Accumulation of arsenic, lead, copper, and zinc, and synthesis of phytochelatins by indigenous plants of a mining impacted area

Several native plants, able to grow in an unconfined mining impacted area that is now in close vicinity with urban areas, were evaluated for their ability to accumulate heavy metals. The main soil contaminants were As, Pb, Cu, and Zn. Sampling of the rhizospheric metal polluted soil showed that Euphorbia prostrata Aiton, Parthenium incanum Kunth, and Zinnia acerosa (DC.) A. Gray were able to grow in the presence of high amounts of mixtures of these elements. The plants accumulated the metals in the above ground parts and increased the synthesis of thiol molecules. E. prostrata showed the highest capacity for accumulation of the mixture of elements (588 μg g DW^?1). Analysis of the thiol-molecules profile showed that these plants synthesized high amounts of long-chain phytochelatins, accompanied by low amounts of monothiol molecules, which may be related to their higher resistance to As and heavy metals. The three plants showed translocation factors from roots to leaves >1 for As, Pb, Cu, and Zn. Thus, by periodically removing aerial parts, these plants could be useful for the phytoremediation of semi-arid and arid mining impacted areas, in which metal hyper-accumulator plants are not able to grow.     

Determination of sixteen pesticides in peppers using high-performance liquid chromatography/mass spectrometry

A method for the detection and quantification of 16 pesticides: flufenoxuron, fenoxycarb, dimethomorph, acetamiprid, imidacloprid, lufenuron, thiacloprid, thiabendazole, thiophanate-methyl, spinosad, fenbutatin oxide, methoxyfenozide, oxamyl, clothianidin, thiamethoxam and carbendazim has been developed based on high-performance liquid chromatography-mass spectrometry. Pesticide residues were extracted from the samples according to the QuEChERS method which stands for quick, essay, cheap, effective, rugged and safe. Homogenised analytical portions (10 g ± 0.1) of samples of peppers were spiked at two levels (10 and 100 μg kg?1) with a small volume of an appropriate standard mixture solution containing each pesticide. Analyses were performed using electrospray ionization (ESI) and a MSD trap system. Chromatography separation was achieved using a ZORBAX SB-C18 3.5 μm particle size analytical column, 2.1 × 50 mm from Agilent, with gradient elution at a flow-rate of 0.4 mL/min with mobile phases: waters-0.1 % HCOOH-5 mM HCOONH? and MeOH-5 mM HCOONH?. The method has been validated based on the SANCO European Guidelines. Under the optimized conditions the recoveries (n = 7) were in the range 70-110 % with satisfactory precision (CV ≤ 20 %). A linear dynamic range was obtained over a range of concentrations from 10 to 100 μg kg?1 for each of the analytes, with correlation coefficients >0.997.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Remediation procedure used for contaminated soil and underground water: A case study from the chemical industry

This is a case study of contamination by a non-aqueous phase liquid (NAPL) that leaked from a chemical plant. The remediation procedure adopted for the initial phase of the plume migration was a plastic diaphragm wall coupled with a series of water extraction wells designed to avoid environmental impact on the surrounding ecosystems. Monitoring has shown that the containment is successful, and additional measures that contribute to accelerating remediation have been adopted. The authors wished to investigate how remediation might be further enhanced. The use of in situ aeration coupled with a system of soil vapor extraction (AS/SVE) has been chosen, since the remediation of sites with characteristics similar to those in this study, if based exclusively on dissolved-phase control, would take several decades to be completed. The transport of contaminant plumes has been simulated by using an analytical model to evaluate the effectiveness of the natural attenuation of the contaminant. The results of the simulation have confirmed the limited effectiveness of the natural attenuation of the contaminant, as well as the effective increase of remediation that would occur if the AS/SVE system is applied. A sensitivity analysis that included several combinations of increments of parameters that correspond to the decay rate of the source and the dissolved plume has simulated what might happen if the AS/SVE system is implemented.     

Speciation of arsenic in plants by HPLC-HG-AFS: extraction optimisation on CRM materials and application to cultivated samples

A recently developed method for the determination of arsenic species (arsenite, arsenate, monomethylarsonate, MMAA, and dimethylarsinate, DMAA) has been applied to the study of arsenic speciation in plants. This method uses ion-exchange liquid chromatography coupled on-line to atomic fluorescence spectrometry through continuous hydride generation. Various extraction procedures have been studied in detail using three plant certified reference materials. None of the procedures tested revealed fully satisfying results with all kinds of plant samples; microwave assisted extraction with 0.3 mol dm-3 orthophosphoric acid was found to be the most convenient for dealing with terrestrial plants. Species stability appears good. This method was applied to real world cultivated plant parts. Arsenate appears to predominate in soils, roots and leaves; unidentified species (probably arsenosugars) play an important role (60%) in rice fruits. Carrot was found to be the most contaminated edible plant part, containing 1 mg kg-1 essentially as arsenate species. MMAA was detected in all soils and some plant parts especially shallots at low levels, whereas DMAA was found only in one soil sample and in hot pepper leaves. Arsenite is a minor component of all soils; it is also present in some plant parts at low levels. However, no evident relationships were found between As speciation in the various plant parts and much more detailed studies will be necessary to elucidate As behaviour in plants.     

