Uranium contents in plants and mushrooms grown on a uranium-contaminated site near Ronneburg in Eastern Thuringia/Germany

Uranium concentrations in cultivated (sunflower, sunchoke, potato) and native plants, plant compartment specimens, and mushrooms, grown on a test site within a uranium-contaminated area in Eastern Thuringia, were analyzed and compared. This test site belongs to the Friedrich-Schiller University Jena and is situated on the ground of a former but now removed uranium mine waste leaching heap. For determination of the U concentrations in the biomaterials, the saps of the samples were squeezed out by using an ultracentrifuge, after that, the uranium concentrations in the saps and the remaining residue were measured, using ICP-MS. The study further showed that uranium concentrations observed in plant compartment and mushroom fruiting bodies sap samples were always higher than their associated solid residue sample. Also, it was found that the detected uranium concentration in the root samples were always higher than were observed in their associated above ground biomass, e.g., in shoots, leaves, blossoms etc. The highest uranium concentration was measured with almost 40 ppb U in a fruiting body of a mushroom and in roots of butterbur. However, the detected uranium concentrations in plants and mushrooms collected in this study were always lower than in the associated surface and soil water of the test site, indicating that under the encountered natural conditions, none of the studied plant and mushroom species turned out to be a hyperaccumulator for uranium, which could have extracted uranium in sufficient amounts out of the uranium-contaminated soil. In addition, it was found that the detected uranium concentrations in the sap samples, despite being above the sensitivity limit, proved to be too low—in combination with the presence of fluorescence quenching substances, e.g., iron and manganese ions, and/or organic quenchers—to extract a useful fluorescence signal, which could have helped to identify the uranium speciation in plants.     

Dietary intake of PCDD/F by small children with different food consumption measured by the duplicate method

The dietary intake of PCDD/F by 42 small children, 21 boys and 21 girls in the age range 14-47 months, with different food consumption behaviour living in urban and rural areas of Germany was measured by the duplicate method with a 7 day sampling period from May to September 1998. The PCDD/F-levels in the food duplicates were in the range 39.2-325 fg I-TEq/g(dry weight) (median: 90.7; arithmetic mean: 96.6) and the doses were in the range 0.681-5.43 with a median of 1.56 and an arithmetic mean (AM) of 1.60 pg I-TEq/(kg(body weight) x d). Children living in an urban industrialized area with food consumption including products from the family owned vegetable gardens or the surrounding area and/or products from domestic animals showed no statistically significant different concentrations in the food duplicates or in the dietary intake of PCDD/F, calculated as I-TEq, than children living in a rural area with similar food consumption behavior or than children consuming exclusively food from the supermarket.     

Identification of microcystins in cyanobacteria from the Bleiloch former drinking-water reservoir (Thuringia, Germany).

The presence of microcystins in cyanobacterial samples collected from the Bleiloch reservoir, formerly an important drinking-water supply in Thuringia, Germany, was proven by application of a combination of recently developed analytical methods. The raw extracts were cleaned by size-exclusion chromatography (SEC) or solid-phase extraction (SPE). The determination of microcystins was achieved by different HPLC separation followed by the application of alternative detection methods (UV, diode array detection (DAD), and mass spectrometry (MS), respectively). Furthermore, the different results of clean-up by SPE and SEC are demonstrated. The identity of microcystins was verified by MS/MS measurements. In the cyanobacterial sample from 1998, microcystin-RR, -LR and -YR were found, whereas in 1999 only microcystin-LR and -YR were detectable. In addition to detection of cell-bound microcystins, in 1999 traces of dissolved microcystins in water from the Bleiloch reservoir were detected. It can be assumed that not only the Bleiloch reservoir is contaminated with hepatotoxins but also many similar lakes still used for drinking water supply.     

The influence of time on lead toxicity and bioaccumulation determined by the OECD earthworm toxicity test

