Changes in copper, lead and zinc concentrations in plants from paper mill sludge-treated soils

Effects of paper mill sludge addition on the availability of metals were studied on different soils both laboratory and naturally polluted; copper, lead and zinc concentrations were determined in Hordeum Distichum plants grown on the untreated and on sludge-treated soils. In some case a decrease of metal concentration is observed on sludge-treated soils; these results are consistent with the reduction of metal mobile forms in the soil, before plant growth. The decrease of metal availability in sludge-treated soils may be related with the pH value of the soil after sludge addition.     

造纸污泥添加剂对麦秆灰烧结熔融特性的影响

利用灰熔点测试仪、XRD及XRF等仪器,对比研究了造纸污泥(脱墨污泥、造纸废水污泥)、城市废水污泥作为添加剂对麦秆灰熔融特性的影响,考察了烧结和熔融过程中的组分变化,分析了污泥添加剂对麦秆灰的作用机理;进一步将污泥添加剂与常规添加剂进行灰熔融特性对比研究。研究发现,添加比例控制为3%-10%,造纸污泥(脱墨污泥、造纸废水污泥)软化温度提升效果均优于城市废水污泥;在添加比例控制为5%时,造纸废水污泥对麦秆灰软化温度提升效果最好;增大添加比例过程中,造纸废水污泥Al_2O_3修饰骨架作用明显,但灰中长石类物质逐渐增多使得软化温度提升效果下降;在不同温度下,脱墨污泥主要是通过形成硅铝榴石使得灰熔点提升,造纸废水污泥则主要是通过生成高熔点物质CaSiO_3抑制低熔点硅酸盐形成,城市废水污泥升温中存在明显SiO_2晶态转变过程;使用污泥添加剂作为抗结渣添加剂具有良好应用前景。     

石墨炉原子吸收法测定土壤中铅、镉、钴、锑、铍

建立石墨炉原子吸收法测定土壤中铅、镉、钴、锑、铍含量的方法。优化了石墨炉原子吸收光谱法测定条件,在最佳实验条件下,采用硝酸-盐酸-氢氟酸-双氧水混合酸体系微波消解土壤样品,选用抗坏血酸-硝酸镁混合溶液为基体改进剂。铅、镉、钴、锑、铍的质量浓度在各自的范围内与吸光度成良好的线性关系,相关系数均大于0.999,各元素的检出限为0.008~0.06 μg/g。样品加标回收率为90.5%~104.0%,测定结果的相对标准偏差均小于2.5%(n=6)。该方法样品前处理简便,灵敏度高,检出限低,测定结果准确、可靠,可用于土壤中铅、镉、钴、锑、铍的测定。     

The increase of iron phytoavailability in soils ammended with paper mill sludge

In soils characterized by low organic matter and high pH values (7.5-8.59) iron availability to plants is limited even if the content of total Fe(III) is high. We have studied by Hordeum distichum plants the capability of paper mill sludge to increase the iron phytoavailable fraction in an alkaline soil. The effect of paper mill sludges adding to an iron-deficient soil was evaluated both considering the phyto-available fraction of iron and the distribution of organic carbon (hydrophobic, fulvic and humic carbon) in the soil before and after sludge adding. Iron concentration was determined in the different portions of Hordeum distichum plants grown on soils with and without paper mill sludges. Application of paper mill sludge induces an increase in the concentration of available Fe. This effect is probably due to the production of Fe chelators by soil microorganisms acting on sludge organic matter. The Fe chelators produced result in the solubilization of not soluble Fe-complexes present in the soil.     

Laboratory studies on waste water sludge application for acid soil remediation

In this work the effects of sludge disposal on pH values, buffer capacity and adsorption capacity of an acid soil were studied. A stabilized waste water sludge and a paper mill sludge were employed; the pH values of both sludges were higher than 8. The observed differences between soil-urban sludge and soil-paper mill sludge systems can be ascribed to the nature of the compounds present in the sludges and adsorbed on the soil. Both kinds of sludge are able to modify the natural pH of the soil, the buffer capacity and its capacity to retain metal. These modifications increase with increasing soil-sludge contact time and are higher for paper mill sludges. Temperature affects only the modifications due to urban sludge treatment.     

