Source and Distribution of Heavy Metals in Food†

Diet is the major route of exposure to contaminants, therefore food monitoring programs are essential to estimate the degree of human risk. We present a study undertaken in Austria dealing with the total uptake of mercury, cadmium, arsenic and lead. The dates were calculated from diet as well as from commercial food. Higher contaminated foodstuffs are registered and a comparison was made between body burden of babies and adults on the basis of bodyweight. It was pointed out, that cooked or washed food ready to eat has a lower burden of lead and cadmium than non prepared food due to household processing, which may decontaminate food to some extent’ Arsenic content was not reduced, because it is bound chemically and not primarily deposited on the surface of food such as in the case of lead. It was mentioned that the type of compound plays an important role in the assessment of action of those elements on humans.

Their biological activity is not necessarily related to their concentration in food. As in the case of selenium and chromium one has to take into consideration that there is a narrow range between benefit and harm, toxicity, and minor supply.

Therefore we conclude, that due to interactions of elements, their different biological activity and due to the difference of compounds present in food, we have to relativate the terms toxicity and essentiality. Then we can get a more profound insight into the problems of trace elements in food.     

贵阳市冬季PM_(2.5)中典型重金属元素的化学形态分析与健康风险评价

为了更准确地研究重金属的生物有效性和对环境与人体的潜在生态危害,采用改进BCR法分析了贵阳市冬季PM_(2.5)中Cu、Mn、Co、Cd、Pb这5种重金属元素的化学形态,并评价了它们的生物有效性和健康风险。结果表明:不同重金属元素形态分布存在差异,Cu主要是弱酸溶态,其次是可氧化态;Mn主要是弱酸溶态,其次是残渣态;Co没有检测出可还原态,而在其他3种形态分布比较平均;Pb和Cd绝大部分都是弱酸溶态。生物有效性系数(K)分析结果表明:重金属生物有效性强弱顺序为CdPbMnCuCo,其中Cd和Pb的K0.8,属于生物可利用性元素;Mn、Cu、Co的K值在0.4~0.7之间,属于潜在生物可利用性元素。健康风险评价表明:成人的致癌风险比儿童大,尤其Cd对成年人存在潜在的致癌风险,且成年男性高于成年女性;Mn存在潜在非致癌风险,且对儿童的风险最大。     

Molecular modeling in environmental science∗

Quantum mechanic computer models are often used in chemistry to predict properties of molecules and to simulate reaction pathways. Such models calculate bond lengths, bond angles, dihedral angles, the energy of the molecular‐orbitals (MO's), the dipole moment, the ionisation potential, and the heat of formation. These results lead to detailed information on electronic structures like bond orders, electronic charges and levels of frontier orbitals (HOMO, LUMO).

It is possible to calculate properties of ground state molecules as well as ionic and radicalic structures, or reaction intermediates and other compounds with very short lifetimes.

From the exact knowledge of electronic structure, frontier orbitals, and reaction intermediates it is possible to predict stability of chemicals in the environment but also of fictive chemicals, which are not yet synthesized. Some authors have shown that there are correlations between electronic structure and toxicity.

The most interesting models for environmental chemistry are semiempirical models, such as MINDO, MNDO or MOPAC. Theses programs are able to handle molecules with 30 and more heavy atoms (all elements without hydrogen), and it is possible to install them on main frame computers (CPU‐time several minutes to hours) and on personal computers, with coprocessors (CPU‐time several hours to a few days).

Normally the molecule is read in from a Z‐matrix (a matrix of polar coordinates of atoms connected in the molecule) and with symmetry data. Furthermore, programs are available which create a Z‐matrix from the molecular structure plotted on the screen with a mouse.     

Simulation model of universal law of school size distribution applied to southern bluefin tuna (Thunnus maccoyii) in the Great Australian Bight

A universal law of animal group size distribution correlates well to observed fish school size distribution from fisheries catch data. I applied the law to fisheries independent aerial survey data of southern bluefin tuna (Thunnus maccoyii) collected over a 10-year period in the Great Australian Bight. The law does not correlate to the observed school size distribution. A computer model originally demonstrated the formation of the universal law from simple rules. I redesigned this model as an individual-based simulation model calibrated from acoustic tag observations and state a mathematical formula for a resultant new family of transient group size distributions. The new formula correlates accurately to the simulation and to the aerial survey data. I use the mathematical model to estimate area of aggregation and total abundance. This approach is new as it does not seek stationary states of group size distribution and because it demonstrates a quantitative relationship between individual behaviour and group size distribution. This work elevates the pattern of group size distribution from a curiosity to a useful tool, and introduces a new family of transient distributions that may have a general application to other grouping phenomena.     

