Recovery of biomass cellulose from waste sewage sludge

In our previous work, the primary sludge from wastewater treatment plants was shown to contain a considerable amount of cellulose (about 20%, based on suspended solids) owing to the discharge of toilet paper. For the purpose of using the cellulose as a biomass resource, this study examined a simple method for its recovery. When fibrous cellulose was suspended in 0.3% sulfuric acid and autoclaved at 130°C for 60 min, 85%–88% of the initial solids remained without dissolving. Under these conditions, an activated sludge sample not containing cellulose was strongly hydrolyzed and only 7% of the initial solids remained. The prescribed amounts of cellulose added to the activated sludge sample were quantitatively recovered by the autoclaving treatment. In the treatment of primary sludge containing >20% cellulose, residual solids with relatively high levels of cellulose (>69%) could be obtained. The results indicate that the method proposed here could recover cellulose practically from waste sewage sludge for biomass utilization. Received: July 17, 2000 / Accepted: July 4, 2001     

Biobased Contents of Organic Fillers and Polycaprolactone Composites with Cellulose Fillers Measured by Accelerator Mass Spectrometry Based on ASTM D6866

The biobased contents of raw materials such as starches, sugar, chitin, or wood powders for biomass plastics were measured using Accelerator Mass Spectrometry (AMS) based on ASTM D6866. AMS measures the isotope carbon ratio of ¹⁴C to ¹²C and ¹³C in graphite derived from sample powders. The biobased contents of starches, sugar or chitin were almost 100% which means that they are fully biobased. The biobased contents of the wood powders were over 140% due to the effect of the post 1950s ¹⁴C injection due to nuclear testing. Poly(ε-caprolactone) (PCL) composite samples were prepared using the polymerization and direct molding method. The starting compound was the ε-caprolactone monomer liquid combined with cellulose and inorganic fillers using aluminum triflate as a catalyst at 80 °C for 6 or 24 h. PCL cylinder-shaped composite samples with a homogeneously dispersed cellulose filler were prepared with M_n = 4,600 (M_w/M_n = 2.9). The biobased content of the PCL composite with 50 wt% cellulose filler (51.67%) measured using AMS was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol%). This is due to the higher biobased content (112.70%) of the cellulose filler used in this study. The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc.     

A New Test Method for Determining Biodegradation of Plastic Material Under Controlled Aerobic Conditions in a Soil-Simulation Solid Environment

A new test method is described for assessing biodegradation of plastic material under simulated soil conditions. An inert substrate can be activated with soil extract and nutrient and used in place of soil in biodegradation tests. The biodegradation level is evaluated by determining the carbon dioxide (CO₂) production released by the test reactors. Effects of substrate nature, solution pH, nutrient composition, soil extract concentration, and activation duration on CO₂ production were investigated, and the experimental conditions were optimized. Results obtained with cellulose showed a biodegradation rate of 80% within 28 days. Moreover, with this kind of substrate, reaction products and residues can be easily extracted and analysed.     

Transport and Immobilization of 2,4,6 15N-Trinitrotoluene in Soil Microcosms Subjected to Long Term Incubation Under Aerobic Conditions

¹⁵N-labeling and solid-state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy was applied to study the immobilization of 2,4,6 trinitrotoluene (TNT) into soil organic matter (SOM). Uncontaminated soil from the Ap horizon of a Luvisol was mixed with ¹⁵N-TNT (enrichment: 99 atm%) and laid over an unspiked layer of the same material. The latter covered soil from the Bt horizon. The microcosms were aerobically incubated under laboratory conditions for up to 11 months. After 1 week, within the total microcosm approximately 90% of the added ¹⁵N (¹⁵N_add) were recovered, mostly in the top layer (87%). After 11 months, this amount decreased to 71%, indicating losses due to denitration or transamination. Within two months, half of ¹⁵N_add had been immobilized in the residues not extractable with organic solvents and water. The amount of the sequestered ¹⁵N_add remained fairly constant until the end of the experiment pointing towards a high stability of TNT-SOM associates. Solid-state ¹⁵N NMR revealed their formation by covalent binding, most tentatively as amides. Complete reduction of TNT to triaminotoluene (TAT) was not prerequisite. The most pronounced downwards movement of ¹⁵N-TNT occurred during the first two months. The major part of it, however, experienced quick immobilization, leaving approximately 10% of ¹⁵N_add recovered in the leachate at the end of the experiment. Calculations indicated contributions of inorganic ¹⁵N_add. Approximately 25% of its organic ¹⁵N_add originated from condensed N, suggesting that in soils the transport of partly reduced TNT is in close association with the organic matter of the soil solution to which they are covalently bound.     

