Plutonium isotopes in the lower reaches of the River Rhône over the period 1945-2000: fluxes towards the Mediterranean Sea and sedimentary inventories

Plutonium isotopes in the Rh?ne River originate from both the weathering of the catchment basin contaminated by global atmospheric fallout, and the liquid effluents released from the Marcoule reprocessing plant since 1961. Due to a new treatment process applied to the liquid effluents, a decrease of two orders of magnitude in the industrial plutonium discharged into the River Rh?ne has been registered from 1991. Today, 238Pu industrial inputs to the River Rh?ne are still about 10 times higher than those derived from global fallout, while 239+240Pu inputs from industrial and global fallout sources are of similar importance, i.e. 1 GBq y(-1). Our results indicate that the river sedimentary compartment act either as a sink or a delayed-source term of plutonium for the freshwaters depending on the hydraulic regime and flood events. This compartment may then represent an important industrial delayed-source term for the River Rh?ne freshwaters in the coming years as the Marcoule reprocessing plant is being dismantled. These results were obtained from samples collected from the lower course of the River Rh?ne over the 1987-1998 period and analysed for 238Pu and 239+240Pu activities. Both river sedimentary inventories of plutonium isotopes and effective outputs from the River Rh?ne towards the Gulf of Lions have been estimated for each year over the 1945-2000 period. Regarding 239+240Pu, the sedimentary inventory accumulated since 1945 is estimated to be 172+/-35 GBq. If mobile, this amount represents a significant delayed-source term of plutonium on the scale of the Rh?ne watershed.     

Seasonality and the evolutionary divergence of plant parasites

The coexistence of closely related plant parasites is widespread. Yet, understanding the ecological determinants of evolutionary divergence in plant parasites remains an issue. Niche differentiation through resource specialization has been widely researched, but it hardly explains the coexistence of parasites exploiting the same host plant. Time-partitioning has so far received less attention, although in temperate climates, parasites may specialize on either the early or the late season. Accordingly, we investigated whether seasonality can also promote phenotypic divergence. For plant parasites, seasonality generally engenders periodic host absence. To account for abrupt seasonal events, we made use of an epidemic model that combines continuous and discrete dynamics. Based on the assumption of a trade-off between in-season transmission and inter-season survival, we found through an "evolutionary invasion analysis" that evolutionary divergence of the parasite phenotype can occur. Since such a trade-off has been reported, this study provides further ecological bases for the coexistence of closely related plant parasites. Moreover, this study provides original insights into the coexistence of sibling plant pathogens which perform either a single or several infection cycles within a season (mono- and polycyclic diseases, or uni- and multivoltine life cycles).     

Determination of atrazine in surface waters by combination of POCIS passive sampling and ELISA detection

Polar organic compound integrative samplers (POCIS) in combination with instrumental techniques such as LC-MS-MS were previously used to monitor environmental pollutants but the performance of alternative immunochemical methods such as ELISA (enzyme-linked immunosorbent assay) has been explored less. In the present study, POCIS technology was applied to surface water sampling in the Czech Republic, and ELISA was used as a detection technique for the herbicide atrazine. In the first study, 28 samples from streams around small municipal waste water treatment plants (WWTPs) were collected using two different devices (POCISpest and POCISpharm) over the course of 21 days. Elevated atrazine concentrations (up to 25 ng per POCIS) were found in samples down-stream of WWTPs. This observation was also confirmed in another two year study (4 sampling periods) investigating 7 river sites around a major city of Brno as well as the inlet and outlet of the city's WWTP. High atrazine levels were systematically determined at the outlet from the WWTPs (120-605 ng per POCIS). A decreasing trend in the atrazine concentrations in rivers around the city of Brno has been observed, with the highest levels observed within the first sampling period in spring 2007 (100-600 ng per POCIS, with an extreme value of 2760 ng per POCIS). Results of the atrazine ELISA were closely correlated with LC-MS/MS, which confirmed good applicability of ELISA as a cost-effective screening tool.     

Estimating metabolic rate for butadiene at steady state using a Bayesian physiologically-based pharmacokinetic model