Chromium accumulation,transport and toxicity in plants∗

The predominant pathway for human exposure to chromium in non‐occupationally exposed individuals is via food with a daily intake of around 30–100 μgd^–1, with vegetables providing a major contribution. Unlike reports of chromium essentiality to man and animals, plants appear not to require chromium in spite of some early reports of a stimulatory growth effect.

Most reports on chromium in plants have been concerned with their growth on soils amended with sewage sludge, pF‐ash, tannery waste, or on ultra basic soils, which contain extreme concentrations of the element. Experimental studies with plants grown in hydroponic solution have often been undertaken at unrealistically high concentrations to examine the uptake of chromium in various forms, either as CrIII or CrVI at different pHs. In most cases, reports on chromium in plants deal with element concentrations and plant/soil relationships rather than detailed biochemical and physiological processes.

In general, chromium is largely retained in the roots of plants, although the oxidation state of chromium, pH, presence of humates and fulvates and plant species, affect plant uptake and transport. Leaves usually contain higher concentrations than grains. The uptake of CrIII is largely a passive process, whereas CrVI uptake is a metabolically mediated process via the sulphate pathway and is thus readily transported around the plant. The presence of a compound similar to trioxalate CrIII has been recorded while little chromium has been reported to be associated with cell organelles or soluble proteins.     

Effect of pH on Pb biouptake by the freshwater alga<Emphasis Type="Italic"> Chlorella kesslerii</Emphasis>

The effect of pH on Pb bioaccumulation by Chlorella kesslerii was studied. Both Pb uptake fluxes and Pb bound to membrane transport sites increased with an increase in pH from 4.0–5.0, were relatively stable in the pH interval 5.0–6.5, and increased again at pH 7.0 and 8.0. Protons affected Pb adsorption to the algal surface by competing directly for surface sites, by modifying the overall algal surface charge and by modifying the chemical speciation of Pb in solution. These results indicate a failure of the free-ion activity or biotic ligand models above pH 6.5, possibly due to the bioaccumulation of hydroxo or carbonato Pb complexes.     

Trace-element speciation and partitioning in environmental geochemistry and health

Establishment of the chemical form and associations of trace elements is important in the scientific and medical fields related to environmental geochemistry and health. Fundamental understanding of trace-element behaviour, the realistic formulation of historical perspectives of trace-element contamination, an assessment of environmental transformation processes and a thorough appraisal of environment-related ill health and disease all depend on knowledge of the chemical speciation and partitioning of trace elements. These topics and the development of analytical speciation techniques and procedures are discussed with reference to trace-element studies in the Department of Forensic Medicine and Science, University of Glasgow, on lacustrine sediments and water, the atmosphere, soil and street dirt of an urban environment and human biological fluids.     

Interactions of 233Pa with tissues of Mytilus galloprovincialis and Carcinus mediterraneus

Uptake of ²³³Pa from sea water by mussels Mytilus galloprovincialis L. and shore crabs Carcinus mediterraneus Csrn. was studied. Results indicate a high contamination factor in digestive tract, gills and skeleton of both investigated species and an increment of the contamination factor in mussel byssus. In spite of this, reproductive system, muscle and hemolymph were only negligibly contaminated. The presence of complexone EDTA in sea water has no effect on uptake of ²³³Pa in the animal tissues tested.     

Choice of chelating antidotes for acute cadmium intoxication∗

During acute oral intoxication by cadmium compounds, gastrointestinal epithelial damage contributes to immediate toxicity. However, secondary systemic toxicity may develop due to intestinal uptake of cadmium. This review presents an evaluation of the effects of chelators on the acute toxicity of cadmium after parenteral or oral exposure and on the intestinal uptake of cadmium. This review shows:

1. Chelating agents may affect the acute toxicity of cadmium in a variety of ways depending on the exposure route for cadmium and administration route for the chelator.

