Speciation of Zn,Cu, and Pb in the soil depending on soil texture and fertilization with sewage sludge compost

Background, aim, and scope  Heavy metal (HM) mobility in soil depends on the HM species in it. Therefore, knowledge of the HM speciation in soil allows the prediction of HM impact on the environment. HM speciation in soil depends on the metal chemical origin, soil texture, and other factors such as the origin and level of soil contamination. Recently, the problem of organic waste utilization is of great importance as the amount of this recyclable material is continually increasing. One of the possible ways of recycling is the use of processed organic wastes for agricultural needs. In this research, aerobically composted sewage sludge was used, the utilization of which is of essential importance. But one of the most serious restrictions is HM transfer from such material to the soil. Therefore, a prediction of HM mobility in soil and its migration in the environment is an important issue when using sewage sludge compost (SSC) in agriculture. Zn, Cu, and Pb speciation was performed according to the modified methodology of Tessier et al. (Anal Chem 51:844–851, 1979) in two different (sandy and clay) soils with background HM amounts and in soil samples amended with aerobically digested SSC to find out the predominant species of the investigated HM and to predict their potential availability. Materials and methods  The modified method of sequential extraction initially proposed by Tessier et al. (Anal Chem 51:844–851, 1979) is designed for HM speciation into five species where HM mobility decreases in the order: F1—exchangeable HM (extracted with 1 M MgCl₂ at an initial pH of 7 and room temperature), F2—carbonate-bound HM (extracted with 1 M CH₃COONa buffered to pH 5 at room temperature), F3—Fe/Mn oxide-bound HM (extracted with 0.04 M NH₂OH·HCl at an initial pH of 2 at 96°C), F4—organic matter-complexed or sulfide-bound HM (extracted with 0.02 M HNO₃ and 30% (v/v) H₂O₂ at a ratio of 1:1 and an initial pH of 2 at 85°C), and F5—the residual HM (digested with HNO₃, HF, and HCl mixture). After digestion, HM amounts in solution were determined by atomic absorption spectrometry (AAS ‘Hitachi’). Mixtures of uncontaminated soils of different textures (clay and sandy) with SSC in ratios 20:1, 10:1, and 5:1 were used to simulate the land application with SSC. During a period of 7 weeks, changes in Zn, Cu, and Pb content within species were investigated and compared weekly in soil–SSC mixtures with their speciation in pure soil and in the SSC. Results  Results in the SSC showed that more HM were found as mobile species compared to the soils, and in sandy soil, more were found in the mobile species than in clay soil. But the HM speciation strongly depended on the metal chemical origin. According to the potential availability, HM ranked in the following order: Zn>Pb>Cu. Zinc generally occurred in the mobile species (F1 and F3), especially in sandy soils amended with SSC, and changes of the Zn speciation were insignificant at the end of the experiment. Pb transfer to insoluble compounds (F5) was evident in the SSC–soil mixtures. This confirms that Pb is extremely immobile in the soil. However, the observed increase of Pb amounts in the mobile species (F1 and F2) during the course of experiment shows a critical trend of Pb mobilization under anthropogenic influence. Copper in the soil–SSC mixtures had a trend to form compounds of low mobility, such as organic complexes and sulfides (F4) and nonsoluble compounds (residual fraction F5). Initially, the amounts of mobile Cu species (F1 and F2) increased in the soils amended with SSC, probably due to the influence of SSC of anthropogenic origin with lower pH and high organic matter content, but Cu mobility decreased nearly to the initial level again after 3–4 weeks. Hence, the soil has a great specific adsorption capacity to immobilize Cu of anthropogenic origin. Discussion  Zn mobility and environmental impact was greater than that seen for Cu and Pb, while mobility of both Cu and Pb was similar, but variable depending on soil texture and contamination level. The effect on the shift of HM mobility and potential availability was greater in sandy SSC-amended soils than in clay soils and increased with an increasing amount of SSC. Conclusions  Usage of SSC for land fertilization should be strictly regulated, especially regarding Pb amounts. Recommendations and perspectives  The influence of SSC on Cu and Zn mobility and potential availability was more significant only in the case of sandy soil with a higher SSC ratio. Nevertheless, this waste product of anthropogenic origin increased Pb mobility in all cases in spite of only moderate Pb mobility in SSC itself. Therefore, aerobic processing of sewage sludge must be strictly regulated, especially regarding Pb amounts, and SSC ratios must be in control regarding HM amounts when using it for on-land application.     

