Copper complexation by dissolved organic matter and uncertainty assessment of their stability constants

The interaction of Cu with dissolved organic matter (DOM, extracted from an organic forest floor) was investigated and the resulting data was evaluated in terms of their uncertainty. The speciation of Cu over ‘free’ Cu (as analysed by diffusive gradients in thin films (DGT)), dissolved Cu–DOM complexes and precipitated Cu–DOM was determined as a function of pH (3.5, 4.0 and 4.5) and Cu/C ratio. The dissolved organically bound fraction was highest at pH 4.5, but this fraction decreased with increasing Cu/C ratio, which was observed for all pH levels. In the range of Cu/C=7×10⁻⁵–2.3×10⁻² (mol/mol) the precipitated fraction was very small. The speciation of both Al and Fe was not affected by increasing Cu concentrations. From a continuous distribution model using the Scatchard approach, we calculated the optimal fit and corresponding upper and lower 95% uncertainty bounds of the overall stability constants (K_o) with the shuffled complex evolution Metropolis (SCEM) algorithm. Although the optimal equation fitted the data very well, the uncertainty of the, according to literature, most reliable approach to establish stability constants, was still large. Accordingly, the usually reported intrinsic stability constants exhibited large uncertainty ranging from logK_i=6.0–7.1 (optimal 6.7) for pH 3.5, logK_i=6.5–7.1 (optimal 6.8) for pH 4.0, and logK_i=6.4–7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH.     

Bumblebees as model organisms to study male sexual selection in social insects

Social-insect males are often regarded as being merely short-lived "flying sperm containers", which ignores their potential influence on females and paternity patterns as found in other animals. Consequently, social-insect males have received only marginal attention and sexual selection has almost never been studied in these species. Here I present a review of the mating biology of bumblebees (Bombus spp.), which are the best-studied social insects to date. I follow a male's pathway from his birth until he successfully contributes to the next generation, and show that males have evolved adaptations and behaviors to influence paternity patterns at various stages of their life, which are similar to those exhibited by males of non-social insects. By comparing the available bumblebee data with more sparse studies of male reproductive behavior in other social Hymenoptera, I argue that such male adaptations may indeed be widespread in social insects. I suggest that current paradigms on sexual selection should be challenged by using social insects as model systems, because they offer unique features, and a solid theoretical background in which clear predictions can be made and appropriate experimental tests of them can be designed.Communicated by A. Cockburn     

Biogeochemical processes at the fringe of a landfill leachate pollution plume: potential for dissolved organic carbon, Fe(II), Mn(II), NH4, and CH4 oxidation

Various redox reactions may occur at the fringe of a landfill leachate plume, involving oxidation of dissolved organic carbon (DOC), CH4, Fe(II), Mn(II), and NH4 from leachate and reduction of O2, NO3 and SO4 from pristine groundwater. Knowledge on the relevance of these processes is essential for the simulation and evaluation of natural attenuation (NA) of pollution plumes. The occurrence of such biogeochemical processes was investigated at the top fringe of a landfill leachate plume (Banisveld, the Netherlands). Hydrochemical depth profiles of the top fringe were captured via installation of a series of multi-level samplers at 18, 39 and 58 m downstream from the landfill. Ten-centimeter vertical resolution was necessary to study NA within a fringe as thin as 0.5 m. Bromide appeared an equally well-conservative tracer as chloride to calculate dilution of landfill leachate, and its ratio to chloride was high compared to other possible sources of salt in groundwater. The plume fringe rose steadily from a depth of around 5 m towards the surface with a few meters in the period 1998-2003. The plume uplift may be caused by enhanced exfiltration to a brook downstream from the landfill, due to increased precipitation over this period and an artificial lowering of the water level of the brook. This rise invoked cation exchange including proton buffering, and triggered degassing of methane. The hydrochemical depth profile was simulated in a 1D vertical reactive transport model using PHREEQC-2. Optimization using the nonlinear optimization program PEST brought forward that solid organic carbon and not clay minerals controlled retardation of cations. Cation exchange resulted in spatial separation of Fe(II), Mn(II) and NH4 fronts from the fringe, and thereby prevented possible oxidation of these secondary redox species. Degradation of DOC may happen in the fringe zone. Re-dissolution of methane escaped from the plume and subsequent oxidation is an explanation for absence of previously present nitrate and anaerobic conditions in pristine groundwater above the plume. Stable carbon isotope (delta13C) values of methane confirm anaerobic methane oxidation immediately below the fringe zone, presumably coupled to reduction of sulfate, desorbed from iron oxide. Methane must be the principle reductant consuming soluble electron-acceptors in pristine groundwater, thereby limiting NA for other solutes including organic micro-pollutants at the fringe of this landfill leachate plume.     