Sorption, desorption and extraction of cadmium from some arable and forest soils

Summary The behavior of cadmium labeled with ¹⁰⁹Cd in different depth horizons of arable and forest soils were studied under static (batch) conditions in three interconnected processes, which consist of sorption, desorption and extraction. In the sorption, Cd²⁺ was applied in the aqueous calcium nitrate solution. Both untreated soils and peroxide treated soils were used in order to remove organic matter from some of the soil samples used in parallel. The influence of the V/m ratio on the sorption coefficients was investigated in preliminary experiments with untreated soils. Contrary to the usually short-term sorption, a long-term sorption of cadmium was investigated in untreated and treated soil horizons, which lasted more than fortnight. Kinetic studies of sorption were carried out and cadmium concentration dependence in aqueous phase of the second order kinetic constants was observed. For evaluation of sorption and desorption processes Freundlich isotherms were used. It was found that the Freundlich adsorption intensity coefficient is more time dependent than the absorption capacity coefficient, and the sorption itself consists of rapid and slow processes according to the soil constituents. Desorption and extraction processes revealed the possibility of cadmium recovery from various soil horizons. Based on the obtained results two- or three-stage theory of cadmium retention in soils was proposed. Some new insight into the role of organic matter in the sorption/desorption process of cadmium is also presented.     

Sorption of cadmium in some arable and forest soils

The sorption of cadmium labeled with ¹⁰⁹Cd in nitrate form, from aqueous solutions in different horizons of some arable and forest soils was studied under static (batch) conditions. Before sorption, a method of sequential soil treatment was applied, which consist in the consecutive removal of individual soil components by the use of appropriate reagents and procedures. Three sorption isotherms were tested. Kinetic studies showed that the sorption of cadmium is rather rapid and it can be well described by a Freundlich or a linear isotherm, whereas the closeness of Langmuir isotherm to the experimental results is lower. From the different sorption isotherms, it would also be possible to estimate the effect of individual components on the sorption of cadmium in soils. It was found that the untreated soils exhibit the highest sorption and the sorption decreases in the order of untreated > acetate treated > water treated > peroxide treated > dithionite treated soil. Sorption of cadmium increases with the depth of the studied soils disregarding their chemical treatment.This revised version was published online in November 2005 with corrections to the Cover Date.     

Sorption of cobalt(II) on soil: effects of birnessite and humic acid

To study the sorption behavior of Co(II) on soil and soil components such as birnessite, humic acid (HA) and their mixture, a series of experiment were conducted using the batch equilibrium technique on parameters such as equilibrium time, ionic strength, solution pH, and temperature. The soil samples collected from location near radioactive waste repository in Korea were used and birnessite was synthesized using a method by McKenzie for experiment. The experimental results indicate that Co sorption on soil, birnessite and soil with birnessite are strongly affected by the pH of solution. Typical for metal sorption to soils, the fraction of Co adsorbed increased as a function of pH at the experimental conditions. For sorption isotherm, the Freundlich equation provides a good fit for sorption on soil and soil with birnessite. Adsorption of HA on birnessite decreased with increase of pH, with a sharp decrease at pH 5?C6. From Co sorption experiment in a ternary system of Co, birnessite, and HA, the presence of HA enhanced Co adsorption at pH below 6.5 and reduced the Co sorption at the intermediate and high pH.     

Interaction and fractionation of added cadmium in some typical soils of the Danubian Lowland

This study was conducted to investigate the effect of time on cadmium (¹⁰⁹Cd) availability in four typical soils of the Danubian Lowland through the modified Tessier’s sequential extraction procedure as well as its short-term sorption in the bulk soils and their two grain-size fractions. Results of the fractionation study showed that there were significant changes in the proportional distribution of cadmium in all studied soils during 180 days of incubation with spiked cadmium. Generally, the proportions of cadmium associated with the most weakly bound fractions (water soluble and exchangeable) tended to decrease with corresponding increases in the residual fraction during the incubation. The extent of cadmium sorption in all studied soils was high, exceeding 95% of the spiked amount after 60 min of incubation, likely due to slightly alkaline character of the soils. The finding that soil particles less than 10 μm sorbed up to 51% of the spiked cadmium in soils is of great importance since they could play a role in colloid-facilitated transport of cadmium through preferential pathways, as previously observed in the region. Addition of 1 M ammonium nitrate into the soil solution generally decreased cadmium sorption in all four soils. The lowest extractabilities of Cd were obtained using 1 M ammonium nitrate as a single extractant, whereas 0.025 M ammonium ethylenediaminetetraacetate solution extracted the highest proportions of cadmium from the studied soils.     