西瓜、瓜叶及瓜田土壤中乙撑硫脲残留量的液相色谱分析方法研究

建立了一种采用高效液相色谱仪测定乙撑硫脲（ETU）在西瓜、瓜叶和瓜田土壤中残留量的分析方法。空白样品标准添加浓度为0.05-10.0mg/kg时,平均回收率为83.2%-90.7%,变异系数＜12.5%,样品中ETU的最低检出浓度为0.02mg/kg。该方法的准确度和灵敏度较高。应用本方法测定西瓜、瓜叶和瓜田土壤的 ETU残留量,取得了满意的结果。     

Phosphate recovery from phosphorus-rich solution obtained from chicken manure incineration ash

The recovery of phosphorus from waste is very important for Japan because Japan has no natural phosphorus resources. In order to recover phosphorus from incineration ash of chicken manure, an acid dissolution–alkali precipitation method was investigated. Phosphorus content in the ash was 8%. The ash was treated with hydrochloric acid to obtain phosphorus-rich solution. Phosphorus could then be recovered as a precipitant by adding sodium hydroxide solution into the phosphorus-rich solution and gradually changing the pH in the solution to 3, 4, and 8. At pH 3, a small amount of phosphorus was precipitated to remove iron, which would cause coloring of subsequent precipitants. At pH 4, 84% of the phosphorus in the original solution could be recovered as CaHPO₄ · 2H₂O with a purity of 92%. At pH 8, 8% of the phosphorus in the phosphorus-rich solution could be recovered as identified hydroxyapatite. A recovery rate of 92% phosphorus as CaHPO₄ · 2H₂O and identified as hydroxyapatite was achieved.     

Recovery of yttrium from fluorescent powder of cathode ray tube,CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2² full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3 M of sulphuric acid, 10% v/v of H₂O₂ concentrated solution at 30% v/v, 10% w/w pulp density, 70 °C and 3 h of reaction.Two series of precipitation tests for zinc are carried out: a 2² full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2–2.5% and 10–12% v/v of Na₂S concentrated solution at 10% w/v. In these conditions the coprecipitation of yttrium is of 15–20%.Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75–80%.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

Studies on materials containing polysaccharides as soil amendments 1: effects on animal waste water purification in a potting experiment

A potting experiment was carried out to determine the effects of soil amendments containing polysaccharides and earthworms on a land application system for the purification of animal waste water. The following soil amendments were used: purified Konjak powder (KP, powder containing glucomannan made from the root system of devil's tongue, Amorphophalus rivieri Dur.), crystallized cellulose (CC), and a mixture of the two (MX). These soil amendments were added to the pots, and then Chrysanthemum corondria were planted in the earthworm pots (A pots), the nonearthworm pots (B pots), and the control pots (C pots); the first two plots received primary-treated animal waste water, and the other one received tap water. The following items were then measured: pH, electrical conductivity, chemical oxygen demand (COD_Mn), total nitrogen (TN), total phosphorus, the volume of drained water from each pots, the height and dry matter weight of plants, and the water permeability into the soil. The MX-A pots, i.e., the pots containing both soil amendments and earthworms, gave good results, especially for water permeability, plant growth, the purification of COD_Mn, and TN. These results suggest that the presence of soil amendments and earthworms may enhance the improvement of water quality in land application systems using vegetation. Received: December 9, 1998 / Accepted: February 8, 2000     

Aluminium recovery vs. hydrogen production as resource recovery options for fine MSWI bottom ash fraction

Waste incineration bottom ash fine fraction contains a significant amount of aluminium, but previous works have shown that current recovery options based on standard on-step Eddy Current Separation (ECS) have limited efficiency. In this paper, we evaluated the improvement in the efficiency of ECS by using an additional step of crushing and sieving. The efficiency of metallic Al recovery was quantified by measuring hydrogen gas production. The ash samples were also tested for total aluminium content with X-ray fluorescence spectroscopy (XRF). As an alternative to material recovery, we also investigated the possibility to convert residual metallic Al into useful energy, promoting H₂ gas production by reacting metallic Al with water at high pH. The results show that the total aluminium concentration in the <4 mm bottom ash fraction is on average 8% of the weight of the dry ash, with less than 15% of it being present in the metallic form. Of this latter, only 21% can be potentially recovered with ECS combined with crushing and sieving stages and subsequently recycled. For hydrogen production, using 10 M NaOH at 1 L/S ratio results in the release of 6–11 l of H₂ gas for each kilogram of fine dry ash, equivalent to an energy potential of 118 kJ.     