Heavy metal contamination near major highways,industrial and urban areas in belgian grassland

An investigation was made of the Zn, Cu, Mn, and Pb contents in samples of soil and grass collected along highways and in fields adjoining industrial zones in Belgium. Soil contamination by Zn and Pb was quite pronounced along highways and in some cases contamination by Mn was also observed. Contamination by these heavy metals decreased rapidly with increasing distance from the highway. High values of metal accumulation in plants located near highways were observed. The accumulation of Pb was particularly pronounced. Contamination by Cu, Zn, Pb and possibly Mn in soils of some urban gardens was also recorded.     

Near-infrared spectroscopy for analysis of chemical and microbiological properties of forest soil organic horizons in a heavy-metal-polluted area

In industrial areas, heavy metals may accumulate in forest soil organic horizons, affecting soil microorganisms and causing changes in the chemical composition of the accumulated organic matter. The objectives of this study were to test the ability of near-infrared spectroscopy (NIRS) to detect heavy metal effects on the chemical composition of forest soil O horizons and to test whether NIRS may be used to quantitatively determine total and exchangeable concentrations of Zn and Pb (Zn_t, Pb_t, Zn_ex, Pb_ex) and other chemical and microbial properties in forest soil O horizons polluted with heavy metals. The samples of O horizons (n = 79) were analyzed for organic C (C_org), total N and S (N_t, S_t), Zn_t, Pb_t, Zn_ex, Pb_ex, basal respiration (BR), microbial biomass (C_mic) and C_mic-to-C_org ratio. Spectra of the samples were recorded in the Vis-NIR range (400–2,500 nm). To detect heavy-metal-induced changes in the chemical composition of O horizons principal components (PC1–PC7) based on the spectral data were regressed against Zn_t + Pb_t values. A modified partial least squares method was used to develop calibration models for prediction of various chemical and microbial properties of the samples from their spectra. Regression analysis revealed a significant relationship between PC3 and PC5 (r = −0.27 and −0.34, respectively) and Zn_t + Pb_t values, indicating an effect of heavy metal pollution on the spectral properties of the O horizons and thus on their chemical composition. For quantitative estimations, the best calibration model was obtained for C_org-to-N_t ratio (r = 0.98). The models for C_org, N_t, and microbial properties were satisfactory but less accurate. NIRS failed to accurately predict S_t, C_org-to-S_t, Zn_t, Pb_t, Zn_ex, and Pb_ex.     

Contents and chemical forms of heavy metals in school and roadside topsoils and road-surface dust of Beijing

Purpose

The concentration of human activities in urban systems generally leads to urban environmental contamination. Beijing is one of ancient and biggest cities on the world. However, information is limited on Beijing’s soil contamination, especially for roadside and campus soils. Thus, the aims of this study were to investigate the contents and chemical forms of toxic heavy metals Cd, Cr, Cu, Ni, Pb, and Zn in the road-surface dust, roadside soils, and school campus soils of Beijing. In addition, enrichment and spatial variation of these toxic heavy metals in the soils and dust were assessed.

Materials and methods

Topsoil samples were collected from the schools and roadside adjacent to main ring roads, and dust samples were collected from the surface of the main ring roads of Beijing. These samples were analyzed for total contents and chemical forms of Cd, Cr, Cu, Ni, Pb, Sc, Zn, Al, and Fe. Enrichment factors (EFs, relative to the background content) were calculated to evaluate the effect of human activities on the toxic heavy metals in soils.

Results and discussion

Heavy metal contents in the road dust ranged from 0.16 to 0.80, 52.2 to 180.7, 18.4 to 182.8, 11.9 to 47.4, 23.0 to 268.3, and 85.7 to 980.9 mg kg^?1 for Cd, Cr, Cu, Ni, Pb, and Zn, respectively. In the roadside soil and school soil, Cd, Cr, Cu, Ni, Pb, and Zn contents ranged from 0.13 to 0.42, 46.1 to 82.4, 22.7 to 71.6, 20.7 to 29.2, 23.2 to 180.7, and 64.5 to 217.3 mg kg^?1, respectively. The average EF values of these metals were significantly higher in the dust than in the soils. In addition, the average EF values of Cd, Cu, Pb, and Zn in the soils near second ring road were significantly higher than those near third, fourth, and fifth ring roads. Anthropogenic Cd, Pb, and Zn were mainly bound to the carbonates and soil organic matter, while anthropogenic Cu was mainly bound to oxides. The mobility and bioavailability of these metals in the urban soils of Beijing generally decreased in the following order: Cd?>?Zn?>?Pb?>?Cu?>?Ni?>?Cr; while in the dust, they decreased in the following order: Zn, Cu, and Cd?>?Pb?>?Ni?>?Cr.

