Seasonal variations in hepatic Cd and Cu concentrations and in the sub-cellular distribution of these metals in juvenile yellow perch (Perca flavescens)

Temporal fluctuations in metal (Cd and Cu) concentrations were monitored over four months (May to August) in the liver of juvenile yellow perch (Perca flavescens) sampled from four lakes situated along a metal concentration gradient in northwestern Quebec: Lake Opasatica (reference lake, low metal concentrations), Lake Vaudray (moderate metal concentrations) and lakes Osisko and Dufault (high metal levels). The objectives of this study were to determine if hepatic metal concentrations and metal-handling strategies at the sub-cellular level varied seasonally. Our results showed that Cd and Cu concentrations varied most, in both absolute and relative values, in fish with the highest hepatic metal concentrations, whereas fish sampled from the reference lake did not show any significant variation. To examine the sub-cellular partitioning of these two metals, we used a differential centrifugation technique that allowed the separation of cellular debris, metal detoxified fractions (heat-stable proteins such as metallothionein) and metal sensitive fractions (heat-denaturable proteins (HDP) and organelles). Whereas Cd concentrations in organelle and HDP fractions were maintained at low concentrations in perch from Lakes Opasatica and Vaudray, concentrations in these sensitive fractions were higher and more variable in perch from Lakes Dufault and Osisko, suggesting that there may be some liver dysfunction in these two fish populations. Similarly, Cu concentrations in these sensitive fractions were higher and more variable in perch from the two most Cu-contaminated lakes (Dufault and Osisko) than in perch from the other two lakes, suggesting a breakdown of homeostatic control over this metal. These results suggest not only that metal concentrations vary seasonally, but also that concentrations vary most in fish from contaminated sites. Furthermore, at the sub-cellular level, homeostatic control of metal concentrations in metal-sensitive fractions is difficult to maintain in perch with high hepatic metal concentrations.     

Accumulation, distribution and cellular partitioning of mercury in several halophytes of a contaminated salt marsh

This work evaluates the role of a plant community in mercury (Hg) stabilization and mobility in a contaminated Portuguese salt marsh. With this aim, the distribution of Hg in below and aboveground tissues, as well as the metal partitioning between cellular fractions (soluble and insoluble) in four different species (Triglochin maritima L., Juncus maritimus Lam, Sarcocornia perennis (Miller) A.J. Scott, and Halimione portulacoides (L.) Aellen) was assessed. Mercury accumulation, translocation and compartmentation between organs and cellular fractions were related to the plant species.Results showed that the degree of Hg absorption and retention was influenced both by environmental parameters and metal translocation/partitioning strategies. Different plant species presented different allocation patterns, with marked differences between monocots (T. maritima and J. maritimus) and dicots (S. perennis, H. portulacoides). Overall, the two monocots, in particular T. maritima showed higher Hg retention in the belowground organs whereas the dicots, particularly S. perennis presented a more pronounced translocation to the aboveground tissues. Considering cellular Hg partitioning, all species showed a higher Hg binding to cell walls and membranes rather than in the soluble fractions. This strategy can be related to the high degree of tolerance observed in the studied species. These results indicate that the composition of salt marsh plant communities can be very important in dictating the Hg mobility within the marsh ecosystem and in the rest of the aquatic system as well as providing important insights to future phytoremediation approaches in Hg contaminated salt marshes.     

Remediation of metal polluted mine soil with compost: co-composting versus incorporation

Trace element contamination of post-industrial sites represents a major environmental problem and sustainable management options for remediating them are required. This study compared two strategies for immobilizing trace elements (Cu, Pb, Zn, and As) in mine spoil: (1) co-composting contaminated soil with organic wastes and (2) conventional incorporation of mature compost into contaminated soil. Sequential chemical extraction of the soil was performed to determine temporal changes in trace element fractionation and bioavailability during composting and plant growth. We show that mine spoil can be co-composted successfully and this action causes significant shifts in metal availability. However, co-composting did not lead to significant differences in metal partitioning in soil or in plant metal uptake compared with simply mixing mine spoil with mature compost. Both treatments promoted plant growth and reduced metal accumulation in plants. We conclude that co-composting provides little additional benefit for remediating trace-element-polluted soil compared with incorporation of compost.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (northern England)

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.     

