Pathway of 17��-estradiol degradation by Nitrosomonas europaea and reduction in 17��-estradiol-derived estrogenic activity

In recent years, natural and synthetic estrogens have been recognized as endocrine disruptors in aquatic organisms. Although natural and synthetic estrogens are known to be degraded by microbes, only limited information about their degradation pathways is available. Here, we studied the degradation pathways of a natural estrogen, 17β-estradiol, by the nitrifying microorganism Nitrosomonas europaea, and we determined whether the degradation products of 17β-estradiol had estrogenic activity. To identify the degradation products, we subjected the culture solution to solid-phase extraction, and the extract was analyzed by gas chromatography–mass spectrometry. The potential estrogenic activity of the degradation products was investigated by means of a yeast two-hybrid assay. 1,3,5(10),16-Estratetraen-3-ol (estratetraenol) was newly identified as a degradation intermediate produced by dehydration of 17β-estradiol. Estratetraenol was also degraded by N. europaea, and its degradation rate was faster than that of 17β-estradiol. The two-hybrid assay confirmed that estratetraenol acted as a ligand for the estrogen receptor; estratetraenol thus has potential estrogenic activity. N. europaea eliminated the estrogenic activity derived from 17β-estradiol. This paper is the first to report dehydration as a mechanism of microbial estrogen degradation.     

Assessment of acute toxicity of ��-cyhalothrin to a freshwater catfish, Clarias batrachus

Acute static bioassays were conducted for 96 h period with λ-cyhalothrin to determine its acute toxicity to a freshwater catfish, Clarias batrachus. The 96 h LC₅₀ value was estimated to be 5.00 μg l⁻¹ (95% confidence limit: 4.114–5.712). The alterations in behavioral pattern, such as change in the color of skin, hyperactivity, loss of balance, rapid swimming, increased surfacing activity, enhanced rate of opercular activity, as well as prominent rates of convulsions in treated fish were observed with the increasing concentrations of insecticide as compared to the control fish. The results indicate that λ-cyhalothrin is highly effective even at very low concentrations.     

Modified ��-cyclodextrins as prospective agents for improving water solubility of organic pesticides

The drawback of some organic pesticides is their low water solubility. Cyclodextrins are used as agents for improving pesticides water solubility. However, the stabilization of the crystalline lattice can reduces to a large extent the solubility of cyclodextrins, especially β-cyclodextrin. Here, searching for the water soluble β-cyclodextrin derivatives, a set of new “host” compounds were prepared by the reaction of β-cyclodextrin with methyl epoxycinnamate. The reactants ratio was varied in to study the substitution degree of the obtained derivatives. The structure was determined by the ¹H-NMR and FT IR spectra. The average degree of substitution was determined by integration of the corresponding NMR signals and by elemental analysis. The solubility of four selected pesticides: dimethoate, simazine, linuron and thiram, in water with and without addition of the new modified β-cyclodextrin was measured by ultraviolet spectrophotometry. Our results showed that the modified β-cyclodextrins significantly improve solubility of pesticides.     

Collective Contents of Volume 12 of Ecology and Environment

No.1 Research Papers Effect of digestion on measurement of total mercury in topsoil …………………………………………………………… DING Zhen-hu, WANG Wen-hua(1) The characteristics of adsorption and desorption of humic acids on copper…………………………………………………… LI Guang-ling, WEI Shi-qiang(4) Influence of electrolyte on adsorption of copper in soils……………………………………………………… LI Ying, LI Hong-jun, ZHANG Gui-yin, et al.(8) Comparative studies on availabl…     

Mutagenic and carcinogenic effects of cadmium†

There is limited evidence to suggest that certain compounds of cadmium may be mildly mutagenic. Some compounds of cadmium have given rise to fibrosarcoma and rhabdomyosarcoma following subcutaneous or intramuscular injection in the rat and also to interstitial cell tumours of the testis as a sequel to cellular damage and testicular atrophy. Cadmium chloride aerosol inhalation has induced a high incidence of dose‐related lung cancer in the rat. Epidemiological observations suggest that mortality from prostatic and possibly from lung cancer has been increased in cadmium workers who had experienced the very high levels of cadmium, mainly as oxide dust or fume, which existed in the past. The more recent epidemiological studies have not added further evidence in support of the carcinogenic role of cadmium.     

