Heavy metals in flue gas cleaning residue

During combustion, most of the inorganic nutrients and trace elements in the fuel are retained and enriched in the ash. However, here we show that, due to the low total heavy metal concentrations, the flue gas cleaning residue (i.e. the fly ash) originating from the wet scrubber device at a medium-sized (32 MW) municipal district heating plant, is a potential forest fertilizer. Furthermore, the easily soluble calcium (1,980 mg kg⁻¹; d.w.) and phosphorus (50 mg kg⁻¹; d.w.) concentrations indicate that the flue gas cleaning residue is a potential agent for soil remediation and for improving soil fertility.     

Field crops for phytoremediation of metal-contaminated land. A review

The use of higher plants to remediate contaminated land is known as phytoremediation, a term coined 15 years ago. Among green technologies addressed to metal pollution, phytoextraction has received increasing attention starting from the discovery of hyperaccumulator plants, which are able to concentrate high levels of specific metals in the above-ground harvestable biomass. The small shoot and root growth of these plants and the absence of their commercially available seeds have stimulated study on biomass species, including herbaceous field crops. We review here the results of a bibliographical survey from 1995 to 2009 in CAB abstracts on phytoremediation and heavy metals for crop species, citations of which have greatly increased, especially after 2001. Apart from the most frequently cited Brassica juncea (L.) Czern., which is often referred to as an hyperaccumulator of various metals, studies mainly focus on Helianthus annuus L., Zea mays L. and Brassica napus L., the last also having the greatest annual increase in number of citations. Field crops may compensate their low metal concentration by a greater biomass yield, but available data from in situ experiments are currently very few. The use of amendments or chelators is often tested in the field to improve metal recovery, allowing above-normal concentrations to be reached. Values for Zn exceeding 1,000 mg kg⁻¹ are found in Brassica spp., Phaseolus vulgaris L. and Zea mays, and Cu higher than 500 mg kg⁻¹ in Zea mays, Phaseolus vulgaris and Sorghum bicolor (L.) Moench. Lead greater than 1,000 mg kg⁻¹ is measured in Festuca spp. and various Fabaceae. Arsenic has values higher than 200 mg kg⁻¹ in sorghum and soybean, whereas Cd concentrations are generally lower than 50 mg kg⁻¹. Assisted phytoextraction is currently facilitated by the availability of low-toxic and highly degradable chelators, such as EDDS and nitrilotriacetate. Currently, several experimental attempts are being made to improve plant growth and metal uptake, and results are being achieved from the application of organic acids, auxins, humic acids and mycorrhization. The phytoremediation efficiency of field crops is rarely high, but their greater growth potential compared with hyperaccumulators should be considered positively, in that they can establish a dense green canopy in polluted soil, improving the landscape and reducing the mobility of pollutants through water, wind erosion and water percolation.     

Genotypic variation in element concentrations in brown rice from Yunnan landraces in China

The mineral elements present in brown rice play an important physiological role in global human health. We investigated genotypic variation of eight of these elements (P, K, Ca, Mg, Fe, Zn, Cu, and Mn) in 11 different grades of brown rice on the basis of the number and distance coefficients of 282 alleles for 20 simple sequence repeat (SSR) markers. Six-hundred and twenty-eight landraces from the same field in Yunnan Province, one of the largest centers of genetic diversity of rice (Oryza sativa L.) in the world, formed our core collection. The mean concentrations (mg kg⁻¹) of the eight elements in brown rice for these landraces were P (3,480) > K (2,540) > Mg (1,480) > Ca (157) > Zn (32.8) > Fe (32.0) > Cu (13.6) > Mn (13.2). Mean P concentrations in brown rice were 6.56 times total soil P, so the grains are important in tissue storage of P, but total soil K is 7.82 times mean K concentrations in brown rice. The concentrations of the eight elements in some grades of brown rice, on the basis of the number and distance coefficients of alleles for 20 SSR markers for the landraces, were significantly different (P < 0.05), and further understanding of the relationship between mineral elements and gene diversity is needed. There was large variation in element concentrations in brown rice, ranging from 2,160 to 5,500 mg P kg⁻¹, from 1,130 to 3,830 mg K kg⁻¹, from 61.8 to 488 mg Ca kg⁻¹, from 864 to 2,020 mg Mg kg⁻¹, from 0.40 to 147 mg Fe kg⁻¹, from 15.1 to 124 mg Zn kg⁻¹, from 0.10 to 59.1 mg Cu kg⁻¹, and from 6.7 to 26.6 mg Mn kg⁻¹. Therefore, germplasm evaluations for Ca, Fe, and Zn concentrations in rice grains have detected up to sevenfold genotypic differences, suggesting that selection for high levels of Ca, Fe, and Zn in breeding for mass production is a feasible approach. Increasing the concentrations of Ca, Fe, and Zn in rice grains will help alleviate chronic Ca, Zn, and Fe deficiencies in many areas of the world.     