Conclusions

Both EF and chemical forms documented that Cr and Ni in the soils and dust mainly originated from native sources, while Cd, Cu, Pb, and Zn partially originated from anthropogenic sources. In overall, Beijing’s road dust was significantly contaminated by Cd and Cu and moderately contaminated by Cr, Pb, and Zn, while Beijing’s roadside soil and school soil were moderately contaminated by Cd and Pb. However, the maximal hazard quotients (HQs) for individual Cd, Cr, Cu, Ni, Pb, and Zn and comprehensive hazard index (HI) of these metals in the dust and soil were less than 1, indicating that the heavy metals in the dust and soil generally do not pose potential health effects to children, sensitive population.     

Lead and zinc levels and chemical fractionation in road-side soils of Caracas,Venezuela

Twenty five soil samples located nearby highways and streets of Caracas, Venezuela were collected and chemical, physical and mineralogical analysis were done to characterize them. The soils have light textures, neutral or slightly alkaline pH, medium to high organic matter content, and all of them have carbonate. Kaolinite and mica were the dominant clay minerals in all soil samples. Lead and Zn were extracted with 1N-₃ to investigate the levels of these polluting heavy metals in these roadside soils. A very high level of Pb was found in the soils (average enrichment factor of 151.4), while Zn levels were much lower (average enrichment factor of 5.25), but still higher than normal soils' levels. These results are indication of strong metal pollution (especially by Pb) of Caracas' roadside soils, due to heavy transit of motor vehicles as well as to the exclusive use of highly leaded gasoline in Venezuela. Nevertheless both metals accumulate only on the surface layers of those soils located within 5 m from the roadside. These facts were taken as evidence of the low vertical and horizontal mobility of the metals, which was mainly attributed to the high pH of the studied soils (between 7.5 and 7.8). Three surface soil samples having high Pb and Zn levels were selected for chemical fractionation by McLaren and Crawford's (1973) methodology. It was found that less than 1% Pb and below 5.5% Zn were in exchangeable form in these soils. Therefore, Pb and Zn are predominantly present in non-exchangeable forms in the studied soils. These non-exchangeable metals tend to become associated with different soils materials. Lead is mainly associated with the organic fraction, as well as to the inorganic and residual fractions, and Zn is mainly associated to the inorganic and residual fractions, and also the iron oxides, being practically absent in the organic fraction.     

Estimation of soil pollution by the main ecotoxicants in the Vorob’evy Gory nature park

Soils of the Vorob’evy Gory nature park (Moscow) are characterized by a high content of technogenic ecotoxicants. Dangerous levels of pollution are fixed on ∼60% of soil cover for benzopyrene, ∼40% of soil cover for heavy metals, and ∼6% of soil cover for mineral oils. Besides the total high aerogenic load, the local sources of soil pollution in cities are highways; increased concentrations of heavy metals are also registered near unauthorized dumps. Benzopyrene and mineral oils are characterized by high migratory ability in soils and can form secondary auras of pollution in accumulative landscape facies.     

Soil contamination with emissions of non-ferrous metallurgical plants

The upper soil horizons are strongly contaminated in the area influenced by the Mid-Urals copper smelter. In the technogenic desert and impact zones, the contents of a number of elements (Cu, Zn, As, Pb, P, and S) by many times exceed their clarke values and the maximum permissible concentrations (or provisional permissible concentrations). The degree of technogeneity (Tg) for these elements is very high in these zones. In the far buffer zone, Tg is about zero for many elements and increases up to Tg = 27–42% for four heavy elements (Cu, Zn, Pb, and As) and up to 81–98% for P and S. The buffer capacity of the humus horizon depends on the soil’s location within the technogeochemical anomaly and also on the particular pollutant. In the impact zone, it is equal to 70–77% for lead and arsenic, although other technogenic elements (Zn, Cr, S, and P) are poorly retained and readily migrate into the deeper horizons (the buffer capacity is equal to 14–25%). Nearly all the heavy metals enter the soil in the form of sulfides. The soils in the area affected by the Noril’sk mining and smelting metallurgical enterprise are subdivided into two groups according to the degree of their contamination, i.e., the soils within Noril’sk proper and the soils in its suburbs to a distance of 4–15 km. The strongest soil contamination is recorded in the city: the clarke values are exceeded by 287, 78, 16, 4.1, and 3.5 times for Cu, Ni, Cr, Fe, and S, respectively. The major pollutants enter the soil from the ferruginous slag. The soil’s contamination degree is lower in the suburbs, where heavy metal sulfides reach the soils with the aerial emission from the enterprise.     