Alkylation of metals and the activity of metal‐alkyls†

The biochemical basis for resistance to metal ion toxicity is emerging though it is complicated by the different resistance mechanisms. Several strategies for resistance to toxic metal ions have been identified:

1. The development of energy driven efflux pumps which keep toxic element levels low in the interior of the cell. Such mechanisms have been described for Cd(II) and As(V).

2. Oxidation (e.g. AsO^2‐ to AsO₄ ^3‐) or reduction (e.g. Hg²⁺ to Hg⁰) can enzymatically and intracellularly convert a more toxic form of an element to a less toxic form.

3. The biosynthesis of intracellular polymers which serve as traps for the removal of metal ions from solution such as traps have been described for cadmium, calcium, nickel and copper.

4. The binding of metal ions to cell surfaces.

5. The precipitation of insoluble metal complexes (e.g. metal sulfides and metal oxides) at cell surfaces.

6. Biomethylation and transport through cell‐membranes by diffusion controlled processes.

In this short review I shall discuss the implications of biomethylation as a detoxification mechanism for microorganisms as well as for certain higher organisms.     

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.     

Comments on the Carcinogenicity and Mutagenicity of metals and their compounds†

The carcinogenicity of metals has received extensive study, both epidemiologically and in the laboratory. These have included case reports of occasional human occurrence or clusters of cancer cases as well as extensive epidemiologic studies; in addition, there has been significant laboratory research on the whole animals and in vitro systems. This body of information will be examined selectively.

I will not in this paper attempt a comprehensive review of the mutagenicity and carcinogenicity of metals and their compounds. Rather, I will attempt to set forth some historical perspectives, and to comment on some current gaps and needs.

Other papers in this workshop have presented thorough and very current reviews of most of the topics briefly noted in this presentation and do not require repetition here.

The cancer issue has been studied and reported on far more extensively than that relating to heritable mutations. There has been in recent years increasing interest in the use of short term tests for mutagenicity and cell transformation. These, however, are primarily with respect to their relationship to cancer production rather than to germ cell injury. Interest in cancer from metal compounds goes back a long time; in fact, one of the earliest reports was on the carcinogenicity of arsenic not many decades after the pioneering report of Sir Perceval Pott on cancer in chimney sweeps. Since then cancer has been definitely associated in humans with chromium compounds, nickel, and with less assurance but probably definitely with beryllium and cadmium. The confirmation of these findings in laboratory animals has been uneven. In the case of arsenic, for example, there has been only limited success in the production of cancer in laboratory animals with arsenic.

Many other metals have been found in laboratory studies to produce cancer, although with most of these, evidence of production of cancer in humans is either absent or extremely uncertain.

The extensive body of recent information relating to the testing of metals with a variety of short term tests will be briefly reviewed.     

Analysis of the toxicity of glyphosate and Faena® using the freshwater invertebrates Daphnia magna and Lecane quadridentata

With the present contribution an evaluation of the toxicity of the pure herbicide glyphosate and its commercial formulation Faena® is reported using the cladoceran Daphnia magna Strauss and the rotifer Lecane quadridentata Ehrenberg. LC₅₀, EC₅₀, NOEC, and LOEC values for each toxicant and for both test organisms are obtained. Regarding acute toxicity, Faena was 11-fold more toxic to L. quadridentata than pure glyphosate and slightly more toxic to D. magna (1.7-fold). Inhibition of esterase activity in L. quadridentata by glyphosate was the most sensitive end-point; the EC₅₀ was 1500-fold smaller than the LC₅₀. The implications of these results and their comparison with established international and national limit values for glyphosate are discussed.     

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.     

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.     

Enzymatic and cellular level effects of nickel∗

The effects of Ni on hepatic enzymes of tilapia, viz. acid‐ and alkaline phosphatases, catalase and glucose‐6‐phosphatase, both under in vivo and in vitro conditions reflected the following tendencies. In vivo conditions indicated maximal increase in activity for acid phosphatase at 3.00 ppm, equivalent to 28.5%, followed by a slight decrease and increase thereafter. As for alkaline phosphatase, gradual increase in activity was observed with maximal activity at 9 ppm of Ni, equivalent to 16.8%. Catalase demonstrated similar tendencies with maximal activity at 9.0 ppm, equivalent to 101.2%. In the case of glucose‐6‐phosphatase, the tendency was the reverse with maximal inhibition at 9.00 ppm, i.e. 41.9%. In contrast to in vivo conditions, in vitro systems indicated that all investigated enzymes were inhibited in the region of 4–10% except for catalase which demonstrated a slight increase by 5–6% in activity between concentrations of 10–15 ppm of Ni but thereafter continuous inhibitory effects prevailed.

