Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

Molecular phylogeny and population structure of tideland snails in the genus Cerithidea around Japan

Phylogenetic relationships and genetic population structures were analyzed for tideland gastropods in the genus Cerithidea around Japan on the basis of partial sequence of the mitochondrial COI gene. Large genetic divergence was shown between individuals of Cerithidea cingulata in the southern Ryukyus and those in the central Ryukyus and the Japanese Islands. Haplotypes of C. cingulata from the Japanese Islands were paraphyletic with the exclusion of a monophyletic group from the central Ryukyus. Genetic differentiation of C. cingulata was also detected between Amami-Oshima Island and Okinawajima Island. No genetic divergence was found between Cerithidea rhizophorarum in the Japanese Islands and its subspecies C. rhizophorarum morchii in the Ryukyu Islands. The lack of genetic divergence of Cerithidea largillierti between continental China and Japan suggests relatively recent migration between the Japanese Islands and the Asian continent. For all three Cerithidea species distributed in both the Japanese Islands and the Ryukyu Islands, the Tokara Gap and the Kerama Gap were shown to have acted as barriers to the dispersal.     

Exploratory Analysis of the Winter Chemistry of Five Lakes on the North Slope of Alaska1

Abstract: Lakes are important water resources on the North Slope of Alaska. Freshwater is required for oilfield production as well as exploration, which occurs largely on ice roads and pads. Since most North Slope lakes are shallow, the quantity and quality of the water under ice at the end of winter are important environmental management issues. Currently, water‐use permits are a function of the presence of overwintering fish populations, and their sensitivity to low oxygen concentrations. Sampling of five North Slope lakes during the winter of 2004‐2005 shed some light on the winter chemistry of four lakes that were used as water supplies and one undisturbed lake. Field analysis was conducted for oxygen, conductivity, pH, and temperature throughout the lake depth, as well as ice thickness and water depth. Water samples were retrieved from the lakes and analyzed for Na, Ca, K, Mg, Fe, dissolved‐organic carbon, and alkalinity in the laboratory. Lake properties, rather than pumping, were the best predictors of oxygen depletion, with the highest dissolved‐oxygen levels maintained in the lake with the lowest concentration of constituents. Volume weighted mean dissolved‐oxygen concentrations ranged from 4 to 94% of saturation in March. Dissolved oxygen and specific conductance data suggested that the lakes began to refresh in May.     

Influence of urbanization and tourist activities on the water quality of the Potrero de los Funes River (San Luis – Argentina)

A study of the water quality of the Potrero de los Funes River (San Luis – Argentina) was carried out in order to evaluate the possible effect of the anthropogenic activities on the river developed in the homonymous town. Samples were collected during the period March 2000–November 2005 at three selected sampling sites (RP₁, RP₂ and RP₃). Different physicochemical and bacteriological parameters (turbidity, pH, conductivity, suspended solids, alkalinity, potassium, sodium, calcium, magnesium, chlorides, nitrates, phosphates, sulphates, chemical oxygen demand (COD), 5-day biological oxygen demand (BOD₅), dissolved oxygen, total coliforms, Escherichia coli and total heterotrophic bacteria) were analysed according to the Standard Method for the Examination of Water and Wastewater. When comparing the values of total coliforms, E. coli, total heterotrophic bacteria, COD, BOD₅ and phosphates from the zone without anthropogenic influence (RP₁) and the urban zones (RP₂ and RP₃) an important variation in the parameters was observed. These results indicate that the urban activity produces a serious and negative effect on the water quality, thus constituting a sanitary risk and may have a major impact on the trophic status of the Potrero de los Funes dam. As case study, we report on the use of General Quality Index (GQI) to evaluate spatial and seasonal changes in the water quality of Potrero de los Funes River. Results revealed a significant degradation of the water quality at RP₂ and RP₃.     

