Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part II.

This is Part II of a review covering the wide range of issues associated with all aspects of the use and responsible disposal of foam and plastic wastes containing toxic or potentially toxic flame retardants. We identify basic and applied research needs in the areas of responsible collection, pretreatment, processing, and management of these wastes. In Part II, we explore alternative technologies for the management of halogenated flame retardant (HFR) containing wastes, including chemical, mechanical, and thermal processes for recycling, treatment, and disposal.

Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I.

Flame retardants (FRs) are added to foams and plastics to comply with flammability standards and test requirements in products for household and industrial uses. When these regulations were implemented, potential health and environmental impacts of FR use were not fully recognized or understood. Extensive research in the past decades reveal that exposure to halogenated FRs, such as those used widely in furniture foam, is associated with and/or causally related to numerous health effects in animals and humans. While many of the toxic FRs have been eliminated and replaced by other FRs, existing products containing toxic or potentially toxic chemical FRs will remain in use for decades, and new products containing these and similar chemicals will permeate the environment. When such products reach the end of their useful life, proper disposal methods are needed to avoid health and ecological risks. To minimize continued human and environmental exposures to hazardous FR chemicals from discarded products, waste management technologies and processes must be improved. This review discusses a wide range of issues associated with all aspects of the use and responsible disposal of wastes containing FRs, and identifies basic and applied research needs in the areas of responsible collection, pretreatment, processing, and management of these wastes.

UGT2B17 copy number gain in a large ankylosing spondylitis multiplex family.

BACKGROUND: The primary objective of this study is to identify novel copy number variations (CNVs) associated with familial ankylosing spondylitis (AS). A customized genome-wide microarray was designed to detect CNVs and applied to a multiplex AS family with six (6) affected family members. CNVs were detected using the built-in DNA analytics aberration detection method-2 (ADM-2) algorithm. Gene enrichment analysis was performed to observe the segregation. Subsequent validation was performed using real time quantitative fluorescence polymerase reaction (QF-PCR). The frequency of copy number variation for the UGT2B17 gene was then performed on two well-defined AS cohorts. Fisher exact test was performed to quantify the association. RESULTS: Our family-based analysis revealed ten gene-enriched CNVs that segregate with all six family members affected with AS. Based on the proposed function and the polymorphic nature of the UGT2B17 gene, the UGT2B17 gene CNV was selected for validation using real time QF-PCR with full concordance. The frequency of two copies of the UGT2B17 gene CNV was 0.41 in the Newfoundland AS cases and 0.35 in the Newfoundland controls (OR = 1.26(0.99-1.59); p < 0.05)), whereas the frequency of two (2) copies of the UGT2B17 gene CNV was 0.40 in the Alberta AS cases and 0.39 in the Alberta controls (OR = 1.05(95% CI: 0.83-1.33); p < 0.71)). CONCLUSIONS: A genome-wide microarray interrogation of a large multiplex AS family revealed segregation of the UGT2B17 gene CNV among all affected family members. The association of the UGT2B17 CNV with AS is particularly interesting given the recent association of this CNV with osteoporosis and the proposed function as it encodes a key enzyme that inhibits androgens. However, two copies of the UGT2B17 gene CNV were only marginally significant in a uniplex AS cohort from Newfoundland but not in a uniplex AS cohort from Alberta.

Quantifying factors limiting aerobic degradation during aerobic bioreactor landfilling.

A bioreactor landfill cell at Yolo County, California was operated aerobically for six months to quantify the extent of aerobic degradation and mechanisms limiting aerobic activity during air injection and liquid addition. The portion of the solid waste degraded anaerobically was estimated and tracked through time. From an analysis of in situ aerobic respiration and gas tracer data, it was found that a large fraction of the gas-filled pore space was in immobile zones where it was difficult to maintain aerobic conditions, even at relatively moderate landfill cell-average moisture contents of 33-36%. Even with the intentional injection of air, anaerobic activity was never less than 13%, and sometimes exceeded 65%. Analyses of gas tracer and respiration data were used to quantify rates of respiration and rates of mass transfer to immobile gas zones. The similarity of these rates indicated that waste degradation was influenced significantly by rates of oxygen transfer to immobile gas zones, which comprised 32-92% of the gas-filled pore space. Gas tracer tests might be useful for estimating the size of the mobile/immobile gas zones, rates of mass transfer between these regions, and the difficulty of degrading waste aerobically in particular waste bodies.