Influence of organic loading on an anaerobic sequencing biofilm batch reactor (ASBBR) as a function of cycle period and wastewater concentration

The effect of organic loading on the performance of a mechanically stirred anaerobic sequencing biofilm batch reactor (ASBBR) has been investigated, by varying influent concentration and cycle period. For microbial immobilization 1-cm polyurethane foam cubes were used. An agitation rate of 500 rpm and temperature of 30+/-2 degrees C were employed. Organic loading rates (OLR) of 1.5-6.0gCODl(-1)d(-1) were applied to the 6.3-l reactor treating 2.0 l synthetic wastewater in 8 and 12-h batches and at concentrations of 500-2000mgCODl(-1), making it possible to analyze the effect of these two operation variables for the same organic loading range. Microbial immobilization on inert support maintained approximately 60 gTVS in the reactor. Filtered sample organic COD removal efficiencies ranged from 73 to 88% for organic loading up to 5.4gCODl(-1)d(-1). For higher organic loading (influent concentration of 2000mgCODl(-1) and 8-h cycle) the system presented total volatile acids accumulation, which reduced organics removal efficiency down to 55%. In this way, ASBBR with immobilized biomass was shown to be efficient for organic removal at organic loading rates of up to 5.4gCODl(-1)d(-1) and to be more stable to organic loading variations for 12-h cycles. This reactor might be an alternative to intermittent systems as it possesses greater operational flexibility. It might also be an alternative to batch systems suspended with microorganisms since it eliminates both the uncertainties regarding granulation and the time necessary for biomass sedimentation, hence reducing the total cycle period.     

Chromium (III) recovery from waste acid solution by ion exchange processing using Amberlite IR-120 resin: batch and continuous ion exchange modelling

The use of ion exchange technology was studied to remove chromium (III) from acidic waste solution by Amberlite IR-120 resin. Batch and column experimental tests were conducted to provide data for theoretical models and verify the system performance of the adsorption process. Results of batch equilibrium tests indicated that Langmuir isotherm describes well the adsorption process, whereas experimental data also provide evidence that, under the present experimental conditions, chromium (III) adsorption by Amberlite IR-120 resin is film-diffusion controlled; on the other hand, the theoretical model used in the present investigation was found to predict reasonably well the ion exchange breakthrough performance.     

Heavy metals in fish (Solea vulgaris, Anguilla anguilla and Liza aurata) from salt marshes on the southern Atlantic coast of Spain

Comparisons were made of metal concentrations in water and sediment with those in the muscle and livers of three species of fish caught in four seawater reservoirs (two in the Odiel estuary and two in the Bay of Cádiz). The concentrations of a large number of metals in the water, sediment and fish were higher in the Odiel reservoirs than in those in Cádiz. We found high metal-enrichment factors in the livers as compared to muscle (over 100 for Fe and Cu and around 5 for Zn, Ni, Cd and Pb). The three fish species showed differences in metal content. For example, eels accumulated more metals in muscle and grey mullet in the liver. The metal levels found in muscle in the three species were below the legal limits for human consumption, although Cu in the liver was above the limit in the three species taken from the Odiel reservoirs, and Zn levels in liver were over the maximum in eels from one of the Odiel marshes. Significant correlations (p<0.05) were obtained for the levels of numerous metals in water, sediment and fish.     

Fed-batch and batch operating mode analysis of a stirred anaerobic sequencing reactor with self-immobilized biomass treating low-strength wastewater

This work presents an analysis of a stirred anaerobic sequencing discontinuous reactor with different substrate feeding strategies resulting in batch, fed-batch/batch and fed-batch operating modes. The reactor, containing granulated biomass, was fed with approximately 2.0L of synthetic domestic wastewater with Chemical Oxygen Demand of nearly 500 mg/L per cycle and operated at 30 degrees C and 50 rpm. Three feeding strategies with a total cycle time of 6 h, including 30-min settling, were adopted: batch mode with a fill cycle of 6 min, a fed-batch/batch mode with fill cycles of 60, 120 and 240 min and fed-batch mode with a fill cycle of 320 min. The system attained average non-filtered and filtered substrate removal efficiency of 78 and 84%, respectively, for all operating conditions, presenting good stability, solid retention and no granule break-up. A first order kinetic model with a residual organic matter concentration was proposed to analyze the influence of the feeding strategy on the performance during a cycle and bicarbonate alkalinity and total volatile acids concentration profiles were also quantified in order to verify the transient stability behavior.