High intervality explained by phylogenetic constraints in host-parasite webs

The finding of invariant structures in species interaction webs is of central importance for ecology, with the greatest challenge remaining the elucidation of the processes governing these universal web patterns. Here we quantify the degree of intervality of seven fish-metazoan and 33 mammal-flea webs, i.e., the number of irreducible gaps in parasite diets along the host spectrum, and then challenge the idea that some invariant structures may emerge in host-parasite webs. Using a null model of random links between parasite and host species we find that empirical host-parasite webs exhibit a strong bias toward contiguity of parasite diet, i.e., toward intervality. Going one step further, we demonstrate that a null model with phylogenetic constraints on host-parasite links produced webs very similar to empirical ones, particularly when phylogenetic constraints occur at the family level, that is, when two hosts from the same family are more likely to be infected than two random hosts. In addition, we propose a new standardized measure of intervality which describes a novel "facet" of natural networks as it is independent of connectance or web size. We suggest using this measure as a surrogate of web maturity or saturation as phylogenetic constraints can drive webs toward intervality.     

A comparison of fine particle and aerosol strong acidity at the interface zone (1540 m) and within (452 m) the planetary boundary layer of the Great Gulf and Presidential-Dry River Class I Wildernesses on the Presidential Range,New Hampshire USA

Mount Washington, NH in the White Mountain National Forest, is flanked to the north-northeast and south by two Class I Wilderness areas, the Great Gulf and Presidential Range-Dry River Wildernesses, respectively. The Clean Air Act protects Class I Area natural resource values from air pollution. Aerosol sulfate, a fine particulate component that is often transported long distances, is a known contributor to visibility degradation and acidic deposition. We examined summertime fine particulate aerosol mass and sulfate, strong acidity and ammonium concentrations from 1988 to 2007 on Mount Washington at two elevations, 452 and 1540 m (msl). The former site is often within, and the latter at the interface of, the planetary boundary layer. Comparisons of sampling interval durations (10 and 24 h) and site vs. site are made. We also examine the extent to which aerosol sulfate is neutralized.Ten hour (daytime) compared to 24 h samples have higher mass and aerosol sulfate concentrations, however paired samples are well correlated. Fine mass concentrations compared between the 452 m and 1540 m sites (standard temperature and pressure corrected) show a weak positive linear relationship with the later being approximately 32% lower. We attribute the lack of a strong correlation to the facts that the 1540 m site is commonly at the interface of and even above the regional planetary boundary layer in summer and that it can intercept different air masses relative to the 452 m site. Sulfate is ～18% lower at the higher elevation site, but comprises a greater percentage of total fine mass; 42% compared to 37% for the high and low elevation site, respectively. Aerosol strong acidity was found to increase with increasing sulfate concentrations at both sites. Further the ratio of hydrogen to sulfate ion was greater in 24 h than 10 h samples at the higher elevation site likely due to overnight transport of fresh acidic aerosols.     

Seasonal dynamics in leachate hydrochemistry and natural attenuation in surface run-off water from a tropical landfill

Open waste dump systems are still widely used in Indonesia. The Jatibarang landfill receives 650-700 tons of municipal waste per day from the city of Semarang, Central Java. Some of the leachate from the landfill flows via several natural and collection ponds to a nearby river. The objectives of the study were to identify seasonal landfill leachate characteristics in this surface water and to determine the occurrence of natural attenuation, in particular the potential for biodegradation, along the flow path. Monthly measurements of general landfill leachate parameters, organic matter-related factors and redox-related components revealed that leachate composition was influenced by seasonal precipitation. In the dry season, electrical conductivity and concentrations of BOD, COD, N-organic matter, ammonia, sulphate and calcium were significantly higher (1.1-2.3 fold) than during the wet season. Dilution was the major natural attenuation process acting on leachate. Heavy metals had the highest impact on river water quality. Between the landfill and the river, a fivefold dilution occurred during the dry season due to active springwater infiltration, while rainwater led to a twofold dilution in the wet season. Residence time of leachate in the surface leachate collection system was less than 70 days. Field measurements and laboratory experiments showed that during this period hardly any biodegradation of organic matter and ammonia occurred (less than 25%). However, the potential for biodegradation of organic matter and ammonia was clearly revealed during 700 days of incubation of leachate in the laboratory (over 65%). If the residence time of leachate discharge can be increased to allow for biodegradation processes and precipitation reactions, the polluting effects of leachate on the river can be diminished.     

Detection of fetal cells in transcervical samples and prenatal diagnosis of chromosomal abnormalities

Transcervical samples collected by lavage, aspiration, and cytobrush from women between 6 and 13 weeks of gestation were tested for the presence of fetal cells using fluorescence in situ hybridization (FISH) with probes for chromosomes X, Y, 1, and 21, and by polymerase chain reaction (PCR) amplification of DNA sequences derived from chromosomes X, Y, and 21. With a few exceptions, a good correlation was observed between the results of sexing the fetuses using FISH or PCR on transcervical cell (TCC) samples retrieved by lavage and those obtained by testing fetal (placental) tissue. In a comparative study between TCC samples collected by lavage or cytobrush, the sex of the fetus was correctly diagnosed by PCR amplification of a Y-derived DNA sequence. Variable results were observed with samples obtained by aspiration, mainly because this procedure was found to be more prone to failure to remove thick mucus without previous injection of physiological saline. Chromosome 21-derived small tandem repeats (STRs) of fetal origin were successfully detected in about 40 per cent of TCC samples recovered by lavage. Two cases of chromosomal abnormalities, one of trisomy 21 and one of triploidy, were detected in TCC samples in the course of our investigations.