Nickel and other metal uptake and accumulation by species of Alyssum (Brassicaceae) from the ultramafics of Iran

Some plants growing on serpentine (ultramafic) soils are able to hyperaccumulate nickel in their above-ground parts. The genus Alyssum L. contains the greatest number of Ni-hyperaccumulator plants so far reported. There are substantial areas of serpentine soils at many locations in Iran. This paper presents the analyses for Ni, Cr, Mn, Fe, Mg and Ca in soils and Alyssum species from the ultramafics of west and northwest Iran. Soil analysis for total elements in these areas indicates that typical concentrations of Ni, Cr, Mn, Fe, Mg and Ca are up to about 1240, 365, 800, 51,150, 152,390 and 11,790 microg g(-1), respectively. During this study, seven Alyssum species were collected. Analysis of leaf dry matter shows that Alyssum bracteatum can contain up to 2300 microg Nig(-1), while the other species contain much lower concentrations of Ni and other elements. A. bracteatum is endemic to Iran and the first Ni hyperaccumulator reported from this species.     

Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment

The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.     

Elemental composition of Juncus bulbosus in an acidified freshwater reservoir

Concentrations of the major nutrients (N, P, Mg, K, Na and trace elements (Fe, Mn, Zn) were determined in tissues of the submerged aquatic plant Juncus bulbosus L. collected from the acidified Freshwater Reservoir of Uusikaupunki in SW Finland. The heavy metals showed markedly elevated concentrations, mainly due to the enhanced solubility and availability of metals in the reservoir receiving acidic, sulphate-rich discharges from the catchment area. Tissue analyses of J. bulbosus could be used to reveal specific transport patterns in the reservoir. Multivariate principal components ordination of the data of the elemental analyses demonstrated local differences in the availability of metals.     

Airborne heavy metal pollution and its effects on foliar elemental composition of Empetrum hermaphroditum and Vaccinium myrtillus in Sør-Varanger, northern Norway

Uptake of Al, Cu, Fe, Mn, Ni, Ca, K, Mg, P, and S in Empetrum nigrum L. ssp. hermaphroditum Hagerup and Vaccinium myrtillus L. from Ni, Cu and SO2 contaminated sites in S?r-Varanger, northern Norway, were investigated. The primary objective was to study the effect of airborne heavy metal pollution on foliar element composition of these two dwarf shrubs. Ni distribution and availability in soils clearly indicate atmospheric deposition of Ni particulates in S?r-Varanger. Foliar Ni concentrations in E. hermaphroditum and V. myrtillus increased in relation to plant available Ni in corresponding soils. Leaves of E. hermaphroditum generally contained higher concentrations of Ni than leaves of V. myrtillus. Emissions influenced some features of leaf elemental composition of the two species in very different ways. In leaves of V. myrtillus, S increased in proportion to Ni and Cu, while levels of Mn decreased. In leaves of E. hermaphroditum, Fe increased in proportion to Ni and Cu, while levels of Ca decreased.     

Chemical and morphological characteristics of key tree species of the Carpathian Mountains

Concentrations of Al, B, Ca, Cu, Fe, K, Mg, Mn, N, Na, P, S and Zn in the foliage of white fir (Abies alba), Norway spruce (Picea abies) and common beech (Fagus sylvatica) from 25 sites of the Carpathian Mts. forests (Czech Republic, Poland, Romania, Slovakia and Ukraine) are discussed in a context of their limit values. S/N ratio was different from optimum in 90% of localities when compared with the European limit values. Likewise we found increase of Fe and Cu concentrations compared with their background levels in 100% of locations. Mn concentrations were increased in 76% of localities. Mn mobilization values indicate the disturbance of physiological balance leading to the change of the ratio with Fe. SEM-investigation of foliage waxes from 25 sites in the Carpathian Mts. showed, that there is a statistically significant difference in mean wax quality. Epistomatal waxes were damaged as indicated by increased development of net and amorphous waxes. The most damaged stomata in spruce needles were from Yablunitsa, Synevir and Brenna; in fir needles from Stoliky, and in beech leaves from Malá Fatra, Morské Oko and Beregomet. Spruce needles in the Carpathian Mts. had more damaged stomata than fir needles and beech leaves. Spruce seems to be the most sensitive tree species to environmental stresses including air pollution in forests of the Carpathian Mountains. Foliage surfaces of three forest tree species contained Al, Si, Ca, Fe, Mg, K, Cl, Mn, Na, Ni and Ti in all studied localities. Presence of nutrition elements (Ca, Fe, Mg, K and Mn) on foliage surface hinders opening and closing stomata and it is not physiologically usable for tree species.     

