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1.
Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.  相似文献   

2.
This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal–SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb2+ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.  相似文献   

3.
This paper deals with the use of derivative potentiometric stripping analysis (dPSA) as a rapid and precise method to determine Cd(II), Cu(II), Pb(II), and Zn(II) levels in red and white wine samples from Sicily, Campania, and Tuscany and to investigate the possible connection between the content of these metals and the pesticide treatments used in vine-growing to control plant diseases and pests. dPSA allowed direct quantitation of heavy metals in acidified wines without any sample pretreatment. Mean recoveries of Cd(II), Cu(II), Pb(II), and Zn(II) ranged from 95.5 to 99.2% for white wine samples and from 96.1 to 100.0% for red wine samples. The obtained results showed that Cd(II) was not found in any sample and that Cu(II), Pb(II), and Zn(II) levels were always lower than the toxicity limits in both fungicide- and water-treated wines. Nevertheless, the contents of metals were increased in samples from organic and inorganic pesticides treatment with respect to the water-treated samples. In particular, quinoxyfen, dinocap-penconazole, and dinocap applications considerably increased Cu(II) and Zn(II) contents in white and red wines. The levels of lead were significantly raised by azoxystrobin and sulfur treatments.  相似文献   

4.
Metals are commonly determined in aquatic organisms, primarily using bivalves to provide important data on their bioavailability. The technique of diffusive gradients in thin films (DGTs) has also been employed to assess the concentration of metals in freshwater and marine environments, determining their lability. The present work evaluated and compared the labile and bioavailable concentrations of Cd, Co, Cu, Mn, Ni and Pb in seawater from Ilha Grande Bay, RJ, using DGT and transplanted bivalves (Nodipecten nodosus), respectively. The scallops and DGTs were immersed in water at three sampling locations within the bay from July to September 2012 (winter campaign) and from December 2012 to February 2013 (summer campaign). The metals were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). DGT technique was successfully used to determine the concentrations of metals in waters, except for Pb when short deployment times were used. All metals were determined using transplanted bivalves (N. nodosus), but pre-exposure to Cd was evident, which made the interpretation of the data for this analyte difficult. The data on metal lability in Ilha Grande Bay waters obtained from the DGT technique were correlated with the metal bioavailability determined in the soft tissues of the transplanted N. nodosus for Co, Cu, Mn, Ni and Pb. This is the first evaluation of this type for this area of high environmental concern. Both techniques revealed that Náutico was the location with the highest concentration of metals in the study area.  相似文献   

5.

Purpose

The aim was to study Cu (II), Zn (II), and Pb (II) forms in technogenically transformed soils adjacent to the Karabashmed copper smelter.

Materials and methods

Studies were performed in the plume zone of the Karabash smelter and in the floodplains of Ryzhii Brook and Sak-Egla River. Geomorphological and geochemical migration processes prevail in technogenic landscapes. The differentiation of landscape-geochemical conditions plays the dominant role, which determines the localization of metals. The total Mn, Cr, Ni, Cu, Zn, Pb, Cd, and As contents and the macroelement compositions of soils were determined by X-ray fluorescence. The composition of Cu, Pb, and Zn compounds in soils was determined by the Tessier sequential fractionation. The determination of the geochemical fractions of heavy metals in soils is a key issue in the study of their mobility. The metals were fractionated into the following five fractions: exchangeable, bound to carbonates, bound to Fe and Mn oxides, bound to organic matter, and residual fractions.

Results and discussion

It is shown that the total Zn and As contents in the 0- to 5-cm layer of soils on monitoring plots exceed their lithosphere clarks in hundreds of times, and the total Cu, Pb, and Cr contents exceed their lithosphere clarks in tens of times. Factors and processes controlling the distribution and transport of Cu, Pb, and Zn forms in soils were determined. According to landscape-geochemical differentiation, the eluvial (automorphic) catena (plot T4) takes the main technogenic load of dust fallouts from the Karabash copper smelter. The accumulation of material brought from above and the geochemical precipitation of discharges from tailings dumps occur in superaqual catenas (plots T1, T2, and T3). In the technogenically transformed soils, the basic stabilizers of the mobility of Cu is organic matter, for Pb it is Fe-Mn (hydro) oxides, and for Zn - it is clay minerals.