Soil biogeochemical properties of Angren industrial area, Uzbekistan

Background, aim, and scope  The present study examined air pollution effects on soil health applying microbiological parameters. It was carried out near the Angren heavy industry complex in a semiarid region of Uzbekistan. This area was selected in order to establish a national monitoring program for assessing environmental condition of areas remote but downwind from greater emission sources. Moreover, little information exists about how air pollution affects microbiological functioning of soils in semiarid and arid regions of the world, and especially those of Central Asia. Materials and methods  Soil samples were collected in May 2005 along a 20-km NE–SW river valley transect downwind from the industrial complex. Soil chemical analyses included electrical conductivity, pH, water soluble Na, Ca, and K, total soluble nitrogen, and mineralizable nitrogen content upon a 1:2 digestion by deionized water. Major elements and heavy metal inventory in solids was measured by X-ray fluorescence and atomic absorption spectrometry. Microbiological ecosystem properties were assessed by biological indicators such as basal respiration (R _B), microbial biomass related C and N contents, and microbial community functioning coefficients like the metabolic quotient qCO₂. Results  There was a significant spatial dependence and differences for all soil chemical and microbiological parameters tested. The highest contents were found for the relatively volatile metals Zn (≤1,136 mg/kg) and Pb (≤373 mg/kg) in upper soil layers near the power station suggesting that the metal pollutants are derived from local stack emissions. Soil microflora was obviously affected by heavy metals. Significant positive correlations (p ≤ 0.001) were found between the metal content, R _B, and qCO₂, while a negative one was found for the mineralizable N and C _mic/C _org ratio. A high total number of nematodes was found only most distant from the industrial emission sources. Discussion  The results disclosed remarkable spatial dependence not only of the heavy metal impact onto the soil but also of microbiological soil properties in the study area. The latter suggests bioavailability of the anthropogenic metals in the soil affecting the soil microbial community. This is suggested by less biomass formation and higher qCO₂ values in heavy metal-contaminated compared to less-polluted soil plots. Conclusions  Knowledge of these spatial ecosystem functioning patterns and dependence could be very useful in determining and delineating specific land use and management programs that would be suited and feasible for the highly polluted area. Results of this study can be utilized to develop a monitoring program that may quantify harmful effects on the soil health and impact of any future remediation activities. Recommendations and perspectives  Studies on the relationship between soil biota and pollution levels have raised the question regarding the status of natural soil microbial health, stressing the importance of background data of environmental conditions, and elucidating the importance of this environmental monitoring approach even in semiarid and arid regions. Soil microbiological parameters, in particular the metabolic quotient qCO₂ as one of the most sensitive bioindicators identified for that region, should clearly become part of the national environmental monitoring program.     

The importance of dust material in urban soil formation: the experience on study of two young Technosols on dust depositions

Purpose

The volume of dust deposition on the soil surface in Moscow is big enough and make several tens of grams per square meter annually. The role of dust as a soil-forming material is especially high in places with practically no other soil parent materials. It is necessary to consider solid atmospheric precipitation as a parent soil material in urban conditions and its impact on soil properties.

Materials and methods

Samples of two soil bodies were taken near two major highways of Moscow, and airborne solid deposit samples were collected from the roadside barrier in summer and from plant leaves after snowmelt. The fallout samples were studied by methods used for soil because of its silicate matrix (Si～30 % total). Main complex characteristics of samples were obtained by chemical analysis and with a scanning electron microscope with energy-dispersive X-ray spectrometer. Bulk elemental composition, available phosphorus and potassium, carbonates, organic carbon and oil hydrocarbon contents, pH, redox potential, magnetic susceptibility, and particle-size distribution of dust and soils were determined.

Results and discussion

Near the highways, where the process of dust transfer is activated, there are possibilities of dust inclusion into soil and formation of new soil horizons on these deposits. Pedofeatures are formed during a very short period of time. The soil-forming processes are connected with both soil organic matter and mineral compound transformation. Chemical properties of the studied soils correspond to those of usual Moscow soil horizons and dust samples studied previously by Prokofyeva et al. (2011) and Prokof’eva et al. (2015). It was established that atmospheric solid aerosol imports organic carbon, carbonates, and other salts; pollutants such as oil hydrocarbons; and heavy metals into the soil. Airborne deposits influence soil physical properties by enriching the soil with clay and coarse silt fractions.

Conclusions

Investigation of dust deposit composition provides data for characterizing material being continuously deposited on the urban soil surface. The atmospheric fallouts together with construction waste and natural rocks provide the common geochemical properties of urban soils.