Internationally agreed standard protocols for assessing chemical toxicity of contaminants in soil to worms assume that the test soil does not need to equilibrate with the chemical to be tested prior to the addition of the test organisms and that the chemical will exert any toxic effect upon the test organism within 28 days. Three experiments were carried out to investigate these assumptions. The first experiment was a standard toxicity test where lead nitrate was added to a soil in solution to give a range of concentrations. The mortality of the worms and the concentration of lead in the survivors were determined. The LC50s for 14 and 28 days were 5311 and 5395 microgPb g(-1)soil respectively. The second experiment was a timed lead accumulation study with worms cultivated in soil containing either 3000 or 5000 microgPb g(-1)soil. The concentration of lead in the worms was determined at various sampling times. Uptake at both concentrations was linear with time. Worms in the 5000 microg g(-1) soil accumulated lead at a faster rate (3.16 microg Pb g(-1)tissue day(-1)) than those in the 3000 microg g(-1) soil (2.21 microg Pb g(-1)tissue day(-1)). The third experiment was a timed experiment with worms cultivated in soil containing 7000 microgPb g(-1)soil. Soil and lead nitrate solution were mixed and stored at 20 degrees C. Worms were added at various times over a 35-day period. The time to death increased from 23 h, when worms were added directly after the lead was added to the soil, to 67 h when worms were added after the soil had equilibrated with the lead for 35 days. In artificially Pb-amended soils the worms accumulate Pb over the duration of their exposure to the Pb. Thus time limited toxicity tests may be terminated before worm body load has reached a toxic level. This could result in under-estimates of the toxicity of Pb to worms. As the equilibration time of artificially amended Pb-bearing soils increases the bioavailability of Pb decreases. Thus addition of worms shortly after addition of Pb to soils may result in the over-estimate of Pb toxicity to worms. The current OECD acute worm toxicity test fails to take these two phenomena into account thereby reducing the environmental relevance of the contaminant toxicities it is used to calculate.     

Endocrine disrupting nonyl- and octylphenol in infant food in Germany: considerable daily intake of nonylphenol for babies

Nonylphenol and octylphenol are persistent endocrine disrupters that are priority substances of the European Union Water Framework Directive. Their presence in the environment has caused increasing concern about their impact to human health. Infants are more sensitive to hormonal impacts of environmental chemicals than adults. The results of the present study indicate that nonylphenol is ubiquitous in foodstuffs for babies and toddlers commercially available in Germany, while octylphenol could only be determined in 80% of all food samples. The daily intakes based on consumption studies in μg nonylphenol kg⁻¹ body weight per day for high consumers in the baby category (0.23-0.65 μg kg⁻¹ bw d⁻¹) were relatively high. This could lead to a higher risk especially for babies.     

铅同位素解析技术在工业园污染溯源中的应用

针对土壤中重金属污染溯源及解析不同污染源对土壤中铅的相对贡献率问题,以陕西西部某工业园区为例,采集土壤样品、铅锌冶炼厂矿石混合样、热电厂煤样及焦化厂混合煤样共40个,用ICP-MS测定样品的铅浓度及铅同位素比值(208Pb/204Pb、207Pb/204Pb、206Pb/204Pb).借助于铅同位素比值散点图来对比分析采样点土壤、背景点土壤和可能的污染源样品的铅同位素特征分布,判定其主要污染来源.用混合多元模型计算不同污染区域各污染源的贡献率,结果表明,土壤中的铅同位素比值落在铅锌矿石、炼焦用煤及热电燃煤及背景点的铅同位素比值之间,说明各端元介质均有可能对工业园区土壤中的铅污染有贡献.在铅同位素比值散点图中土壤铅浓度大于60 mg/kg的采样点的铅同位素比值集中落在热电燃煤与炼焦用煤附近.统计定量解析结果可知,对工业园区土壤铅污染的贡献大小依次为热电厂、焦化厂和铅锌冶炼厂.研究表明,铅同位素指纹解析技术用于定性与定量解析工业园区土壤铅污染效果较为理想.     

Twenty-five years of biomonitoring lead in the Frankfurt/Main area

The present study is an example of the historical monitoring of heavy metals. The specific question it aims to explore is: to what extent has the lead content of selected organisms used for biomonitoring in Frankfurt/Main—one of the cities in Germany most heavily affected by automobile traffic—changed as a result of legislation on leaded gasoline?

Data on the lead content of the moss speciesBryum argenteum Hedw. from the years 1974, 1975 and 1978 and data on the lead content of the outer bark of the ash speciesFraxinus excelsior L. from 1973 served as the basis for the repeated measurements. Remeasurement was successful in 76.5% (i.e. 124 trees at 26 growth sites). The study produced the following results:

• ? As was expected, the lead content of the short-term accumulatorBryum argenteum Hedw. was distinctly lowered with a decreasing particulate lead concentration. However, the reduction factor varied greatly between the different growth sites.
• ? On the other hand, the lead content measured in the outer bark layers ofFraxinus excelsior L. has risen markedly during the past two decades. Whereas in 1973 nearly all trees examined displayed very low concentrations of lead (< 38 ppm), only 9.5% were still in this category in 1997 and nearly 30% exhibited high or even unacceptable lead concentrations (< 150 ppm → > 225 ppm). Various factors have to be taken into account to explain this increase. First of all, bark is a long-term accumulator for heavy metals like lead and its enrichment capacity could have increased as the surface becomes rougher over time. Furthermore, lead is most probably leached out of the bark to a lesser degree now than in the 1970s, owing to the reduced concentration of sulphuric acid in the rain. The dramatic growth of automobile traffic in the Frankfurt/Main area during the period covered by the study undoubtedly plays an important role as well.