Selected drugs in solid matrices: a review of environmental determination, occurrence and properties of principal substances

After intake, drugs absorbed by human or animal organisms are subject to metabolic reactions, such as hydroxylation, cleavage or glucuronation. However, a significant amount of the original or the metabolized substance leaves the organism via urine or feces. Thanks to improvements in analytical chemistry, many pharmaceutical compounds and endocrine disrupters are more easily detected in the surface-water and waste-water environmental compartments, at ppb concentrations.But what contaminates our solid environmental matrices? These substances can be eliminated by sorption or biodegradation but, at present, there is not enough data to allow evaluation of the behavior of the substances through the solid compartment, such as soil, sludge and bio-waste.This article provides an overview of the occurrence of pharmaceutical compounds in solid matrices on the basis of the quantities used, their physico-chemical properties and data from literature indicating the potential of the drug to persist in sediment, soil or sludge.     

造纸污泥薄层干燥实验及动力学模型分析

通过造纸污泥薄层干燥实验,考察了温度对造纸污泥干燥特性的影响,引入薄层干燥模型对污泥干燥动力过程进行模拟。结果表明,泥层越薄和干燥温度越高,污泥干燥的速率就越快,当干燥温度从80℃上升到160℃时,相对应的最大干燥速率从0.008g/(g·min)上升到0.030g/(g·min);Modified page模型描述了薄层造纸污泥在烘箱中的干燥过程,应用Fick扩散模型,薄层造纸污泥在干燥温度为80℃～160℃时,有效扩散系数为2.2×10^-10m²/s~3.96×10^-10m²/s。通过Arrhenius方程建立温度和有效扩散系数之间的关系,得出水分扩散的活化能为9.435kJ/mol。     

Biodegradation of PVA-based formulations

Investigation of the biodegradability of water soluble poly(vinyl alcohol) (PVA) based blown films was carried out under different lab-scale environmental conditions. In particular respirometric tests were utilized in order to evaluate the biodegradability of PVA films in composting, in modified Sturm test and in soil burial simulation tests. Several microbial inocula present in river water, mature compost, forest and farm soils as well as sewage sludge from municipal and paper mill wastewater treatments plants were utilized for the relevant tests. A mixed PVA-degrading microbial culture was obtained by a common enrichment procedure by using sewage sludge from paper mill as inoculum; this culture was tentatively utilized for the isolation of single PVA-degrading microorganisms. As a first result we can stress that significant biodegradation extent in fairly low incubation time can be obtained only in the presence of acclimated microbial populations such as those deriving from paper mill sewage sludge, in liquid cultures. Nevertheless separation of single degrading microbial species was impossible most likely due to the establishment of symbiotic or commensal interactions between the single components of the PVA-degrading mixed cultures. On the other hand, limited mineralization rates were recorded in solid cultures in the presence of soil or compost. Finally, a mechanism of degradation of polymer chains unlike random or unzipping was suggested in the presence of either PVA-degrading mixed culture and its filtrate by means of viscometric determinations of molecular weight within the time.     

Thermodynamics of interactions between lead(II) and cadmium(II) ions and azulene-based complexing polymer films

In order to understand the essential processes/interactions between the metal ions and modified electrodes which are based on complexing polymeric films, access to thermodynamic characteristics is compulsory. The paper enlarges the information concerning the sorption of metal ions within complexing polymer films, particularly based on azulene, which can be involved in metal detection sensors. Interactions between lead(II) or cadmium(II) ions and complexing polymer films have been studied using chemical preconcentration–anodic stripping method. The films have been obtained by controlled potential electrolysis in millimolar solutions of 4-azulen-1-yl-2,6-bis(2-thienyl)pyridine (L) in acetonitrile. PolyL films affinities towards these metal ions have been quantified at different temperatures by means of sorption isotherms. Parameters for sorption of lead(II) and cadmium(II) ions within polyL films have been calculated for Freundlich, Langmuir and Redlich–Peterson isotherms. The best fit was obtained when using Langmuir isotherm. The results evidence that lead ions are better sorbed than cadmium within polyL film. Thermodynamic parameters for the chemical sorption of lead(II) and cadmium(II) ions within polyL films have been calculated.     