Comparison of thermophilic anaerobic and aerobic treatment processes for stabilization of green and food wastes and production of soil amendments.

The management of organic wastes is an environmental and social priority. Aerobic digestion (AED) or composting and anaerobic digestion (AD) are two organic waste management practices that produce a value-added final product. Few side-by-side comparisons of both technologies and their digestate products have been performed. The objective of this study was to compare the impact of initial feedstock properties (moisture content and/or C/N ratio) on stabilization rate by AED and AD and soil amendment characteristics of the final products. Green and food wastes were considered as they are two of the main contributors to municipal organic waste. Stabilization rate was assessed by measurement of CH4 and CO2 evolution for AD and AED, respectively. For AD, CH4 yield showed a second-order relationship with the C/N content (P < 0.05); the optimal C/N ratio indicated by the relationship was 25.5. For AED, cumulative CO2 evolution values were significantly affected by the C/N ratio and moisture content of the initial feedstock (P < 0.05). A response surface model showed optimal AED stabilization for a C/N of 25.6 and moisture of 64.9% (wet basis). AD final products presented lower soluble chemical oxygen demand (COD) but lower humification degree and aromaticity than the products from AED. This lower stability may lead to further degradation when amended to soil. The results suggest that composting feedstocks with higher C/N produces an end-product with higher suitability for soil amendment. The instability of end products from AD could be leveraged in pest control techniques that rely on organic matter degradation to produce compounds with pesticidal properties.

Ambient-temperature co-digestion of low-solids municipal and industrial waste mixtures: Insights from molecular analyses.

The performance of ambient temperature anaerobic co-digestion was investigated for mixtures of six substrates: canned tomato and salsa waste, portable toilet waste, septic tank waste, winery waste, beer and cider waste, and fats, oils, and grease (FOG). Laboratory semi-continuous reactor studies and molecular biological analyses revealed that beer/winery, and tomato/FOG/winery/beer mixtures resulted in the best performance in terms of biogas production (515 and 371 mL CH4/g VS, respectively) and methanogenic populations. A portable toilet/septage mixture resulted in the overall poorest performance and inhibition of microbial activity was evident. Average methane content was ~70% for all mixtures tested. The findings of this study reveal that healthy methanogen populations were present, further supporting the feasibility of biogas production via the novel feedstock mixtures in ambient temperature lagoons. Implications: Disposal of septic tank waste and other high chemical oxygen demand (COD) 10 industrial food processing waste at a small wastewater treatment plant is uncommon, because it can upset the treatment process and requires additional power for treatment. Ambient-temperature covered lagoon digesters can be an alternative low-cost technology for co-digestion of these recalcitrant waste streams while generating bioenergy. The results of this study demonstrated that there is potential for implementation of unheated covered lagoon digester systems 15 for conversion of liquid wastes for production of renewable biomethane while eliminating the need to treat these wastes at a wastewater treatment plant.

Review of state of the art methods for measuring water in landfills.

In recent years several types of sensors and measurement techniques have been developed for measuring the moisture content, water saturation, or the volumetric water content of landfilled wastes. In this work, we review several of the most promising techniques. The basic principles behind each technique are discussed and field applications of the techniques are presented, including cost estimates. For several sensors, previously unpublished data are given. Neutron probes, electrical resistivity (impedance) sensors, time domain reflectometry (TDR) sensors, and the partitioning gas tracer technique (PGTT) were field tested with results compared to gravimetric measurements or estimates of the volumetric water content or moisture content. Neutron probes were not able to accurately measure the volumetric water content, but could track changes in moisture conditions. Electrical resistivity and TDR sensors tended to provide biased estimates, with instrument-determined moisture contents larger than independent estimates. While the PGTT resulted in relatively accurate measurements, electrical resistivity and TDR sensors provide more rapid results and are better suited for tracking infiltration fronts. Fiber optic sensors and electrical resistivity tomography hold promise for measuring water distributions in situ, particularly during infiltration events, but have not been tested with independent measurements to quantify their accuracy. Additional work is recommended to advance the development of some of these instruments and to acquire an improved understanding of liquid movement in landfills by application of the most promising techniques in the field.

