Interaction effects of metals and salinity on biodegradation of a complex hydrocarbon waste

The presence of high levels of salts because of produced brine water disposal at flare pits and the presence of metals at sufficient concentrations to impact microbial activity are of concern to bioremediation of flare pit waste in the upstream oil and gas industry. Two slurry-phase biotreatment experiments based on three-level factorial statistical experimental design were conducted with a flare pit waste. The experiments separately studied the primary effect of cadmium [Cd(II)] and interaction effect between Cd(II) and salinity and the primary effect of zinc [Zn(II)] and interaction effect between Zn(II) and salinity on hydrocarbon biodegradation. The results showed 42-52.5% hydrocarbon removal in slurries spiked with Cd and 47-62.5% in the slurries spiked with Zn. The analysis of variance showed that the primary effects of Cd and Cd-salinity interaction were statistically significant on hydrocarbon degradation. The primary effects of Zn and the Zn-salinity interaction were statistically insignificant, whereas the quadratic effect of Zn was highly significant on hydrocarbon degradation. The study on effects of metallic chloro-complexes showed that the total aqueous concentration of Cd or Zn does not give a reliable indication of overall toxicity to the microbial activity in the presence of high salinity levels.     

Influence of heavy metals on the microbial degradation of diesel fuel

The degradation of diesel fuel by a microbial community from a soil polluted by heavy metals (h.m.) in the presence of Cu, Ni, Zn, Pb, Cd, Hg and Cr (as chromate) was investigated. Experiments were conducted with soil slurries and the extracted community in liquid cultivation. The concentrations applied were in the sub-mM and mM range. Whereas the slurries displayed no significant effect, degradation in liquid culture was increasingly inhibited by higher metal concentrations. The course of degradation in suspension was demonstrated by the oxygen consumption. The order of toxicity was found to be: Hg > Cr(VI) > Cu > Cd > Ni > Pb > Zn. The absence of any effect for slurries was due to the non-availability of the metals in the soil, and to precipitation or adsorption to the soil in the case of amendment. The paper also includes results on the availability of h.m. and changes to the community after exposure.     

Role of microbial inoculation and chitosan in phytoextraction of Cu, Zn, Pb and Cd by Elsholtzia splendens--a field case

A field experiment was carried out to study the effect of microbial inoculation on heavy metal phytoextraction by Elsholtzia splendens and whether chitosan could have a synergistic effect with the microbial inocula. The microbial inocula consisted of a consortium of arbuscular mycorrhizal fungi and two Penicillium fungi. Three treatments were included: the control, inoculation with microbial inocula, and the inoculation combined with chitosan. Microbial inoculation increased plant biomass especially shoot dry weight, enhanced shoot Cu, Zn and Pb concentrations but did not affect Cd, leading to higher shoot Cu, Zn, Pb and Cd uptake. Compared with microbial inoculation alone, chitosan application did not affect plant growth but increased shoot Zn, Pb and Cd concentrations except Cu, which led to higher phytoextraction efficiencies and partitioning to shoots of Zn, Pb and Cd. These results indicated synergistic effects between microbial inocula and chitosan on Zn, Pb and Cd phytoextraction.     

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

Effects of cross-substrate interaction on biotrickling filtration for the control of VOC emissions