     

Development of a technique for the determination of lead and bromine in atmospheric particles by X-ray fluorescence

A methodology has been developed for determining the lead and bromine content of atmospheric particles collected on membrane filters. In a novel calibration procedure, standards were prepared by drying fine precipitates of lead molybdate and silver bromide on to filters. Such standards were evidently free from bromine loss during analysis and storage, and more accurately represent real samples than conventional solution-impregnated filters. Elemental loadings in the range 0.1–10μg could be measured. Inhomogeneous efficiency of detection across the surface of samples was noted, and was accounted for by applying correction factors obtained from an intercomparison of XRF and atomic absorption analyses. Good comparability between Br determinations by XRF and neutron activation analysis was found. Problems of noncomparability between standards and samples of low concentration were noted in some cases.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

Nonmethane hydrocarbons (NMHC) in the Greater Munich Area/Germany

During several field campaigns in the years 1993–1997 quasi-continuous measurements of NMHC data were obtained at various locations (urban/suburban/rural) within the Greater Munich Area (GMA) by means of on-line gaschromatographic methods. Though limited to NMHC between C₆ and C₉ it comprises the first comprehensive data base for this region that features high temporal resolution. The results for the downtown area show relatively low NMHC values compared to other cities worldwide. Propene-eqivalent analysis suggests that aromatic compounds such as toluene and m & p-xylenes play a major role in the formation of urban photochemical smog in the GMA. Since aromatic compounds were found to be ubiquitous at all measurement sites (altogether 8 sites) the pattern of these NMHC were investigated thoroughly. The results suggest that aromatic compounds are most effective in the urban/rural transition zone where VOC-limitation of ozone formation can be expected.     

Control of lead solubility in soil contaminated with lead shot: effect of soil pH

An incubation experiment was carried out to assess the rate of oxidation of Pb shot and subsequent transfer of Pb to the soil under a range of soil pH conditions. Lead shot corrosion was rapid, so that soil solution and fine earth (<1mm) Pb concentrations increased rapidly within a few months. Corrosion products, dominated by hydrocerussite (Pb(3)(CO(3))(2)(OH)(2)), developed in crusts surrounding individual Pb pellets. However, irrespective of pH, Pb(2+) activities in the soil solutions, modelled using WHAM 6, were much lower than would be the case if they were controlled by the solubility of the dominant Pb compounds present in the Pb shot crust material. In contrast, modelling of soil solid-solution phase distribution of Pb, again using WHAM 6, suggested that, at least during the 24 months of the study, soil solution Pb concentrations were more likely to be controlled by sorption of Pb by the soil solid phase.     

Controlling lead concentrations in human blood by regulating the use of lead in gasoline

After having been emitted at maximum rates in the 1960s and 1970s, lead has become less ubiquitous in industrialized countries as a result of increasingly stringent policies to limit the use of this heavy metal as an anti-knock additive in gasoline. Using a detailed reconstruction of lead emissions in Europe (PbE), of the air concentration of lead in Europe (PbC) and repeated measurements of lead concentrations in human blood (PbB) in Germany since about 1980, we have constructed an empirical model that estimates PbB given PbE. This model is used for 2 purposes: i)To estimate PbB levels for the 1960s and 1970s in Germany, when emissions were maximum and monitoring blood levels had not yet begun. It turns out that PbB peak emissions were reaching a mean level, which health officials considered potentially harmful for fetuses and small children. ii) To estimate how PbB levels may have developed if regulations of the use of lead in gasoline had been implemented differently. In case of no or delayed regulations, the model estimates that PbB levels well beyond the critical level would have emerged. Thus, the regulation instituted in Germany since the 1970s has reduced significant health hazards.     

废铅酸蓄电池铅膏柠檬酸浸出动力学研究

通过研究废铅酸蓄电池铅膏柠檬酸-柠檬酸钠浸出过程中PbSO4转化率随时间变化,考查了物料粒度、搅拌速度和浸出温度对转化率的影响,建立了反应的动力学方程,并计算了浸出反应表观活化能。结果表明,减小物料粒度、提高浸出温度和适当提高搅拌速度,均可提高硫酸铅转化率。浸出反应表观活化能为67.82 kJ/mol,浸出反应受化学反应步骤控制。     

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg⁻¹) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO₄, PbSO₄·PbO, α-PbO and Pb⁰. Morphology investigations revealed that PM_2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl₂ extraction.     