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Arsenic and Mn levels in Isaza (Gymnogobius isaza) during the mass mortality event in Lake Biwa, Japan

The present study measured the concentrations of 25 elements (Li, Mg, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb and Bi) in the whole body of Isaza which is an endemic fish species to Lake Biwa, Japan, and compared the values in the specimens from the mass mortality Isaza (MMI) and normal fresh Isaza (NFI). The mean levels of Mn and total As (T-As) were relatively higher in MMI than in NFI. In the T-As, highly toxic inorganic As was detected in MMI. Moreover we found Mn and As concentrations in surface sediment were extremely high and temporally increased. From all these results, we could infer that the dissolution of Mn and As from surface sediment of Lake Biwa might have been one of the cause for the mass mortality of Isaza.     

Dissolution kinetics of high explosives particles in a saturated sandy soil

Solid phase high explosive (HE) residues from munitions detonation may be a persistent source of soil and groundwater contamination at military training ranges. Saturated soil column tests were conducted to observe the dissolution behavior of individual components (RDX, HMX, and TNT) from two HE formulations (Comp B and C4). HE particles dissolved readily, with higher velocities yielding higher dissolution rates, higher mass transfer coefficients, and lower effluent concentrations. Effluent concentrations were below solubility limits for all components at superficial velocities of 10-50 cm day(-1). Under continuous flow at 50 cm day(-1), RDX dissolution rates from Comp B and C4 were 34.6 and 97.6 microg h(-1) cm(-2) (based on initial RDX surface area), respectively, significantly lower than previously reported dissolution rates. Cycling between flow and no-flow conditions had a small effect on the dissolution rates and effluent concentrations; however, TNT dissolution from Comp B was enhanced under intermittent-flow conditions. A model that includes advection, dispersion, and film transfer resistance was developed to estimate the steady-state effluent concentrations.     

The effect of nitrogen form on rhizosphere soil pH and zinc phytoextraction by Thlaspi caerulescens

The phytoextraction of Zn may be improved by applying N fertilizers to increase the biomass and Zn content of shoots. Rhizosphere-pH change from uptake of different N forms will affect Zn phyto-availability in the rhizosphere and Zn phytoextraction. This glasshouse study examined the effect of N form on Zn phytoextraction by Thlaspi caerulescens (Prayon). The plants were grown in a Zn-contaminated soil (total Zn 250 mg kg-1 soil; pHwater 5.7) and supplied with (NH4)2SO4, Ca(NO3)2 or urea [(NH2)2CO]. The form was maintained by applying the nitrification inhibitor dicyandiamide. A biodegradable chelator ethylenediaminedisuccinic acid (EDDS) was included for comparison. The addition of N doubled the shoot biomass. The highest shoot Zn content occurred in the Ca(NO3)2 treatment and was associated with the highest rhizosphere pH. The lowest shoot dry weight occurred in the EDDS treatment. The Zn concentration in the shoots increased as the rhizosphere pH increased. A significant correlation occurred between Ca and Zn concentrations in the shoots. This study demonstrated that Ca(NO3)2 is a more effective treatment than , urea or EDDS for enhancing Zn phytoextraction in a mildly acidic soil.     

用于CO2捕集的Mg(OH)2粉末溶解速率

氢氧化镁是一种正在研究的用于脱除烟气中低浓度CO2的化学吸收剂。为了掌握工业用氢氧化镁粉末的溶解速率,利用缓冲溶液,在不改变溶液体积的情况下对不同悬浊液浓度、溶液温度、溶液pH值和搅拌速率情况下的氢氧化镁粉末溶解速率进行了研究。提高悬浊液浓度、提高溶液温度、降低溶液pH值和提高搅拌速率均能增大氢氧化镁的溶解速率。悬浊液浓度从0.1 mol/L增加到1 mol/L时,溶解速率增大了2.2倍;温度从23℃增加到52℃时,溶解速率增大了4.3～9.5倍;pH值从9.8降低到6.6时,溶解速率增大了78～225倍;搅拌速率从350 r/min增加到700 r/min时,溶解速率增大了1～2倍。     

用于CO2捕集的Mg（OH）2粉末溶解速率

氢氧化镁是一种正在研究的用于脱除烟气中低浓度CO2的化学吸收剂。为了掌握工业用氢氧化镁粉末的溶解速率,利用缓冲溶液,在不改变溶液体积的情况下对不同悬浊液浓度、溶液温度、溶液pH值和搅拌速率情况下的氢氧化镁粉末溶解速率进行了研究。提高悬浊液浓度、提高溶液温度、降低溶液pH值和提高搅拌速率均能增大氢氧化镁的溶解速率。悬浊液浓度从0.1 mol/L增加到1 mol/L时,溶解速率增大了2.2倍;温度从23℃增加到52℃时,溶解速率增大了4.3～9.5倍;pH值从9.8降低到6.6时,溶解速率增大了78～225倍;搅拌速率从350 r/min增加到700 r/min时,溶解速率增大了1～2倍。     