In a study of 133 volunteer subjects, demographic, physiologic and pharmacokinetic data through exposure to 1,3-Butadiene (BD) were collected in order to estimate the percentage of BD concentration metabolized at steady state, and to determine whether this percentage varies across gender, racial, and age groups. During the 20 min of continuous exposure to 2 parts per million (ppm) of BD, five measurements of exhaled concentration were made on each subject. In the following 40 min washout period, another five measurements were collected. A Bayesian hierarchical compartmental physiologically-based pharmacokinetic model (PKPB) was used. Using prior information on the model parameters, Markov Chain Monte Carlo (MCMC) simulation was conducted to obtain posterior distributions. The overall estimate of the mean percent of BD metabolized at steady state was 12.7% (95% credible interval: 7.7–17.8%). There was no significant difference in gender with males having a mean of 13.5%, and females 12.3%. Among the racial groups, Hispanic (13.9%), White (13.0%), Asian (12.1%), and Black (10.9%), the significant difference came from the difference between Black and Hispanic with a 95% credible interval from −5.63 to −0.30%. Those older than 30 years had a mean of 12.2% versus 12.9% for the younger group; although this was not a statistically significant difference. Given a constant inhalation input of 2 ppm, at steady state, the overall mean exhaled concentration was estimated to be 1.75ppm (95% credible interval: 1.64–1.84). An equivalent parameter, first-order metabolic rate constant, was also estimated and found to be consistent with the percent of BD metabolized at steady state across gender, race, and age strata.     

Sex pheromone composition and reproductive isolation in two Busseola species (Lepidoptera: Noctuidae) in Kenya

Closely related species provide an interesting and useful model to understand mate communication diversification. Pre-mating isolation is the result of selection processes and is achieved by utilization of different sex pheromones, but also by different ecological and life traits such as geographic distribution, host-plant specialization and allochrony of sexual behavior. Here, we report sex pheromone identifications and pre-mating isolation of two closely related species of stemborers: Busseola segeta and the yet undescribed Busseola nov. sp., developing on different host-plants and in different geographical locations in Kenya. GC–MS analyses showed that the two species produced the same pheromone components, but in slight different ratios. The respective synthetic pheromone mixtures tested in the field were attractive for males of each species. The low inter-specific variation in the pheromone mixture would allow possible interbreeding in case of accidental introduction of both species in the same environment. Under laboratory conditions, allochrony of the mating period is total and might prevent interbreeding if confirmed in natural conditions. This point would ensure the reproductive isolation between the two species in case of modifications of ecological factors. This study and the chemical structures of the identified pheromone components clearly demonstrate that these Busseola species are closely related although they differ in morphology.     

Determinants of brominated flame retardants in breast milk from a large scale Norwegian study

Brominated flame retardants (BFRs), particularly polybrominated diphenyl ethers (PBDEs), are widely present in human populations. In order to investigate human exposure pathways and associations with socioeconomic and lifestyle factors, 393 breast milk samples from mothers living in various regions throughout Norway were analyzed. Up to ten PBDE congeners were measured in all the samples, hexabromocyclododecane (HBCD) and BDE-209 in subsets of 310 and 46, respectively. The median concentrations of the sum of the seven most prominent PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183), BDE-209 and HBCD were 2.1, 0.32 and 0.86 ng/g lipids, respectively. These concentrations are comparable to the levels generally observed in human populations in Europe. The frequency distributions were quite skewed with long tails towards higher concentrations. Maternal age, parity, education, having a cohabitant employed as electrician, and ventilation were factors significantly associated with some of the BFRs, although these factors only explained a small amount of the variability (R² 0.04–0.16). The mothers' diet was not found to influence the breast milk PBDE and HBCD levels. Our results show that sources other than the diet are important for the variability seen in breast milk BFR concentrations and that exposure from the indoor atmosphere should be emphasized in future studies.     

Evolution of bacterial community during bioremediation of PAHs in a coal tar contaminated soil

The monitoring of a windrow treatment applied to soil contaminated by mostly 2-, 3- and 4-ring PAHs produced by coal tar distillation was performed by following the evolution of both PAH concentration and the bacterial community. Total and PAH-degrading bacterial community structures were followed by 16S rRNA PCR-DGGE in parallel with quantification by bacterial counts and 16 PAH measurements. Six months of biological treatment led to a strong decrease in 2-, 3- and 4-ring PAH concentrations (98, 97 and 82% respectively). This result was associated with the activity of bacterial PAH-degraders belonging mainly to the Gamma-proteobacteria, in particular, the Enterobacteria and Pseudomonas genera, which were detected over the course of the treatment. This group was considered to be a good bioindicator to determine the potential PAH biodegradation of contaminated soil. Conversely, other species, like the Beta-proteobacteria, were detected after 3months, when 2-, 3- and 4-ring PAHs were almost completely degraded. Thus, presence of the Beta-proteobacteria group could be considered a good candidate indicator to estimate the endpoint of biotreatment of this type of PAH-contaminated soil.     

Occurrence and temporal variations of TMDD in the river Rhine,Germany

Background, aim, and scope

The chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104® and the related ethoxylates are also available as Surfynol® 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5?µg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008.

Materials and methods

The sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city Mannheim. The water from the middle of the river (MWL2) is largely composed of water from the upper Rhine. Water samples were collected in 1-L bottles by an automatic sampler. The water samples were concentrated by use of solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). The quantification was carried out with the internal standard method. Based on these results, concentration variations were determined for the day profiles and week profiles. The total number of analyzed samples was 219.