The effects of cross-substrate interaction to the performance of a gas-phase biotrickling filter for treating a mixture of volatile organic compounds (VOCs), including three structural heterologous in acetone, toluene, and trichloroethylene, were investigated. The biotrickling filter was inoculated with microbial consortium containing at least seven bacterial species utilizing either acetone or toluene, or both, as their carbon sources. In the performance study, the column operating under variable conditions typifying the waste gas emission from the microelectronics fabrication processes achieved a total hydrocarbon (THC) removal efficiency in excess of 85% and a mineralization capacity over 50% for THC mass loading as high as 36.2 g-CH4 m-3h-1. The cross-substrate effects were examined by correlating the relative changes in the mass removal of each substrate with the biodegradative capability of the microbial consortium. The degradation of trichloroethylene was primarily due to co-metabolism by the toluene-oxidizing enzymes, but the results also indicated that trichloroethylene partially induced its own degradation. Concentration increases in acetone appeared to cause a diauxie effect that suppressed degradation of toluene and trichloroethylene, and shifted the microbial population toward the selective acetone-degraders. No irrecoverable toxicity or inhibitory effects were observed throughout the experiments. These results suggest that the relative VOC concentration in the waste gas mixture is a factor as important as the biodegradative function of the microbial consortium, and thus should be carefully evaluated to satisfy the treatment objectives.     

Australian native plant species Carpobrotus rossii (Haw.) Schwantes shows the potential of cadmium phytoremediation

Many polluted sites are typically characterized by contamination with multiple heavy metals, drought, salinity, and nutrient deficiencies. Here, an Australian native succulent halophytic plant species, Carpobrotus rossii (Haw.) Schwantes (Aizoaceae) was investigated to assess its tolerance and phytoextraction potential of Cd, Zn, and the combination of Cd and Zn, when plants were grown in soils spiked with various concentrations of Cd (20–320 mg kg^?1 Cd), Zn (150–2,400 mg kg^?1 Zn) or Cd + Zn (20?+?150, 40?+?300, 80?+?600 mg kg^?1). The concentration of Cd in plant parts followed the order of roots > stems > leaves, resulting in Cd translocation factor (TF, concentration ratio of shoots to roots) less than one. In contrast, the concentration of Zn was in order of leaves > stems > roots, with a Zn TF greater than one. However, the amount of Cd and Zn were distributed more in leaves than in stems or roots, which was attributed to higher biomass of leaves than stems or roots. The critical value that causes 10 % shoot biomass reduction was 115 μg g^?1 for Cd and 1,300 μg g^?1 for Zn. The shoot Cd uptake per plant increased with increasing Cd addition while shoot Zn uptake peaked at 600 mg kg^?1 Zn addition. The combined addition of Cd and Zn reduced biomass production more than Cd or Zn alone and significantly increased Cd concentration, but did not affect Zn concentration in plant parts. The results suggest that C. rossii is able to hyperaccumulate Cd and can be a promising candidate for phytoextraction of Cd from polluted soils.     

Effect of nitroethane and nitroethanol on the production of indole and 3-methylindole (skatole) from bacteria in swine feces by gas chromatography

Indole and 3-methylindole (skatole) are odor pollutants in livestock waste, and skatole is a major component of boar taint. Skatole causes pulmonary edema and emphysema in ruminants and causes damage to lung Clara cells in animals and humans. A gas chromatographic method that originally used a nitrogen–phosphorus detector to increase sensitivity was modified resulting in an improved flame ionization detection response for indole and skatole of 236% and 207%, respectively. The improved method eliminates the large amount of indole decomposition in the injector. A 10 μ g mL^–1 spike of indole and skatole in water and swine fecal slurries resulted in recovery of 78.5% and 96% in water and 76.1% and 85.8% in fecal slurries, respectively. The effect of the addition of nitroethane and nitroethanol at 21.8 mM in swine fecal slurries was studied on the microbial production of indole and skatole. Nitroethane and nitroethanol decreased the production of skatole in swine fecal slurries at 24 h. The nitroethane effect on l-tryptophan-supplemented fecal slurries after 6 and 24 h incubation resulted in a decrease of 69.0% (P = 0.02) and 23.5% skatole production, respectively, and a decrease of 14.9% indole at 6 h, but an increase in indole production of 81.1% at 24 h.     