Conclusions

The distributions of Cu, Zn, and Pb forms in the studied technogenically transformed soils are due to a number of factors: First, these are the composition of technogenic pollutants contaminating ecosystems and the time during which the contamination occurred, and second, this is the combination of physicochemical properties controlling the buffer properties of the polydisperse system of soils and parent materials.
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6.
The first part of this paper deals with the sorption of Na, Cs, Sr, Ni, Cu and Pb on two humic fractions derived from a soil. The sorption data for individual elements were obtained using the continuous-flow stirred-cell (CFSC) technique, in which the metal sorptive solution is pumped through a cell containing a known mass of the humic acid retained by a filter and the solution emerging from the cell was analysed by either atomic absorption spectrometry (Cu, Ni and Pb) or by the combined use of radioisotope dilution and gamma-ray spectroscopy (Na, Cs and Sr). Sorption isotherms were determined at two flow rates. It was found that, in general, the sorption isotherms for all the metals studied could be described by the Langmuir equation and parameters derived from the fitted line provided information on the metal-humate binding strengths and the maximum amount of metal sorbed per unit mass of humic acid. Caesium showed anomalous behaviour at certain flow rates in both its sorption and desorption behaviour. In the second part of the paper we discuss the sequential sorption and desorption of one metal by another on the same humic fraction, using Na, Cs, Zn and Cd. The aim was to elucidate the nature of the binding process when several metals were competing simultaneously for the functional groups on the humic acids. In addition, at the end of the experiment, the humic material was isolated and analysed by gamma-ray spectroscopy to determine the metals still bound in this fraction. Some tentative conclusions concerning the nature of the metal-humate complexes are made on the basis of these data.  相似文献   

7.
The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior. Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers.  相似文献   

8.
The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.  相似文献   

9.
Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.  相似文献   

10.
3种改良剂对油菜生物量及其吸收重金属的影响   总被引：2，自引：0，他引：2  
通过连续三季盆栽试验研究粉煤灰、膨润土、腐殖酸提高油菜生物量,降低油菜Cd、Pb、Cu、Zn浓度的效果。结果表明,膨润土、腐殖酸、粉煤灰的施入提高油菜生物量的效果第二季好于第一、三季。仅考虑对生物量的影响,改良剂效果为膨润土>腐殖酸>粉煤灰。第二季膨润土降低油菜Cd浓度效果较好;第二季粉煤灰、第二季膨润土及第二、三季腐殖酸降低油菜Pb浓度效果较好,3种改良剂均有降低油菜中Pb浓度的效果;3种改良剂均未显著影响油菜中Cu浓度;第二季膨润土降低油菜Zn浓度效果较好。3种改良剂抑制土壤重金属进入油菜的效果不同,应用时可根据改良剂特点适时施入土壤,充分发挥改良剂吸附、固定重金属的作用。  相似文献   

11.
This study evaluated the effect of lead (Pb(II)), zinc (Zn(II)) and copper (Cu(II)) on growth and sporulation of four Halophytophthora species (Halophytophthora vesicula, Halophytophthora elongata, Halophytophthora spinosa var. lobata, and an oogonia-producing Halophytophthora sp.) isolated from different mangrove sites in Taiwan. Results show that all isolates grew well or even better at 1 ppm concentration of the heavy metals tested. Growth of all test isolates was totally inhibited at 500 ppm, except for H. spinosa var. lobata exposed to Zn(II). For sporulation, all isolates produced moderate to abundant zoosporangia or oogonia at 1 ppm Pb(II) and Zn(II). Production of zoosporangia by H. vesicula, H. elongata and H. spinosa var. lobata was significantly affected or totally inhibited at 1 ppm Pb(II) and Zn(II) and all concentrations of Cu(II). Abnormal oogonia were produced by Halophytophthora sp. at 10 ppm Cu(II) and 100 ppm of the three heavy metals. In general, Cu(II) and Zn(II) were found to be the most toxic, and the least toxic was Pb(II). H. spinosa var. lobata was the most tolerant to all the heavy metals, while H. vesicula and H. elongata were the most sensitive. Results of this study shows that increased concentrations of Pb(II), Cu(II), and Zn(II) in the mangrove environment can significantly affect growth and impair normal reproduction of Halophytophthora species.  相似文献   