Bioremediation of trace organic compounds found in precious metals refineries' wastewaters: a review of potential options

Platinum group metal (PGM) refining processes produce large quantities of wastewater, which is contaminated with the compounds that make up the solvents/extractants mixtures used in the process. These compounds often include solvesso, beta-hydroxyxime, amines, amides and methyl isobutyl ketone. A process to clean up PGM refinery wastewaters so that they could be re-used in the refining process would greatly contribute to continual water storage problems and to cost reduction for the industry. Based on the concept that organic compounds that are produced biologically can be destroyed biologically, the use of biological processes for the treatment of organic compounds in other types of waste stream has been favoured in recent years, owing to their low cost and environmental acceptability. This review examines the available biotechnologies and their effectiveness for treating compounds likely to be contained in precious metal extraction process wastewaters. The processes examined include: biofilters, fluidized bed reactors, trickle-bed bioreactors, bioscrubbers, two-phase partitioning bioreactors, membrane bioreactors and activated sludge. Although all processes examined showed adequate to excellent removal of organic compounds from various gaseous and fewer liquid waste streams, there was a variation in their effectiveness. Variations in performance of laboratory-scale biological processes are probably due to the inherent change in the microbial population composition due to selection pressure, environmental conditions and the time allowed for adaptation to the organic compounds. However, if these factors are disregarded, it can be established that activated sludge and membrane bioreactors are the most promising processes for use in the treatment of PGM refinery wastewaters.     

Measurement of dynamic mobilization of trace metals in sediments using DGT and comparison with bioaccumulation in Chironomus riparius: first results of an experimental study

Sediments in aquatic ecosystems are often contaminated as a result of anthropogenic activities. Sediments and benthic organisms have been used to monitor trace metals contamination. However, due to the high variability of contaminant bioavailability, the attempt to link metal concentration in sediments and contamination of the organisms or ecotoxicological effect often lead to disappointing results. The technique of diffusive gradients in thin films (DGT) has been proposed as a relevant tool to study metal bioavailability, for example for accumulation in plants. In the present study, laboratory microcosm experiments were conducted with six contaminated sediments to compare metal accumulation in DGT and bioaccumulation in a chironomid (Chironomus riparius) for Cu, Cd and Pb . Metal accumulation in DGT was measured over time then modelled to determine two parameters of the dynamic response of the metals to DGT deployment: the size of the particulate labile pool and the kinetic of the solid-dissolved phase exchange. The mobility of metals was found metal and sediment dependent. A significant relationship between metal accumulated in DGT and bioaccumulated in chironomids was found for Cu and Pb. However, total metals in sediments were the best predictors of bioaccumulation. Nevertheless, the knowledge of the metals dynamic enhanced our ability to explain the different biological uptake observed in sediments of similar total metal concentrations.     

Allocation plasticity and plant-metal partitioning: meta-analytical perspectives in phytoremediation

In this meta-analysis of plant growth and metal uptake parameters, we selected 19 studies of heavy metal (HM) phytoremediation to evaluate trends of allocation plasticity and plant-metal partitioning in roots relative to shoots. We calculated indexes of biomass allocation and metal distribution for numerous metals and plant species among four families of interest for phytoremediation purposes (e.g. Brassicaceae, Fabaceae, Poaceae, and Solanaceae). We determined that plants shift their biomass and distribute metals more to roots than shoots possibly to circumvent the challenges of increasing soil-HM conditions. Although this shift is viewed as a stress-avoidance strategy complementing intrinsic stress-tolerance, our findings indicate that plants express different levels of allocation plasticity and metal partitioning depending on their overall growth strategy and status as ‘fast-grower’ or ‘slow-grower’ species. Accordingly, we propose a conceptual model of allocation plasticity and plant-metal partitioning comparing ‘fast-grower’ and ‘slow-grower’ strategies and outlining applications for remediation practices.     

A Model Analysis of Metal Partitioning

The 1984 Amendments to the Solid Waste Act require that wastes listed under the Resource Conservation and Recovery Act (RCRA) be analyzed to assess the feasibility of further banning from land disposal. Incineration is expected to be used more often for disposing of either the banned wastes directly or the residues of various treatment processes. Incineration of hazardous wastes, municipal wastes and industrial sludges produces some extent of trace metals. This paper provides a preliminary model concept for analyzing metal partitioning during incineration. The paper concludes that a model for predicting metal partitioning phenomena is feasible and could reduce costs in conducting metal emission testing in the field.     