At cellular level, exposure of tilapia to a lethal dose of 9 ppm of Ni indicated not much of an adverse effect except for a slight depletion in fat and glycogen content. In the case of mitochondria, they were normal and a few large secondary lysosomes were observed. In relation to the cell membrane no dramatic change was detected.     

Organic carbon and environmental quality of riverine and off-shore sediments from the Gulf of Cádiz,Spain

Here we show that heavy metal geoaccumulation is apparent in the Tinto and Odiel estuary and, at a lower magnitude, in off-shore sediments. Values above probable effects level (PEL) are recorded for As, Cu, Hg, Pb and Zn in the Tinto and Odiel estuary, for As and Hg in the associated off-shore sediments and for As in the Guadiana River. Significant correlations were found between total organic carbon (TOC) and Cr, Cu, Ni and Zn in the Tinto and Odiel estuary, and Cr, Cu, Ni, Pb, Hg and As in the Guadiana River. PCA analysis differentiated the three studied locations.     

Enzymatic and cellular level effects of chromium∗

Exposure of Cr to four hepatic enzymes activities of tilapia, viz. acid‐ and alkaline phosphatases, catalase and glucose‐6‐phosphatase, was contrary to the results obtained for Cd and Ni. This is the only heavy metal investigated thus far that dramatically augmented glucose‐6‐phosphatase by approximately 83% at a concentration of 12 mg L^‐1 in vivo in lieu of the fact of an initial inhibition of approximately 45 % at a lower concentration of Cr; 6 mg L^‐1. In the case of acid phosphatase and catalase activities progressive increment was observed up to 50 and 217% respectively at a concentration of 12 mg L^‐1 Cr. On the other hand, in contrast to all the investigated enzymes interestingly alkaline phosphatase was inhibited continuously at all concentrations up to 46% at 12 mgL^‐1 Cr. In vitro experiments were contrary to the above mentioned results, whereby all hepatic enzymes were inhibited with major inhibition observed for acid phosphatase of approximately 60% from 5 mgL^‐1 Cr onwards in the system.

At cellular level, Cr exposure at a lethal dose of 12 mgL^‐1 demonstrated similar effects to that of Cd. In general, the glycogen and fat reserves were depleted while lysosomal activity is increased. As compared to the effects of Cd, the mitochondria did not indicate any prominent reflection in the formation of intramitochondrial bodies. Further, similar to Cd, the cell membrane as well as nucleus were not affected.     

Speciation and carcinogenic classification—some limits of assessment and prevention procedures—the case of “nickel”

The speciation of nickel is of the highest importance for the definition of lists of substances for regulatory activity in terms of prevention, regarding possible cancer risk. A review is made of the different attitudes of outstanding administrations in front of nickel speciation. Some of them show a maximum of care in chemical definition, others reflect a lack of scientific rigor leading to generic classifications, more or less abusive. The great complexity of the chemistry and physicochemistry of nickel imposes the “two‐level speciation concept” (chemical and physicochemical), at least for compliance with the “Good Laboratory Practice” as far as experimental toxicology is concerned. Recommendations are exposed for the attention of toxicologists and regulators who have been for some years now extremely solicited for prevention aims.     

Chemical composition and antifungal activity of Chelidonium majus extracts – antagonistic action of chelerythrine and sanguinarine against Botrytis cinerea

This study discusses the similarities and differences between the antifungal activity of Chelidonium majus L. extracts and chelerythrine/sanguinarine, the main alkaloids in these extracts, against the plant pathogenic fungus, Botrytis cinerea. The obtained data show that the Ch. majus L. extracts inhibit the growth of B. cinerea very effectively. The extracts activity is significantly greater than that of chelerythrine/sanguinarine standard solutions alone and it does not always reflect the total content of alkaloids in the extracts. It has been proved that B. cinerea exhibits very diverse resistance to chelerythrine and sanguinarine. The IC₅₀ values for chelerythrine and sanguinarine equal 5.41?mg/mL and 1.76?mg/mL, respectively. In the mixture the antifungal activity of chelerythrine and sanguinarine is antagonistic in the concentration dependent way. Based on the presented data it is not clear, however, which alkaloids present in the Ch, majus extracts at significantly lower concentration levels enhance the activity of chelerythrine and sanguinarine so that the extracts activity is considerably greater than that of both main alkaloids mixtures.     

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.     

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.