New insight into molecular interaction of heavy metal pollutant—cadmium(II) with human serum albumin

Cadmium (Cd) is an extremely toxic metal commonly found as an environmental contaminant from industrial and agricultural sources, posing severe risks to human health. In this study, the binding mechanism of Cd(II)–human serum albumin (HSA) complex and the effect of Cd(II) on the conformational stability and structural state of HSA were comprehensively investigated through a series of efficient and appropriate methods. X-ray photoelectron spectroscopy accurately described the microenvironmental changes around protein C, N, and O atoms in the presence of Cd(II). Fluorescence results indicated that the probable mechanism of Cd(II)–HSA interaction is a static quenching process. Fourier transform infrared spectroscopy and dynamic light scattering showed Cd(II) complexation altered HSA conformation and the microenvironments of Trp and Tyr residues, accompanied by the size increases of HSA aggregates. This research will be helpful for understanding the toxic effects of Cd(II) on protein function in vivo.

Cadmium and zinc in Mytilus edulis L. from the Bothnian Sea and the northern Baltic proper

Contents of Cd and Zn in the blue mussel, Mytilus edulis, collected on the coast of the southern Bothnian Sea and the northern Baltic proper, were determined using flame AAS. The observed concentrations ranged from 4.7 to 10.8 mg kg(-1) dw for Cd and from 121 to 215 mg kg(-1) dw for Zn. The Zn/Cd ratio was around 20 at a majority of the investigated locations. Cd exhibited an approximate two-fold gradual increase from south to north in the study area. It is likely that this increase was due largely to enhanced bioavailability for Cd at lower salinity. However, it is not possible to eliminate the influence from a generally elevated overall concentration of cadmium in the southern Bothnian Sea caused by natural and anthropogenic input. Compared to mussels from marine waters on the west coast of Sweden, Cd concentrations were 5-10 times higher, similarity indicating an influence of low salinity. Zn did not show these salinity correlated differences. The high Zn content found south of the outlet of the river Dal?lven and gradually decreasing southwards was possibly caused by the high riverine input.     

Influences of salinity on the biokinetics of Cd, Se, and Zn in the intertidal mudskipper Periophthalmus cantonensis

The biokinetics (aqueous uptake, dietary assimilation, and elimination) of Cd, Se, and Zn in the intertidal mudskipper, Periophthalmus cantonensis, were examined at different acclimated salinities using the radiotracer technique. The dietary assimilation efficiency from ingested radiolabeled polychaetes was the highest for Se (32–40%), followed by Zn (5–7%) and Cd (2–3%), and was not influenced by salinity within a range of 10–30 psu. Uptake from the dissolved phase typically exhibited a linear pattern within the first 12 h of exposure, followed by a second slower uptake. The highest concentration factor (CF) was found for Zn, followed by Cd and Se. Differences in salinity did not significantly affect the CF of the three metals within the first 12 h, but the CFs were significantly higher at lower salinities (10–20 psu) than at the highest salinity (30 psu) by the end of 48 h exposure. Because the degrees to which the uptake of Se (a metalloid) and Cd/Zn were affected by salinity were comparable, we concluded that metal speciation as a result of salinity change was not important in leading to a change in metal CF. Physiological changes may be responsible for the increasing uptake at lowered salinity. The elimination rates of the three metals (0.01–0.06 d⁻¹) were not significantly affected by salinity, but Se was eliminated at a faster rate following aqueous uptake than following dietary ingestion. There was no consistent influence of exposure routes on Cd and Zn elimination. The accumulated Cd was mainly associated with the gut, whereas the muscle was the dominant target site for Se and Zn accumulation.     