A synchronized amphibian metamorphosis assay as an improved tool to detect thyroid hormone disturbance by endocrine disruptors and apolar sediment extracts

Amphibian metamorphosis assays are used to evaluate potential effects of endocrine disrupting compounds on the thyroid hormone axis. In this study, Xenopus laevis tadpoles are kept in a solution of 0.2% thiourea (TU) to arrest and synchronise them in their development. The advantage of this synchronized amphibian metamorphosis assays is that synchronised tadpoles are available at any time to start metamorphosis experiments, and experimental groups are much more homogenous at the start of experimental exposure compared with groups selected from an untreated pool of animals. The water volume per animal was kept constant throughout the experimental period to overcome the influence of declining numbers of animals per aquarium due to metamorphosis and mortality on the density dependent development of the remaining tadpoles. Clophen A50 (a technical PCB mixture), the single congener 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and apolar sediment extracts that were previously tested positive in the T-Screen, an in vitro proliferation assay for thyroid hormone disruption, were tested in the Synchronized Amphibian Metamorphosis Assay. Endpoints studied were mortality, malformations, body weight, and percentage of metamorphosed froglets at the end of the 60-day experimental period, percentage of tadpoles in different developmental stages, and developmental stage-dependent awarded penalty points. Dietary exposure to Clophen A50 (0.2-50mg/kg food) resulted in a significant increased percentage of tadpoles that did not pass metamorphosis at concentrations higher than 2mg/kg food. Time until metamorphosis in those animals that were able to metamorphose after the 60-days experimental period was significantly decreased. Dietary exposure to PCB 77, a congener that can be readily metabolised, did not result in significant effects in any exposure group (2-500 microg/kg food). Apolar sediment extracts from two of the three sites that are contaminated with a wide variety of chemicals significantly decreased the percentage of metamorphosed animals and significantly increased the number of tadpoles that remained in early and late metamorphic stages. These effects already occurred when the extracts where diluted more than 1000 times (on an organic carbon base) compared to environmental concentrations. The rank of potency was comparable to results obtained with the T-screen. This suggests the presence of thyroid hormone disrupting compounds in the aquatic environment and possible effects of such compounds on animal development in the wild.     

Treibhausgasemissionen zukünftiger Erdgasbereitstellung für Deutschland

Ohne Zusammenfassung Original erschienen in UWSF – Z Umweltchem ?kotox 20(2):133–144 (2008) DOI: Herausgeber: Martin Pehnt und Eckard Helmers     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

CHemical and Biological Assessment of an Urban, Estuarine marsh in Northeastern New Jersey USA

Oritani Marsh in the Hackensack Meadowlands of urbanized northeastern New Jersey USA was assessed in 2000 for vegetation, soil/sediment chemistry, abundance/diversity of benthic invertebrates, and bird and mammal usage. Vegetatively, both marsh and uplands are dominated by tall, dense Phragmites australis. Small patches (less than 2 hectares total) dominated by Spartina spp. were found at the lowest elevations. Soil/sediment cores were sliced into 5 intervals and analyzed for metals, pesticides and volatile/semivolatile organic compounds. Thirteen locations had at least one chemical above Long et al.’s [Environmental Management, 19, 1995, 81--97] “Effects Range-Median” (ERM). Seven metals and nine organics exceeded ERM in at least one sample, with mercury showing the most exceedances. The surface 15 cm interval was generally more contaminated with metals than the 15 to 30 cm interval; the reverse was true for semivolatile organic compounds. Twenty taxa of benthic macroinvertebrates were collected, with each location producing from 1 to 9 taxa. Abundance ranged from 11 to 3,889 individuals/m². Number of taxa was moderately (r ² between 0.40 and 0.70) negatively correlated with zinc, beryllium, nickel and arsenic concentrations; no other chemical’s r ² was above 0.25. Diversity was moderately negatively correlated with arsenic and beryllium. These correlations were unexpected: zinc, beryllium, nickel and arsenic were not the chemicals found at the highest concentrations relative to benchmarks. Number of taxa, abundance and diversity were moderately (negatively) correlated with elevation; organic carbon was moderately (positively) correlated with abundance. All other correlations were weak (r ² < 0.35). Live traps captured only one mammal species, the meadow jumping mouse. Bird observations revealed 39 species, dominated by a few common species.