Results

The results of this study provide information on the temporal concentration variability of TMDD in river Rhine in a cross section at one particular sampling point (443.3 km). TMDD was detected in all analyzed water samples at high concentrations. The mean concentrations during the 2 days were 314 ng/L in MWL1, 246 ng/L in MWL2, and 286 ng/L in MWL4. The variation of concentrations was low in the day profiles. In the week profiles, a trend of increasing TMDD concentrations was detected particularly in January 2008, when TMDD concentrations reached values up to 1,330 ng/L in MWL1. The mean TMDD concentrations during the week profiles were 540 ng/L in MWL1, 484 ng/L in MWL2, and 576 ng/L in MWL4. The loads of TMDD were also determined and revealed to be comparable in all three sections of the river. The chemical plant located at the left side of the Rhine is not contributing additional TMDD to the river. The load of TMDD has been determined to be 62.8 kg/d on average during the entire period. By extrapolation of data obtained from seven week profiles the annual load was calculated to 23 t/a.

Discussion

The permanent high TMDD concentrations during the investigation period indicate an almost constant discharge of TMDD into the river. This observation argues for effluents of municipal wastewater treatment plants as the most likely source of TMDD in the river. Another possible source might be the degradation of ethoxylates of TMDD (Surfynol® series 400), in the WWTPs under formation of TMDD followed by discharge into the river. TMDD has to be considered as a high-production-volume (HPV) chemical based on the high concentrations found in this study. In the United States, TMDD is already in the list of HPV chemicals from the Environmental Protection Agency (EPA). However, the amount of TMDD production in Europe is unknown so far and also the biodegradation rates of TMDD in WWTPs have not been investigated.

Conclusions

TMDD was found in high concentrations during the entire sampling period in the Rhine river at the three sampling points. During the sampling period, TMDD concentrations remained constant in each part of the river. These results show that TMDD is uniformly distributed in the water collected at three sampling points located across the river. ‘Waves’ of exceptionally high concentrations of TMDD could not be detected during the sampling period. These results indicate that the effluents of WWTPs have to be considered as the most important sources of TMDD in river Rhine.

Recommendations and perspectives

Based also on the occurrence of TMDD in different surface waters of Germany with concentrations up to 2,500 ng/L and its presence in drinking water in the USA, more detailed investigations regarding its sources and distribution in the aquatic environment are required. Moreover, the knowledge with respect to its ecotoxicity and its biodegradation pathway is scarce and has to be gained in more detail. Further research is necessary to investigate the rate of elimination of TMDD in municipal and industrial wastewater treatment plants in order to clarify the degradation rate of TMDD and to determine to which extent effluents of WWTPs contribute to the input of TMDD into surface waters. Supplementary studies are needed to clarify whether the ethoxylates of TMDD (known as Surfynol 400® series) are hydrolyzed in the aquatic environment resulting in formation of TMDD similar to the well known cleavage of nonylphenol ethoxylates into nonylphenols. The stability of TMDD under anaerobic conditions in groundwater is also unknown and should be studied.

     

Effects of mono-(2-ethylhexyl) phthalate (MEHP) on chicken germ cells cultured in vitro

In recent decades, many toxicological tests based on in vivo or in vitro models, mainly from mammalian (rat–mouse) and fish species, were used to assess the risks raised by contact or ingestion of molecules of pharmaceutical, agricultural, or natural origin. But no, or few, in vitro tests using other non-mammalian models such as bird have been explored despite their advantages: the embryonic gonads of birds have a high plasticity of development sensitive to estrogen, and sperm production is nearly two times faster than in rodents. Hence, we have established an in vitro culture of germ cells and somatic cells from chicken post-natal testis, and we have evaluated the sensitivity against the endocrine disruptor compound mono-(2-ethylhexyl) phthalate (MEHP) in comparison to previous studies using rodent and human models. After 96 h of exposure in presence of 10 μM MEHP, chicken seminiferous tubules cultures present a structural alteration, a reduction in cell proliferation and in germ cells population. Apoptosis of germ and somatic cells increases in presence of 1 μM MEHP. Furthermore, MEHP does not affect inhibin B and lactate production by Sertoli cells. These results are in accordance with previous studies using rat, mice, or human culture of testicular cells and in similar range of exposures or even better sensitivity for some “end-points” (biological parameters). In conclusion, the establishment of this postnatal testicular cells culture could be considered as an alternative method to in vivo experiments frequently used for evaluating the impact on the terrestrial wildlife species. This method could be also complementary to mammal model due to the limiting number of animals used and its elevated sensitivity.