Biological activity in metal-contaminated calcareous agricultural soils: the role of the organic matter composition and the particle size distribution

Organic matter (OM) plays a key role in microbial response to soil metal contamination, yet little is known about how the composition of the OM affects this response in Mediterranean calcareous agricultural soils. A set of Mediterranean soils, with different contents and compositions of OM and carbonate and fine mineral fractions, was spiked with a mixture of Cd, Cu, Pb, and Zn and incubated for 12 months for aging. Microbial (Biolog Ecoplates) and enzyme activities (dehydrogenase, DHA; β-galactosidase, BGAL; phosphatase, PHOS; and urease, URE) were assessed and related to metal availability and soil physicochemical parameters. All enzyme activities decreased significantly with metal contamination: 36–68 % (DHA), 24–85 % (BGAL), 22–72 % (PHOS), and 14–84 % (URE) inhibitions. Similarly, catabolic activity was negatively affected, especially phenol catabolism (～86 % compared to 25–55 % inhibition for the rest of the substrates). Catabolic and DHA activities were negatively correlated with ethylenediaminetetraacetic acid (EDTA)-extractable Cd and Pb, but positively with CaCl₂, NaNO₃, and DTPA-extractable Cu and Zn. Soluble OM (water- and hot-water-soluble organic C) was positively related to enzyme and catabolic activities. Recalcitrant OM and fine mineral fractions were positively related to BGAL and PHOS. Conversely, catabolic activity was negatively related to clay and positively to silt and labile OM. Results indicate that the microbial response to metal contamination is highly affected by texture and OM composition.     

Plant accumulation of potentially toxic elements in sewage sludge as affected by soil organic matter level and mycorrhizal fungi.

Leek (Allium ameloprasum) was grown in pot trials in two clay loams of contrasting organic contents, with and without indigenous mycorrhizal propagules. Sewage sludges containing varying levels of Cd, Cu and Zn were added. Extractable soil metals, plant growth, major nutrient content and accumulation of metals, and soil microbial indices were investigated. The aim was to establish whether soil organic content and mycorrhizal status affected plant and microbial exposure to these metals. Extractable metals were higher and responses to inputs more pronounced in the arable, lower organic matter soil, although only Cd showed a soil difference in the CaCl2 fraction. There were no metal toxic effects on plants and some evidence to suggest that they promoted growth. Uptake of each metal was higher in the larger plants of the grassland, higher organic matter soil. Inoculation with arbuscular mycorrhizal fungi increased root Cd and Zn concentrations. With the exception of Cd (roots) and Zn (shoots), higher inputs of sludge metals did not increase plant metals. Zn and Cu, but not Cd, concentrations were higher in roots than in shoots.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Effects of heavy metals on growth and arsenic accumulation in the arsenic hyperaccumulator Pteris vittata L

The effects of Cd, Ni, Pb, and Zn on arsenic accumulation by the arsenic hyperaccumulator Pteris vittata were investigated in a greenhouse study. P. vittata was grown for 8 weeks in an arsenic-contaminated soil (131 mg As kg(-1)), which was spiked with 50 or 200 mg kg(-1) Cd, Ni, Pb, or Zn (as nitrates). P. vittata was effective in taking up arsenic (up to 4100 mg kg(-1)) and transporting it to the fronds, but little of the metals. Arsenic bioconcentration factors ranged from 14 to 36 and transfer factors ranged from 16 to 56 in the presence of the metals, both of which were reduced with increasing metal concentration. Fern biomass increased as much as 12 times compared to the original dry weight after 8 weeks of growth (up to 19 g per plant). Greater concentrations of Cd, Ni, and Pb resulted in greater catalase activity in the plant. Most of the arsenic in the plant was present as arsenite, the reduced form, indicating little impact of the metals on plant arsenic reduction. This research demonstrates the capability of P. vittata in hyperaccumulating arsenic from soils in the presence of heavy metals.     