     

Distribution of Road Salt Residues, Heavy Metals and Polycyclic Aromatic Hydrocarbons across a Highway-Forest Interface

Automobile traffic pollutes roadside environments with a range of contaminants. In this study, we investigate the distribution patterns of different contaminant classes in topsoils across a highway-forest interface north-east of Vienna, Austria, in order to assess spatial pollutant distribution and evaluate the filtering effect of roadside forests. We collected soil samples along transects perpendicular to the highway, and analyzed the soils for road salt residues (Na), total and mobile heavy metals (Pb, Cd, Cu, Zn, Ni, Cr) as well as polycyclic aromatic hydrocarbons (PAHs). Roadside soil pollution was highly heterogeneous. All contaminants followed an exponential-like decrease with distance from the road, reaching background levels at 5 to 10 m from the road curb. Traffic-born heavy metals in the immediate roadside zone tended to be more mobile than heavy metals of predominantly geogenic origin at greater distances from the road; the presence of road salt residues could have contributed to the elevated heavy metal mobility near the road. The forest vegetation acted as filter for PAHs shown by a sharp concentration increase at the forest edge. PAHs are likely transported with airborne soot particles that are scavenged by the wax-coated coniferous needles at our study site.     

污灌对潮土重金属含量及分布的影响——以开封市化肥河污灌区为例

以开封市化肥河污灌区为例,研究了污水灌溉对潮土中重金属(Cd、Pb、Cr、Cu、Zn、Ni和 As)含量及分布的影响。结果表明,污水灌溉已经导致了该区潮土较明显的重金属累积,其中Cd和As平均含量分别达1．70 mg/kg和26．28 mg/kg,远远超出了土壤环境二级标准值。进入潮土的重金属主要累积在潮土的耕作层,随着土壤深度的增加,重金属含量逐渐减少;相对其他重金属而言,As更易于在潮土表层滞留。污灌区潮土 Cu、As与Cd含量与距污染源距离呈线性相关。相关分析表明,污灌区土壤Cu、Zn、Pb、Ni和As含量与土壤理化性质及其他重金属含量有关,而土壤Cd和Cr含量则与其他重金属含量及土壤性质的相关性不明显。     

Long-term dynamics of the anthropogenic salinization of soils in Moscow (by the example of the Eastern district)

The long-term (1989–2010) and seasonal dynamics of the anthropogenic salinization of soils related to the use of deicing mixtures in the Eastern Administrative District of Moscow were examined. Data on the chemical composition of deicing mixtures and on the contents of soluble salts in the snowmelt and in the soil profiles of different functional zones were analyzed. The maps of soil salinization were compiled for 1989, 2005, and 2010; on their basis, the resulting map of the degree of soil degradation was developed. The areas with abnormal concentration of salts in the soils expanded during the study period (21 yrs), and the average content of salts in such areas increased by 3.2 times. The maximum total content of salts was found in the spring season in the soils along major highways.     

Road-deposited sediment, soil and precipitation (RDS) in Bratislava, Slovakia: compositional and spatial assessment of contamination

Background, aim and scope  The urban environment in Bratislava is, in association with rapid urbanisation and industrialisation, significantly influenced by several potential sources of pollution, including automobile exhaust and industry emmissions. Urban road-deposited sediments contain many potentially toxic elements such as Pb, Cr, Cu, Zn and also Fe at concentrations much higher than in soil. In this study, the chemical composition and spatial variability of road-deposited sediments in urban area of Bratislava were assessed for the elements As, Cd, Cr, Cu, Hg, Ni, Pb, Fe and Mn. Additional evaluation of archive data for soil, snow and atmospheric dust was undertaken to provide an integrated view on urban environment contamination. Materials and methods  Urban road-deposited sediments (RDS) were collected during summer 2003 and 2004 mainly from major city crossroads. RDS samples were analysed for total metal content, pseudo-total metal content (HNO₃ digestion) and by a sequential extraction method, grain fraction composition and mineralogical composition (X-ray analysis). Metal concentrations in soil and snow samples from urban and non urban city area were compared. Results and discussion  The highest concentrations for all metals were found in the finest RDS fraction (<0.125 mm). Whilst in the fraction <1 mm mean concentrations of Cr, Cu and Pb reached 55.2, 143.8 and 34.4 mg kg⁻¹, respectively, for the fraction <0.125 mm, markedly higher contents of these elements were documented at the level of 86.8, 218.4 and 63.1 mg kg⁻¹, respectively. The soil contents of potentially toxic risk elements in the urban area including As, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn were higher than in the non-urban area (except for Cd with similar contents). This distribution pattern of evaluated chemicals in urban and non-urban area is more evident in the case of winter precipitation (snow). The snow concentrations of As, Cr, Cu, Fe, Mn, Pb and Zn in the urban area were two tot five times higher than in non-urban area. Conclusions and recommendations  Monitoring of road-deposited sediments, dust, soil and precipitation has confirmed the significant contamination of the urban environment in Bratislava with potentially toxic elements that can pose a threat for the health of its residents. Future works should be based on analyses of temporal variability of RDS and analyses of organic matter content.     