Assessment of the impacts of municipal solid waste dumps on soils and plants

The study aimed at evaluating the impacts of open municipal solid wastes dumps on soil and vegetation near the main roads linking major cities in Nigeria. We hypothesised that the metals from the wastes exerted substantial impacts at the dump sites which affect the soil and plants. Data were analysed from five dump sites and five control sites. The result revealed that the effects of the heavy metals (HM) were significant and higher at the dump sites where their concentrations were far above the EU, and Canadian environmental quality permissible limits for agricultural soils and vegetation. In contrast with dump sites, a significant relationship (R²?=?0.70; p??Cr?>?Pb at both dump sites and control sites. Further study on the effects of more HM on soil and plant is recommended in the area. Recycling and bio-phytoremediation processes should also be introduced.     

Phytoextraction of Cr(VI) from soil using Portulaca oleracea

Cr(VI) represents an environmental challenge in both soil and water as it is soluble and bioavailable over a wide range of pH. In previous investigations, Portulaca oleracea (a plant local to the United Arab Emirates (UAE)) demonstrated particular ability for the phytoextraction of Cr(VI) from calcareous soil of the UAE. In this publication, the results of the evaluation of P. oleracea phytoextraction of Cr(VI) from UAE soil at higher concentrations are reported. P. oleracea was exposed to nine different concentrations of Cr(VI) in soil from 0 to 400 mg kg^?1. The uptake of Cr(VI) increased as its concentration in soil increased between 50 and 400 mg kg^?1, with the most efficient removal in the range from 150 to 200 mg kg^?1. The total chromium concentrations exceeded 4600 mg kg^?1 in roots and 1400 mg kg^?1 in stems, confirming the role of P. oleracea as an effective Cr(VI) accumulator. More than 95% of the accumulated Cr(VI) was reduced to the less toxic Cr(III) within the plant.     

Sequestration of As by iron plaque on the roots of three rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.) cultivars in a low-P soil with or without P fertilizer

A pot experiment was carried out in a greenhouse to investigate the sequestration of As in iron plaques on root surface of three rice (Oryza sativa L.) cultivars. Phosphate (P) fertilization increased both plant biomass and tissue P concentrations significantly, indicating that the soils used in this study was highly P-deficient. Results from this study confirmed that low P supply improved the formation of iron plaque on rice roots. As a consequence, arsenic (As) concentrations in DCB-extracts with no P addition were significantly higher than those with P fertilization. Arsenic was highly sequestrated in iron plaque; arsenic concentration in iron was up to nearly 120 mg kg⁻¹, while arsenic concentrations in roots were just several mg kg⁻¹. Both arsenic and phosphate concentrations in iron plaque were highly positively correlated with the amounts of iron plaque (DCB-extractable Fe). Contrary to normal understanding that increasing P supply could reduced As accumulation in plants, results from the present study showed that P fertilization did not inhibit the As uptake by plants (As accumulation in aboveground), which was probably due to the fact that iron plaque formation was improved under low P conditions, thus leading to more As sequestration in the iron plaque. Thus results obtained in this study indicated that the iron plaque may inhibit the transfer of As from roots to shoots, and thus alter the P–As interaction in plant As uptake processes.     

