakes (Rissa tridactyla), thick-billed murres (Uria lomvia) and black guillemots (Cepphus grylle) were collected from several sites throughout the Canadian Arctic. Samples were analyzed for organochlorines as well as mercury and selenium. Glaucous gulls breeding at sites in the High Arctic showed higher levels of organochlorine contamination than those in the western Low Arctic. This was likely due to dietary differences among colonies as suggested by stable isotope data, although different overwintering areas may also play a role. Levels of sigmaPCB, sigmaDDT, sigmaCHLOR, sigmaCBz and dieldrin were significantly lower in thick-billed murres from Prince Leopold Island in the High Arctic compared with colonies in the eastcrn Low Arctic. This difference was likely due to the combined effects of different atmospheric deposition patterns in the High and Low Arctic and different overwintering areas since murres from Prince Leopold Island may winter farther north than murres from the other colonies sampled. Eggs from colonies at higher latitudes generally contained higher concentrations of mercury. The trophic and dietary differences/similarities suggested by stable-nitrogen and carbon isotope data in this study were useful in explaining the spatial patterns of contaminant concentrations observed among colonies of seabirds such as the glaucous gull and the black-legged kittiwake where variation in latitudinal atmospheric deposition patterns and different overwintering grounds did not appear to be confounding factors.     

Multiple regression models: a methodology for evaluating trihalomethane concentrations in drinking water from raw water characteristics

The presence of trihalomethanes (THMs) in drinking water has attracted the attention of both researchers and professionals, because of the harmful effects of these substances on human health. A multiple regression model was developed to estimate THM concentrations in finished drinking water, using data from the Menidi Treatment Plant of Athens. A number of routinely measured characteristics--including chlorine dose, chlorophyll a, temperature, pH and bromide--of raw water, were used to generate a reliable methodology for predicting both total THM and individual species concentrations. Seasonality effects were also considered during the analysis. In general, these models were found to give acceptable fits, estimating accurately lows and highs over the annual cycle.