Models of multi-media partitioning of multi-species chemicals: The fugacity/aquivalence approach

The fugacity or aquivalence approach to environmental modelling is extended to treat chemicals which may be present as several inter-converting species in a multi-media environment. Species-specific and total Z values are defined expressing the capacity of each phase for each species of chemical. Similarly, species-specific and total D values are defined to quantify transport and transformation rates. Fugacity or aquivalence is used as the criterion for partitioning behaviour or physical equilibrium. By defining species proportions on an aquivalence or fugacity fraction basis, the equations for multiple species can be consolidated into a single “pseudo single-component” mass balance equation. Steady-state multi-species, multi-compartment mass balance models can be assembled for such systems and solved in various ways to give mass balances and distributions for all species amounts, concentrations, fluxes and species conversion rates.

Examples are presented for a hypothetical substance present as three species in a system under equilibrium and non-equilibrium, steady-state conditions.     

Channel flow and trichloroethylene treatment in a partly iron-filled fracture: experimental and model results

Technical developments have now made it possible to emplace granular zero-valent iron (Fe(0)) in fractured media to create a Fe(0) fracture reactive barrier (Fe(0) FRB) for the treatment of contaminated groundwater. To evaluate this concept, we conducted a laboratory experiment in which trichloroethylene (TCE) contaminated water was flushed through a single uniform fracture created between two sandstone blocks. This fracture was partly filled with what was intended to be a uniform thickness of iron. Partial treatment of TCE by iron demonstrated that the concept of a Fe(0) FRB is practical, but was less than anticipated for an iron layer of uniform thickness. When the experiment was disassembled, evidence of discrete channelised flow was noted and attributed to imperfect placement of the iron. To evaluate the effect of the channel flow, an explicit Channel Model was developed that simplifies this complex flow regime into a conceptualised set of uniform and parallel channels. The mathematical representation of this conceptualisation directly accounts for (i) flow channels and immobile fluid arising from the non-uniform iron placement, (ii) mass transfer from the open fracture to iron and immobile fluid regions, and (iii) degradation in the iron regions. A favourable comparison between laboratory data and the results from the developed mathematical model suggests that the model is capable of representing TCE degradation in fractures with non-uniform iron placement. In order to apply this Channel Model concept to a Fe(0) FRB system, a simplified, or implicit, Lumped Channel Model was developed where the physical and chemical processes in the iron layer and immobile fluid regions are captured by a first-order lumped rate parameter. The performance of this Lumped Channel Model was compared to laboratory data, and benchmarked against the Channel Model. The advantages of the Lumped Channel Model are that the degradation of TCE in the system is represented by a first-order parameter that can be used directly in readily available numerical simulators.     

Particulate-associated heavy metals in the urban environment: their transport from source to deposit, Coventry, UK.

A sequential digest was used to examine the speciation of particulate-associated heavy metal pollutants in a holistic approach to the study of the movement of sediment within the urban environment. Sediments were classified according to whether they mainly acted as sources, were mostly transported, or had become deposited and were fractionated into two particle sizes to reflect sediment deposited in lakes (< 63 microns) and transported in rivers (< 2 mm). Results showed that the two particle size fractions yielded the same data, but that trends were found in terms of dominant heavy metal species as the sediment moved through the source-transport-deposit cascade. Whilst the results highlighted the complexity of the urban environment, a sequential digestion of the samples enabled comments to be made in terms of risk which could subsequently feed in to a management strategy for polluted urban sediments.     

Metal partitioning and uptake in central Ontario forests

Evaluation of the potential environmental risk posed by metals depends to a great extent on modeling the fate and mobility of metals with soil-solution partitioning coefficients (Kd). However, the effect of biological cycling on metal partitioning is rarely considered in standard risk assessments. We determined soil-solution partitioning coefficients for 5 metals (Cd, Zn, Pb, Co and Ni) at 46 forested sites that border the Precambrian Shield in central Ontario, where soil pHaq varied from 3.9 to 8.1. Foliage from the dominant tree species and forest floor samples were also collected from each site to compare their metal levels with Kd predictions. Analogous to other studies, log Kd values for all metals were predicted by empirical linear regression with soil pH (r2=0.66-0.72), demonstrating that metal partitioning between soil and soil solution can be reliably predicted for relatively unpolluted forest mineral soils by soil pH. In contrast, whereas the so-called bioavailable water-soluble metal fraction could be predicted from soil pH, metal concentrations in foliage and the forest floor at each site were not consistently related to pH. Risk assessment of metals should take into account the role of biota in metal cycling and partitioning in forests, particularly if metal bio-accumulation and chronic toxicity in the food chain, rather than metal mobility in soils, are of primary concern.     