Effect of fluoride on pH, organic matter and solubility of elements in soils

The effect of NaF addition on pH, organic matter and the solubilities of fifteen elements was investigated on twenty-eight surface soil samples. Four concentrations of NaF were added: 0, 10(-2.7), 10(-1.7) and 10(-1.0)m F in solution. Addition of NaF increased the pH and the solubility of organic matter for all soils. The magnitude of these increases was higher for acid than for alkaline soils. Aluminum, Fe and Ca showed the greatest increases in solubility while Mg, K, Mn and P showed intermediate increases. The elements Cd, Cr, Ni, Cu, Zn, B, Mo and Ba showed only slight increases in solubility. Another experiment was conducted to test whether the effects of NaF on pH, organic matter and the solubilities of various elements were due to F or Na. Four levels of NaCl similar to those for NaF were added to three acid and two alkaline soils. The results confirmed the effects of F on soil pH, organic matter and the solubilities of all elements investigated except those of K, Ca and Mg. Addition of Na as NaF resulted in release of K, Ca and Mg from the exchange sites on solid surfaces into solution.     

Soil solution Zn and pH dynamics in non-rhizosphere soil and in the rhizosphere of Thlaspi caerulescens grown in a Zn/Cd-contaminated soil

Temporal changes in soil solution properties and metal speciation were studied in non-rhizosphere soil and in the rhizosphere of the hyperaccumulator Thlaspi caerulescens J. & C. Presl (population from Prayon, Belgium) grown in a Zn- and Cd-contaminated soil. This paper focuses on soil solution Zn and pH dynamics during phytoextraction. The concentration of Zn in both non-rhizosphere and rhizosphere soil solutions decreased from 23 mg/l at the beginning to 2 mg/l at the end of the experiment (84 days after transplanting of seedlings), mainly due to chemical sorption. There was no significant difference in overall Zn concentration between the planted and the unplanted soil solutions (P > 0.05). Soil solution pH decreased initially and then increased slightly in both planted and unplanted soil zones. From 60 to 84 days after transplanting, the pH of the rhizosphere soil solution was higher than that of non-rhizosphere soil solution (P<0.05). Zn uptake by the hyperaccumulator plants was 8.8 mg per pot (each containing 1 kg oven-dry soil) on average. The data indicate that the potential of T. caerulescens to remove Zn from contaminated soil may not be related to acidification of the rhizosphere.     

Accumulation of phenanthrene and pyrene in rhizosphere soil

A study was conducted to determine PAH concentrations in the rhizosphere of plants grown in soil containing phenanthrene or pyrene. The rhizosphere of tall fescue and wheat grown in sterile soil contained 4-5-fold higher pyrene concentrations than unplanted soil. The rhizosphere of several plant species grown in non-sterile soil temporarily contained appreciably more phenanthrene or pyrene than unplanted soil, but those PAHs were degraded with time. The data suggest that plants accumulate such hydrophobic compounds in the rhizosphere after facilitating their transport toward the roots.     

Olivine dissolution from Indian dunite in saline water

The rate and mechanism of olivine dissolution was studied using naturally weathered dunite FO_98.21(Mg_1.884Fe_0.391SiO₄) from an Indian source, that also contains serpentine mineral lizardite. A series of batch dissolution experiments were carried out to check the influence of temperature (30–75 ^°C), initial dunite concentration (0.5 and 20 g/L), and salinity (0–35 g/L NaCl) under fixed head space CO₂ pressure (P\(_{\text {CO}_{2}}\) = 1 barg) on dunite dissolution. Dissolved Mg, Si, and Fe concentrations were determined by inductive coupled plasma atomic emission spectroscopy. End-product solids were characterized by scanning electron microscopy and X-ray diffraction. Initially, rates of dissolution of Si and Mg were observed to be in stoichiometric proportion. After 8 h, the dissolution rate was observed to decline. At the end of the experiment (504 h), an amorphous silica-rich layer was observed over the dunite surface. This results in decay of the dissolution rate. The operating conditions (i.e., salinity, temperature, and mineral loading) affect the dissolution kinetics in a very complex manner because of which the observed experimental trends do not exhibit a direct trend.     

