Recent Recovery of Lake Water Quality in Southern Québec Following Reductions in Sulfur Emissions

Since 1985, monitoring activities have been conducted in a networkof 43 lakes comprising the Québec portion of the Long-Range Transport of Airborne Pollutants (LRTAP) program. The results to date indicate that Québec lakes generally are responding positively to the generalized decline in precipitation sulfate (SO₄ ^2-), with 40 of the 43 lakes now showing steep declines in SO₄ ^2- concentrations. The drop in SO₄ ^2- was associated with a significant decrease in Ca²⁺ concentrations in 77% of the lakes (67% for Mg²⁺ concentrations). Overall, the acid-neutralizing capacity was increasing in 19 lakes and decreasing only in three, while 21 lakes showed no temporal trends. Compared with previous trend studies of the LRTAP-Québec network for the period of 1985–1993, the longer period (1985–1999) shows a clear improvement, with the proportion of lakes that were acidifying changing from 24 to 7% and with the proportion of lakes that were recovering changing from 16 to 35%. These observations suggest that the recent drop in SO₄ ^2- deposition in the northeastern U.S. and eastern Canada was significant enough to allow chemical recovery for a significant proportion of Québec lakes.     

Heat budget for a waste lift placed under freezing conditions at a landfill operated in a northern climate

A landfill operated in Ste. Sophie, Québec, Canada was instrumented to better understand the waste stabilization process in northern climates. Instrument bundles were placed within the waste to monitor temperature, settlement, oxygen, moisture content, total load, mounding of leachate and electrical conductivity. A finite element model was developed to simulate the heat budget for the first waste lift placed in the winter months and was calibrated using the first 10.5 months of collected temperature data. The calibrated model was then used to complete a sensitivity analysis for the various parameters that impact the heat budget. The results of the analysis indicated that the heat required for phase change to thaw the liquid fraction within frozen waste had a significant impact on the heat budget causing sections of waste to remain frozen throughout the simulation period. This was supported by the data collected to date at Ste. Sophie and by other researchers indicating that frozen waste placed during the winter months can remain frozen for periods in access of 1.5 years.     

Kinetics of scrap tyre pyrolysis under vacuum conditions

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene–butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene–butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability.The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.     

Critical Loads and Exceedances of Acid Deposition and Associated Forest Growth in the Northern Hardwood and BorealConiferous Forests in Québec,Canada

We used the Québec forest monitoring network (`Réseaud'Étude et de Surveillance des Écosystèmes Forestiers' or RESEF)along with its atmospheric monitoring stations to assess criticalS and N loads and their combined soil acidification exceedancesfor natural ecosystems of the northern hardwood and borealconiferous forests in Québec, Canada. Critical loads (CL) forforest soil acidification were calculated using the simple mass-balance (SMB) approach and with the steady-state PROFILE model.Atmospheric deposition rates for water, S, N, Ca, Mg, Na, and K,for the years 1989–1993, and detailed, plot-specific forest andsoil characteristics were used as input. The SMB model alsorequired information regarding nutrient uptake and storage in theaboveground woody biomass. The CL calculations indicated that,from the 31 RESEF plots, 18 received atmospheric acidic inputs inexcess of their CL (55 and 61% of the hardwood and coniferousplots, respectively). The range of CL exceedance varied from 60to 470 eq ha^-1 yr^-1 for the hardwood stands, and from 10to 590 eq ha^-1 yr^-1 for the coniferous stands. The standswith CL exceedance were mainly located in the western and centralpart of the province. Stand growth associated with exceedanceclass of acidity was determined using the RESEF plots along withselected permanent forest survey plots having similar sitecharacteristics, but for which longer growth records wereavailable. We found a significant negative correlation betweenforest growth rates and critical soil acidification exceedancefor both the northern hardwood and the boreal conifer sites.Specifically, plots with critical load exceedances were found tohave a growth reduction of about 30% during the 1974–1982 andthe 1972–1990 measurement (plots with no soil acidificationexceedance served as a control). While this correlation is notnecessarily causal, it is nevertheless consistent with theexpectation that increased losses of soil base cations on accountof increased soil acidification should and could lead todeteriorating forest health conditions.     