Dynamic modelling of recovery from acidification of lakes in Killarney Park,Ontario, Canada

During much of the 1900s, the lakes in Killarney Provincial Park have been exposed to high levels of acid deposition due to sulfur emissions from the nearby metal smelters in Sudbury. The sulfur emissions from this large point source have decreased to about 10% of what they were in the 1960s. Lake water quality in Killarney Park has greatly changed in response to reduced emissions, with noticeable declines in sulfate, aluminum and calcium concentrations. Here we apply the dynamic acidification model MAGIC to 3 lakes in Killarney Park. The lakes, which have different buffering capacities and response times, were selected to represent fast, intermediate and slow recovery from acidification. The model was calibrated to match observed data for the lakes and 4 different forecast scenarios for future sulfur deposition reductions were applied. The results indicate that there is still a large potential for improvement in the water quality in Killarney. The recovery time for the different lakes varies greatly. For the lake having the slowest response time several decades are needed for the chemistry to stabilize after implementation of deposition reductions.     

Update on Building and Structure Decontamination

Cleanup of the nation’s hazardous waste sites is a top environmental priority. Since the ultimate objective of many cleanup programs is to return the contaminated site and buildings on the site to active use, additional information regarding both established and emerging technologies for building decontamination is needed.

A pilot scale study was performed at an actual Superfund Site to evaluate, side by side, the efficacy of PCB removal using two decontamination processes. One process entails use of a shotblasting technique in which contaminated concrete surfaces are cut away and physically removed. The other process involves application of an alkali metal/polyethylene glycolate mixture directly to contaminated concrete surfaces for insitu degradation of PCBs.     

Trace metal accumulation and fish pathologies in areas affected by mining and metallurgical enterprises in the Kola Region, Russia

Throughout the Kola region of Russia there has been a substantial increase of metal concentrations in water, which are related to local discharges from metallurgical and mining industry, transboundary transmissions as well as indirect leaching of elements by acid precipitation. This study presents data on the levels of Ni, Cu, Sr, Al, Zn, Co, Mn, Pb, Cd, Hg in the organs and tissues of fish, and evaluates relationships with water chemistry. Special attention is paid to fish pathologies, whose aetiology is related to the accumulation of metals and the associated changes of the elementary ratios within the organism. Ecotoxicological assessment of the copper nickel, strontium and acidification regimes also is considered in this article. In general we observed a large number of lakes that are heavily contaminated by Ni and Cu. Fish in these lakes contain high concentrations of Ni and Cu and display frequent pathologies, mostly associated with the kidneys. In lakes contaminated with Sr, there also are high Sr levels in fish and pathologies associated with skeletal tissues. Exposure to acidified water appears to increase the transport of metals (including Al, Ni and Cu) into fish and hence the toxic effects.     

The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

Thermal venting to recover less-volatile hydrocarbons from the unsaturated zone, 1. Theory

Thermal venting is a remediation technique suitable to the liquid unsaturated zone to enhance recovery of less-volatile residual hydrocarbon contaminants. Thermal venting is different to traditional soil venting because heated air instead of air at ambient conditions is applied to the contaminated zone. The vapor pressure of a less-volatile contaminants is typically increased by temperature causing the gas-phase concentrations to increase by three- to five-fold over a temperature increase of 20–30°C. The work described in this first paper provides the theoretical framework of analysis related to thermal venting. The analysis included nonisothermal gas flow, thermal energy transport and multicomponent mass transport in a multiphase porous medium. The transient gas flow analysis included the effect of temperature on fluid properties and gas compressibility. The heat energy transport analysis was performed under the thermodynamic equilibrium condition with phase-summed effective thermal properties. Multi-component mass transport was performed under local equilibrium for partitioning between phases. Model verification was performed to the extend possible using analytical and available experimental data for different physical processes. The second paper of this two-part series will demonstrate the applicability of thermal venting technique through numerical simulations of hypothetical laboratory and field-scale scenarios.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.