Transport of volatile compounds in porous media in the presence of a trapped gas phase

The presence of an immobile gaseous phase in an otherwise-saturated porous medium affects the transport of volatile compounds. The linear theory of partitioning tracers suggests that a volatile tracer introduced into such a system should be retarded with a constant retardation factor. Using high concentrations, however, the saturation of the gaseous phase will change as an effect of the tracer test itself. Competitive gas transfer among all volatile compounds and the change of saturation may lead to tracer concentrations that are temporarily higher than those injected. We analyze the system in the framework of the coherence theory by Helfferich [Soc. Pet. Eng. J. 21 (1) (1981) 51]. The governing equations are formulated as functions of total concentration, i.e., the mass of solutes in all phases per pore volume. Neglecting dispersion and mass-transfer kinetics, we derive the characteristic form of the resulting system of hyperbolic equations. In a system with N volatile compounds, a variation of the concentrations splits up into N waves, each traveling with its own characteristic velocity. If the presence of a gaseous phase is sustained, one wave will be a standing one. We perform numerical model calculations for tracers with various Henry's law coefficients and show that the results agree with the semi-analytical solution obtained by coherence theory.     

Advection and resulting CO2 exchange uncertainty in a tall forest in central Germany

Potential losses by advection were estimated at Hainich Forest, Thuringia, Germany, where the tower is located at a gentle slope. Three approaches were used: (1) comparing nighttime eddy covariance fluxes to an independent value of total ecosystem respiration by bottom-up modeling of the underlying processes, (2) direct measurements of a horizontal CO2 gradient and horizontal wind speed at 2 m height in order to calculate horizontal advection, and (3) direct measurements of a vertical CO2 gradient and a three-dimensional wind profile in order to calculate vertical advection. In the first approach, nighttime eddy covariance measurements were compared to independent values of total ecosystem respiration by means of bottom-up modeling of the underlying biological processes. Turbulent fluxes and storage term were normalized to the fluxes calculated by the bottom-up model. Below a u(*) threshold of 0.6 m/s the normalized turbulent fluxes decreased with decreasing u(*), but the flux to the storage increased only up to values less than 20% of the modeled flux at low turbulence. Horizontal advection was measured by a horizontal CO2 gradient over a distance of 130 m combined with horizontal wind speed measurements. Horizontal advection occurred at most of the evenings independently of friction velocity above the canopy. Nevertheless, horizontal advection was higher when u(*) was low. The peaks of horizontal advection correlated with changes in temperature. A full mass balance including turbulent fluxes, storage, and horizontal and vertical advection resulted in an increase of spikes and scatter but seemed to generally improve the results from the flux measurements. The comparison of flux data with independent bottom-up modeling results as well as the direct measurements resulted in strong indications that katabatic flows along the hill slope during evening and night reduces the measured apparent ecosystem respiration rate. In addition, anabatic flows may occur during the morning. We conclude that direct measurements of horizontal and vertical advection are highly necessary at sites located even on gentle hill slopes.     

Xenoestrogens in the River Elbe and its tributaries

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

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.     

Partitioning of dioxins and dibenzofurans: Whole blood, blood plasma and adipose tissue

It has become relatively common to estimate human dioxin body burden and to document dioxin exposures by measuring dioxin and dibenzofuran congeners in adipose tissue, whole blood or blood plasma, and reporting these values on a lipid basis. It has not been determined whether these three types of specimens contain identical dioxin and dibenzofuran levels. This paper compares paired plasma and adipose tissue and paired whole blood and adipose tissue in analyses from two groups of patients. The first group consists of twenty U.S. veterans with paired plasma and adipose specimens. The second group consists of four German adults with whole blood compared to adipose tissue. Forty-eight analyses were performed. The results suggest that for some higher chlorinated compounds, such as OCDD, plasma lipid values may be higher than adipose lipid values, but whole blood lipid values for the higher as well as lower chlorinated PCDD/Fs may be relatively similar. On the other hand, the values for the lower chlorinated PCDD/Fs, such as TCDD, are similar in blood plasma, adipose tissue and whole blood. Total PCDD/F dioxin “toxic equivalents” are similar within each of the two series reported here, using the current “International Dioxin Toxic Equivalent” system.     

Which visibility indicators best represent a population’s preference for a level of visual air quality?