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.     

Recycling of waste lead storage battery by vacuum methods

Waste lead storage battery is the most important recyclable lead material not only in various European and other OECD countries but also in China. Pollution control of lead has become the focus of people’s attention in the world. A vacuum process for recycling waste lead storage battery was developed in this work. The experimental results showed that all the valuable materials in waste lead storage battery could be satisfactorily recycled by vacuum technologies. The vacuum melting of lead grids and the vacuum reduction of lead pastes produce the lead bullion with the direct recovery ratio of 96.29% and 98.98%, respectively. The vacuum pyrolysis of plastics can produce pyrolysis oil with yield of more than 93 wt.%. These vacuum recycling technologies offer improvements in metallurgical and environmental performance.     

Evaluation of a soil‐amendment process demonstration for reducing the bioavailability of lead

The U.S. Environmental Protection Agency (EPA) evaluated an in‐situ application of a soil‐amendment process at a residential site that was contaminated with lead. The goal of the evaluation was to determine if the soil‐amendment process resulted in lower concentrations of bioavailable lead in the contaminated soils. The relative bioavailability of lead (bioaccessible lead) was measured by an in vitro test procedure that uses a highly acidic extraction procedure to simulate human digestive processes. The soil‐amendment demonstration showed that the 11.2 percent mean reduction in bioavailable lead concentration between untreated and treated soils was not statistically different. © 2002 Wiley Periodicals, Inc.     

Soil washing for volume reduction of radioactively contaminated soils

The Office of Radiation and Indoor Air of the U.S. Environmental Protection Agency has demonstrated a soil washing plant for the treatment of radioactively contaminated soils from two Superfund sites in New Jersey. The plant employs unit operations that are widely used in the processing of minerals and coal. These operations were examined and tested to determine how they would apply to volume reduction of these contaminated soils. In this context, they are considered to be innovative candidates for remediation of other sites with large volumes of soil contaminated with low-level radioactivity. Laboratory testing of soil characteristics and behavior in unit processes is used to assess the applicability of volume reduction/chemical extraction (VORCE) technology to specific sites.     

Catalytic pyrolysis of car tire waste using expanded perlite

In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100 mL/min and a heating rate of 10 °C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02 wt.% at 425 °C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11 wt.% at the ratio of 0.10 with the yield increase of 8.48 wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, ¹H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C₅-C₁₅ organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties.     

Recycling of organic materials and solder from waste printed circuit boards by vacuum pyrolysis-centrifugation coupling technology

Here, we focused on the recycling of waste printed circuit boards (WPCBs) using vacuum pyrolysis-centrifugation coupling technology (VPCT) aiming to obtain valuable feedstock and resolve environmental pollution. The two types of WPCBs were pyrolysed at 600°C for 30 min under vacuum condition. During the pyrolysis process, the solder of WPCBs was separated and recovered when the temperature range was 400-600°C, and the rotating drum was rotated at 1000 rpm for 10 min. The type-A of WPCBs pyrolysed to form an average of 67.91 wt.% residue, 27.84 wt.% oil, and 4.25 wt.% gas; and pyrolysis of the type-B of WPCBs led to an average mass balance of 72.22 wt.% residue, 21.57 wt.% oil, and 6.21 wt.% gas. The GC-MS and FT-IR analyses showed that the two pyrolysis oils consisted mainly of phenols and substituted phenols. The pyrolysis oil can be used for fuel or chemical feedstock for further processing. The recovered solder can be recycled directly and it can also be a good resource of lead and tin for refining. The pyrolysis residues contained various metals, glass fibers and other inorganic materials, which could be recovered after further treatment. The pyrolysis gases consisted mainly of CO, CO(2), CH(4), and H(2), which could be collected and recycled.     