Quantifying capture efficiency of gas collection wells with gas tracers.

A new in situ method for directly measuring the gas collection efficiency in the region around a gas extraction well was developed. Thirteen tests were conducted by injecting a small volume of gas tracer sequentially at different locations in the landfill cell, and the gas tracer mass collected from each test was used to assess the collection efficiency at each injection point. For 11 tests the gas collection was excellent, always exceeding 70% with seven tests showing a collection efficiency exceeding 90%. For one test the gas collection efficiency was 8±6%. Here, the poor efficiency was associated with a water-laden refuse or remnant daily cover soil located between the point of tracer injection and the extraction well. The utility of in situ gas tracer tests for quantifying landfill gas capture at particular locations within a landfill cell was demonstrated. While there are certainly limitations to this technology, this method may be a valuable tool to help answer questions related to landfill gas collection efficiency and gas flow within landfills. Quantitative data from tracer tests may help assess the utility and cost-effectiveness of alternative cover systems, well designs and landfill gas collection management practices.

Performance of green waste biocovers for enhancing methane oxidation.

Green waste aged 2 and 24months, labeled "fresh" and "aged" green waste, respectively, were placed in biocover test cells and evaluated for their ability to oxidize methane (CH4) under high landfill gas loading over a 15-month testing period. These materials are less costly to produce than green waste compost, yet satisfied recommended respiration requirements for landfill compost covers. In field tests employing a novel gas tracer to correct for leakage, both green wastes oxidized CH4 at high rates during the first few months of operation - 140 and 200g/m(2)/day for aged and fresh green waste, respectively. Biocover performance degraded during the winter and spring, with significant CH4 generated from anaerobic regions in the 60-80cm thick biocovers. Concurrently, CH4 oxidation rates decreased. Two previously developed empirical models for moisture and temperature dependency of CH4 oxidation in soils were used to test their applicability to green waste. Models accounted for 68% and 79% of the observed seasonal variations in CH4 oxidation rates for aged green waste. Neither model could describe similar seasonal changes for the less stable fresh green waste. This is the first field application and evaluation of these empirical models using media with high organic matter. Given the difficulty of preventing undesired CH4 generation, green waste may not be a viable biocover material for many climates and landfill conditions.

Assessing methods to estimate emissions of non-methane organic compounds from landfills.

The non-methane organic compound (NMOC) emission rate is used to assess compliance with landfill gas emission regulations by the United States Environmental Protection Agency (USEPA). A recent USEPA Report (EPA/600/R-11/033) employed a ratio method to estimate speciated NMOC emissions (i.e., individual NMOC emissions): speciated NMOC emissions=measured methane (CH4) emission multiplied by the ratio of individual NMOCs concentration relative to CH4 concentration (C(NMOCs)/C(CH4)) in the landfill header gas. The objectives of this study were to (1) evaluate the efficacy of the ratio method in estimating speciated NMOC flux from landfills; (2) determine for what types of landfills the ratio method may be in error and why, using recent field data to quantify the spatial variation of (C(NMOCs)/C(CH4)) in landfills; and (3) formulate alternative models for estimating NMOC emissions from landfills for cases in which the ratio method results in biased estimates. This study focuses on emissions through landfill covers measured with flux chambers and evaluates the utility of the ratio method for estimating NMOC emission through this pathway. Evaluation of the ratio method was performed using CH4 and speciated NMOC concentration and flux data from 2012/2013 field sampling of four landfills, an unpublished landfill study, and literature data from three landfills. The ratio method worked well for landfills with thin covers (<40 cm), predicting composite NMOC flux (as hexane-C) to within a factor of 10× for 13 out of 15 measurements. However, for thick covers (⩾40 cm) the ratio method overestimated NMOC emissions by ⩾10× for 8 out of 10 measurements. Alternative models were explored incorporating other chemical properties into the ratio method. A molecular weight squared (MW)(2)-modified ratio equation was shown to best address the tendency of the current ratio method to overestimate NMOC fluxes for thick covers. While these analyses were only performed using NMOC fluxes through landfill covers measured with flux chambers, results indicate the current USEPA approach for estimating NMOC emissions may overestimate speciated NMOC emission ⩾10× for many compounds.