Production of technical grade phosphoric acid from incinerator sewage sludge ash (ISSA)

The recovery of phosphorus from sewage sludge ash samples obtained from 7 operating sludge incinerators in the UK using a sulfuric acid washing procedure to produce a technical grade phosphoric acid product has been investigated. The influences of reaction time, sulfuric acid concentration, liquid to solid ratio and source of ISSA on P recovery have been examined. The optimised conditions were the minimum stoichiometric acid requirement, a reaction time of 120 min and a liquid to solid ratio of 20. Under these conditions, average recoveries of between 72% and 91% of total phosphorus were obtained. Product filtrate was purified by passing through a cation exchange column, concentrated to 80% H₃PO₄ and compared with technical grade H₃PO₄ specifications. The economics of phosphate recovery by this method are briefly discussed.     

The Transit of 35SO4 2- and 3H2O Added In Situ to Soil in a Boreal Coniferous Forest

A solution containing ³⁵SO₄ ^2- and ³H₂O was applied to four plots (5 × 5 m) in a boreal coniferous forest in the Laflamme Lake watershed, Québec, under two contrasting conditions: in summer (plots 1 and 2), and on the snowpack before snowmelt (plots 3 and 4). The transit of both these tracers in the soil solution was then followed through a network of soil lysimeters located at different depths. Four months after the summer application, ³H₂O had infiltrated the whole soil profile at plot 1, while ³⁵SO₄ ^2- was only observed in the LFH and Bhf horizons. A ³⁵SO₄ ^2- budget calculated from mid-August to November indicated that 89 and 10.6% of the added ³⁵SO₄ ^2- was retained within the LFH and the Bhf layers, respectively. Fifteen months later, the added ³⁵SO₄ ^2- was distributed in the following proportions within the soil horizons: LFH (73.7%), Bhf (11.8%) and Bf (12.8%), for a total retention rate of 98.3%. The superficial penetration of ³H₂O at plot 2 was indicative of a major lateral water movement that prevented the calculation of a ³⁵SO₄ ^2- budget. This situation also was observed at plot 4 during snowmelt. At plot 3, ³H₂O moved freely through the soil profile and a significant fraction of the added ³⁵SO₄ ^2- reached the B horizons, where it was presumably adsorbed on aluminum (Al) and ferric (Fe) oxides. The ³⁵SO₄ ^2- budget for plot 3 from March to November indicated that 87% of the added ³⁵SO₄ ^2- was retained within the soil profile, with most being retained in the B horizons (LFH = 33.1%, Bhf = 33.1%, Bf = 20.8%). The contrasting retention patterns of ³⁵SO₄ ^2- within the soil profile following the summer addition and snowmelt likely was caused by the contrastingsoil temperatures and soil solution residence times within the differentsoil layers. The persistence of ³⁵SO₄ ^2- in the soil solution of the entire profile long after the initial tracer infiltration, and the relative temporal stability of specific activity of SO₄ ^2-, point to the establishment of an isotopic equilibrium between the added ³⁵SO₄ and the active S-containing reservoirs within a given soil horizon. Overall, the results clearly illustrate the very strong potential for ³⁵SO₄ ^2- retention and recycling in forest soils.     

Determination of suitable TPH remediation approach via MANOVA and inferential statistics assessment

Soil contamination resulting from petroleum hydrocarbon contaminants poses a fairly substantial hazard to human health and the environment. Phytoremediation, land farming, and chemico–biological stabilization were used to treat total petroleum hydrocarbons (TPHs) and polycyclic aromatic hydrocarbons (PAHs) at a crude oil polluted soil site in Nigeria. A field pilot study was conducted by preparing nine cells with subcells attached to each serving as a control with an overall area of 1.53 m². A complete block design method was used for the study. The prepared soil sample cells were divided into three groups with each group having approximately 300 kg of soil and delineated as low, medium, and high test plots. The low samples were spiked with 6.1 kg of crude oil, the medium samples were spiked with 12.2 kg of crudeoil, and the high samples were spiked with 18.3 kg of crude oil. Each row containing three cells with low, medium, and high concentrations were treated separately using the three treatment methods. The ratio of the soil sample to the organic amendment for the treatments was 2:1. The results showed over 90% degradation in the initial concentration of TPH and PAHs across different contaminant levels except in the control subcells where only 30% of degradation was recorded. Multivariate analysis of variance was employed to assess the significant difference in each treatment group while inferential statistics using a mean performance plot was used to ascertain the optimum treatment method. Land farming, chemico–biological stabilization, and phytoremediation ranked 1, 2, and 3, respectively. In conclusion, the three treatment methods employed all degraded the contaminants (TPH and PAHs) with land farming emerging as the best method.     