Several studies have been carried out over the past 20 or so years to assess the level of visual air quality that is judged to be acceptable in urban settings. Groups of individuals were shown slides or computer-projected scenes under a variety of haze conditions and asked to judge whether each image represented acceptable visual air quality. The goal was to assess the level of haziness found to be acceptable for purposes of setting an urban visibility regulatory standard. More recently, similar studies were carried out in Beijing, China, and the more pristine Grand Canyon National Park and Great Gulf Wilderness. The studies clearly showed that when preference ratings were compared to measures of atmospheric haze such as atmospheric extinction, visual range, or deciview (dv), there was not a single indicator that represented acceptable levels of visual air quality for the varied urban or more remote settings. For instance, using a Washington, D.C., setting, 50% of the observers rated the landscape feature as not having acceptable visual air quality at an extinction of 0.19 km^?1 (21 km visual range, 29 dv), while the 50% acceptability point for a Denver, Colorado, setting was 0.075 km^?1 (52 km visual range, 20 dv) and for the Grand Canyon it was 0.023 km^?1 (170 km visual range, 7 dv). Over the past three or four decades, many scene-specific visibility indices have been put forth as potential indicators of visibility levels as perceived by human observers. They include, but are not limited to, color and achromatic contrast of single landscape features, average and equivalent contrast of the entire image, edge detection algorithms such as the Sobel index, and just-noticeable difference or change indexes. This paper explores various scene-specific visual air quality indices and examines their applicability for use in quantifying visibility preference levels and judgments of visual air quality.

Implications: Visibility acceptability studies clearly show that visibility become more unacceptable as haze increases. However, there are large variations in the preference levels for different scenes when universal haze indicators, such as atmospheric extinction, are used. This variability is significantly reduced when the sky–landscape contrast of the more distant landscape features in the observed scene is used. Analysis suggest that about 50% of individuals would find the visibility unacceptable if at any time the more distant landscape features nearly disappear, that is, they are at the visual range. This common metric could form the basis for setting an urban visibility standard.     

Verteilung chemischer Elemente in der Nahrung und Milch stillender Mütter

Goal and Scope

The transfer of various chemical elements from maternal food into human milk was investigated. Transfer factors (hereafter TF) food/mother’s milk were taken to represent those nuclides pertinent to radiation protection in order to estimate possible radioactive burdens of breast-fed babies.

Methods

A total of 23 mothers, mainly from the Euroregion Neisse (PL, CZ, D; all being in their mature phases of lactation), took part in this study (1998–2001), for time periods between two to eight weeks (8805 samples were analyzed). The diurnal uptake of elements was determined by the duplicate method.

Results and Conclusions

TF values determined for Ag, Au, Ba, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, I, La, Mn, Mo, Nb, Ni, P, Pb, Ra, Rb, Re, Ru, Sb, Sr, Te, Th, Ti, U_o, Y, Zn, Zr were theoretically analyzed with the following result: metal ions transfer into mother’s milk mainly in coordinated states (i.e. bound to anionic ligands), with TF values which increase according to complex stabilities. Therefore it can be assessed that neither Cd nor Ba, both forming only weak complexes, pose hazards to breastfed children.

Outlook

There are relationships between transfer factors pertaining to certain elements and the amounts of others consumed by the mother; i.e. (changes in) consumption of one element influence the transfer towards women’s milk of another element. Accordingly, strategies can be developed to keep off hazardous substances — including fissiogenic radionuclides — from milk which is far more efficient than traditional isotopic dilution; however, iodide tablets are useful here, too.     

Mercury Contamination of Fish and Its Implications for Other Wildlife of the Tapajós Basin, Brazilian Amazon

Abstract: Since 1979 the gold rush in the Brazilian Amazon has caused serious environmental damage to one of the most complex ecosystems on Earth. Mainly due to the toxicity of mercury to humans, this problem has received wide public attention and prompted many studies. Although these studies have involved sampling of fish, the negative effect of mercury contamination to fish themselves and other wildlife has been largely ignored. To assess the present level of mercury contamination of fish, and its implication for fish and other animals, we collected and examined data on mercury concentration in fish of the Brazilian Amazon, especially for the Tapajós basin, between 1991 and 1996. We conclude that omnivores and piscivores that live nearer to gold mining areas in the Tapajós basin are already at high risk of mercury toxification, especially reproductive failure. Mercury concentrations in these fish are also high enough to have detrimental effects on animals at higher trophic levels. The same conclusion applies to other mercury-contaminated areas in the Brazilian Amazon. Because most Amazonian rivers or their tributaries have favorable conditions for mercury contamination, we can expect the problem to persist in the Amazon for a long time, and the consequences are likely to become more significant in the future. These conclusions have important implications for all tropical rainforests where gold mining operations have caused extensive mercury pollution.