洛川苹果园地土壤重金属污染调查与评价

通过对洛川苹果园地土壤样品的采集、监测,依据无公害果园产地土壤环境质量标准和绿色食品产地土壤环境质量标准,重点分析评价了对土壤环境及人体危害较大的Cd、As、Cr、Pb等重金属元素的污染现状。评价结果表明:以无公害果园产地土壤环境质量为评价标准,洛川苹果园地土壤重金属污染程度有As>Cr>Cd>Pb的特征,土壤重金属综合污染指数为0.51,土壤Cd、As、Cr、Pb单项污染指数平均值均小于0.7,土壤环境中的重金属元素含量现状水平符合无公害苹果生产的要求;以绿色食品产地土壤环境质量为评价标准,洛川苹果园地土壤重金属污染程度有As>Pb>Cr>Cd的特征,土壤重金属综合污染指数为0.64,土壤Cd、Cr、Pb单项污染指数平均值均小于0.7,土壤As单项污染指数平均值大于0.7,但小于1。土壤环境中的重金属含量现状水平符合绿色食品苹果生产的要求。但土壤As单项污染指数平均值为0.74,已超过绿色食品产地土壤污染警戒线。洛川苹果园地土壤重金属As污染程度较高,主要是由于人为长期不合理使用含As农药、化肥所致。因而,洛川苹果生产中应将土壤环境中的As作为严控的土壤污染物。     

工业型城乡交错区土壤重金属含量及其空间分异的特征-以无锡典型城乡交错区为例

Phosphorus （P） is necessary for growth and nitrogen fixation, and thus its deficiency is a major factor limiting legume production in most agricultural soils. The effect of phosphorus supply on nodule development and its role in soybeans （Glycine max L.） was studied in a nutrient solution. Plants were inoculated with Bradyrhizobium japonicum and grown for 35 days in a glasshouse at a day and night temperature of 25℃ and 15℃, respectively. Although increasing P supply increased the concentrations of P and N in the shoots and roots, the external P supply did not significantly affect the P concentration in the nodules, and the N fixed per unit nodule biomass decreased with increasing P supply. The nitrogen content in the shoots correlated well with the P content （r=0.92＊＊）. At an inoculation level of 10^2 cells mL^-1, the P supply did not affect the number of nodules; however, at inoculation levels of 10^3.5 and 10^5 cells mL^-1, increasing P supply increased both the number and size of nodules. Irrespective of the inoculation level, increasing P supply increased the nodule biomass relative to the biomass of the host plant. It is suggested that the P deficiency specifically inhibited the nodule development and thereby the total N2 fixation.     

Heavy metals and arbuscular mycorrhizal (AM) fungi can alter the yield and chemical composition of volatile oil of sweet basil (<Emphasis Type="Italic">Ocimum basilicum</Emphasis> L.)

The effects of increasing levels of metals (10 and 20 mg of Cr kg^-1 and 25 and 50 mg of Cd, Pb, and Ni kg^-1 soil) and arbuscular mycorrhizal (AM) fungi Glomus intraradices on the yield, chemical composition of volatile oil, and metal accumulation in sweet basil (Ocimum basilicum L.) were investigated in a pot experiment. The shoot yield, content of essential oil, and root yield of sweet basil were increased by the application of low dose of Cd, Pb, and Ni as compared to control. The application of high level of metals had deleterious effect on the yield. In soil with low dose of metal applied, AM fungi inoculation significantly enhanced the metal concentration in shoots and had adverse effect on the yield, whereas in soil with high dose of metal applied, AM fungal inoculation reduced the metal concentration in shoot and had beneficial effect on the yield. The content of linalool in basil oil was decreased and that of methyl chavicol was increased by the application of Cr, Cd, and Pb in soil as compared to control. Similarly, the level of linalool and methyl chavicol was decreased and that of methyl eugenol was increased by the application of Ni as compared to control. However, AM fungal inoculation led to maintain the content of linalool, methyl chavicol, and methyl eugenol in volatile oil, which were either increased or decreased by the application of metals. We conclude that the AM–sweet basil symbiosis could be used as a novel approach to enhance the yield and maintain the quality of volatile oil of sweet basil under metal-contaminated soils.     