2. With regard to survival, systemic toxicity of absorbed cadmium is of major importance, as intraperitoneal administration of chelators could eliminate or reduce mortality due to orally administered cadmium chloride.

3. Lipophilicity of chelators and their cadmium complexes may result in extensively augmented intestinal uptake. However, hydrophilic chelators may efficiently reduce the intestinal cadmium uptake.

4. For hydrophilic chelators, the stability of the cadmium complex is an important determining factor of efficacy.

5. The optimal oral antidote towards orally administered cadmium are the BAL analogs, especially DMSA, while the optimal intraperitoneal antidotes towards orally or intraperitoneally administered cadmium are the higher members of the polyaminopolycarboxylate family, especially TTHA.

6. When administered simultaneously (DMSA orally and TTHA intraperitoneally), these chelators synergistically reduce the whole‐body retention of cadmium.

In conclusion, chelation treatment in acute oral cadmium intoxication should first prevent/reduce intestinal damage and uptake by rapid oral administration of a chelating antidote and then alleviate systemic toxicity due to absorbed cadmium and enhance renal/biliary cadmium excretion by parenteral administration of a chelating antidote.     

About plant species potentially promising for phytoextraction of large amounts of toxic trace elements

There is no information yet about plant species capable of accumulating many different metals/metalloids. The plants feasible for phytoremediation aims must grow fast, have high biomass, deep roots, and should accumulate and tolerate a range of toxicants in their aerial parts. In our research, greenhouse and field experiments have been performed to investigate accumulation and tolerance of not well-studied trace elements such as Br, Eu, Sc, Th (and also U) in couch grass and wheat. We compared bioaccumulation abilities of the plants with those of some other plant species grown under the same conditions. Additionally, we tested the effects of inoculation of seeds with Cellulomonas bacteria on phytoextraction of the trace elements from contaminated soils. For determination of elements, we used neutron activation analysis and ICP-MS. It was found that couch grass and wheat can grow in heavily contaminated soils and accumulate different toxic trace elements to levels that exceed physiological requirements typical for most plant species. Infection of seeds with bacteria resulted in a significant increase in the uptake of various trace elements and their translocation to upper plant parts. The use of couch grass and/or wheat, either alone or in combination with microorganisms, is a promising way to phytoextract metals/metalloids from contaminated soils.

     

Schadstoffbelastung durch Persorption von Bodenpartikeln

The term persorption describes the paracellular uptake of particles from the digestive tract. It has been shown that solid, hard microparticles such as starch granules, cellulose particles, fibres and crystals are incorporated from the digestive tract. It is likely that an uptake of soil contaminants may also occur via this mechanism, thereby increasing the health risks of children through soil ingestion. The aim of this study was to evaluate the significance of such soil contaminant absorption via this mechanism using data from the literature. Since no information was available on the persorption of soil particles, studies using other models had to be evaluated. The results of these studies show that a persorption of soil particles must be expected. The maximum persorption rate occurs for diameters of <35 μm which is in the range of diameters of street dust, clay and coarse clay. The persorption of these particles is therefore of significance. Data from the literature, however, does not allow an estimation of the magnitude of persorption of such soil particles. Basically, it is conceivable that a relevant ingestion of less mobile pollutants is possible through their persorption in the gastrointestinal tract. Aside from an increased internal exposure via the persorption of soil particles carrying contaminants, additional health risks may occur through the long-term deposit of such particles, the presence of potential allergens as well as through the embolisation of small vessels.     