Effects of phytoextraction on heavy metal concentrations and pH of pore-water of biosolids determined using an in situ sampling technique

Heavy metal concentrations and pH of pore-water in contaminated substrates are important factors in controlling metal uptake by plants. We investigated the effects of phytoextraction on these properties in the solution phase of biosolids and diluted biosolids in a 12-month phytoextraction column experiment. Phytoextraction using Salix and Populus spp. temporarily decreased pore-water pH of the substrates over the experimental period followed by a return to initial pH conditions. Salix × reichardtii and Populus balsamifera effectively extracted Ni, Zn and Cd and actively mobilized these metals from the solid to the solution phase. S. × reichardtii had the stronger effect on mobilization of metals due to its larger root system. Phytoextraction did not affect Cu in the solution phase of the biosolids. Heavy metals were leached down to lower depths of the columns during the phytoextraction process.     

Magnesium and the regulation of lead in three populations of the garden snail Cantareus aspersus

Helicid snails appear to regulate Pb more closely than other toxic metals, though it is reported as the least toxic. No regulatory mechanism has been described in animals, and the possible role of Mg in limiting Pb assimilation is examined here for the first time. Three populations of Cantareus aspersus were fed Pb and Ca with three levels of Mg for up to 64 days. Metal assimilation and production efficiency was calculated for each of 108 snails. Populations differed in their pattern of uptake but soft tissue Pb was unaffected by dietary Mg. The proportion of Pb assimilated did not change as soft tissue concentrations increased, indicating no specific regulatory mechanism. The daily addition of Pb to the soft tissues increases with growth rate suggesting uptake is instead some function of growth or cell turnover. Bioconcentration factors varied with time and are unreliable indicators of an evolved regulatory mechanism for Pb.     

用微电极测定曝气量对SBR系统中硝化作用的影响

为了研究曝气量对硝化作用的影响,实验采用3个相同的SBR装置,分别在曝气量为4、10和16 L/h的条件下处理人工污水,并采用自制的溶解氧、NO3-、NH4+和pH微电极测定了活性污泥絮体内部微元环境中相应基质的浓度。结果表明,曝气量为4 L/h时,活性污泥絮体内存在厌氧微区,NO3--N浓度减小了,发生了反硝化作用;而曝气量为10 L/h和16 L/h时,活性污泥絮体内发生的都是硝化反应,且NH4+-N浓度的减小量、NO3--N浓度的增大量都随着曝气量的增大而增大,pH随着曝气量的增大而减小。     

Dietary intake of PCDD/Fs and dioxin-like PCBs from the Chinese total diet study in 2007

Concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in 96 food composite samples from eight varieties of food groups from the Chinese total diet study (TDS) in 2007. The concentrations of samples, expressed as WHO toxic equivalents (TEQ), ranged from 0.001 pg TEQ g^?1 to 0.85 pg TEQ g^?1 (fresh weight). Dietary intake of PCDD/Fs and dl-PCBs of 12 age/gender subgroups of the Chinese population subsequently estimated ranges from 15.4 pg TEQ kg^?1 bw month^?1 to 38.7 pg TEQ kg^?1 bw month^?1 for average population and from 68.5 pg TEQ kg^?1 bw month^?1 to 226.1 pg TEQ kg^?1 bw month^?1 for high consumers (the 97.5th percentile). Dietary exposure of children (mean: 32.5 pg TEQ kg^?1 bw month^?1) is significantly higher than that of the adults (mean: 21.5 pg TEQ kg^?1 bw month^?1) (p < 0.01) presumably due to more food consumed by children relative to their body weight compared to adults. There is no difference of dietary exposure, expressed as pg TEQ kg^?1 bw, found between different genders. Across various regions in China, there are large differences of dietary exposure of adult population and pattern of contribution of food groups to total exposure due to different contamination level and food habits. Dietary exposures of average population of various subgroups were all below the PTMI recommended by JECFA, but those of higher consumers were found exceeding or comparable to the PTMI.     

Occurrence of aminopolycarboxylates in the aquatic environment of Germany

Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 1,3-propylenediaminetetraacetic acid (1,3-PDTA), beta-alaninediacetic acid (beta-ADA), and methylglycinediacetic acid (MGDA), are used in large quantities in a broad range of industrial applications and domestic products in order to solubilize or inactivate various metal ions by complex formation. Due to the wide field of their application, their high polarity and partly low degradability, these substances reach the aquatic environment at considerable concentrations (in the microg/L-range) and have also been detected in drinking water. This review evaluates and summarizes the results of long-term research projects, monitoring programs, and published papers concerning the pollution of the aquatic environment by aminopolycarboxylates in Germany. Concentrations and loads of aminopolycarboxylates are presented for various types of water including industrial and domestic waste waters, surface waters (rivers and lakes), raw waters, and drinking waters.