In vitro genotoxicity of fly ash leachate in earthworm coelomocytes

Fly ash is the major coal combustion byproduct from thermal power plants. Considering its plant–nourishing constituents, its soil amendment in farmland is one of its promoted disposal methods. A substantial amount of heavy metals present in fly ash, which may leach out due to rainwater or irrigation water, may cause serious problem with long term use, especially to soil organisms. These metals may cause DNA damage through Reactive Oxygen Species (ROS) generation. In the present study, single cell gel electrophoresis [(SCGE) i.e., comet assay] was used to detect DNA damage in earthworm (Dichogaster curgensis) coelomocytes, following an in vitro exposure. Significant DNA damage was observed at the lowest concentration of fly ash leachate (6.25%) examined. DNA damage by all the tested concentrations (6.25%, 12.5%, 25%, 50%) differed significantly (p?<?0.001) from that of the negative control. Hence, long-term application of fly ash might prove harmful for earthworm populations.     

Mercury contamination in agricultural soils from abandoned metal mines classified by geology and mineralization

Lead (Pb) contents and partition in soils collected from eleven vegetable-growing lands in Fujian Province, China, were investigated using a modification of the BCR (Community Bureau of Reference) sequential extraction procedure coupled with the Pb isotope ratio technique. Pb contents in Chinese white cabbage (B. Chinensis L.) grown on the lands for this study were also measured. Results showed that Pb concentrations in fifty samples of topsoil ranged from 456 to 21.5 mg kg⁻¹, with each mean concentration of six sampling lands exceeding the national standard (50 mg kg⁻¹); while Pb concentrations in edible portions of thirty-two vegetable samples ranged from 0.009 to 2.20 mg kg⁻¹, with four sampling sites exceeding the national sanitary standard (0.2 mg kg⁻¹). A significant correlation (r = 0.971, P < 0.01) of Pb contents in the acid-extractable fractions by BCR approach and the vegetables was observed, which indicates that the acid-extractable Pb is useful for evaluating the metal bioavailability for plants and potential risk for human health in soils. The determination of lead isotope ratios in different chemical forms of soils by BCR sequential extraction procedures provides useful information on the Pb isotopic composition associated with different soil fractions (especially in the acid-extractable fractions), and the result is helpful for the further study on controlling and reducing Pb contamination in vegetable-growing soils.     

Effects of benzo[a]pyrene toxicity on morphology and ultrastructure of Hordeum sativum

Many studies have been devoted to investigation of toxic benzo(a)pyrene (BaP) compound, but studies involving changes at the cellular level are insufficient to understand the mechanisms of polycyclic aromatic hydrocarbons (PAHs) effect on plants. To study the toxicity of BaP, a model vegetation experiment was conducted on cultivation of spring barley (Hordeum sativum distichum) on artificially polluted BaP soil at different concentrations. The article discusses the intake of BaP from the soil into the plant and its effect on the organismic and cellular levels of plant organization. The BaP content in the organs of spring barley was determined by the method of saponification. With an increase in the concentration of BaP in the soil, its content in plants also rises, which leads to inhibition of growth processes. The BaP content in the green part of Hordeum sativum increased from 0.3 µg kg^?1 in control soil up to 2.6 µg kg^?1 and 16.8 µg kg^?1 under 20 and 400 ng/g BaP applying in soil, as well as in roots: 0.9 µg kg^?1, 7.7 µg kg^?1, 42.8 µg kg^?1, respectively. Using light and electron microscopy, changes in the tissues and cells of plants were found and it was established that accumulation of BaP in plant tissues caused varying degrees of ultrastructural damage depending on the concentration of pollutant. BaP had the greatest effect on the root, significant changes were found in it both at histological and cytological levels, while changes in the leaves were observed only at the cytological level. The results provide significant information about the mechanism of action of BaP on agricultural plants.

     

Numerical modelling of biostabilisation for a coal mine overburden dump slope

An integrated study on biological stabilisation of the dump slope has indicated that biological reclamation should be considered for long term stability of dump. The grasses have good soil binding capacity and help to control soil erosion and improve dump stability. Native grasses viz. Bamboo (Dendrocalmus strictus) and Kashi (Saccharum spontaneum) are the important constituents of grass species which can stabilise the dump slopes. Field observation of root development of these grass species has indicated that the roots can proliferate upto 0.5 m depth on a coal mine overburden dump after three years of vegetation. From the numerical modelling it has been analysed that roots of these grasses which significantly enhance the factor of safety of dump slope from 1.2 to 1.4 have a positive role in maintaining long term stability.     

Cadmium accumulation by green algae Cladophora glomerata (L.) Kutz. (Chlorophyta) in presence of Nile tilapia Oreochromis niloticus (L.)