Incorporating the perceptual range of animals into connectivity models

The perceptual range of an animal towards different landscape elements affects its movements through heterogeneous landscapes. However, empirical knowledge and modeling tools are lacking to assess the consequences of variation in the perceptual range for movement patterns and connectivity. In this study we tested how changes in the assumed perception of different landscape elements affect the outcomes of a connectivity model. We used an existing individual-based, spatially explicit model for the dispersal of Eurasian lynx (Lynx lynx). We systematically altered the perceptual range in which animals recognize forest fragments, water bodies or cities, as well as the probability that they respond to these landscape elements. Overall, increasing the perceptual range of the animals enhanced connectivity substantially, both qualitatively and quantitatively. An enhanced range of attraction to forests had the strongest impact, doubling immigration success; an enhanced range of attraction to rivers had a slightly lower impact; and an enhanced range of avoidance of cities had the lowest impact. Correcting the enhancement in connectivity by the abundance of each of the landscape elements in question reversed the results, indicating the potential sensitivity of connectivity models to rare landscape elements (in our case barriers such as cities). Qualitatively, the enhanced perception resulted in strong changes in movement patterns and connectivity. Furthermore, model results were highly parameter-specific and patch-specific. These results emphasize the need for further empirical research on the perceptual capabilities of different animals in different landscapes and conditions. They further indicate the usefulness of spatially explicit individual-based simulation models for recognizing consistent patterns that emerge, despite uncertainty regarding animals’ movement behavior. Altogether, this study demonstrates the need to extend the concept of ‘perceptual ranges’ beyond patch detection processes, to encompass the wide range of elements that can direct animal movements during dispersal through heterogeneous landscapes.     

Experimental evidence for direct nutrient assimilation by the lophophore of articulate brachiopods

The uptake of inorganic and non-nutritive organic molecules has been compared with uptake of nutritive molecules by the articulate brachiopod Terebratalia transversa (Sowerby). Only minimal uptake of Na₂ ¹⁴CO₃ and ¹⁴C-urea was observed, while ¹⁴C-glucose was concentrated extensively. After administration of a dilute solution of ¹⁴C-glucose over timed intervals, whole organ counts and autoradiographs showed that labelled material was accumulated along the exposed ciliated epidermal tissue of the lophophore and mantle and concentrated along the peritoneal lining of the coelom even before appearing in the gastrointestinal tract. The presence or absence of bacteria had little discernible effect upon extent and rate of uptake. The uptake experiments suggest that the lophophore not only creates an inhalent and exnalent current as is common in other filter-feeders, but also appears to be adapted for extraction of dilute nutrients in seawater. This ability of the lophophore to extract nutrients may help explain the evolutionary trend of the lengthening of the articulate lophophore and the reduction of the intestine to a short blind-ended gut.This work was supported by National Science Foundation Grant GB-20067.     

Uptake of cadmium into cells in culture∗

Cadmium has been recognized as pollutant of the environment for many years and numerous studies on its toxic effects have been carried out. Little, however, is known about its metabolic behaviour e.g. why the metal is accumulated so extremely rapidly into the organs of men and animals. Since the study of the individual metabolic steps is very difficult in vivo cell cultures may be used to obtain first indications of what happens in the whole animal.

We used CHO cells in monolayer culture to study the conditions under which the uptake of cadmium occurs. From serumfree medium the metal is accumulated rapidly in the cells. The uptake is inhibited very strongly by the presence of serum or albumin. Accumulation occurs against a concentration gradient and is dependent on the incubation temperature. Below 10°C no cadmium uptake is seen. Several substances which are known to affect cell metabolism have been used to influence cadmium accumulation. Neither inhibitors of energy production nor microtubule or microfilament disruptors showed any substantial effect. In contrast SH‐group blocking agents markedly reduced cadmium uptake.

The results show that cadmium uptake does not occur by passive diffusion but by some active mechanism.     

Removal of chromium (VI) from water streams: a thermodynamic study

The chemical speciation of water solutions containing chromium oxyanions in various ratios is calculated (with the aid of available computer code Mineql Plus, Geochemist Workbench and Visual Minteq) and discussed. The effect of solution pH, total concentration of each species studied, and the presence of other species in solution are calculated and presented in the form of thermodynamic speciation diagrams. Electrochemical diagram (correlating pH to Eh) has been calculated as well. The conditions of Cr(VI) reduction to Cr(III) and the subsequent solid phase precipitation are given as a function of redox potential and pH. Surface reactions that might occur between the chromate ions in the solution and redox couples as Fe²⁺/Fe³⁺ on the surface of sorbents are also discussed. Moreover, experimental sorption data of hexavalent chromium onto synthetic magnetite are presented and discussed with the aid of the calculated diagrams. A mechanism is elucidated for the efficient removal of Cr(VI) from water streams at low pH values, and zeta potential data of synthetic magnetite with and without Cr(VI) are presented, which agree well with the mechanism proposed.     

