Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

The heavy metal burden of the soil and of earthworms from representative long-term forest observation plots has been measured since 1984 as one component of the media-embracing environmental monitoring network of the State of Baden-Wuerttemberg. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis

Methods

So-called characteristic curves for the metals Cd, Cu, Ni, Pb, and Zn were developed for the assessment. Earthworm toxicity data and background values in soil served as criteria. This procedure facilitates a comparative assessment of different pollutants. The mobility of the metals, which greatly influences their bioavailability and toxicity, was taken into account for the effects assessment.

Results and Conclusion

Besides inventorying the heavy metals (Part 1), the question of threshold values for toxic reactions as well as for accumulation was raised. The metal concentrations were assessed in the soil with regard to its habitat function. The ecotoxicological assessment revealed that the heavy metal burden of the investigated plots lies within the background- or precautionary range, well below the screening value established here to indicate the effect threshold in earthworms. This result means that a pollution of the forest observation plots with the metals cadmium, copper, lead, nickel, and zinc is low or absent. Only the distribution of the lead content is centered slightly above background (but clearly below the toxicity threshold). This slight lead burden of the soil of the observation plots can be explained by emissions from motor vehicles. Investigations at sites that are contaminated with either chromium or copper or cadmium showed that an accumulation of these metals in the body of the worms can be observed only above a threshold concentration of several hundred micrograms of mobile metal per kilogram in the upper layer of the soil.

Recommendations and Perspectives

The hitherto unknown threshold values for the accumulation in the body of the earthworm should be statistically validated and extended to other elements. Further research is needed in order to build a well founded basis for the ecotoxicological assessment of soil pollution. Acute and chronic earthworm effect thresholds are neither available yet for arsenic, cobalt, and mercury nor for some other elements occurring less frequently as soil pollutants. Background values depending on the kind of rock have been measured so far for total chromium only. They are lacking for the more toxic chromium (VI) which is a frequent soil pollutant but naturally occurs in traces only.     

Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

Since 1984 the Environmental Protection Agency (LfU) of the State of Baden-Wuerttemberg has been investigating the heavy metal burden of earthworms from representative long-term forest observation plots. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis.

Methods

At first only lead and cadmium were measured in the worms; in repetitive measurements over the years further metals or metalloid elements such as aluminum, arsenic, chromium, cobalt, copper, manganese, mercury, nickel, thallium, vanadium, and zinc were added to the agenda.

Results and Conclusion

The frequency distribution of the metals in the earthworms was characterized statistically. For the first time state-wide background values, normal values and threshold values were established for all the elements measured. A comparable study with a similar range of parameters is known neither nationally nor internationally. Time trend studies have been available for lead and cadmium since 1985/86, and for zinc since 1987. The studies show a steady decrease of the heavy metals on a state-wide average and especially in the ‘Odenwald’ and ‘Black Forest’ hills with their formerly highly polluted earthworm habitats. Today, the level of these metals in the earthworms is low with few exceptions. This holds true for other heavy metals as well.

Recommendations and Perspectives

The state-wide decreasing very low heavy metal burden of forest observation plots far from known emission sources can be considered a success of air pollution abatement measures. Because of the ongoing atmospheric deposition of heavy metals, regular observation should continue in order to estimate time trends and to recommend the reduction of emissions when precautionary values (part 2) are exceeded.     

Ecological stoichiometric characteristics of carbon,nitrogen, and phosphorus in three forests in the Lüliang Mountainous Area of Shanxi Province北大核心CSCD