Photoacoustic infrared spectroscopy for conducting gas tracer tests and measuring water saturations in landfills.

Gas tracer tests can be used to determine gas flow patterns within landfills, quantify volatile contaminant residence time, and measure water within refuse. While gas chromatography (GC) has been traditionally used to analyze gas tracers in refuse, photoacoustic spectroscopy (PAS) might allow real-time measurements with reduced personnel costs and greater mobility and ease of use. Laboratory and field experiments were conducted to evaluate the efficacy of PAS for conducting gas tracer tests in landfills. Two tracer gases, difluoromethane (DFM) and sulfur hexafluoride (SF(6)), were measured with a commercial PAS instrument. Relative measurement errors were invariant with tracer concentration but influenced by background gas: errors were 1-3% in landfill gas but 4-5% in air. Two partitioning gas tracer tests were conducted in an aerobic landfill, and limits of detection (LODs) were 3-4 times larger for DFM with PAS versus GC due to temporal changes in background signals. While higher LODs can be compensated by injecting larger tracer mass, changes in background signals increased the uncertainty in measured water saturations by up to 25% over comparable GC methods. PAS has distinct advantages over GC with respect to personnel costs and ease of use, although for field applications GC analyses of select samples are recommended to quantify instrument interferences.

Performance evaluation of an anaerobic/aerobic landfill-based digester using yard waste for energy and compost production.

The objective of this study was to evaluate a new alternative for yard waste management by constructing, operating and monitoring a landfill-based two-stage batch digester (anaerobic/aerobic) with the recovery of energy and compost. The system was initially operated under anaerobic conditions for 366 days, after which the yard waste was aerated for an additional 191 days. Off gas generated from the aerobic stage was treated by biofilters. Net energy recovery was 84.3MWh, or 46kWh per million metric tons of wet waste (as received), and the biochemical methane potential of the treated waste decreased by 83% during the two-stage operation. The average removal efficiencies of volatile organic compounds and non-methane organic compounds in the biofilters were 96-99% and 68-99%, respectively.

Long-term follow-up of different refractory systemic vasculitides treated with rituximab.

There is increasing interest in rituximab (RTX) as an alternative to cyclophosphamide (CYC) for remission induction in systemic vasculitis. Recent studies have reported high remission rates, but it is not clear how long the initial remission lasts [1, 2]. A retrospective study was undertaken of 15 cases of refractory systemic vasculitis (11 Wegener's granulomatosis, 1 Churg-Strauss syndrome, 1 cutaneous polyarteritis nodosa and 2 cryoglobulinaemic vasculitis) treated with RTX, with a mean follow-up of 34 months. All had previously received CYC, and 14, at least one other immunosuppressive drug. All had active disease when treated (median Birmingham Vasculitis Activity Score (BVAS) 2003, 13). All cases achieved remission (BVAS 2003, 0). Thirteen required re-treatment, nine due to relapse (mean, 9 months after initial treatment) and four because of repopulation or rising ANCA in the context of CYC intolerance or previous CYC refractory disease. Relapsing cases have been successfully re-treated up to five further cycles, either at B cell repopulation or at six monthly intervals. Infections were rare. Mean IgG levels fell significantly, and IgM levels became subnormal in six cases. There were three cases of neutropenia, one severe at 10 months post-treatment. These results provide further evidence that RTX is an effective induction agent in systemic vasculitis. The optimal and long-term outcome of re-treatment remains to be defined.

Mitigating methane emissions and air intrusion in heterogeneous landfills with a high permeability layer.