Accumulation of metals by aquatic organisms is mostly affected by other biological components in environments. In this study, cadmium (Cd) accumulation in green algae, Cladophora glomerata (L.) Kutz., exposed to 0.1 and 1.0 mg L^?1 of Cd for 15 and 30 days was examined in laboratory conditions in the presence of Nile tilapia Oreochromis niloticus (L.). The green algae C. glomerata accumulated Cd concentrations as 690 ± 70 and 3430 ± 470 mg kg^?1 on day 15, and 1130 ± 180 and 6830 ± 1540 mg kg^?1 on day 30. There were significant increases (p < 0.05) in metal accumulation by green algae as the exposure time and metal concentration increased. The results also indicated that the presence of Nile tilapia in the medium led to a significant Cd accumulation in the green algae compared to control (p < 0.05).     

Distribution of arsenic compounds in Plantaginaceae and Cyperaceae plants growing in contaminated soil

The ability of plant species to accumulate arsenic (As) species in the biomass from As-contaminated soils is variable. Among the plants widely grown at the As-contaminated locations, Plantaginaceae and Cyperaceae families belong to the frequent ones. In this study, the ability of Plantago lanceolata (Plantaginaceae) and three wetland plant species representing the family Cyperaceae (Carex praecox, Carex vesicaria, and Scirpus sylvaticus) naturally occurring in the soils with an elevated As in the Czech Republic were investigated. The plants were cultivated under controlled conditions in an As-contaminated soil reaching 735?mg?kg^?1 of the total As. The total As in plants reached up to 8.3?mg?kg^?1 in leaves, and up to 155?mg?kg^?1 in roots of C. praecox. Dominant As compounds were arsenite and arsenate with a small abundance of dimethylarsinic acid (DMA) in all the plant species. In Cyperaceae, small percentages of arsenobetaine (AB) and arsenocholine (AC) were detected, suggesting the ability of these plants to transform As into less toxic compounds. Moreover, the important role of As(V) sequestration on iron plaque on the root surface of Cyperaceae was confirmed. In this context, root washing with oxalic acid partially disrupted the iron plaque for the better release of arsenate.     

Accumulation and phytoavailability of benzo[a]pyrene in an acid sandy soil

Effects of benzo[a]pyrene (B[a]P) on ryegrass (Lolium perenne L.) growth, plant accumulation and dissipiation of B[a]P in a red sandy soil (Hapli-Udic Argosol) were studied in a pot experiment. The plants were grown for 61 days in soil spiked with B[a]P at 0, 12.5, 25 and 50 mg kg⁻¹. Control pots without plants were also set up. Soil extractable B[a]P, plant shoot and root biomass, and concentrations of B[a]P in plant shoots and roots were determined. Ryegrass biomass was increased by addition of B[a]P and root B[a]P concentrations were significantly correlated with B[a]P application rate, but no such correlation was found for shoot B[a]P concentrations. This indicates that B[a]P enhanced the growth of the ryegrass. The extractable B[a]P concentration in the planted soil was significantly lower than that in the unplanted control soil at the rate of 50 mg B[a]P kg⁻¹. This indicates that ryegrass may help to dissipate B[a]P in soil at concentrations over 50 mg kg⁻¹ soil although the mechanism for this is not understood.     

Environmental impact of leaching of trace elements from fly ash dumps on aquatic ecosystems

Ten sampling points were selected in Kanhan River, situated near the ash dump sites of Koradi Thermal Power Plant, Nagpur. The leaching of trace elements from fly ash dumps was experimentally determined by acid digestion, batch leaching and toxicity characteristic leaching procedure tests. Elemental concentrations in river water, sediment, plankton and five commonly prevailing fish species (Catla catla, Labeo bata, Cyprinus carpio, Cirrhinus reba, Puntius ticto) were determined using a Flame Atomic Absorption Spectrophotometer during the pre-monsoon and post-monsoon seasons. Metal concentrations (Cr, Mn, Zn, Cu, Fe, Ni, Cu and Pb) in river water were higher during the pre-monsoon season compared to the post-monsoon season. Zn (30.65?mg/kg) was observed to be the most predominant metal in plankton during the pre-monsoon season while, during the post-monsoon season, Fe (21.19?mg/kg) showed the maximum concentration. Muscles of C. catla had metal concentrations (Cr, Mn, Zn, Fe, Cu and Pb) above the permissible limits of Food and Agricultural Organization (FAO 1983) during the pre-monsoon season. Bioaccumulation factor (BAF) was found highest for Cr (37.5) in muscles of C. catla during the pre-monsoon season, while BAF was observed to be maximum in L. bata for Cu (28.09), which may be detrimental for human consumption.     

