Elimination of endocrine disrupting chemicals nonylphenol and bisphenol A and personal care product ingredient triclosan using enzyme preparation from the white rot fungus Coriolopsis polyzona

The biocatalytic elimination of the endocrine disrupting chemicals (EDC) nonylphenol (NP) and bisphenol A (BPA) and the personal care product ingredient triclosan (TCS) by the enzyme preparation from the white rot fungus Coriolopsis polyzona was investigated. Analysis of variance methodology showed that the pH and the temperature are statistically significant factors in the removal of NP, BPA and TCS. The elimination of NP and TCS was best at a temperature of 50 degrees C and the disappearance of BPA at 40 degrees C, whereas the most suitable pH for all three micropollutants was 5. After a 4-h treatment of the three target compounds at concentrations of 5 mg l(-1) all of the NP and BPA were eliminated. In the case of TCS, 65% was removed after either a 4 or an 8-h treatment. The utilisation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) in the laccase/mediator system significantly increased the efficiency of the enzymatic treatment. The elimination of NP and BPA was directly associated with the disappearance of the estrogenic activity. Mass spectrometry analysis showed that the enzymatic treatment produced high molecular weight metabolites through a radical polymerization mechanism of NP, BPA and TCS. These oligomers were produced through the formation of C-C or C-O bonds. The polymerization of NP produced dimers, trimers, tetramers and pentamers which had molecular weights of 438, 656, 874 and 1092 amu respectively. The polymerization of BPA produced dimers, trimers and tetramers which had molecular weights of 454, 680 and 906 amu. Finally, the polymerization of TCS produced dimers, trimers and tetramers which had molecular weights of 574, 859 and 1146 amu.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

Use of inert C&D materials for seawall foundation: quality control measures

The technical viability of using inert construction and demolition (C&D) materials for the construction of seawall and breakwater foundations has been established by laboratory testing of the materials, numerical analysis of foundation stability, and a pilot field-scale engineering performance evaluation. However, quality control measures are still required so that only suitable materials are used for seawall and breakwater foundation construction. The development of different quality control measures for different site conditions is presented in this paper. The rationale, practicality, and implementation of these quality control measures are also discussed.     

A review of Henry's law coefficients for chlorine-containing C1 and C2 hydrocarbons

Experimentally determined Henry's law coefficients of 18 chlorinated C(1) and C(2) hydrocarbons reported in the literature as a function of temperature and at the single temperatures 20 and 25 degrees C were compiled and converted to common units of concentration and pressure: K(H) (moldm(-3)atm(-1)). The individual values are plotted in the ln(K(H)) versus reciprocal absolute temperature coordinate frame, data not in harmony with others were deleted, and the resulting data sets treated by linear regression analysis to derive averaged parameters in the general equation ln(K(H))=A+B/T. The quality of the evaluation was further checked by comparison of values calculated from the resulting parameter values with averages obtained from the direct measurements at 20 degrees C. Good agreement was observed for 15 compounds, larger discrepancies arise only for chloroethane, 1,2-dichloroethane and hexachloroethane. In all three cases the data base is poor and needs to be improved. The results are used to derive heats of solution for the C(1) and C(2) chlorinated hydrocarbons in water, Gibbs energies of solution and standard Henry's law coefficients at 298.15K. Henry's law coefficients calculated from the ratio of solubility of the compound in water and the saturation vapor pressure of the pure compound reported by Sangster [Sangster, J.M., 2003. Henry's law constants for compounds stable in water. In: Fogg, P.G.T., Sangster, J.M. (Eds.), Chemicals in the Atmosphere - Solubility, Sources and Reactivity. Wiley, Chichester, West Sussex, England, pp. 255-397] provide good agreement with the experimental data in eight out of eleven cases treated.     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

Toxic effects of low concentrations of Cu on nodulation of cowpea (Vigna unguiculata)

Although Cu is phytotoxic at Cu(2+) activities as low as 1-2 microM, the effect of Cu(2+) on the nodulation of legumes has received little attention. The effect of Cu(2+) on nodulation of cowpea (Vigna unguiculata (L.) Walp. cv. Caloona) was examined in a dilute solution culture system utilising a cation exchange resin to buffer solution Cu(2+). The nodulation process was more sensitive to increasing Cu(2+) activities than both shoot and root growth; whilst a Cu(2+) activity of 1.0 microM corresponded to a 10% reduction in the relative yield of the shoots and roots, a Cu(2+) activity of 0.2 microM corresponded to a 10% reduction in nodulation. This reduction in nodulation with increasing Cu(2+) activity was associated with an inhibition of root hair formation in treatments containing > or =0.77 microM Cu(2+), rather than to a reduction in the size of the Rhizobium population.     

