Effect of agricultural antibiotics on the persistence and transformation of 17beta-estradiol in a Sequatchie loam

A laboratory incubation study was conducted to investigate the effect of agricultural antibiotics (sulfamethazine, tylosin, and chlortetracycline) on the persistence and transformation of 17beta-estradiol in Sequatchie loam. We measured concentrations of 17beta-estradiol and its primary metabolite (estrone) in soils spiked with antibiotics and 17beta-estradiol. Dehydrogenase activity (DHA) was also measured as an indicator of the total microbial activity of the soils. The presence of antibiotics significantly decreased transformation of 17beta-estradiol to estrone. There was a positive correlation between the DHA and the concentrations of estrone in soil spiked with 17beta-estradiol only, implying that the reaction is mainly catalyzed by dehydrogenases. However, the positive correlation was weakened in soil spiked with 17beta-estradiol and antibiotics together. We recommend that any study evaluating the fate and transport of estrogenic hormones in soil should include the effect of agricultural antibiotics because antibiotics and estrogenic hormones are commonly excreted together in environmental samples.     

Tylosin sorption to silty clay loam soils, swine manure, and sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 micro mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K(f)) or K(d) values, were calculated. K(f) values for the silty clay loams were similar, not influenced by landscape position, and averaged 1,350 with isotherm slopes ranging from 0.85 to 0.93. K(f) values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K(d) values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K(f) values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.     

Factors controlling the biodegradation of 17beta-estradiol, estrone and 17alpha-ethinylestradiol in different natural soils

We conducted a series of laboratory microcosm incubations with [(14)C]-labeled 17beta-estradiol (E2), estrone (E1) and 17alpha-ethinylestradiol (EE2) in 17 different natural soils to characterize hormone mineralization. A significantly higher mineralization was observed for E1 (2.0-37.6%) and E2 (4.2-50.2%) than for EE2 (0.5-2.6%) in all test soils after 21 days. Soil physical or chemical parameters were not related to estrogen mineralization. Although sorption parameters varied greatly for E2 (K(F)=21.9-317.5 mL g(-1)), for E1 (K(F)=46.0-517.5 mL g(-1)) and for EE2 (K(F)=29.9-326.1 mL g(-1)) this apparently did not control estrogen bioavailability since it showed no effects on hormone mineralization. In order to elucidate the controlling factors, experiments with combined additions of radiolabeled estrogens and different substrates were conducted. Additions of ammonium nitrate or alanine to soil samples generally increased EE2 mineralization, thus indicating N-limitation. Additions of glucose induced higher E2 and EE2 degradation in comparison to control samples which is attributed to co-metabolism. Additions of saw dust, catechol or streptomycin influenced the microbial population in the test soils and affected the mineralization of E2 and EE2. Thus, we clearly demonstrate that different microbial communities are responsible for E2 and EE2 degradation in soils. We suggest that EE2 is mineralized by white-rot fungi and E2 by bacteria.     

活性污泥总DNA提取方法的比较

从处理某制药废水的MBR反应器中采集活性污泥,评价不同DNA提取方法对其总DNA提取效率的影响。DNA提取分细胞裂解和DNA纯化2步,对细胞裂解比较了珠磨匀浆法、反复冻融法、十二烷基磺酸钠（sodium dodecyl sulfate,SDS）裂解法等7种方法;对DNA纯化比较了酚/氯仿纯化法和胶回收纯化法。结果表明,SDS裂解法、酚氯仿纯化法最优。通过条件优化实验,确定SDS裂解酚/氯仿纯化法在污泥量1.1 g,10 000 r/min离心5 min的操作条件下,获得的DNA产量（10 774 μg/g泥重）和纯度（OD₂₆₀∶OD₂₈₀=1.84）等综合指标最好。     

Dissolved and colloidal transport of Cd, Pb, and Zn in a silt loam soil affected by atmospheric industrial deposition.

As a result of processing of metal ores, trace metals have contaminated large areas of northern France. Metal migration from the soil to groundwater presents an environmental risk that depends on the physico-chemical properties of each contaminated soil. Soil water samples were obtained over the course of 1 year with zero-tension lysimeters from an acidic, loamy, metal contaminated soil. The average trace metal concentrations in the soil water were high (e.g. for Zn 11 mg l-1 under the surface horizon), but they varied during the sampling period. Zn concentrations were not correlated with pH or total organic carbon in the solutions but were correlated with Cd concentrations. On average, 95% of the Zn and Cd but only 50% of Pb was present in a dissolved form. Analytical transmission electron microscopy was used to identify the Zn or Pb carriers. Colloids containing Pb and Zn were biocolloids, whereas colloids containing only Zn were smectites.     