Using a standard plot method, the stoichiometry of carbon (C), nitrogen (N), and phosphorus (P) in leaves, litter, and soil (0-20 cm depth) was investigated for three forest types: Populus davidiana, Larix principis-rupprechtii, and Pinus tabuliformis. The results showed that the stoichiometry of C, N, and P of the same component in the three forests were significantly different. The C and N contents in leaves, litter, and soil in P. davidiana forest were higher than those in L. principis-rupprechtii and P. tabuliformis forests were. However, P in the L. principis-rupprechtii forest was higher than that in the P. davidiana forest and P. tabuliformis forests were. The C, N, and P contents of the components in the three forests were, in order, leaves > litter > soil, and the three nutrient contents were significantly higher in leaves and litter than they were in soil. C:N and C:P in the three forests exhibited a trend of litter > leaves > soil, whereas that for N:P was leaves > soil > litter. There were highly significant positive relationships in N:P between the litter and the soil in the P. davidiana forest. Leaf C:N and litter C:P in the L. principis-rupprechtii forest were significantly negatively correlated, whereas N:P in the leaves and soil was positively correlated. There was a significant positive correlation in N:P between the leaves and the soil in the P. tabuliformis forest. In conclusion, the N contents in leaves and soil exhibited a significant positive correlation, whereas there was no significant correlation between C, N, and P in litter or soil. Environmental factors had a large influence on the stoichiometry of C, N, and P in soil. In particular, latitude and altitude had the most significant effects on C, N, P, C:N, and C:P and were significantly p ositively correlated. T hese results provide a scientific basis for f urther studies on nutrient utilization a nd t he cyclic characteristics of different forests in this area. © 2018 Science Press. All rights reserved.     

Butterfly effects in mimicry? Combining signal and taste can twist the relationship of Müllerian co-mimics

Müllerian co-mimics are aposematic species that resemble each other; sharing a warning signal is thought to be mutually beneficial for the co-mimics by reducing per capita predation risk. In Batesian mimicry, edible mimics avoid predation by resembling an aposematic model species. The protection of both the model and the mimic is weakened when the mimics are abundant compared to the models. The quasi-Batesian view suggests that defended (Müllerian) co-mimics, when unequal in their defences, could also show a Batesian-like trend of increasing mortality with increasing abundance of a less defended “mimic”. We manipulated frequencies of unequally distasteful artificial co-mimics that were prey for great tits. The co-mimics had different signals (imperfect mimicry) but were equally preferred by the birds when palatable. Unexpectedly, when unpalatable, one of the signals was easier for the birds to learn to avoid. Consequently, during predator learning, the signal design of the prey strongly affected mortality of the co-mimics; there was an interaction between the signal and frequency treatments, but increasing the frequency of a less defended “mimic” did not increase co-mimic mortalities as predicted. In contrast, in a memory test that followed, the effect of signal design disappeared; if the birds had experienced high frequency of “mimics” during learning, co-mimic mortalities did subsequently increase. Since the effect of co-mimic frequencies on mortalities changed depending on the signal design of the prey and predator experience, the results suggest that mimetic relationship may be an unpredictable interplay of several factors in addition to taste and abundance.     

Input and fate of anthropogenic estrogens and gadolinium in surface water and␣sewage plants in the hydrological basin of Prague (Czech Republic)

The concentration of the estrogens 17β-estradiol, estriol, estrone, 17α-ethinylestradiol, mestranol and norethisterone and of the anthropogenic gadolinium (Gd_ant) has been determined in the creeks and rivers, sewage treatment plants and water works of the city of Prague. The rapid degradation of estrogens in surface water allows the estrogen concentration gradient to be used as a very precise and sensitive guideline by which to pin-point sewage leaks into surface run-off water. The rather conservative behavior of Gd_ant in surface and ground water documents in the present case the presence of sewage water in the surface water cycle.     

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.     

Effects of β-cyclodextrin on adsorption and desorption of carbofuran in soils of divergent texture

Laboratory studies were conducted to determine the adsorption/desorption equilibrium of carbofuran between four divergently textured soils and distilled water and an aqueous solution of 0.01?mol?L^?1 β-cyclodextrin using a batch equilibrium technique. The determined adsorption isotherms for silt loam soils were of L-shaped, for sandy loam soil S-shaped, in agreement with a Freundlich isotherm. In the presence of β-cyclodextrin, the adsorption of carbofuran to the four soils was lower than with distilled water. Positive hysteresis was observed in all soils with distilled water, negative hysteresis when using a solution of β-cyclodextrin as desorbent. The results indicate the potential use of β-cyclodextrin for remediation of pesticide-contaminated soils.     