Bioavailability and accumulation of trace elements in soils and plants of a highly contaminated estuary (Domingo Rubio tidal channel,SW Spain)

The Domingo Rubio tidal channel (Palos de la Frontera, Huelva, Spain) is an estuary located in the mouth of the Tinto River. The estuary is affected by different sources of pollution (waters of the Tinto River, contaminated with trace elements from the Iberian Pyrite belt, and effluent from the Huelva chemical industrial area). Soil and the most frequent plant species were collected in 2004 and 2006 at six different locations on the estuary. In general, N-Kjedahl, Total Organic Carbon values, salinity and contamination (total trace elements up to 1,000 mg kg⁻¹ As, 6 mg kg⁻¹ Cd, 2,500 mg kg⁻¹ Cu, 1,900 mg kg⁻¹ Pb and 1,300 mg kg⁻¹ Zn) tended to increase downstream of the tidal channel. Soil biochemical properties were not negatively affected either by the high salinity or by trace element contamination. Despite the high values of the trace elements, analysed plant samples showed that Cu was the only metal that could be a serious risk for the food chain.     

Temporal changes of Collembola population and alterations of life history parameters and acetylcholinesterase and superoxide dismutase activities in Cyphoderus javanus (Collembola) as biomarkers of fly ash pollution in lateritic soil

Fly ash is applied in agricultural fields to improve soil quality and crop yield; however, there are concerns regarding environmental hazards and toxicity to ecologically important soil organisms. The soil microarthropod fauna is a vital component of detritus food web, and major groups like Collembola are sensitive indicators of soil quality; however, information is scanty on their biomarker potentials against xenobiotics in tropical soils. The present study was aimed to evaluate temporal changes of Collembola population in fly ash amended field plots, and assess the biomarker potentials of life history parameters and biochemical responses such as acetylcholinesterase (AChE) and superoxide dismutase (SOD) activities in Cyphoderus javanus Borner (Collembola, Insecta), exposed to fly ash treated soil in microcosms. The field study using 5% (50 t ha^?1) and 20% (200 t ha^?1) doses of fly ash revealed dose-dependent and persistent decline in the density and relative abundance of Collembola population in sandy loam lateritic soil. The microcosm experiments showed negligible lethal effect of fly ash on C. javanus, but major life history parameters namely survival success, fecundity, and molting were significantly inhibited by fly ash treatments. The activity of AChE was downregulated, whereas activity of SOD was upregulated within 7 days of exposure of C. javanus to fly ash treated soil. These biological and biochemical parameters in Collembola are potential biomarkers, and therefore, the effects of fly ash are significant in C. javanus, an ecologically relevant species in the tropical soils of India.     

Sequential extraction of cadmium in different soil phases and plant parts from a former industrialized area

Cd concentrations in mobile phases of soil are more representative than total Cd concentration for estimating Cd bioavailability, physicochemical reactivity and mobility. In this study, selective sequential extraction procedures were used to determine Cd in different soil phases. Soil samples and plants grown in these soils were collected from a serpentine and copper-mining area in Maden-Elazig-Turkey. The extracted fractions were exchangeable/carbonate, reducible-iron/manganese oxides, oxidizable-organic matter and sulfides, and residual phases except silicates. Concentrations of Cd in soils and plant samples were determined by flame atomic absorption spectrometry and inductively coupled plasma-mass spectrometry. We found that Cd concentrations in the EDTA and NH₂OH·HCl extracts are higher in most soil samples compared to the other extracts. We conclude that Cd levels in mobile phases are unexpectedly high. The observed Cd concentrations are in ranges of 0.03–3.4 mg kg⁻¹ for soil and 0.02–2.5 mg kg⁻¹ for plant parts. The percentages of cadmium up to 56% in exchangeable and carbonates fractions were observed to be significantly higher than in those values less than 2% reported in literature. This study has shown that the modified extraction method can be usefully applied to determine Cd concentrations in potentially mobile phase of soil. Furthermore, it was concluded that Brassicasea and Rumex leaves can be used as hyperaccumulator plants because their translocation factor and/or enrichment coefficient values were found to be higher than 1.0.     