微波消解-ICP-MS测定电镀污泥中的重金属

采用微波消解系统对某电镀污泥进行消解,利用ICP-MS对污泥中的重金属进行测定。称取制备后样品,置于消解罐中充分反应后,赶酸、定容后利用电感耦合等离子体质谱法进行测定。电镀污泥中的铬为18845.2mg/kg、镉为10.3mg/kg、镍为5200.0mg/kg、铅为189.7mg/kg、铜为3271.7mg/kg、锌为49632.6mg/kg。测定结果表明所检测项目工作曲线线性关系好,相关系数r均大于0.999。铬加标回收率在91.6～97.7%之间、镉加标回收率在92.0～97.0%之间、镍加标回收率在95.1～98.0%之间、铅加标回收率在94.3～95.2%之间、铜加标回收率在97.1～102%之间、锌加标回收率在96.3～98.7%之间,均满足相关测定要求。计算的潜在生态危害系数、潜在生态危害指数结果表明,电镀污泥中的铬、镉、铅、铜、锌为轻微生态危害,镍为强生态危害;潜在生态危害指数RI计算值为216.69,属于中等生态危害。     

Starch coated titanium dioxide nanoparticles as a challenging sorbent to separate and preconcentrate some heavy metals using graphite furnace atomic absorption spectrometry

In this study, a challenging nanosorbent was described for preconcentration/separation method based on the sorption of cadmium, cobalt, copper, nickel, lead on starch coated titanium dioxide nanoparticles and its analysis by graphite furnace atomic absorption spectrometry. Optimum conditions were investigated for quantitative sorption. By using the proposed technique, the analyte elements were determined in spiked tap-water samples in the range of 95% confidence level. Limit of detection (3δ) was 0.05, 0.28, 1.90, 3.10 and 0.11 µg/L (3σ, N = 10) for cadmium, cobalt, copper, nickel and lead, respectively. The optimised technique is fast, easy handled, simple and environmental friendly.     

Thermal analysis of growing media obtained from mixtures of paper mill waste materials and sewage sludge

This study deals with thermal analysis of growing media obtained from mixtures of paper will waste materials (one de-inking paper sludge, HP, and one reject from paper mill producing paper from virgin wood, RT) with sewage sludge. For the growing media formulation, one sewage sludge (L) was mixed with both paper mill waste materials at 10, 20, and 30% in volume. An incubation experiment was designed in order to study their carbon mineralization. Addition of sewage sludge significantly increases the carbon mineralization of growing media based on RT. In case of HP, carbon mineralization increases after addition of sewage sludge in 30% (HP + 30L treatment). Thermogravimetric analysis (TG and DTG) of growing media was performed before and after incubation experiment in order to study the organic matter transformation. The higher the carbon mineralization, the greater the difference between TG curves of samples before and after the incubation. The WL₃/WL₂ ratio increases after incubation of samples as a result of organic matter stabilisation. For HP growing media, the highest value corresponds to HP + 30L whereas HP + 20L, and HP + 10L show similar values. In case of RT, the WL₃/WL₂ index shows a progressive increase with sewage sludge content.     

Insight into the Sorption of 5-Fluorouracil and Methotrexate onto Soil–pH,Ionic Strength,and Co-Contaminant Influence

Nowadays anticancer drugs (ADs), like other pharmaceuticals, are recognized as new emerging pollutants, meaning that they are not commonly monitored in the environment; however, they have great potential to enter the environment and cause adverse effects there. The current scientific literature highlights the problem of their presence in the aquatic environment by publishing more and more results on their analytics and ecotoxicological evaluation. In order to properly assess the risk associated with the presence of ADs in the environment, it is also necessary to investigate the processes that are important in understanding the environmental fate of these compounds. However, the state of knowledge on mobility of ADs in the environment is still very limited. Therefore, the main aim of our study was to investigate the sorption potential of two anticancer drugs, 5-fluorouracil (5-FU) and methotrexate (MTX), onto different soils. Special attention was paid to the determination of the influence of pH and ionic strength as well as presence of co-contaminants (cadmium (Cd²⁺) and another pharmaceutical—metoprolol (MET)) on the sorption of 5-FU and MTX onto soil. The obtained distribution coefficient values (K_d) ranged from 2.52 to 6.36 L·kg⁻¹ and from 6.79 to 12.94 L·kg⁻¹ for 5-FU and MTX, respectively. Investigated compounds may be classified as slightly or low mobile in the soil matrix (depending on soil). 5-FU may be recognized as more mobile in comparison to MET. It was proved that presence of other soil contaminants may strongly influence their mobility in soil structures. The investigated co-contaminant (MET) caused around 25-fold increased sorption of 5-FU, whereas diminished sorption of MTX. Moreover, the influence of environmental conditions such as pH and ionic strength on their sorption has been clearly demonstrated.     