Effective low-temperature thermal aeration of soils

Low-temperature thermal aeration (LTTA) is a remedial technology developed by Canonie Environmental Services Corp. (Canonie) for use on soils containing nonchlorinated hydrocarbons, chlorinated solvents, volatile organic compounds (VOCs), chlorinated pesticides, and low levels of polynuclear aromatic hydrocarbons (PAHs). The LTTA system separates these hazardous constituents from excavated soils and allows the treated soils to be redeposited on-site without restriction. This article describes the various components and operation of LTTA systems for the remediation of soils contaminated with chlorinated and nonchlorinated constituents. The article also details the results of projects completed to date, principally for soil impacted with chlorinated hydrocarbons, and discusses the general characteristics and results of systems used for soils contaminated with nonchlorinated hydrocarbons (gasoline, etc.).     

Total recycling of CCA treated wood waste by low-temperature pyrolysis

A system to turn a potentially harmful stream of solid waste into a set of substreams with either commercial value or highly concentrated residual streams is presented. The waste which is considered is metal impregnated (in particular Chromated Copper Arsenate (CCA) treated) wood waste and timber, such as telephone poles, railway sleepers, timber from landscape and cooling towers, wooden silos, hop-poles, cable drums and wooden playground equipment. These waste streams sum up to several 100,000 tons of material per year currently to be dumped in every major country of the European Community (EC). Technologies need to be developed to reduce this CCA treated wood waste, such that all of the metals are contained in a marketable product stream, and the pyrolysis gases and/or pyrolysis liquid are used to their maximum potential with respect to energy recuperation. Pyrolysing the CCA treated wood waste may be a good solution to the growing disposal problem since low temperatures and no oxidising agents are used, which result in lower loss of metals compared to combustion. An experimental labscale pyrolysis system has been developed to study the influence of the pyrolysis temperature and the duration of the pyrolysis process on the release of metals and the mass reduction. The macrodistribution and microdistribution of the metals in the solid pyrolysis residue is studied using Inductively Coupled Plasma Mass Spectrometry (ICP–MS) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis (SEM–EDXA). Furthermore, a complete mass balance is calculated over the pyrolysis system. Based on these results a semi-industrial pyrolysis system (pilot plant scale) has been developed consisting of three stages: grinding, packed bed pyrolysis and metal separation. Special types of equipment have been developed to carry out the three stages. A new grinding system has been developed, based on a crushing mechanism rather than a cutting mechanism. The crushed wood is introduced by means of a screw feeding system into a reaction column. In this pyrolysis reactor the wood is heated by subjecting it to a flow of hot gases. This causes an adiabatic pyrolysis, which results in volatilisation of the volatile compounds whereas the mineral compounds (containing the metals) remain entrapped in a coal-type residue which is very rich in carbon. The condensable compounds in the pyrolysis gas condense while leaving the reaction zone due to the inverse temperature gradient. The pyrolysis gas leaving the reactor is used as fuel for the hot gas generator. The charcoal which is extracted at the bottom of the reactor, is cooled, compressed, removed and stored, ready to feed the subsequent stage. A specially developed grinder is used to remove the metal particles from the charcoal and the separation between metal and charcoal particles is accomplished in a pneumatic centrifuge as a result of the difference in density. Using this system the ultimate waste is less than 3% of the initial wood mass. Results obtained with a semi-industrial scale prototype confirm the effectiveness of the process.     

Electrochemical remediation of heavy metal contaminated soils

Over the years, many soils have been contaminated with toxic heavy metals as a result of a variety of industrial and military activities. Electrokinetic soil treatment is an emerging technology that could prove to be very effective in the remediation of these sites. “Real-world” heavy metal contaminated (Pb(II), Cd(II), and Cr(III)) soils from three military sites with varying soil properties were subjected to electrokinetic treatment in the laboratory. Metal extractants (chelating agents and acids) were studied and found to be effective in enhancing the electrokinetic process. Results indicated that heavy metal removal efficiencies varied in the three soils tested. In one case, removal efficiencies of 90 percent and 60 percent were obtained for Cd and Cr, respectively, for the nitric acid amended experiments. For another case, over 60 percent of the total Pb in the system was deposited near the cathode for the non-amended and the citric-acid amended tests. Conversely, in the third case, the electrokinetic soil-washing treatment process failed to produce significant removal of any metal contaminant. The discrepancies that exist between the metal removal results of the three soils were attributed to the different physiochemical characteristics of each soil.     