12.
Conventional methods of measuring labile chemical species of trace metals in soil solutions, such as chemical competition following centrifuging, are inadequate if the speciation changes during sampling and extraction. A new technique, diffusive gradients in thin films (DGT), measures labile species of trace metals in natural waters and sediments in situ. A well-defined diffusive gel layer distinguishes it from other resin-based techniques. It perturbs the soil in a controlled way by introducing an in situ local sink for metal ions. Resulting fluxes to the device are quantitatively measured, allowing assessment of re-supply kinetics and in some cases measurement of in situ soil solution concentrations. We used DGT to measure fluxes of Cd, Co, Cu, Ni, Pb and Zn in a sludge-treated soil at various moisture contents (27–106%). Replicate measurements showed that the precision of DGT-measured fluxes was within 10%. For moisture contents exceeding the field capacity (42%), the DGT response reflected soil water concentrations. At smaller moisture contents, changes related to tortuosity and dilution were reflected in the measurements. This technique has the potential for in situ measurements in the field where it should provide quantitative flux data on individual soils and provide a good surrogate for bioavailable metal.  相似文献   

13.
Bioavailability as a Factor in Risk Assessment of Metal-Contaminated Soil   总被引：1，自引：0，他引：1  
To accurately assess the risks of metal contaminants in soil, the bioavailability of the metals need to be considered. The bioavailable concentrations determined from homogenized, dried soils are not necessarily representative of in situ conditions of undisturbed field soils. In this study, we investigated the accumulation of metals in wheat (Triticum aestivum) grown in undisturbed contaminated (Pb, Zn, Cu, and Cd) soil cores, in relation to total soil, leachate, and diffusive gradients in thin films (DGT)-labile metal concentrations. Despite the fact that many of the samples contained metal concentrations above guideline values, no significant effects were observed on wheat growth. The bioavailability of metals in the most contaminated samples was estimated to be medium to low, possibly explaining why few effects were observed in the bioassay. For Cu, Zn, and especially for Pb, leachate and DGT-labile concentrations were better predictors of uptake by wheat than total concentrations based on correlations. It is suggested that DGT and leachate concentrations in combination with bioassays in undisturbed soil cores can be used to account for metal bioavailability in soil. These tests could be used during the ecological risk screening stage, in conjunction with total concentrations and guideline values to better estimate receptor exposure.  相似文献   

14.
Fulvic acid is a water-soluble humic material that occurs widely in soils and waters and that tends to form water-soluble and water-insoluble complexes with a variety of metal ions, some of which are toxic. This paper presents information on the conditions under which the different types of FA-metal complexes are formed. The solubility in water, separately and after mixing, of FA (2 to 30 mg/100 ml) and eleven metal ions (Fe(III), Al, Cr(III), Pb, Cu, Hg(II), Zn, Ni, Co, Cd and Mn; 1 × 10?5 moles of each metal ion) was investigated over the pH range 4 to 9. After mixing, the solubility of the components was significantly affected by pH only when less than 20 mg of FA was present. As the systems became richer in FA (22 to 30 mg), most of the metal ions remained in the aqueous phase, likely due to the formation of FA-metal complexes, inhibiting the formation of metal hydroxides. The order in which the eleven metal ions tended to form water-insoluble FA-metal complexes depended on the pH. At pH 6 it was: Fe = Cr = Al > Pb = Cu > Hg > Zn = Ni = Co = Cd = Mn. This order appeared to correlate with the valence, 1st hydrolysis constants and effective hydrated ionic diameters of the metal ions. In general, FA/metals weight ratios of > 2 favored the formation of water-soluble FA-metal complexes; at lower ratios, water-insoluble complexes, which could accumulate in soils and sediments, were formed.  相似文献   

15.
Complexation of Cu, Pb, and Cd by hot water soluble humic substances II. The stability of the complexes Soxhlet extracts of terrestrial and underwater soils were used to determine polarographically the stability of heavy metal complexes. Stability constants were calculated using the law of mass action. They were independent of concentration at levels higher than 2 mg Cd or 5 mg Pb/g humic substance, respectively. For Cu, constants increased below 8 mg Cu/g. At pH values in the polarographic medium between 4 and 8, the stability of the Pb complexes increased markedly with increasing pH. In most cases this was also valid for the copper complexes, cadmium complexes were either not influenced by pH or stability maximum was obtained at about pH 5. Drying of the samples before extraction did not alter significantly complex stabilities. Complex stabilities increased with increasing degree of humification for oligotrophic, underwater soils and nutrient poor, low moor peat, but reduced horizons of eutrophic gyttjas exhibited lower stability values.  相似文献   