Untersuchungen zur Eignung wildlebender Wanderratten (Rattus norvegicus) als Indikatoren der Schwermetallbelastung

The objective of the current attempt was to investigate the suitability of wild-living rats (Rattus norvegicus) as a passive bioindicator using quantitative determinations of 12 chemical elements in different organs taken from rats which were caught in the Zoological Garden of Zittau. Aside from the determinations of so-called background levels, the focus of interest was with accumulations of certain elements within the organs depending on either sex or age of the rats. There were different affinities of the elements towards certain organs. Because of apparent sex and age-related differences in element concentrations and accumulation features, a well-planned sampling strategy for the use of rats as possible passive bioindicators is indeed required. The consideration of element distribution patterns within the organ system of Rattus norvegicus (based on body burden calculations (in part 2 of this work)) allows an effective use of the rat for purposes of integrative monitoring.     

Personality trait differences between mainland and island populations in the common frog (Rana temporaria)

Understanding and predicting species range expansions is an important challenge in modern ecology because of rapidly changing environments. Recent studies have revealed that consistent within-species variation in behavior (i.e., animal personality) can be imperative for dispersal success, a key process in range expansion. Here we investigate how habitat isolation can mediate differentiation of personality traits between recently founded island populations and the main population. We performed laboratory studies of boldness and exploration across life stages (tadpoles and froglets) using four isolated island populations and four mainland populations of the common frog (Rana temporaria). Both tadpoles and froglets from isolated populations were bolder and more exploratory than conspecifics from the mainland. Although the pattern can be influenced by possible differences in predation pressure, we suggest that this behavioral differentiation might be the result of a disperser-dependent founder effect brought on by an isolation-driven environmental filtering of animal personalities. These findings can have important implications for both species persistence in the face of climate change (i.e., range expansions) and ecological invasions as well as for explaining rapid speciation in isolated patches.     

北京PM2.5化学物种的质量平衡特征

以北京2个采样点连续采集的样品对PM2.5中的元素、水溶性离子和含碳组分进行分析．车公庄和清华园PM2.5中有机物的含量分别为27．8％和30．9％,是含量最丰富的物种,其次是二次无机粒子、土壤尘、元素碳和微量元素．PM2.5中约有24％的质量未能鉴别成分,相关性分析表明,含碳物种的估算所引起的偏差可能是主要的原因．采暖期重污染周和春季沙尘周PM2.5的化学物种构成悬殊,反映了季节性变化的源排放和特殊气象条件的综合作用．     

Determination of minimum inhibitory concentration and half maximal inhibitory concentration of antibiotics and their degradation products to assess the eco-toxicological potential

Abstract

Numerous studies have been reported on today’s ubiquitous presence of antibiotics in surface waters causing the emergence of multidrug-resistant bacteria. Advanced water treatment procedures aim at the complete prevention and elimination of antibiotics from entering natural water bodies. In this study, photoinduced degradation processes using UVC-irradiation were applied toward selected fluoroquinolone, tetracycline, macrolide, and sulfonamide antibiotics. Photodegradation products were elucidated using high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS). Rate constants and quantum efficiencies were determined for the active substances and their photo-transformation products. As a measure of ecotoxicity, minimum inhibitory and half-maximal inhibitory concentrations were determined against the Gram-negative bacterium Pseudomonas fluorescens and the Gram-positive Bacillus subtilis in a standard assay format. These values were further recorded as a function of UV exposure time. The irradiation time-dependent increase of minimum inhibitory concentration (MIC) values agreed well with the kinetic models. After 10?min of irradiation, the compound solutions ceased to inhibit bacterial cell growth, indicating removal of the pharmaceutical activity. These findings were found in agreement with quantitative structure–activity relationship analysis. The combination of microbiological activity testing, molecular structure analysis, chemical kinetic investigation, and quantitative structure–activity relationship models proved to be able to predict irradiation times and evaluate potential ecotoxicological hazard of the irradiated drugs.