Pyrolysis technologies for municipal solid waste: A review

Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO₂ and NH₃, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested.     

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

Valorisation of waste tyre by pyrolysis in a moving bed reactor

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.     

Analysis of good practices,barriers and drivers for ELTs pyrolysis industrial application

Boosting of eco-innovative solutions for End of Life Tyres (ELTs) management, under the principles of the EU Resource Efficiency Roadmap and the Waste Framework Directive, can not only diminish the environmental hazards and the consequent societal cost, but also result to the establishment of a novel perception regarding ELTs; thus, a valuable stock of resources that can be exploited. Despite the extensive scientific research of the previous years on ELTs depolymerisation via pyrolysis highlighting its eco-innovative characteristics, the use of pyrolysis to process scrap tyres has not yet achieved a broad commercial success, with economic viability and product standardization to constitute the primary impediments. More specifically, pyrolysis was not applied to an extensive industrial scale so far, due to deficient market analysis, legislative barriers, economic instability and sometimes public acceptance. All the above issues are addressed by the present study. Modifications on current EU legislation can prevent or reduce delays or derailment of efforts on pyrolysis, through its differentiation from incineration. The attainment of economic viability could be realized through the valorization of the pyrolytic char towards activated carbon production for environmental depollution applications; needless to say, the penetration on niche and well-organised markets is more than essential.     

Co-pyrolysis of swine manure with agricultural plastic waste: Laboratory-scale study

Manure-derived biochar is the solid product resulting from pyrolysis of animal manures. It has considerable potential both to improve soil quality with high levels of nutrients and to reduce contaminants in water and soil. However, the combustible gas produced from manure pyrolysis generally does not provide enough energy to sustain the pyrolysis process. Supplementing this process may be achieved with spent agricultural plastic films; these feedstocks have large amounts of available energy. Plastic films are often used in soil fumigation. They are usually disposed in landfills, which is wasteful, expensive, and environmentally unsustainable. The objective of this work was to investigate both the energetics of co-pyrolyzing swine solids with spent plastic mulch films (SPM) and the characteristics of its gas, liquid, and solid byproducts. The heating value of the product gas from co-pyrolysis was found to be much higher than that of natural gas; furthermore, the gas had no detectable toxic fumigants. Energetically, sustaining pyrolysis of the swine solids through the energy of the product gas could be achieved by co-pyrolyzing dewatered swine solids (25% m/m) with just 10% SPM. If more than 10% SPM is used, the co-pyrolysis would generate surplus energy which could be used for power generation. Biochars produced from co-pyrolyzing SPM and swine solid were similar to swine solid alone based on the surface area and the ¹H NMR spectra. The results of this study demonstrated the potential of using pyrolysis technology to manage two prominent agricultural waste streams (SPM and swine solids) while producing value-added biochar and a power source that could be used for local farm operations.     

Pneumatic fracturing to remove VOCS

A new process for enhancing in-situ remediation of low-permeability soil and rock formations is presently under development at the Hazardous Substance Management Research Center (HSMRC). The patented process, known as ?pneumatic fracturing,”? consists of injecting high-pressure air or other gas into contaminated geologic formations at controlled flow rates and pressures. In fine-grained soils such as clay, pneumatic fracturing creates conductive channels in the formation, thereby increasing the permeability and exposed surface area of the contaminated soil. The potential benefits of pneumatic fracturing are significant, since in-situ remedial technologies are essentially limited by the pore gas exchange rate of the soil being treated. This article describes the results of a recent demonstration of pneumatic fracturing at an industrial site to enhance a volatile organic compound (VOC) extraction system. After establishing the baseline removal rate of soil gas effluent from the clay, soil surrounding the extraction system was fractured to enhance VOC with drawal. A substantial improvement in the VOC removal rate was observed, including: (1) flush effluent concentrations that increased up to 200 times; and (2) air flows in the formation that increased up to 1,000 times.