Influence of temperature and salinity on heavy metal uptake by submersed plants

Submersed plants can be useful in reducing heavy metal concentrations in stormwater, since they can accumulate large amounts of heavy metals in their shoots. To investigate the effects of water temperature and salinity on the metal uptake of two submersed plant species, Elodea canadensis (Michx.) and Potamogeton natans (L.), these plants were grown in the presence of Cu, Zn, Cd, and Pb at 5, 11, and 20 degrees C in combination with salinities of 0, 0.5, and 5 per thousand. The metal concentrations in the plant tissue increased with increasing temperature in both species; the exception was the concentration of Pb in Elodea, which increased with decreasing salinity. Metal concentrations at high temperature or low salinity were up to twice those found at low temperature or high salinity. Plant biomass affected the metal uptake, with low biomass plants having higher metal concentrations than did high biomass plants.     

Bioremediation of oil-contaminated soil using Candida catenulata and food waste

Even though petroleum-degrading microorganisms are widely distributed in soil and water, they may not be present in sufficient numbers to achieve contaminant remediation. In such cases, it may be useful to inoculate the polluted area with highly effective petroleum-degrading microbial strains to augment the exiting ones. In order to identify a microbial strain for bioaugmentation of oil-contaminated soil, we isolated a microbial strain with high emulsification and petroleum hydrocarbon degradation efficiency of diesel fuel in culture. The efficacy of the isolated microbial strain, identified as Candida catenulata CM1, was further evaluated during composting of a mixture containing 23% food waste and 77% diesel-contaminated soil including 2% (w/w) diesel. After 13 days of composting, 84% of the initial petroleum hydrocarbon was degraded in composting mixes containing a powdered form of CM1 (CM1-solid), compared with 48% of removal ratio in control reactor without inoculum. This finding suggests that CM1 is a viable microbial strain for bioremediation of oil-contaminated soil with food waste through composting processes.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Interactions between accumulation of trace elements and macronutrients in Salix caprea after inoculation with rhizosphere microorganisms

Although the beneficial effects on growth and trace element accumulation in Salix spp. inoculated with microbes are well known, little information is available on the interactions among trace elements and macronutrients. The main purpose of this study was to assess the effect of phytoaugmentation with the rhizobacteria Agromyces sp., Streptomyces sp., and the combination of each of them with the fungus Cadophora finlandica on biomass production and the accumulation of selected trace elements (Zn, Cd, Fe) and macronutrients (Ca, K, P and Mg) in Salix caprea grown on a moderately polluted soil. Dry matter production was significantly enhanced only upon inoculation with Agromyces sp. Regarding the phytoextraction of Cd and Zn, shoot concentrations were mostly increased after inoculation with Streptomyces sp. and Agromyces sp. + C. finlandica. These two treatments also showed higher translocation factors from roots to the leaves for both Cd and Zn. The accumulation of Cd and Zn in shoots was related to increased concentrations of K. This suggests that microorganisms that contribute to enhanced phytoextraction of Cd and Zn affect also the solubility and thus phytoavailability of K. This study suggests that the phytoextraction of Zn and Cd can be improved by inoculation with selected microbial strains.     

Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils

The fate of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils may be affected by several environmental factors including the presence of co-contaminants. This study was conducted in order to assess the effect of metals on (i) the adsorption of 14C-phenanthrene in soils and (ii) its extractability and ability to form non-extractable residues. The first objective was accomplished using batch adsorption experiments with an uncontaminated agricultural soil spiked with the metals Cd, Cu, Pb, and Zn. Adsorption of phenanthrene was significantly higher after the addition of the metals (Kf = 21.48 vs. 8.55) and the desorption less readily reversible when compared to the unspiked soil. The extractability of phenanthrene was assessed with incubation (4 months, laboratory conditions) and microlysimeter experiments (6 months, natural climatic conditions) on three soils spiked with metals. All the soils were labelled with 14C-phenanthrene. The amount of extractable phenanthrene residues was significantly higher when the metals had been added to the soils. Nevertheless, the quantity of non-extractable residues was non-significantly different between the spiked and unspiked soils. The mechanism leading to increased adsorption and extractability of phenanthrene in the presence of metals is still unknown. In perspective, it would be interesting to assess the bioavailability of PAHs in the presence of metals in further experiments.