Effect of Flooding on Contamination of Agricultural Soils with Metals and PAHs: The Middle Vistula Gap Case Study

During the intensive flood in May–June 2010, the floodplains in Little Poland Vistula Gap, used mostly for agriculture, were waterlogged for a period of over 1 month. The aim of the study was to assess the effect of the flood on the level of contamination of the soils in this region. The analysis included basic physicochemical soil properties, contents of ten metals, and concentrations of 16 polycyclic aromatic hydrocarbons (PAHs). The studies cover two territories on opposite sites of the river Vistula (Wilkow and Janowiec) differing in their areas (70 and 4.6 km²) and time of water logging (30 and 10 days). Forty soil samples were collected from both areas immediately after the flood event from the upper (0–30 cm) soil layer together with four samples from the 30–60-cm depth layer. This was supplemented by eight samples from the flood-deposited sediment layer (thickness, 2 cm). The concentrations of identified metals (As, Ba, Cr, Sn, Zn, Cd, Co, Cu, Ni, Pb) at all the sampling points were below the Polish legal limits for the upper layer of soils for agriculture use. The same regarded the median contents of nine PAHs compounds specified in the Polish regulations. In both areas, the median contents of Σ16 PAHs (0.21–0.35 mg kg⁻¹), Zn (10.3–10.6 mg kg⁻¹), Pb (9.2–10.7 mg kg⁻¹), and Cd (0.03 mg kg⁻¹) were much below the mean concentrations of those contaminants in arable soils on the national and European levels. The results show that this severe flooding episode in “clean” agricultural area had no immediate negative impact on the soils as regards the basic physicochemical properties (organic matter content, acidity, nitrogen content) and did not result in excessive soil contamination.     

南京市城乡公路绿地土壤重金属变化及其评价

通过对南京市公路绿地系统(城市干线、绕城公路和城郊公路)土壤重金属的调查和分析,并与相对清洁点植物园植被土壤进行比较,研究了公路绿地土壤重金属分布的特点:公路绿地土壤重金属元素含量一般高于“清洁区”,其中土壤Mo、Zn、As、Cd、Cr、Cu、Fe、Mn的含量以绕城公路最高,土壤Pb的含量以城市干线最高,土壤Al的含量以城郊公路最高。城市干线、绕城公路、城郊公路和相对清洁点的土壤重金属多样性指数分别为0 .2 6 1、0 .2 93、0 2 38、0 2 36 ,仍以绕城公路最高,城市干线次之,城郊公路最低,公路土壤重金属多样性指数均高于“相对清洁点”。应用主成分分析方法对土壤样本进行了排序和聚类分析,结果表明:样本点表现了较好的以取样路线聚类的特点,各取样点土壤重金属含量存在明显的演变分异。土壤重金属演变的趋势可解释为:绕城公路是高Zn、Mo、Cd、As、Cr、Fe、Mg、Cu、Mn、Pb区,城市干线是高Pb区,城郊公路是高Al和Fe区,相对清洁点是低重金属区     

生物炭对铜矿区排土场污染土壤理化性质和重金属形态的影响

为了探讨在重金属胁迫下,不同用量(0,1%,2%,4%)生物炭对土壤pH、有机碳、全氮、全磷以及重金属形态的影响,以铜矿区排土场污染土壤为研究对象,开展室内盆钵试验。结果表明：与对照K相比,在不同剂量生物炭处理下,土壤pH、有机碳、全N和全P增幅分别为3.5%～23.0%,5.6%～13.2%,2.9%～6.8%和3.4%～9.5%,酸溶态Cd, Pb, Cu和Zn含量降幅分别为65.5%～71.2%,49.9%～71.5%,34.6%～50.6%和45.3%～52.1%,可还原态Cd, Pb, Cu和Zn含量降幅分别为71.5%～74.3%,44.4%～63.6%,38.5%～57.8%和29.1～39.1%,可氧化态Cd含量降幅为15.6%～36.9%,可氧化态Pb, Cu和Zn含量增幅分别为16.9%～20.5%、3.9%～26.0%和18.8%～55.9%,残渣态Cd, Pb, Cu和Zn含量增幅分别为42.4%～44.2%,11.0%～23.5%,15.0%～37.9%和20.0%～41.9%。添加生物炭可以提高土壤pH,增加土壤有机碳和全氮含量,对土壤全磷含量也略有增加,但...     