隐孢子虫3种检测方法比较

为建立一套行之有效的隐孢子虫灭活效果评价方法,在构建鸡源隐孢子虫C. baileyi动物模型的基础上,选用3种检测方法（抗酸染色、饱和蔗糖悬浮镜检和荧光检测）,对鸡源隐孢子虫进行镜检、数量统计,并比较3种方法的优劣及适用范围。结果显示：荧光染色法具有最佳的检测效率（检出数量为改良抗酸染色法,饱和蔗糖悬浮镜检法的2.1和2.6倍;检测时间为120 min）,并能够进行隐孢子虫的活性鉴定,可以作为饮用水消毒剂灭活隐孢子虫的评定方法,是一种高效、简便、较为廉价,并具有较大发展前景的检测方法。     

Comparison of methods for the extraction and determination of polychlorinated biphenyls in shiphull antifoulings

A method is presented for the determination of PCBs in chlorinated rubber antifoulings. In ten different brands, no PCB concentrations above 0.5 mg kg^?1 were found.     

Persistence and fate of 17beta-estradiol and testosterone in agricultural soils

Steroidal hormones are constantly released into the environment by man-made and natural sources. The goal of this study was to examine the persistence and fate of 17beta-estradiol and testosterone, the two primary natural sex hormones. Incubation experiments were conducted under aerobic and anaerobic conditions using [4-(14)C]-radiolabeled 17beta-estradiol and testosterone. The results indicated that 6% of 17beta-estradiol and 63% of testosterone could be mineralized to (14)CO(2) in native soils under aerobic conditions. In native soils under anaerobic conditions, 2% of testosterone and no 17beta-estradiol was methanogenized to (14)CH(4). Essentially, no mineralization of either testosterone or 17beta-estradiol to (14)CO(2) occurred in autoclaved soils under aerobic or anaerobic condition. Results also indicated that 17beta-estradiol could be transformed to an unidentified polar compound through abiotic chemical processes; however, 17beta-estradiol was only oxidized to estrone via biological processes. The TLC results also indicated that testosterone was degraded, not by physical-chemical processes but by biological processes. Results also indicated that the assumed risks of estrogenic hormones in the environment might be over-estimated due to the soil's humic substances, which can immobilize majority of estrogenic hormones, and thereby reduce their bioavailability and toxicity.     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.     

Degradation of the fungicide difenoconazole in a silt loam soil as affected by pretreatment and organic amendment

Degradation of the fungicide difenoconazole was examined in a silt loam soil under controlled conditions (60% WHC, 30 degrees C) in the laboratory. Difenoconazole was applied at 0.1 and 1.0 mg kg(-1) dry soil, respectively. The experiments were run with non-pretreated and pretreated field soil, respectively, partly mixed with easily decomposable organic matter (leaf powder). In all experiments, degradation curves showed a sigmoidal shape with clear acclimation phases. Pretreatment with difenoconazole in the field decreased the acclimation phases, DT(50)- and, in some cases, DT(90)-values. The incorporation of easily decomposable organic matter decreased both DT(50)- and DT(90)-values and increased the general microbial activity significantly. We conclude that difenoconazole is metabolized by an acclimated part of the soil microflora. However, the degradation seems to be stimulated in the presence of suitable co-substrates.     

应用于PCR-DGGE分析的活性污泥微生物总DNA提取方法比较

探讨适用于PCR-DGGE分析研究的活性污泥细菌和真菌的DNA提取方法。采用5种方法提取活性污泥微生物基因组DNA,以DNA纯度、含量、片段大小及DGGE条带多样性作为考察指标评价提取方法的优劣,以确定最佳实验方案。紫外吸收法和琼脂糖凝胶电泳结果显示,试剂盒法提取的DNA含量最低,其余4种方法获得的DNA含量无显著差异,就DNA纯度而言,试剂盒法最优;除高温裂解法对真菌细胞壁裂解效果较差外,其他4种方法均能不同程度地裂解细菌和真菌细胞;DGGE结果表明,高温裂解法获得的细菌条带最多,基于SDS的细胞裂解法得到的真菌条带最多。综合分析,高温裂解法更适合于活性污泥中细菌的PCR-DGGE分析,基于SDS的细胞裂解法则更适合于污泥中真菌的PCR-DGGE分析。     

Comparison of three methods of particulate measurement in Chicago air

Simultaneous measurements of suspended particulate concentrations were taken in Chicago over an 8-month period with an integrating nephelometer, a 6-stage fractionating sampler, and a Hi-Vol air sampler. The correlation coefficient (r) between light scattering coefficient, b_scat, and the Hi-Vol measurements was 0.75. The light scattering coefficient was found to be highly correlated with the impactor stages which had cut-off diameters of 0.38 μm (r = 0.79) and 0.84 μm (r = 0.89). These associations were independent of relative humidity. In contrast, correlations between b_scat and all other size fractions, and with TSP, were greatly affected by relative humidity. Relatively strong relationships were also found between NO₂, O₃ and b_scat which support the contention that nephelometer measurements are a reflection of photochemical activity.     