16.
The competing ligand exchange method was used to investigate the competitive binding of Ni(II) by Al(III) and Fe(III) in model aqueous solutions and freshwaters. Graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry were used to monitor the rate of uptake of the Ni by Chelex 100 chelating resin and dimethylglyoxime as the competing ligands, respectively. The results have revealed that Ni(II)–humate complexes were more labile in presence of the mixture of Al(III) and Fe(III), compared to the lability of the Ni(II)–humate complexes when only one of the two, Al(III) or Fe(III), was present. The environmental significance of this work is that in model solutions simulating freshwater containing humic substances and the target trace metal Ni(II) and cations, Al(III) and Fe(III), the competitive binding of Ni(II), Al(III) and Fe(III) by humic substances makes Ni(II)–humate complexes labile, releasing free Ni2+–aqua complex, which reported to be toxic.  相似文献   

17.
Volcanic rock is a potential adsorbent for metallic ions from wastewater. This study determined the capacity of Gisenyi volcanic rock found in Northern Rwanda to adsorb Cd, Cu, Pb and Zn using laboratory scale batch experiments under a variety of experimental conditions (initial metal concentration varied from 1 to 50 mg/L, adsorbent dosage 4 g/L, solid/liquid ratio of 1:250, contact time 120 h, particle size 250–900 μm). The adsorbent had a surface area of 3 m2/g. The adsorption process was optimal at near-neutral pH 6. The maximal adsorption capacity was 6.23, 10.87, 9.52 and 4.46 mg/g for Cd, Cu, Pb and Zn, respectively. The adsorption process proceeded via a fast initial metal uptake during the first 6 h, followed by slow uptake and equilibrium after 24 h. Data fitted well the pseudo second-order kinetic model. Equilibrium experiments showed that the adsorbent has a high affinity for Cu and Pb followed by Cd and Zn. Furthermore, the rock is a stable sorbent that can be reused in multiple sorption–desorption–regeneration cycles. Therefore, the Gisenyi volcanic rock was found to be a promising adsorbent for heavy metal removal from industrial wastewater contaminated with heavy metals.  相似文献   

18.
McLaren and Crawford's method for fractionating soil Cu was modified, and used to fractionate soil Cd, Zn, Pb, and Cu in 38 soil samples from 11 soil profiles from industrially polluted and nearby unpolluted areas. Pollutant metals, especially Cd and Zn, were more soluble than the native soil metals. On average, approximately 45% of Cd was present in the CaCl2 soluble (CA) fraction, whereas corresponding values for the other metals were below 10%. The percentages of each metal in the CA fraction followed the order Cd > Zn > Pb > Cu. The same order was observed for the acetic acid soluble (AAC) fraction. Approximately 30% of total Pb and Cu were present in the pyrophosphate soluble (PYR) fraction, and only 10% of total Cd and Zn. Approximately 20% of total Zn or Pb and 10% of Cd or Cu were present in the free oxide (OX) fraction. Only 20% of Cd and between 40–50% of the other 3 metals were present in the residual (RES) fraction. The results show that Cd is more labile than the other 3 metals.  相似文献   

19.
For the purpose of studying the contamination, bioaccumulation and transfer of heavy metals and understanding the effects of soil properties on these, the work was carried out on a regional scale. A total of 30 sets of soil and pairing rice tissues samples (root, straw and grain) were collected in Xiangzhou of Guangxi, China; soil properties and Cd, Cu, Pb and Zn of different rice tissues were analyzed. The mobility and bioaccumulation of Cd, Cu, Pb and Zn were assessed by transfer coefficients and bioaccumulation factors of them. The results indicated that the excess proportions of Cd and Pb were 50%, 3.33% and 30%, 6.67% in soil and rice grain, respectively, according to Chinese maximum permitted concentrations of heavy metals. Cd and Zn showed stronger bioaccumulation and mobility capability; the bioaccumulation and transfer of Cu were slightly lower than Cd and Zn; Pb had the weakest mobility. The bioaccumulation and mobility of heavy metals from soil to rice were restrained by soil pH, CaO, SOC, Fe oxides and Mn.  相似文献   

20.
长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征   总被引：3，自引：1，他引：3  
为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。  相似文献   

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