Energy-efficient modification of reduction-melting for lead recovery from cathode ray tube funnel glass

Lead can be recovered from funnel glass of waste cathode ray tubes via reduction melting. While low-temperature melting is necessary for reduced energy consumption, previously proposed methods required high melting temperatures (1400 °C) for the reduction melting. In this study, the reduction melting of the funnel glass was performed at 900–1000 °C using a lab-scale reactor with varying concentrations of Na₂CO₃ at different melting temperatures and melting times. The optimum Na₂CO₃ dosage and melting temperature for efficient lead recovery was 0.5 g per 1 g of the funnel glass and 1000 °C respectively. By the reduction melting with the mentioned conditions, 92% of the lead in the funnel glass was recovered in 60 min. However, further lead recovery was difficult because the rate of the lead recovery decreased as with the recovery of increasing quantity of the lead from the glass. Thus, the lead remaining in the glass after the reduction melting was extracted with 1 M HCl, and the lead recovery improved to 98%.     

Accumulation of pollutant nitrogen in calcareous and acidic grasslands: Evidence from N flux and 15N tracer studies

Semi-natural calcareous and acidic grasslands are known to be sensitive to increased atmospheric N deposition. However, the fate of pollutant N within these systems is unknown. This paper reports on the first studies to determine the fate of added N within a calcareous and an acidic grassland subject to long-term simulated enhanced N deposition. Intact soil/turf cores were removed from field plots treated for six years with enhanced N deposition (ambient +0, +35 and +140 kg N ha^?1 year^?1). Cores were inserted into lysimeters and output fluxes of N were monitored in detail. Complete N budgets—calculated from the N flux data—showed considerable accumulation of N within the treated grasslands, up to 76% and 38% of pollutant N in the calcareous and acidic grasslands respectively. In the second study, the short-term (21 day) fate of pollutant N was determined by tracing ¹⁵N labelled ammonium nitrate (+35 kg N ha^?1 year^?1) though the acidic and calcareous lysimeters into plant, soil and leachate pools. Up to 91% and 59% of ¹⁵N was recovered in soils and vegetation of the calcareous and acidic grasslands respectively, with negligible amounts recovered in soil extractable ammonium and nitrate (<0.3%) and in leachate (<0.02%). This rapid short-term immobilisation of pollutant N supports the long-term accumulation of the element calculated from the N flux study.     

Assessment of compost dosage in farmland through ecotoxicological tests

A research project was carried out to evaluate ecotoxicological effects of mature compost addition to agricultural soil, using a battery of ecotoxicological tests. The following species were selected: plant of Lepidium sativum, earthworm Eisenia foetida, aquatic crustacean Daphnia magna and bacteria Vibrio fischeri. The tests were classified as “direct tests” using solid compost samples and “indirect tests” using compost leaching test eluate. The direct bioassays were performed using compost added to artificial soil in concentrations ranging from 2.5 to 100 % (w/w); the indirect ones considered compost eluate, added to a standard solution in the same concentrations used in the direct tests. Both tests aimed at obtaining the ecotoxicological parameters (LC₅₀ and EC₅₀). These values were then utilized to implement the Species Sensitivity Distribution (SSD) analysis and extrapolate the Hazard Concentration (HC), a useful threshold to preserve the biodiversity of agricultural ecosystems. Results indicated an increase in compost toxicity with greater compost concentrations; in particular, for direct tests compost dosage below 10 % showed low toxicity, while for indirect ones the toxicity was higher. Furthermore, SSD analysis showed a Hazardous Concentration (HC₅) for direct bioassays of 3.5 % and for indirect of 14 %.     

Selection of adsorbents for treatment of leachate: batch studies of simultaneous adsorption of heavy metals

The simultaneous adsorption of copper (Cu), cadmium (Cd), nickel (Ni), and lead (Pb) ions from spiked deionized water and spiked leachate onto natural materials (peat A and B), by-product or waste materials (carbon-containing ash, paper pellets, pine bark, and semi-coke), and synthetic materials (based on urea-formaldehyde resins, called blue and red adsorbents) or mixtures thereof was investigated. The adsorbents that gave the highest metal removal efficiencies were peat A, a mixture of peat B and carbon-containing ash, and a mixture of peat A and blue. At an initial concentration of 5 mg/l for each metal, the removal of each species of metal ion from spiked water and spiked leachate solutions was very good (>90%) and good (>75%), respectively. When the initial concentration of each metal in the solutions was twenty times higher (100 mg/l), there was a noticeable decrease in the removal efficiency of Cu²⁺, Cd²⁺, and Ni²⁺, but not of Pb²⁺. Langmuir monolayer adsorption capacities, q_m, on peat A were found to be 0.57, 0.37, and 0.36 mmol/g for Pb²⁺, Cd²⁺, and Ni²⁺, respectively. The order of metal adsorption capacity on peat A was the same in the case of competitive multimetal adsorption conditions as it was for single-element adsorption, namely Pb²⁺ > Cd²⁺ ≥ Ni²⁺. The results show that peat alone (an inexpensive adsorbent) is a good adsorbent for heavy metal ions.     