Contaminated sediments as a potential source of Zn, Pb, and Cd for a river system in the historical metalliferous ore mining and smelting industry area of South Poland

Background, aim, and scope  Elevated levels of heavy metals in the aquatic and soil systems can be caused by the weathering of mineralized rocks. This enrichment is often considerably enlarged by historical and current mining and smelting activities. In Poland, the most contaminated river systems are those in the Silesia region. The metalliferous ore mining and smelting industries have been the main sources of heavy metal pollutions over the last 100–170 years. The previous and present studies have shown very high concentrations of heavy metals in the bottom sediments of the Mala Panew River, the most polluted tributary of the Oder River. The main objective of this work was to study temporary changes of selected metal (Zn, Pb, and Cd) concentrations in upper layer of bottom sediments at the measuring point near the outlet of the Mala Panew River into the Oder River, and to determine the vertical distribution of the metals in the sediment cores from the most polluted middle part of this river. The mobility of the metals and their potential bioavailability were assessed based on metal partitioning in the sediments and metal concentrations in pore waters. The presented data were compared with metal concentrations in aquatic sediments from similar historical mining and smelting sites in Poland and other countries. Methods  The upper layer of bottom sediment samples from the same Mala Panew River measuring point were collected six times in the period 1997–2005, while five sediment cores were collected once from the middle course of Mala Panew River in 2006. Abiotic parameters such as pH and Eh have been determined in situ. Metal contents were determined in the <20 and <63 μm size fractions of sediments after digestion in a microwave oven with aqua regia or concentrated nitric acid. Metal mobility was assessed in the selected sediment cores by the chemical forms of metals (sequential extraction method) and their concentrations in pore waters were investigated. Results  The concentrations of Cd, Pb, and Zn in the upper layer of sediments varied, depending on both the season and the year of sampling. Their mean concentrations (from six samplings) are [mg/kg]: Zn 1,846, Pb 229 and Cd 73. The metal concentrations in the sediment cores varied with the depth in the range of [mg/kg]: 0.18–559 for Cd, 26.2–3,309 for Pb and 126–11,153 for Zn, although the highest accumulations generally could be observed in the deeper layers. The most mobile metal fractions, i.e., exchangeable, carbonate and easily reducible fractions, are typical of Zn and Cd. Cadmium was found to be the most mobile metal and its relative contribution ranges from 84 to 96%, while in the case of Zn it ranged from 45 to 94%. Lead is mainly associated with the moderately reducible fraction (30–60%). Relative contributions of metal chemical forms slightly vary with the depth in the sediment profile. The results obtained for the pore water samples show very high concentrations of the metals studied, especially in the case of Cd (31–960 μg/dm³) and Zn (300–4,400 μg/dm³). Discussion  Accumulation of Cd, Pb, and Zn in the upper layer of the bottom sediments and in the sediment core samples from the Mala Panew River is very high, considerably exceeding the local geochemical background. High contributions of mobile Cd and Zn and the toxicity of cadmium can cause environmental risk. Our measurements also suggest that mobile metals can migrate into groundwater, whereas the groundwater itself can leach some chemicals from river sediments, because of a relatively high water table in the study area, especially during rainfall periods. Comparison of the results obtained with the literature data from the last decade shows that the concentrations of Cd and Zn in the sediments from the Mala Panew River are the highest among other submersed sediments in Poland and other regions (e.g., the Mulde River, Germany). Conclusions  The Mala Panew River is one of the most polluted rivers when compared with similar historical mining and smelting areas in Poland and elsewhere. The sediments studied are strongly polluted with the metals analyzed. In the upper layer of the bottom sediments there has been no reduction of Zn and Cd amounts over the last decade, which could suggests a long-term migration and a secondary contamination. Considerably higher accumulations of metals in overbank sediment cores and in the deeper core section could result from strong contamination in previous decades and translocation of Cd and Zn (secondary pollutants). The relatively high concentrations of the two metals in pore waters support these findings. Cadmium is crucial in the environmental risk assessment because of its high mobility and toxicity. These data are important for water/sediment management in the transboundary Oder River catchment, situated in Poland, Germany and the Czech Republic. Recommendations and perspectives  It is important to assess mobility phase and pore water in the contaminated historical aquatic sediments. Such studies may help explain the changes, which take place in the sediment layers as well as at the water–sediment interface. Obtained results should be used for the risk assessment of the historical contaminated sediments at the local river-basin scale. The treatment of contaminated sediments, e.g., dragging activity, should be considered as very important in management strategies in order to avoid remobilization of metals.