Effects of different concentrations of tetracycline and oxytetracycline on the growth and ecotoxicity in lettuce北大核心CSCD

四环素类抗生素(TCs)是目前我国应用广泛、用量最大的一类抗生素,畜禽粪便和土壤中存在TCs残留,影响蔬菜作物的生长发育. TCs因水溶性较高更容易被植物转运和积累,植物对TCs耐受性机理研究仍不足.为更全面探究土壤TCs对蔬菜的毒性作用,研究不同浓度四环素(TC)和土霉素(OTC)分别对生菜的抗生素残留、生长特征及抗氧化酶系统的影响.结果显示,在0(对照)、2、10、50、250 mg/kg 5个施用水平下,生菜叶片抗生素含量逐渐增加,且土霉素含量始终大于四环素含量.与对照相比,抗生素浓度在50 mg/kg以上时对生菜生长具有显著抑制作用,其中,株高、根长、地上部和地下部鲜重与叶片TC残留量具显著负相关.生菜叶片的脯氨酸含量随浓度增加呈先增加后降低的趋势,在10 mg/kg时达到最大.并且低浓度(2 mg/kg)促进抗氧化酶基因SOD、POD21和CAT的表达,高浓度抗生素(50、250 mg/kg)对其产生抑制作用,10 mg/kg的抗生素处理对SOD、POD21和CAT基因表达的影响在抗生素种类上存在差异.本研究表明抗生素浓度超过50 mg/kg对生菜生长产生抑制作用,脯氨酸和抗氧化酶SOD、POD、CAT的转录水平及其酶活性能快速响应抗生素胁迫,可作为生菜对抗生素抗性的辅助评价指标.(图8表3参19)     

Interrelation of Cd‐lon concentrations and the growth and activities of microorganisms in two growth media†

Partitioning of native or anthropogenic heavy metals in solid and solution phases of soil is a result of network of several physico‐chemical reactions. The attainment of equilibrium between two phases is also regulated by biochemical processes. For practical purposes, the bioavailability of metal present in soil is predominantly regulated by the soil solution phase which is in dynamic equilibrium with the solid phase. The results of a model laboratory and greenhouse growth experiments have been used to investigate the effect of Cd‐ion concentrations (either in soil solution or in nutrient solution) on the growth and activities of microorganisms. The soil solution has been simulated by preparing a suspension of soil with 0.1 M NaNO₃ (1: 2.5) equilibrated for two hours. Important conclusions are as follows:

Increase in Cd‐ion concentration in soil solution or in nutrient solution induces corresponding adverse effect on the growth and activities of microorganisms. Thus, it seems that Cd‐ion concentration is a more sensitive indicator for assessing the effect of metal pollution upon the growth and activities of soil microorganisms in comparison to total Cd contents.

During active microbial growth phase, a large part of the organically bound Cd was released in the soil solution which is largely bioavailable. This process is termed as mobilisation. There was momentary increase of Cd‐ion concentration in soil solution which intoxicated the growing organisms. After this stage, the Cd ions from the solution phase were removed by the newly formed solid phase (nonviable biomass) and were transformed in non‐available form. This process is termed as immobilisation.

The consequences and importance of these results for practical agriculture and in deciding the limits or guidelines on the maximum tolerable metal load in soils are discussed.     

Application of analytical hierarchy process and geographic information systems in land-use suitability evaluation: a case study of Dümrek village (Çanakkale,Turkey)

This study used both analytical hierarchy process (AHP) and geographic information systems (GIS) to make a land-use suitability analysis for the village of Dümrek, NW Turkey. Primarily, alternative land uses for agriculture, meadow–pasture and forest were determined along with criteria for these alternatives and a hierarchical structure was produced and used to determine the weights of the criteria. Spatial data were identified by means of GIS and calculations were made using the suitability values specified and weights obtained from AHP. Suitability maps were then produced for the above land use alternatives. Subsequently, a synthesized suitability map was formed from these maps. According to the weights specified by AHP, the order of land use preferences among the alternatives for rural development of Dümrek was agriculture, forest and meadow. The synthesized suitability map showed that the areas allocated for forest and agriculture were close to the present ratios of use; however, meadow land, which does not exist at present, should be allocated as a land use to constitute 12.5% of the study area. Achieving sustainability in land use is possible by planners and administrators considering results obtained from land suitability mapping studies at the stage of allocating land uses. The method applied in this research is considered useful when taking policy decisions covering the evaluation of rural land use, particularly for subunits of the state administration.     