Contaminant degradation in physically and chemically heterogeneous aquifers

This paper examines the importance of the correlation between hydraulic conductivity (K) and degradation rate constant (k) during the transport of reactive contaminants in heterogeneous aquifers. We simulated reactive transport in an ensemble of two-dimensional heterogeneous aquifers. Two sets of transport simulations were conducted: one in which a perfect positive correlation was assumed between ln(K) and ln(k), and one in which a perfect negative correlation was assumed. We found that the sign of the correlation has important consequences for the contaminant transport. Qualitatively, a negative correlation leads to significantly more pronounced "fingering" of the contaminant plume than does a positive correlation, with potentially important consequences for downgradient receptors. Quantitatively, the expected behavior (as quantified by the contaminant mass remaining in the aquifer) is statistically different between the positive and negative cases: on average, more contaminant mass persists when K and k are negatively correlated. Also, the negative correlation leads to more variability between realizations of the ensemble, whereas a positive correlation induces relatively little variability between realizations. We discuss the implications of these findings for the management of contaminated aquifers.     

Maternal investment in rhesus macaques (Macaca mulatta): reproductive costs and consequences of raising sons

Maternal investment in offspring is expected to vary according to offspring sex when the reproductive success of the progeny is a function of differential levels of parental expenditure. We conducted a longitudinal investigation of rhesus macaques to determine whether variation in male progeny production, measured with both DNA fingerprinting and short tandem repeat marker typing, could be traced back to patterns of maternal investment. Males weigh significantly more than females at birth, despite an absence of sex differences in gestation length. Size dimorphism increases during infancy, with maternal rank associated with son’s, but not daughter’s, weight at the end of the period of maternal investment. Son’s, but not daughter’s, weight at 1 year of age is significantly correlated with adult weight, and male, but not female, weight accounts for a portion of the variance in reproductive success. Variance in annual offspring output was three- to fourfold higher in males than in females. We suggest that energetic costs of rearing sons could be buffered by fetal delivery of testosterone to the mother, which is aromatized to estrogen and fosters fat accumulation during gestation. We conclude that maternal investment is only slightly greater in sons than in daughters, with mothers endowing sons with extra resources because son, but not daughter, mass has ramifications for offspring sirehood. However, male reproductive tactics supersede maternal investment patterns as fundamental regulators of male fitness. Received: 23 July 1999 / Received in revised form: 23 February 2000 / Accepted: 13 March 2000     

Multiple song repertoire characteristics in the willow warbler (Phylloscopus trochilus): correlations with female choice and offspring viability

Male willow warblers have song repertoires which vary in complexity along several dimensions. We examined whether female choice, as measured by date of pairing, was based on these song characteristics in 4 different years. Pairing date was negatively correlated with song repertoire size in 1 year, and with song versatility in another year, but there was no consistent effect of any song characteristic on pairing throughout the years or in the pooled sample. The variable that best explained how soon a male pairs is male arrival date (only males that had settled territories before the first female arrived were considered in the analysis). This correlation is consistently significant in all years. This is most parsimoniously interpreted as females choosing some habitat characteristic in the same way that males do. A small percentage of males (8.3%) attracted and paired with a second female. The likelihood of becoming polygynous was not explained by any measured song characteristic, but it was related to arrival date: early males were more likely to pair with two females. Males with large repertoires fledged more young in their primary nests, and there was a trend for the offspring of these males to have a greater probability of being recruited into the population. In conclusion, the results show that in most years there is no sexual selection by female preference on song characteristics, although the data on reproductive success is consistent with the idea of repertoire size being an indicator of male quality. Received: 4 June 1999 / Received in revised form: 1 December 1999 / Accepted: 31 December 1999