Online Preconcentration Using Surfactant Coated Alumina Modified with 1,5-Diphenylthiocarbazone and Determination of Cadmium in Environmental Samples by Flame Atomic Absorption Spectrometry

A rapid and sensitive method for the determination of trace levels of cadmium in cigarettes, soil, and blood samples by flame atomic absorption spectrometry (FAAS) has been developed. It is based on the online sorption of Cd(II) ions on a minicolumn packed by sodium dodecyl sulfate–coated alumina modified with dithizone. The optimum experimental parameters for the adsorption and desorption of cadmium were investigated. The recovery obtained was found to be 96% with preconcentration factor of 150. The calibration curve was linear between 50–600 µg/L Cd with a detection limit of 3 µg/L, sample frequency of 30 h^?1 and reuse of column for 10 times without loss of sensitivity. The accuracy of the method was confirmed by applying the standard addition method and quantitative recoveries (95–99%) were obtained.     

Determination of cadmium and lead in table salt by sequential multi-element flame atomic absorption spectrometry

In the present paper, a simultaneous pre-concentration procedure for the sequential determination of cadmium and lead in table salt samples using flame atomic absorption spectrometry is proposed. This method is based on the liquid-liquid extraction of cadmium(II) and lead(II) ions as dithizone complexes and direct aspiration of the organic phase for the spectrometer. The sequential determination of cadmium and lead is possible using a computer program. The optimization step was performed by a two-level fractional factorial design involving the variables: pH, dithizone mass, shaking time after addition of dithizone and shaking time after addition of solvent. In the studied levels these variables are not significant. The experimental conditions established propose a sample volume of 250 mL and the extraction process using 4.0 mL of methyl isobutyl ketone. This way, the procedure allows determination of cadmium and lead in table salt samples with a pre-concentration factor higher than 80, and detection limits of 0.3 ng g⁻¹ for cadmium and 4.2 ng g⁻¹ for lead. The precision expressed as relative standard deviation (n = 10) were 5.6 and 2.6% for cadmium concentration of 2 and 20 ng g⁻¹, respectively, and of 3.2 and 1.1% for lead concentration of 20 and 200 ng g⁻¹, respectively. Recoveries of cadmium and lead in several samples, measured by standard addition technique, proved also that this procedure is not affected by the matrix and can be applied satisfactorily for the determination of cadmium and lead in saline samples. The method was applied for the evaluation of the concentration of cadmium and lead in table salt samples consumed in Salvador City, Bahia, Brazil.     

Sorption study of 25 volatile organic compounds in several Mediterranean soils using headspace-gas chromatography-mass spectrometry

A sorption study of 25 volatile organic compounds (VOCs) in different agricultural soils was carried out by using headspace-gas chromatography-mass spectrometry. The extraction of the VOCs from soil samples was carried out following the EPA method with some differences such as addition of potassium chloride and different instrumental conditions which provide higher sample throughput. In addition, a complementary study on several procedures for soil fortification with VOCs was also assayed, fortification with minimal sample handling was selected in order to minimise evaporation losses of the VOCs. The effect of clay minerals (7.0-69.7%) and organic carbon (0.2-3.5%) contents on acid and alkaline (pH 5.3-8.8) soils were evaluated. Based on the results, all compounds assayed were more sorbed in alkaline soils than acid ones; chlorobenzenes interact more strongly with agricultural soils than do alkylbenzenes. The organic carbon content affects the sorption of 25 VOCs in alkaline soils (the highest sorption was found for the most organic soil), while in acid soils VOC sorption increases as the organic carbon content decreases. The clay mineral fraction plays an important role in the sorption of VOCs in acid soil owing to pi-/n-electron interactions, this effect being more marked for chlorobenzenes.