Evaluation and remediation of organics,nutrients and heavy metals in landfill leachate – a case study in Beijing

Leachate pollution in landfill sites is a major source of environmental concern. This study evaluates organics, nutrients and heavy metals in a landfill site in Beijing, and introduces a method combining coagulation–flocculation with filtration for the advanced treatment of leachate. The results confirm that COD_Cr, TN, NH₄⁺ ? N, TP, Mn and As in leachate treated by an anaeobic–oxic biological method are unable to meet discharge or surface water quality standards. When treated with coagulation–flocculation combined with filtration under optimal conditions (cationic polyacrylamide dosage of 8.0 mg/L; polyaluminium chloride dosage of 350 mg/L; 0.4–0.6 mm ceramsite media in the filtration process), the residual NH₄⁺? N, TN, Mn and As in the leachate meet the maximum allowed values for landfill leachate discharge or surface water quality standards in China; the exceptions are chemical oxygen demand and total phosphorus. Leachate treatment processes could be further strengthened or improved.     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.     

Der Fischrückgang in der oberen Donau

Background During the last years, a decrease in fish populations has been documented for several river systems in Europe and North America. Since more than 20 years, similar developments have been documented for the upper Danube River between Sigmaringen and Ulm. The grayling (Thymallus thymallus) represents one of the most affected fish species in the upper Danube, and notable decrease has also been recorded for other species such as the European barbel (Barbus barbus). Despite intensive and continuous stocking and improvement of water quality along the Danube since the 1970s, this negative development of fish populations could not be stopped. Aim This article has been designed to give an overview on various investigations into the decline of fish in the upper Danube River. The major focus of this paper is on the presentation of a weight-of-evidence study carried out since 2003 at the Department of Zoology at the University of Heidelberg. Results and discussion During the 1920s, major parts of the upper Danube River were corrected, thus causing dramatic changes in the hydromorphology of the river. The macrozoobenthos, which represents an important source of nutrition for several fish species, depends on the morphological conditions of a river; recent investigations, however, could not show any dramatic changes in macrozoobenthos composition. Earlier investigations of the Danube River primarily focused on water quality, which has, indeed, been continuously improved by extensive modernization of wastewater treatment plants. Contamination by priority organic pollutants in sediments was not given any attention until the mid 1990s, when a clear decline of, e.?g., PAH concentrations were documented. However, results of more recent analyses showed very high PAH concentrations in two sediment samples (Schwarzach Σ 16 PAHs = 26 mg/kg; Öpfingen Σ 16 PAHs = 5 mg/kg). In 2002, the first ecotoxicological investigations were performed at the upper Danube River. The results of a pilot study showed a high ecotoxicological burden for selected sampling sites. As a conclusion of this study, a weight-of-evidence investigation was initiated to make an attempt to identify major pollutants and possible causes for the fish decline. In addition to, e.?g., liver ultrastructure analyses in barbel, the micronucleus test was used as a definite mutagenicity test using erythrocytes and liver samples. The results of the different in vitro tests showed very good correlation well with in situ parameters. Outlook The investigations within this weight-of-evidence study showed that the pollution situation of the Danube is, indeed, significant enough to potentially affect fish populations. However, further investigations are needed to clarify the specific causes for the fish decline. A bioassay-directed fractionation study is underway to identify specific pollutants as well as their sources. This study will also assess the endocrine disrupting potential of Danube sediments via histopathological analyses of gonads of field fish in combination with different in vitro tests. Furthermore, in the planned joint project COMPSEARCH, comparative investigations will evaluate the ecotoxicological hazard potential of different pollution sources and consequences of changes in land use.     

Progress in study of Salix characteristics and its application in sediment phytoremediation北大核心CSCD

For its difficulty in remediation and possibility of vicious spiral formation, contaminated sediment becomes a hot spot of recent pollution control study. Among all methods, phytoremediation is widely used in treatment of polluted sediment because of its high efficiency and sustainability. The fast-growing willow, a perennial woody plant with long vegetative season and great adaptation in harsh environments, has been suggested to be a low-cost and ecologically sound solution for the phytoremediation of contaminated sediment. This article introduces the characteristics of Salix and the ecological significance of Salix adaption to harsh environment, and reviews research progress and mechanisms including phytoextraction, phytotransformation, phytostabilization, phytodegradation and phytovolatilization of Salix. It also analyzes the effect of Salix in accumulating heavy metal, degrading organic matter and changing the characteristic of sediment, to point out the potential application of Salix in phytoremediation of polluted sediment. The article also puts forward the existing problems and possible solutions in phytoremediation by Salix of sediment, including paying more attention to field experiment, extending of the test cycle, emphasizing on optimal allocation of remediation plant communities.     