Comparison between solid-phase extraction methods for the chromatographic determination of organophosphorus pesticides in water

A solid-phase microextraction (SPME) procedure has been developed to extract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng x mL(-1) for SPE and 1 to 100 ng x mL(-1) for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng x mL(-1) for SPME depending upon the analyte, and 100 ng x mL(-1) for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6% to 5.8% for SPME and 2.4% to 9.2% for SPE. Along with the feature of being a solvent - free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE - 500 mL, SPME - 5 mL).     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

剩余污泥中微生物絮凝剂的提取方法比较

分别采用低浓度和高浓度剩余污泥对剩余污泥中微生物絮凝剂(MBF)的多种提取方法(超声法、树脂法、超声-树脂法、树脂-超声法、超声-树脂-超声法和树脂-超声-树脂法等)进行了比较研究.结果表明,各种复合形式的提取效果均优于超声法或树脂法单独使用的提取效果.在各种复合形式中,以树脂-超声法所提取MBF的含量最高且絮凝效果最好.此外,所提取的MBF浓度与污泥浓度正相关.从剩余污泥中直接提取MBF,在降低MBF生产成本的同时实现了污泥的资源化利用.     

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Influence of agricultural antibiotics and 17beta-estradiol on the microbial community of soil

Agricultural pharmaceuticals are a major environmental concern because of their hazardous effects on human and wildlife. This study analyzed phospholipid ester-linked fatty acids (PLFAs) and quinones to investigate the effects of a steroid (17beta-estradiol) and agricultural antibiotics (chlortetracycline and tylosin) on soil microbes in the laboratory. Two different types of soil were used: Sequatchie loam (0.8% organic matter) and LaDelle silt loam (9.2% organic matter). The soils were spiked with 17beta-estradiol and antibiotics, alone or in combination. In Sequatchie loam, 17beta-estradiol significantly increased the microbial biomass, especially the biomarkers for beta proteobacteria (16:1omega7c, 18:1omega7c, Cy17:0, and UQ-8). The coexistence of antibiotics decreased the stimulatory effect of 17beta-estradiol on the microbial community. In LaDelle silt loam, there were no significant differences in total microbial biomass and their microbial community structure among the treatments. Overall, 17beta-estradiol changed the microbial community of soil and the presence of antibiotics nullified the effect of 17beta-estradiol. However, the effects of 17beta-estradiol and antibiotics on soil microbes were sensitive to the soil properties, as seen in the LaDelle silt loam.     

Juvenile sea bass biotransformation, genotoxic and endocrine responses to beta-naphthoflavone, 4-nonylphenol and 17 beta-estradiol individual and combined exposures

Juvenile sea bass, Dicentrarchus labrax L., were exposed during 2, 4, 8, and 24 h to 0.9 microM beta-naphthoflavone (BNF), 131 nM 17 beta-estradiol (E(2)), 4.05 microM 4-nonylphenol (NP), as well as to BNF combined either to E(2) or NP (maintaining the previous concentrations). Liver cytochrome P450 content (P450), ethoxyresorufin-O-deethylase (EROD), and glutathione S-transferase (GST) activities were measured in order to evaluate biotransformation responses. Genotoxicity was assessed as erythrocytic nuclear abnormalities (ENA) frequency. The effects on endocrine function were evaluated as plasma cortisol and glucose. Cortisol was not affected by xeno/estrogens tested, either in single exposure or mixed with BNF. Nevertheless, the intermediary metabolism was affected since glucose concentration increased after 4 h exposure to E(2), and after all BNF+NP exposure lengths. Moreover, a synergism between BNF and NP was thoroughly demonstrated, whereas a sporadic antagonistic interaction was found at 4 h BNF + E(2) exposure. Liver EROD and GST activities were not significantly altered by single E(2) or NP exposure. However, both compounds were able to induce EROD activity in the presence of BNF. NP single exposure was able to significantly increase liver P450 content, while its mixture with BNF displayed an antagonistic interference. Considering the xeno/estrogens single exposures, only NP induced an ENA increase; however, both mixtures (BNF + E(2) and BNF + NP) displayed genotoxic effects. Fish responses to mixtures of xenobiotics are complex and the type of interaction (synergism/potentiation or antagonism) in a particular mixture can vary with the evaluated biological response.     

Effects of surfactants on extraction of phenanthrene in spiked sand

Problems associated with polynuclear aromatic hydrocarbon (PAH) contaminated site in environmental media have received increasing attention. To resolve such problems, innovative in situ methods are urgently required. This work investigated the feasibility of using surfactants to extract phenanthrene on spiked sand in a batch system. Phenanthrene was spiked into Ottawa sand to simulate contaminated soil. Six surfactants, Brij 30 (BR), Triton X-100 (TR), Tergitol NP-10 (TE), Igepal CA-720 (IG), sodium dodecyl sulfate (SDS) and hexadecyl trimethyl ammonium bromide (HTAB) were used. Adjusting the extraction time, mixing speed and surfactant concentration yielded the optimum extracting conditions. The concentration of phenanthrene was identified with HPLC. Under the experimental conditions, results indicated that those surfactants were highly promising on site remediation since the residual phenanthrene concentration was effectively reduced. The optimum operating conditions were obtained at 30 min, 125 rpm and surfactant concentrations in 4%.