Abstracts to forthcoming papers

Food is the major source of metal exposure for the nonsmoking general population. Food samples of plant and animal origin from Ismailia, Egypt, were analyzed for the content of cadmium (Cd), lead (Pb), chromium (Cr), zinc (Zn), and copper (Cu) using AAS. The Cr, Zn, and Cu concentrations were in the range of 1.7–249?µg?kg^?1 wet weight (ww), 2–66?mg?kg^?1?ww, and 0.5–3.46?mg?kg^?1?ww, respectively. The mean daily intake of Cr, Zn, and Cu was 28.9?µg day^?1, 8.55?mg day^?1, and 1.7?mg day^?1, respectively. The intake estimates are within the range of the recommended intake established internationally. Concentrations of Cd and Pb were in the range of 10–321?µg?kg^?1?ww and 31–1200?µg?kg^?1?ww, respectively. The weekly dietary intake for Cd and Pb (4.02 and 20.4?µg?kg^?1 b.w, respectively) is lower than the FAO/WHO PTWI. Bread is the foodstuff that provided the highest rate of Pb and Cd (62 and 46% of the daily intake) to adults in Ismailia city.     

Contamination characteristics of trace metals in dust from different levels of roads of a heavily air-polluted city in north China

Concentrations of eight trace metals (TMs) in road dust (RD) (particles?<?25 μm) from urban areas of Xinxiang, China, were determined by inductively coupled plasma mass spectrometry. The geometric mean concentrations of Zn, Mn, Pb, As, Cu, Cr, Ni and Cd were 489, 350, 114, 101, 60.0, 39.7, 31.6, and 5.1 mg kg^?1, respectively. When compared with TM levels in background soil, the samples generally display elevated TM concentrations, except for Cr and Mn, and for Cd the enrichment value was 69.6. Spatial variations indicated TMs in RD from park path would have similar sources with main roads, collector streets and bypasses. Average daily exposure doses of the studied TMs were about three orders of magnitude higher for hand-to-mouth ingestion than dermal contact, and the exposure doses for children were 9.33 times higher than that for adults. The decreasing trend of calculated hazard indexes (HI) for the eight elements was As?>?Pb?>?Cr?>?Mn?>?Cd?>?Zn?>?Ni?>?Cu for both children and adults.     

Nickel and copper accumulation strategies in Odontarrhena obovata growing on copper smelter-influenced and non-influenced serpentine soils: a comparative field study

The present investigation is the first in situ comparative study for the identification of Ni and Cu accumulation strategies involved in Odontarrhena obovata (syn. Alyssum obovatum (C.A. Mey.) Turcz.) growing in Cu-rich smelter-influenced (CSI) and non-Cu-influenced (NCI) sites. The total and Na₂EDTA (disodium ethylenediaminetetraacetic acid)-extractable metal concentration in soils and plant tissues (roots, stem, leaves and flowers) were determined for CSI and NCI sites. High concentrations of total Ni, Cr, Co and Mg in the soil suggest serpentine nature of both the sites. In spite of high total and extractable Cu concentrations in CSI soil, majority of its accumulation was restricted to O. obovata roots showing its excluder response. Since the translocation and bioconcentration factors of Ni?>?1 and the foliar Ni concentration?>?1000 μg g^?1, it can be assumed that O. obovata has Ni hyperaccumulation potential for both the sites. No significant differences in chlorophyll content in O. obovata leaves were observed between studied sites, suggesting higher tolerance of this species under prolonged heavy metal stress. Furthermore, this species from CSI site demonstrated rather high viability under extreme technogenic conditions due to active formation of antioxidants such as ascorbate, free proline and protein thiols. The presence of Cu in higher concentration in serpentine soil does not exert detrimental effect on O. obovata and its Ni hyperaccumulation ability. Thus, O. obovata could act as a putative plant species for the remediation of Cu-rich/influenced serpentine soils without compromising its Ni content and vitality.