A comparison of lead exposures in industrial “hot spots” in Jordan and Israel

The aim of this study was to compare two hot spots of lead (Pb) exposure in Israeli and Jordanian occupational settings. The study also sought to assess whether any differences in regulations and legislation regarding occupational health could be identified as a source of exposure disparities. Blood and hair specimens were collected from workers in a battery factory in Jordan and a secondary Pb smelter in Israel and compared. About 33% of the currently exposed group showed blood lead (BPb) levels above the internationally recommended concentration of 40 µg dL^?1. Although the differences of BPb levels between Israel and Jordan were not statistically significant, average levels were lower in Jordan. Beyond the difference in the factory types, disparity in exposure levels might be explained due to a combination of proclivities of factory management, public policies, existing medical surveillance and insurance, as well as cultural differences. Results reveal that despite existing regulations and the growing attention that is dedicated to Pb and metal occupational exposures, there are still hot spots for Pb exposure in Israel and Jordan. The contrasting experience found in the current study raises the possibility that information and technology exchange between the two countries Israel and Jordan, may be beneficial for improving occupational health policy in these two neighboring countries.     

Quantity and activity of ammonia-oxidizing archaea and bacteria and their contribution to ammonia oxidation in farmland soil of Qinghai-Tibet Plateau北大核心CSCD

Ammonia oxidation, the first and rate-limiting step of nitrification, is mainly performed by ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB). However, the activities of AOA and AOB in soil and their relative contribution to ammonia oxidation are unclear, and whether there is a significant correlation between the quantity of AOA and AOB and the ammonia oxidation rate is also controversial. In this study, quantitative PCR combined with acetylene (C2H2) and 1-octyne inhibition methods were used to determine the quantity and activity of AOA and AOB in wheat, highland barley, and oilseed rape soils in Nyingchi, Lhatse, Sangzhuzi, and Sangri counties on the Qinghai-Tibet Plateau. The results showed that the quantity of AOB ((2.34 ± 0.84) ×105 - (2.65 ± 1.07) ×106 copies g-1 dry soil) was significantly higher than that of AOA ((0.20 ± 0.10) ×104 - (4.02 ± 0.39) ×104 copies g-1 dry soil) in all the soil samples. Soil pH was the key factor affecting the quantity of AOB, and the total phosphorus and ammonium nitrogen in soil were the key factors affecting the quantity of AOA. The rates of ammonia oxidation in the farmland soils of Lhatse (2.42 ± 0.73 mg kg-1 d-1) and Sangzhuzi (3.24 ± 1.15 mg kg-1 d-1) were significantly higher than those in the soils of Nyingchi (1.17 ± 0.43 mg kg-1 d-1) and Sangri counties (0.88 ± 0.57 mg kg-1 d-1). The rates of ammonia oxidation in the farmland soils of Lhatse and Sangzhuzi were dominated by AOB, while those in the farmland soils of Nyingchi and Sangri counties were dominated by AOA. For crops, the ammonia oxidation rates of wheat and oilseed rape soils in all four regions were significantly higher than those of highland barley soil, whereas the activity of AOA and AOB was not influenced by crops. The ratio of nitrogen to phosphorus was the key factor influencing AOA activity, whereas soil pH and total carbon were the main factors influencing AOB activity. Additionally, the quantities of AOA and AOB were not significantly correlated with the total ammonia oxidation rates and AOA and AOB activity. Overall, our study suggests that both AOA and AOB play important roles in ammonia oxidation in farmland soils of the Qinghai-Tibet Plateau. Moreover, it is unreliable to predict the activity of AOA and AOB and their relative contribution to ammonia oxidation directly based on their number of amoA genes, and the activity of AOA and AOB should be directly and accurately measured. These results are important for understanding ammonia nitrogen removal processes, slowing nitrate loss, and reducing the emission of the greenhouse gas nitrous oxide in the farmland ecosystem of the Qinghai-Tibet Plateau. © 2022 Science Press. All rights reserved.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.