Nickel tissue residue as a biomarker of sub-toxic exposure and susceptibility in amphibian embryos

Although low level exposure to physicochemical agents is the most common environmental scenario, their effects on living organisms are very controversial. However, there is an increasing need to integrate low level exposures from risk assessment to remediation purposes. This study focus on the possibility to employ Ni tissue residue values as biomarkers of sub-toxic exposure and susceptibility to this metal in a range of almost pristine to sub-toxic concentrations for Rhinella arenarum embryos. For that purpose, three batches of amphibian embryos were pretreated during 10 days with three increasing concentrations of Ni starting in 2, 8 and 20 microg Ni(2+) L(-1) and ending in 16, 64 and 160 microg Ni(2+) L(-1) (in natural fresh waters this value ranges from 2 to 10 microgL(-1); the LC(50)-24h for R. arenarum is 26.2mg Ni(2+) L(-1)). For the experimental conditions, the Ni tissue residue values at 360 h post exposure were 0.5, 2.1 and 3.6 microg Ni g(-1) embryo w/w, respectively, corresponding to BCFs of 31, 33 and 23. The susceptibility to Ni in those experimental embryos was evaluated by means of challenge exposures to three lethal concentrations of this metal (10, 20 and 30 mg Ni(2+) L(-1)), registering survival during the following 10 days of treatment. As a general pattern, the lower, intermediate and higher pretreatments with Ni resulted in enhanced, neutral and adverse effects on embryonic survival, respectively. Thus, sub-toxic exposure to Ni could modify the resistance of the amphibian embryo to this metal and Ni tissue residue values could be considered as biomarkers of both, exposure and susceptibility.     

An engineered plant that accumulates higher levels of heavy metals than Thlaspi caerulescens, with yields of 100 times more biomass in mine soils

Nicotiana glauca transformed with TaPCS1 was tested for its application in phytoremediation. When plantlets were grown in mine soils containing Cu, Zn, and Pb (42, 2600, and 1500 mg kg(-1)) the plant showed high levels of accumulation especially of Zn and Pb. Adult plants growing in mine soils containing different heavy metal concentrations showed a greater accumulation as well as an extension to a wider range of elements, including Cd, Ni and B. The overexpressed gene confers up to 9 and 36 times more Cd and Pb accumulation in the shoots under hydroponic conditions, and a 3- and 6-fold increase in mining soils. When the hyperaccumulator Thlaspi caerulescens was compared, the results were higher values of heavy metal and Boron accumulation, with a yield of 100 times more biomass. Thlaspi was unable to survive in mining soils containing either a level higher than 11000 mg kg(-1) of Pb and 4500 mg kg(-1) of Zn, while engineered plants yielded an average of 0.5 kg per plant.     

Changes in elemental uptake and arbuscular mycorrhizal colonisation during the life cycle of Thlaspi praecox Wulfen

Elemental uptake and arbuscular mycorrhizal (AM) colonisation were studied during the life cycle of field collected Cd/Zn hyperaccumulating Thlaspi praecox (Brassicaceae). Plant biomass and tissue concentrations of Cd, Pb, Zn, Fe and Ni were found to vary during development, while no variation in P, K, Ca, Mn and Cu tissue concentrations were observed. The lowest Cd bioaccumulation in rosette leaves (BAF(RL)) observed during seeding was partially attributed to lower translocation from roots to rosette leaves and partially to high translocation to stalks, indicating a high Cd mobility to reproductive tissues, in line with our previous studies. The highest intensity of AM colonisation (M%) was observed in the flowering phase and was accompanied by increased root Cd, Zn, Pb and Fe contents. In addition, a positive correlation between AM colonisation and Fe contents in rosette leaves was found. The results indicate developmental dependence of AM formation, accompanied by selective changes in nutrient acquisition in T. praecox that are related to increased plant needs, and the protective role of AM colonisation on metal polluted sites during the reproductive period.     

Comparative bioavailability of trace metals using three filter-feeder organisms in a subtropical coastal environment (Southeast Gulf of California)

To evaluate the relative bioavailability of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the coastal waters of one selected site in Mazatlán Harbor, different filter feeder organisms, an oyster (Crassostrea corteziensis), a mussel (Mytella strigata) and a barnacle (Fistulobalanus dentivarians), were sampled during 1 year. Seasonal and interspecific variations in some metal concentrations were evident, especially for Cd, Ni, Pb and Zn. In contrast with Fe, Pb and Zn, the concentrations of Cd varied accordingly in both bivalves. Even though the organisms live in the same site and have a common feeding mechanism, accumulated body Cd concentrations were different. Mussels concentrated significantly higher levels of Ni than the other organisms, while barnacles were better concentrators of Cd, Pb and Zn. A relationship existed between the concentrations of Cd, Fe and Zn in the soft tissues of the two bivalves, which is useful in monitoring studies when only one species occurs.     

Solubilization, solution equilibria, and biodegradation of PAH's under thermophilic conditions

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 degrees C, 40 degrees C and 60 degrees C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energy of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 degrees C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 degrees C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.