Spatially variable refuse gas permeability and landfill gas (LFG) generation rate, cracking of the soil cover, and reduced refuse gas permeability because of liquid addition can all affect CH(4) collection efficiency when intermediate landfill covers are installed. A new gas collection system that includes a near-surface high permeability layer beneath the landfill cover was evaluated for enhancing capture of LFG and mitigating CH(4) emissions. Simulations of gas transport in two-dimensional domains demonstrated that the permeable layer reduces CH(4) emissions up to a factor of 2 for particular spatially variable gas permeability fields. When individual macrocracks formed in the cover soil and the permeable layer was absent, CH(4) emissions increased to as much as 24% of the total CH(4) generated, double the emissions when the permeable layer was installed. CH(4) oxidation in the cover soil was also much more uniform when the permeable layer was present: local percentages of CH(4) oxidized varied between 94% and 100% across the soil cover with the permeable layer, but ranged from 10% to 100% without this layer for some test cases. However, the permeable layer had a minor effect on CH(4) emissions and CH(4) oxidation in the cover soil when the ratio of the gas permeability of the cover soil to the mean refuse gas permeability ≤ 0.05. The modeling approach employed in this study may be used to assess the utility of other LFG collection systems and management practices.

Outcome of systemic sclerosis associated interstitial lung disease treated with intravenous cyclophosphamide.

Our objective was to audit the respiratory outcome, toxicity and long-term survival of systemic sclerosis associated interstitial lung disease (SSc-ILD) treated with intravenous (i.v.) cyclophosphamide. We ascertained whether i.v. cyclophosphamide associates with a better outcome in SSc-ILD diagnosed due to a decline in screening lung function than in those diagnosed due to respiratory symptoms. A retrospective case-note audit was carried out for SSc-ILD patients treated with i.v. cyclophosphamide between January 1999 and March 2009 at the Royal Derby, Kings Mill and Nottingham University Hospitals. Forced vital capacity (FVC) and transfer factor at 6, 12 months after starting i.v. cyclophosphamide were the primary end points. Kaplan-Meier curves were plotted to estimate survival. Thirty-seven i.v. cyclophosphamide treatment cycles were administered to 36 patients (27 women). Fourteen cycles associated with side effects and eight were terminated prematurely. SSc-ILD was diagnosed due to respiratory symptoms in 13 and in response to deteriorating screening pulmonary function test (PFT) in 24 instances. Overall, i.v. cyclophosphamide led to stabilisation in lung function. However, the FVC declined by 7% in SSc-ILD presenting with respiratory symptoms over 12 months. These patients had significantly lower FVC at 6 and 12 month than those with SSc-ILD diagnosed due to decline in screening lung function. The 5-year survival was 76.1% (overall), 62.9% (diagnosed due to respiratory symptoms) and 91.5% (diagnosed due to decline in screening lung function, p = 0.05). I.V. cyclophosphamide stabilises lung function in individuals with SSc-ILD and may associate with better respiratory outcome in patients diagnosed on screening PFTs.

Field application of partitioning gas tracer test for measuring water in a bioreactor landfill.

Two field-scale partitioning gas tracer tests (PGTTs) were performed to evaluate the utility of the PGTT method for measuring water saturation and moisture content in a full-scale bioreactor landfill, where waste biodegradation resulted in elevated temperatures and significant landfill gas production. The average water saturation and moisture content were measured for waste volumes of approximately 20 m(3) and results were compared to gravimetric measurement of moisture content made on samples collected from the landfill. In the center of the landfill, the moisture content estimated from the PGTT was Mc = 0.26 +/-0.03, which was nearly identical to the gravimetric measurement of waste samples taken from the same region (Mc = 0.28). PGTT-estimated moisture contents in a dry area of the landfill were much smaller (Mc = 0.10+/-0.01) and consistent with available gravimetric measurements. Biodegradation of tracers and temporal variations in landfill gas production were minimal and did not influence the tests. These field experiments demonstrate the utility of the PGTT method for measuring water saturation and estimating moisture content in bioreactor landfills with active waste degradation and generation of landfill gases. However, use of the PGTT to estimate the in situ moisture content requires estimates of the refuse porosity, dry bulk density, and temperature, which might limit its application.