Degradation and mineralization of cellulose acetate in simulated thermophilic compost environments

Residual cellulose acetate (CA) films with initial degree of substitution (DS) values of 1.7 and 2.5 (CA DS-1.7 and DS-2.5) were recovered from a simulated thermophilic compost exposure and characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (¹H NMR), and scanning electron microscopy (SEM) to determine changes in polymer molecular weight and DS and to study microbial colonization and surface morphology, respectively. During the aerobic degradation of CA DS-1.7 and CA DS-2.5 films exposed for 7 and 18 days, respectively, the number-average molecular weight (M _n) of residual polymer decreased by 30.4% on day 5 and 20.3% on day 16, respectively. Furthermore, a decrease in the degree of substitution from 1.69 to 1.27 (4-day exposure) and from 2.51 to 2.18 (12-day exposure) was observed for the respective CA samples. In contrast, CA films (DS-1.7 and DS-2.5) which were exposed to abiotic control vessels for identical time periods showed no significant changes inM _n and DS. SEM photographs of CA (DS-1.7 and DS-2.5) film surfaces after compost exposures revealed severe erosion and corresponding microbial colonization. Similar exposure times for CA films in abiotic control vessels resulted in only minor changes in surface characteristics by SEM observations. The conversion of CA DS-1.7 and DS-2.5 to CO₂ was monitored by respirometry. In these studies, powdered CA was placed in a predigested compost matrix which was maintained at 53°C and 60% moisture content throughout the incubation period. A lag phase of 10- and 25-day duration for CA DS-1.7 and DS-2.5, respectively, was observed, after which the rate of degradation increased rapidly. Mineralization of exposed CA DS-1.7 and DS-2.5 powders reported as the percentage theoretical CO₂ recovered reached 72.4 and 77.6% in 24 and 60 days, respectively. The results of this study demonstrated that microbial degradation of CA films exposed to aerobic thermophilic laboratory-scale compost reactors not only results in film weight loss but also causes severe film pitting and a corresponding decrease in chainM _n and degree of substitution for the residual material. Furthermore, conversions to greater than 70% of the theoretical recovered CO₂ for CA (DS 1.7 and 2.5) substrates indicate high degrees of CA mineralization.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Laboratory Measurement of Dry Deposition of Ozone onto Northern Chinese Soil Samples

We used laboratory experiments to investigate surface resistance (R _c) to dry deposition of ozone (O₃) on different types of soil samples collected from the arid deserts and the Loess Plateau of northern China. Furthermore, we measured the factors that affected R _c, which depends on the physical and chemical interaction between trace constituents and the deposition surface, and evaluated deposition velocity (V _d). There was little influence of geometric surface area, soil weight, or O₃ concentration on V _d of O₃. The effect of relative humidity (RH) (i.e. moisture content of the soil) on O₃ uptake was in agreement with results reported in the literature: a distinct RH dependence of V _d and little uptake under water-saturated conditions were observed. R _c values for all the soil samples examined were in the range 0.21–3.3 s mm⁻¹ and were exponentially related to the surface area of the particles and the organic carbon content of each soil sample at RH of both <10 and 60%.     

Biodegradation of Polyaromatics Synthesized by Peroxidase-Catalyzed Free-Radical Polymerization

Polymers formed from peroxidase-based free-radical polymerization reactions were characterized for rates of mineralization against lignin and humic acid controls. Degradation studies were carried out in soil systems over 202 days and cumulative net CO₂ was determined. Whereas mineralization of the humic acid and alkali lignin controls totaled ca. 20% at the end of the test exposure, there was essentially no net mineralization of the hydrolytic lignin control. Mineralization of the test samples totaled 5% for poly(p-ethylphenol) and 11% for poly(m-cresol). At the same time, mineralization of the poly(p-phenyl phenol) totaled 64%. Conversely, the readily biodegradable polymers cellulose and PHB reached values of 91 to 97% in less than 60 days. Our data suggest that the mineralization kinetics of the enzymatically derived polyaromatics mimic those of the naturally occurring heteropolymers.